KR20230112139A - Resin composition, film, optical filter, solid-state imaging device and image display device - Google Patents

Abstract

A resin composition containing a color material A and a resin B, wherein the color material A contains a pigment, and the resin B contains a repeating unit b1-1 having an acid group, a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring, and a resin b1 containing a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2, in the total solids of the resin composition The resin composition whose content of the color material A is 55 mass % or more. A film using a resin composition, an optical filter, a solid-state imaging device, 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 colorant. Moreover, the present invention relates to a film using a resin composition, an optical filter, a solid-state imaging device, and an image display device.

BACKGROUND ART Manufacturing optical filters such as color filters is performed using a resin composition containing a color material.

For example, in Patent Document 1, a color filter is produced using a resin composition containing organic pigment nanoparticles having a number average particle diameter of primary particles of 50 nm or less and a ratio of number average particle diameter to volume average particle diameter ([volume average particle diameter]/[number average particle diameter]) of 1.0 to 2.0, a graft polymer having a repeating unit containing at least an organic dye moiety in the trunk chain, a polymerizable compound, and a photopolymerization initiator. that is listed.

Patent Document 1: Japanese Unexamined Patent Publication No. 2009-084418

In recent years, in solid-state imaging devices, there is a strong demand for miniaturization and thinning. For this reason, in recent years, it has been desired to further thin the film containing a color material such as a color filter used in a solid-state imaging device. In order to achieve thinning while maintaining desired spectral performance, it is necessary to increase the colorant concentration of the resin composition used for film formation.

However, when a colorant containing a pigment is used as the colorant, when the colorant concentration of the resin composition is increased, the ratio of the material that can be adsorbed to the pigment such as the resin is relatively reduced. Therefore, the pigment tends to aggregate during storage of the resin composition or during application of the resin composition, and aggregates of the pigment may occur in a film obtained using the resin composition. If such agglomerates of the pigment are generated in the film, color unevenness tends to occur in that the particle size variation of the pigment existing in the film increases, such as partially having a large particle size pigment.

Accordingly, an object of the present invention is to provide a resin composition capable of forming a film with color unevenness suppressed. Further, the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.

According to the examination of this inventor, it discovered that the said objective can be achieved with the resin composition mentioned later, and came to complete this invention. Accordingly, the present invention provides the following.

<1> A resin composition containing a color material A and a resin B,

The color material A includes a pigment,

The resin B contains a repeating unit b1-1 having an acid group, a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring, and a resin b1 containing a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2;

The resin composition in which content of the said color material A in the total solids of the said resin composition is 55 mass % or more.

<2> The resin composition according to <1>, wherein the color material A contains a phthalocyanine pigment.

<3> The resin composition according to <1> or <2>, wherein the color material A further contains a dye.

<4> The functional group b is 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, a benzoxazine structure, a benzorainurea structure, an isothiazolinone structure , phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxacyine 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, chromane structure, benzimidazolone structure, phthalimide structure, naphthalene-2,3-dicarboxyimide structure, pyrazole structure, pyrazolone structure, isoindoline structure, isoindoline structure, anthraquinone structure, tetrazole structure, benzophenone structure, triazine structure, azobenzene structure, benzalaniline structure, phenazine structure, A group containing a barbituric acid structure, a perylene structure, a perrinone 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, The resin composition according to any one of <1> to <3>.

<5> The functional group b is a naphthalimide structure, an acridone structure, a xanthone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a benzotriazole structure, a benzoxadiazole structure, a benzothiadiazole structure, a phenoxazine structure, a phenothiazine structure, a phenoxacyne structure, a phthalimide structure, a pyrazolone structure, a tetrazole structure, a benzocyanate The resin composition according to any one of <1> to <3>, which is a group containing an azolone structure or a benzoxazolinone structure.

<6> The resin composition according to any one of <1> to <5>, wherein the content of the unit b1-2 in the resin b1 is 10 to 35% by mass.

<7> The resin composition according to any one of <1> to <6>, wherein the repeating unit b1-3 includes a repeating unit having a graft chain having a polyester structure or a polyether structure.

<8> The resin composition according to any one of <1> to <7>, in which the resin B further includes a resin b2 different from the resin b1.

<9> The resin composition according to <8>, wherein the resin b2 contains a resin having an acid group different from that of the resin b1.

<10> The resin composition according to <9>, wherein the resin b2 has an acid group having a smaller pKa than the acid group of the resin b1.

<11> The resin composition according to any one of <8> to <10>, wherein the resin b2 contains at least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is sealed with an acid group.

<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 having the film according to <13>.

<15> A solid-state imaging device having the film according to <13>.

<16> An image display device having the film according to <13>.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form a film with color unevenness suppressed can be provided. In addition, a film, an optical filter, a solid-state imaging device, and an image display device can be provided.

Below, the content of this invention is demonstrated in detail.

In this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit value and an upper limit value.

In the notation of a group (atomic group) in this specification, the notation that does not describe substitution and unsubstitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of light used for exposure include bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron beams, or radiation.

In the present specification, “(meth)acrylate” represents either or both of acrylate and methacrylate, “(meth)acryl” represents both of acryl and methacryl, or either one, and “(meth)acryloyl” represents either or both of acryloyl and methacryloyl.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, a weight average molecular weight and a number average molecular weight are polystyrene conversion values measured by the GPC (Gel Permeation Chromatography) method.

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

In this specification, a pigment means a color material that is difficult to dissolve with respect to a solvent.

In this specification, the term "process" is included in this term, not only as an independent process, but also in cases where the desired 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 color material A and a resin B,

The color material A includes a pigment,

The resin B contains a repeating unit b1-1 having an acid group, a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring, and a resin b1 containing a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2;

It is characterized in that the content of the color material A in the total solid content of the resin composition is 55% by mass or more.

According to the resin composition of the present invention, by including the above-described resin b1, a film with color unevenness suppressed can be formed even when the content of the color material A in the total solids of the resin composition is 55% by mass or more.

The resin composition of the present invention is preferably used as a resin composition for optical filters. As an optical filter, a color filter, a near-infrared transmission filter, a near-infrared cutoff filter, etc. are mentioned, and it is preferable that it is a color filter. Moreover, the resin composition of this invention is used suitably for solid-state imaging devices. More specifically, it is preferably used as a resin composition for optical filters used in solid-state imaging devices, and more preferably used as a resin composition for forming colored pixels in color filters used in solid-state imaging devices.

As the color filter, a filter having a colored pixel that transmits light of a specific wavelength is exemplified. Examples of the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels and the like, preferably green pixels, blue pixels or cyan pixels, more preferably green pixels. The color pixel of the color filter can be formed using a resin composition containing a chromatic color material.

The maximum absorption wavelength of the near-infrared cut filter is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and more preferably in the range of 700 to 1000 nm. In addition, the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Moreover, it is preferable that the transmittance|permeability at at least 1 point in the range of wavelength 700-1800nm is 20 % or less. Further, the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter and the absorbance A550 at a wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500, still more preferably 70 to 450, and particularly preferably 100 to 400. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing colorant.

A near-infrared transmission filter is a filter that transmits at least a part of near-infrared rays. The near-infrared transmission filter is preferably a filter that blocks at least a part of visible light and transmits at least a part of near-infrared light. Preferred examples of the near-infrared transmission filter include filters that satisfy spectral characteristics such that 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 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). can The near-infrared transmission filter is preferably a filter that satisfies any one of the spectral characteristics of (1) to (5) below.

(1): The maximum value of transmittance in the range of wavelength 400-640nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelength 800-1500nm is 70% or more (preferably 75% or more, more preferably 80% or more).

(2): The maximum value of transmittance in the range of wavelength 400-750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelength 900-1500 nm 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 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 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 70% or more (preferably 75% or more, more preferably 80% or more).

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

It is preferable that the solid content concentration of the resin composition of this invention is 5-30 mass %. 7.5 mass % or more is preferable and, as for a minimum, 10 mass % or more is more preferable. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

Hereinafter, each component used in the resin composition of the present invention is described.

<<color material A>>

The resin composition of the present invention contains a color material A (hereinafter referred to as a color material). Examples of the colorant include a white colorant, a black colorant, a chromatic colorant, and a near-infrared ray absorbing colorant. Moreover, a pigment derivative can also be used for a coloring material. Further, in the present invention, the white color material includes not only pure white color material, but also light gray color material close to white (for example, off-white color, light gray color material, etc.).

As for the coloring material contained in the resin composition of this invention, what contains a pigment is used. The pigment may be either an inorganic pigment or an organic pigment, but is preferably an organic pigment from the viewpoints of diversity in color variations, ease of dispersion, safety, and the like. Moreover, it is preferable that the pigment contains at least 1 sort(s) chosen from a chromatic color pigment and a near-infrared absorbing pigment, and it is more preferable that a chromatic color pigment is included.

In addition, the colorant preferably contains at least one selected from phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, azomethine pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments and quinophthalone pigments, and is selected from phthalocyanine pigments, diketopyrrolopyrrole pigments and pyrrolopyrrole pigments. It is more preferable that it contains at least one kind, and it is still more preferable that it contains a phthalocyanine pigment for the reason that the effect of this invention appears more remarkably. Further, the phthalocyanine pigment is preferably a phthalocyanine pigment having no central metal or a phthalocyanine pigment having copper or zinc as the central metal, and more preferably a phthalocyanine pigment having copper or zinc as the central metal. Moreover, it is preferable that a phthalocyanine pigment is a halogenated phthalocyanine pigment.

As for the average primary particle diameter of a pigment, 1-200 nm is preferable. 5 nm or more is preferable and, as for a minimum, 10 nm or more is more preferable. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the resin composition is good. In the present invention, the primary particle size of the pigment can be obtained from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding to the projected area is calculated as the primary particle diameter of the pigment. The average primary particle size in the present invention is the arithmetic mean value of the primary particle size of 400 pigment primary particles. In addition, the primary particle of a pigment refers to an independent particle without aggregation.

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

It is preferable that the color material contained in the resin composition of this invention contains a pigment and a pigment derivative. As a pigment derivative, the compound which has a structure in which the acidic group or basic group couple|bonded with the pigment skeleton is mentioned. Details of the pigment derivative will be described later. The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. A pigment derivative may use only 1 type, and may use 2 or more types together.

The color 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. It is preferable that it is 80 mass parts or less, and, as for an upper limit, it is more preferable that it is 70 mass parts or less. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more. Dye may use only 1 type, and may use 2 or more types together.

Moreover, it is also preferable that the color material contained in the resin composition of this invention does not contain dye substantially. According to this aspect, a film excellent in light resistance and heat resistance can be formed. Substantially not containing a dye means that the content of the dye in the color material is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably not containing it.

(chromatic coloring material)

As a chromatic color material, the color material which has a maximum absorption wavelength in the wavelength range of 400-700 nm is mentioned. For example, yellow color material, orange color material, red color material, green color material, purple color material, blue color material, etc. are mentioned. From the viewpoint of heat resistance, the chromatic color material is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and more preferably a red pigment and a blue pigment. As a specific example of a chromatic pigment, what is shown below is mentioned, for example.

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

As specific examples of the red colorant, C.I. (color index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 22 Red pigments, such as 4, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297, etc., are mentioned. In addition, as a red colorant, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in Japanese Laid-Open Patent Publication No. 2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Japanese Patent Publication No. 6248838, a diketopyrrolopyrrole compound described in International Publication No. 2012/102399, International Publication No. 2 A diketopyrrolopyrrole compound described in Japanese Patent Laid-Open No. 012/117965, a brominated diketopyrrolopyrrole compound described in Japanese Patent Laid-Open No. 2020-085947, a naphtholazo compound described in Japanese Patent Laid-Open No. 2012-229344, a red colorant described in Japanese Patent Publication No. 6516119, a red colorant described in Japanese Patent Publication No. 6525101, Japan Brominated diketopyrrolopyrrole compounds described in Paragraph No. 0229 of Laid-Open Patent Publication No. 2020-090632, anthraquinone compounds described in Korean Patent Laid-Open No. 10-2019-0140741, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, feryl described in Japanese Patent Laid-Open No. 2020-079396 A rene compound, the diketopyrrolopyrrole compound of Paragraph No. 0025 of Unexamined-Japanese-Patent No. 2020-066702 - 0041, etc. can also be used. As a red colorant, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is introduced is bonded to a diketopyrrolopyrrole skeleton can also be used.

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

As a green color material, a phthalocyanine compound, a squarylium compound, etc. are mentioned, It is preferable that it is a phthalocyanine compound, and it is more preferable that it is a phthalocyanine pigment. Moreover, it is preferable that a green color material is a pigment.

As a specific example of the green colorant, C.I. and green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Moreover, as a green colorant, the number of halogen atoms in one molecule is 10-14 on average, the number of bromine atoms is 8-12 on average, and the number of chlorine atoms on average of 2-5 can also be used. As a specific example, the compound of international publication 2015/118720 is mentioned. In addition, as a green colorant, a compound described in the specification of Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric acid ester as a ligand described in International Publication No. 2012/102395, a phthalocyanine compound described in Japanese Laid-Open Patent Publication No. 2019-008014, a phthalocyanine compound described in Japanese Laid-Open Patent Publication No. 2018-180023, a Japanese Laid-Open Patent The compound described in Publication No. 2019-038958, the aluminum phthalocyanine compound described in Unexamined-Japanese-Patent No. 2020-070426, the core-shell type pigment described in Unexamined-Japanese-Patent No. 2020-076995, etc. can also be used.

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

used

As a specific example of the orange color material, C.I. and orange pigments such as Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

Examples of the yellow colorant include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. As a specific example of the yellow colorant, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162 ,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,2 Yellow pigments, such as 14, 215, 228, 231, 232, 233, 234, 235, and 236, are mentioned.

Moreover, as a yellow colorant, the nickel azobarbiturate complex of the following structure can also be used.

[Formula 1]

Moreover, as a yellow colorant, the compound described in Unexamined-Japanese-Patent No. 2017-201003, the compound described in Unexamined-Japanese-Patent No. 2017-197719, the compound described in Paragraph Nos. 0011 to 0062 and 0137 to 0276 of Unexamined-Japanese-Patent No. 2017-171912, and Paragraph No. 001 of Unexamined-Japanese-Patent No. 2017-171913 0 to 0062, a compound described in 0138 to 0295, a compound described in Paragraph Nos. 0011 to 0062, 0139 to 0190 of Japanese Laid-open Patent Publication No. 2017-171914, a compound described in Paragraph Nos. 0010 to 0065, 0142 to 0222 of Unexamined-Japanese-Patent No. -The quinophthalone compound described in Paragraph Nos. 0011 to 0034 of Japanese Patent Laid-Open No. 2014-026228, the quinophthalone compound described in Paragraph Nos. 0013 to 0058 of Japanese Laid-Open Patent Publication No. 2018-062644, the isoindoline compound described in Japanese Unexamined Patent Publication No. 2018-203798 Talon compounds, quinophthalone compounds described in Japanese Patent Laid-Open No. 2018-062578, quinophthalone compounds described in Japanese Patent Publication No. 6432076, quinophthalone compounds described in Japanese Patent Laid-Open No. 2018-155881, quinophthalone compounds described in Japanese Unexamined Patent Publication No. 2018-111757, Japanese Laid-Open Patent Publication 2018-0 40835, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2017-197640, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2016-145282, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2014-085565, a quino described in Japanese Unexamined Patent Publication No. 2014-021139 A phthalone compound, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2013-209614, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2013-209435, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2013-181015, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2013-061622, Japanese Unexamined Patent Publication A quinophthalone compound described in Japanese Patent Laid-Open No. 2013-032486, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2012-226110, a quinophthalone compound described in Japanese Patent Laid-Open No. 2008-074987, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2008-081565, Japanese Unexamined Patent Publication 2008-074986 A quinophthalone compound described in Japanese Patent Laid-Open No. 2008-074985, a quinophthalone compound described in Japanese Patent Laid-Open No. 2008-050420, a quinophthalone compound described in Japanese Patent Laid-Open No. 2008-031281, a quinophthalone compound described in Japanese Patent Publication No. 48-032765, Japan A quinophthalone compound described in Japanese Patent Laid-Open No. 2019-008014, a quinophthalone compound described in Japanese Patent Publication No. 6607427, a methine dye described in Japanese Laid-Open Patent Publication No. 2019-073695, a methine dye described in Japanese Unexamined Patent Publication No. 2019-073696, a methine dye described in Japanese Patent Laid-Open No. 2019-073697, Japan A methine dye described in Korean Patent Laid-Open No. 2019-073698, a compound described in Korean Patent Laid-Open No. 10-2014-0034963, a compound described in Japanese Patent Laid-Open No. 2017-095706, a compound described in Taiwanese Patent Application Laid-Open No. 201920495, a compound described in Japanese Patent Publication No. 6607427, Japanese Patent Laid-Open No. 2020-03 3525, a compound described in Japanese Unexamined Patent Publication No. 2020-033524, a compound described in Japanese Unexamined Patent Publication No. 2020-033523, a compound described in Japanese Unexamined Patent Publication No. 2020-033522, a compound described in Japanese Unexamined Patent Publication No. 2020-033521, a compound described in International Publication No. 2020/045200, International Publication No. A compound described in 2020/045199, a compound described in International Publication No. 2020/045197, an azo compound described in Japanese Patent Laid-Open No. 2020-093994, a perylene compound described in Japanese Patent Laid-Open No. 2020-083982, a perylene compound described in International Publication No. 2020/105346, Japanese Patent Publication No. 2020-5 The quinophthalone compound described in Japanese Patent No. 17791, a compound represented by the following formula (QP1), and a compound represented by the following formula (QP2) can also be used. Moreover, what multimerized these compounds is also used preferably from a viewpoint of color value improvement.

[Formula 2]

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. As a specific example of the compound represented by Formula (QP1), the compound described in Paragraph No. 0016 of Japanese Patent Publication No. 6443711 is mentioned.

[Formula 3]

In Formula (QP2), Y ¹ to Y ³ each independently represent a halogen atom. n and m represent an integer of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or more. As a specific example of the compound represented by Formula (QP2), the compound described in Paragraph No. 0047 of Japanese Patent Publication 6432077 - 0048 is mentioned.

As a specific example of the purple colorant, C.I. and purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

As a specific example of the blue colorant, C.I. and blue pigments such as Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Moreover, as a blue colorant, an aluminum phthalocyanine compound having a phosphorus atom can also be used. As a specific example, Paragraph No. 0022 of Unexamined-Japanese-Patent No. 2012-247591 - 0030, and the compound of Paragraph No. 0047 of Unexamined-Japanese-Patent No. 2011-157478 are mentioned.

In addition, the diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used as a green colorant or a blue colorant.

Regarding the diffraction angle that various pigments preferably have, the descriptions of Japanese Patent Publication No. 6561862, Japanese Patent Publication No. 6413872, Japanese Patent Publication No. 6281345, Japanese Unexamined Patent Publication No. 2020-026503, and Japanese Unexamined Patent Publication No. 2020-033526 can be referred to, and these contents are incorporated herein by reference. In addition, as a pyrrolopyrrole pigment, it is also preferable to use those having a crystallite size of 140 Å or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among eight planes of (±1±1±1) in the crystal lattice plane. Moreover, it is also preferable to set as described in Paragraph No. 0028 of Unexamined-Japanese-Patent No. 2020-097744 - 0073 about the physical property of a pyrrolopyrrole pigment.

Moreover, as a pigment, it is also preferable to use the zinc halide phthalocyanine pigment which has the Raman spectrum of Unexamined-Japanese-Patent No. 6744002 from a viewpoint of improving a spectral characteristic. Moreover, as a pigment, it is also preferable to use the dioxazine pigment which controlled the contact angle of international publication 2019/107166 from a viewpoint of viscosity adjustment.

Dyes can also be used for the chromatic color material. There is no restriction|limiting in particular as a dye, A well-known dye can be used. For example, dyes such as pyrazolazo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazolazo, pyridonazo, cyanine, phenothiazine, pyrrolopyrazole azomethane, xanthene, phthalocyanine, benzopyran, indigo, pyrromethene, etc. can be heard

A dye multimer can also be used for a chromatic color material. It is preferable that a dye multimer is a dye used by being dissolved in a solvent. Moreover, the dye multimer may form particles. When the dye multimer is a particle, it is usually used in a state of being dispersed in a solvent. The pigment multimer in the form of a particle can be obtained, for example, by emulsion polymerization, and the compound and manufacturing method described in Unexamined-Japanese-Patent No. 2015-214682 are mentioned as specific examples. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures in one molecule may be the same dye structure or different dye structures. As for the weight average molecular weight (Mw) of a dye multimer, 2000-50000 are preferable. 3000 or more are more preferable, and, as for a minimum, 6000 or more are still more preferable. As for an upper limit, 30000 or less are more preferable, and 20000 or less are still more preferable. As the dye multimer, compounds described in Japanese Unexamined Patent Publication No. 2011-213925, Japanese Unexamined Patent Publication No. 2013-041097, Japanese Unexamined Patent Publication No. 2015-028144, Japanese Unexamined Patent Publication No. 2015-030742, International Publication No. 2016/031442 can also be used.

Also, as a chromatic colorant, a triarylmethane dye polymer described in Korean Patent Laid-Open No. 10-2020-0028160, a xanthene compound described in Japanese Patent Laid-Open No. 2020-117638, a phthalocyanine compound described in International Publication No. 2020/174991, an isoindoline compound described in Japanese Patent Laid-Open No. 2020-160279 or a salt thereof, Korea A compound represented by Formula 1 described in Patent Publication No. 10-2020-0069442, a compound represented by Formula 1 described in Korean Laid-Open Patent Publication No. 10-2020-0069730, a compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070, a compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069067, A compound represented by Formula 1 described in Korean Laid-open Patent Publication No. 10-2020-0069062, a halogenated zinc phthalocyanine pigment described in Japanese Patent Publication No. 6809649, and an isoindoline compound described in Japanese Patent Laid-Open No. 2020-180176 can be used. The chromatic coloring material may be rotaxane, and the dye skeleton may be used for the cyclic structure of rotaxane, may be used for the rod-like structure, or may be used for both structures.

You may use chromatic color material in combination of 2 or more types. Moreover, when using in combination of 2 or more types of chromatic color materials, black may be formed by the combination of 2 or more types of chromatic color materials. As such a combination, the aspects of the following (1) - (7) are mentioned, for example. In the case where the resin composition contains two or more chromatic colorants and a combination of the two or more chromatic colorants exhibits black color, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter.

(1) An aspect containing a red colorant and a blue colorant.

(2) An aspect containing a red colorant, a blue colorant, and a yellow colorant.

(3) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.

(4) An aspect containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.

(5) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.

(6) An aspect containing a red colorant, a blue colorant, and a green colorant.

(7) An aspect containing a yellow colorant and a purple colorant.

(white color material)

Examples of the white colorant include inorganic pigments (white pigment) such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. The white pigment is preferably a particle having a titanium atom, and more preferably a titanium oxide. Moreover, it is preferable that the white pigment is a particle having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. It is preferable that it is 2.10-3.00, and, as for the refractive index mentioned above, it is more preferable that it is 2.50-2.75.

Further, as the white pigment, titanium oxide described in “Physical properties of titanium oxide and applied technology, Manabu Kiyono, pp. 13 to 45, June 25, 1991, published by Shimpan,” can also be used.

The white pigment is not only composed of a single inorganic substance, but may also be used in combination with other materials. For example, it is preferable to use core and shell composite particles composed of particles having pores or other materials therein, particles in which many inorganic particles are adhered to core particles, and core particles composed of polymer particles and shell layers composed of inorganic nanoparticles. As 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 Japanese Unexamined Patent Publication No. 2015-047520 can be referred to, and this content is incorporated herein by reference.

As the white pigment, hollow inorganic particles can also be used. The 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. As hollow inorganic particles, the hollow inorganic particles described in Unexamined-Japanese-Patent No. 2011-075786, International publication 2013/061621, Unexamined-Japanese-Patent No. 2015-164881 etc. are mentioned, These content is integrated in this specification.

(black color material)

It does not specifically limit as a black color material, A well-known thing can be used. For example, as an inorganic black colorant, inorganic pigments (black pigment), such as carbon black, titanium black, and graphite, are mentioned, Carbon black and titanium black are preferable, and titanium black is more preferable. Titanium black is a black particle containing a titanium atom, and low-order titanium oxide or oxynitride titanium is preferable. The surface of titanium black can be modified as needed for the purpose of improving dispersibility, suppressing aggregation, 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. Moreover, treatment with a water repellent substance as shown in Japanese Unexamined Patent Publication No. 2007-302836 is also possible. As a black pigment, C.I. Pigment Black 1, 7, etc. are mentioned. Titanium black preferably has a small primary particle diameter and an average primary particle diameter of individual particles. Specifically, it is preferable that the average primary particle size is 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 is exemplified. About the said dispersion, Paragraph 0020 of Unexamined-Japanese-Patent No. 2012-169556 - description of 0105 can be considered into consideration, and this content is integrated in this specification. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.), and the like.

Moreover, as an organic black color material, a bisbenzofuranone compound, an azo metaine compound, a perylene compound, an azo compound, etc. are mentioned. Examples of the bisbenzofuranone compound include compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234 and the like, for example, available as "Irgaphor Black" from BASF. As a perylene compound, Paragraph No. 0016 of Unexamined-Japanese-Patent No. 2017-226821 - the compound of 0020, C.I. Pigment Black 31, 32 etc. are mentioned. As an azomethine compound, the compound of Unexamined-Japanese-Patent No. 01-170601, Unexamined-Japanese-Patent No. 02-034664 etc. is mentioned, For example, it can obtain as "chromophine black A1103" by Dainichi Seika Co., Ltd.

The color material used in the resin composition of the present invention may be only the black color material described above or may further contain a chromatic color material. According to this aspect, 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 as the colorant, the mass ratio of both is preferably black colorant:chromatic colorant = 100:10 to 300, and more preferably 100:20 to 200.

As a preferable combination of a black color material and a chromatic color material, the following are mentioned, for example.

(A-1) The aspect containing an organic black color material and a blue color material.

(A-2) The aspect containing an organic black color material, a blue color material, and a yellow color material.

(A-3) An aspect containing an organic black colorant, a blue colorant, a yellow colorant, and a red colorant.

(A-4) An aspect containing an organic black colorant, a blue colorant, a yellow colorant, and a purple colorant.

In the aspect (A-1), the mass ratio of the organic black colorant to the blue colorant is preferably 100:1 to 70, more preferably 100:5 to 60, and still more preferably 100:10 to 50.

In the aspect (A-2), the mass ratio of the organic black colorant, the blue colorant and the yellow colorant is preferably 100:10 to 90:10 to 90, and more preferably 100:15 to 85:15 to 80, and still more preferably 100:20 to 80:20 to 70.

In the aspect of (A-3), the mass ratio of the organic black colorant, the blue colorant, the yellow colorant, and the red colorant is preferably 100:20 to 150:1 to 60:10 to 100, more preferably 100:30 to 130:5 to 50:20 to 90, and 100:40 to 120:1 It is more preferable that it is 0-40:30-80.

In the aspect (A-4), the mass ratio of the organic black colorant, the blue colorant, the yellow colorant, and the purple colorant is preferably 100:20 to 150:1 to 60:10 to 100, more preferably 100:30 to 130:5 to 50:20 to 90, and 100:40 to 120: It is more preferable that it is 10-40:30-80.

(Near-infrared absorbing colorant)

The near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength on a longer wavelength side than the wavelength of 700 nm. Infrared absorption is preferable that it is a compound having a maximum absorption wavelength in the range of more than 700 nm and 1800 nm, and is more preferable that it is a compound having a maximum absorption wavelength in the range of more than 700 nm and a range of less than 1400 nm, and a compound with maximum absorption wavelengths in the range of less than 700 nm and less than 1200 nm. It is especially preferable that it is a compound with maximum absorption wavelengths in the range of more than 700 nm and less than 1000 nm. Further, the ratio A ¹ /A ² of the absorbance A ¹ of the near-infrared absorbing colorant at a wavelength of 500 nm and the absorbance A ² at the maximum absorption wavelength is preferably 0.08 or less, and more preferably 0.04 or less. Moreover, it is preferable that it is a pigment, and, as for a near-infrared absorbing color material, it is more preferable that it is an organic pigment.

Examples of 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, pyromethene compounds, azomethane compounds, anthraquinone compounds, dibenzofuranone compounds, dithiorene metal complexes, metal oxides, and metals. A boride etc. are mentioned. As a pyrrolopyrrole compound, the compound of Paragraph No. 0016 of Unexamined-Japanese-Patent No. 2009-263614 - 0058, the compound of Paragraph No. 0037 - 0052 of Unexamined-Japanese-Patent No. 2011-068731, The compound of Paragraph No. 0010 - 0033 of International Publication No. 2015/166873, etc. are mentioned. As a squarylium compound, the compound described in Paragraph Nos. 0044 to 0049 of Unexamined-Japanese-Patent No. 2011-208101, the compound described in Paragraph No. 0060 to 0061 of Japanese Patent Publication No. 6065169, the compound described in Paragraph No. 0040 of International Publication No. 2016/181987, and the compound described in Japanese Unexamined Patent Publication No. 2015-176046 , A compound described in Paragraph No. 0072 of International Publication No. 2016/190162, a compound described in Paragraph Nos. 0196 to 0228 of Unexamined-Japanese-Patent No. 2016-074649, a compound described in Paragraph No. 0124 of Unexamined-Japanese-Patent No. 2017-067963, a compound described in International Publication No. 2017/135359, Japanese Patent Laid-Open No. 2 The compound described in 017-114956, the compound described in Japanese Patent Publication 6197940, the compound described in International Publication No. 2016/120166, etc. are mentioned. As a cyanine compound, the compound described in Paragraph No. 0044 to 0045 of Unexamined-Japanese-Patent No. 2009-108267, the compound described in Paragraph No. 0026 to 0030 of Unexamined-Japanese-Patent No. 2002-194040, the compound described in Unexamined-Japanese-Patent No. 2015-172004, the compound described in Japanese Unexamined Patent Publication No. 2015-172102 A compound described in Patent Publication No. 2008-088426, a compound described in Paragraph No. 0090 of International Publication No. 2016/190162, a compound described in Japanese Unexamined Patent Publication No. 2017-031394, and the like are exemplified. As a croconium compound, the compound of Unexamined-Japanese-Patent No. 2017-082029 is mentioned. As an iminium compound, the compound described in Unexamined-Japanese-Patent No. 2008-528706, the compound described in Unexamined-Japanese-Patent No. 2012-012399, the compound described in Unexamined-Japanese-Patent No. 2007-092060, and the compound described in Paragraph No. 0048-0063 of International Publication No. 2018/043564 are mentioned, for example. As a phthalocyanine compound, the compound described in Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153, the oxytitanium phthalocyanine described in Unexamined-Japanese-Patent No. 2006-343631, the compound described in Paragraph Nos. A vanadium phthalocyanine compound, a vanadium phthalocyanine compound described in International Publication No. 2020/071486, and a phthalocyanine compound described in International Publication No. 2020/071470 are exemplified. As a naphthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned. Examples of the dithiorene metal complex include compounds described in Japanese Patent Publication No. 5733804. Examples of the metal oxide include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. About the details of tungsten oxide, Paragraph No. 0080 of Unexamined-Japanese-Patent No. 2016-006476 can be considered into consideration, and this content is integrated in this specification. As a metal boride, lanthanum boride etc. are mentioned. As a commercial item of lanthanum boride, LaB ₆ -F (Nippon Shinginzoku Co., Ltd. product) etc. are mentioned. Moreover, as a metal boride, the compound of international publication 2017/119394 can also be used. As a commercial item of indium tin oxide, F-ITO (made by DOWA High-Tech Co., Ltd.) etc. are mentioned.

Moreover, as a near-infrared absorbing colorant, the squarylium compound described in Unexamined-Japanese-Patent No. 2017-197437, the squarylium compound described in Unexamined-Japanese-Patent No. 2017-025311, the squarylium compound described in International Publication No. 2016/154782, the squarylium compound described in Japanese Patent Publication No. 5884953, and Japanese Patent Publication No. 6036689 A squarylium compound described in, a squarylium compound described in Japanese Patent Publication No. 5810604, a squarylium compound described in International Publication No. 2017/213047, Paragraph Nos. 0090 to 0107, a pyrrole ring-containing compound described in Unexamined-Japanese-Patent No. 2018-054760, Paragraph Nos. 0019 to 0075, Japanese Unexamined Patent Publication No. 2018-040955 A pyrrole ring-containing compound described in Paragraph Nos. 0078 to 0082, a pyrrole ring-containing compound described in Paragraph Nos. 0043 to 0069 of Unexamined-Japanese-Patent No. 2018-002773, a squarylium compound having an aromatic ring on the amide α described in Paragraph Nos. An amide-linked squarylium compound described in No. 31, a compound having a pyrrolebis type squarylium skeleton or a croconium skeleton described in Japanese Laid-open Patent Publication No. 2017-141215, a dihydrocarbazolebis type squarylium compound described in Japanese Patent Laid-Open No. 2017-082029, and an asymmetric type described in paragraphs Nos. 0027 to 0114 of Japanese Patent Laid-Open No. 2017-068120 A compound of, a pyrrole ring-containing compound (carbazole type) described in Japanese Unexamined Patent Publication No. 2017-067963, a phthalocyanine compound described in Japanese Patent Publication No. 6251530, a squarylium compound described in Japanese Unexamined Patent Publication No. 2020-075959, a copper complex described in Korean Unexamined Patent Publication No. 10-2019-0135217, etc. can also be used.

(pigment derivative)

In the present invention, a pigment derivative can also be used for the coloring material. In this invention, it is preferable to use together a pigment and a pigment derivative. As a pigment derivative, the compound which has a structure in which the acidic group or basic group couple|bonded with the pigment skeleton is mentioned.

As the pigment skeleton constituting the pigment derivative, quinoline pigment skeleton, benzimidazolone pigment skeleton, benzisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, azo pigment skeleton, azomethine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, anthracyanine pigment skeleton quinone pigment skeleton, quinacridone pigment skeleton, dioxazine pigment skeleton, perrinone pigment skeleton, perylene pigment skeleton, thioindigo pigment skeleton, isoindoline pigment skeleton, isoindolinone pigment skeleton, quinophthalone pigment skeleton, iminium pigment skeleton, dithiol pigment skeleton, triarylmethane pigment skeleton, pyromethene pigment skeleton, and the like.

As an acid group, a carboxyl 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, these salts, etc. are mentioned. Examples of atoms or groups of atoms 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 ions, 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. As the imidic acid group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 is preferable, and -SO ₂ NHSO ₂ R ^X3 is more preferable. R ^X1 to R ^X6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^X1 to R ^X6 may have a substituent. As a substituent, it is preferable that it is a halogen atom, and it is more preferable that it is a fluorine atom.

Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimide methyl group. Examples of atoms or groups of atoms constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, phenoxide ions and the like.

Specific examples of the pigment derivative include the compounds described in the above examples, the compounds described in Japanese Laid-Open Patent Publication No. 56-118462, the compounds described in Japanese Laid-Open Patent Publication No. 63-264674, the compounds described in Japanese Unexamined Patent Publication No. 01-217077, the compounds described in Japanese Unexamined Patent Publication No. 03-009961, the compounds described in Japanese Patent Laid-Open No. 03-026767, and Japanese Unexamined Patent Publication Hei 0 A compound described in Japanese Patent Laid-Open No. 3-153780, a compound described in JP-A-03-045662, a compound described in JP-A-04-285669, a compound described in JP-A-06-145546, a compound described in JP-A-06-212088, a compound described in JP-A-06-240158, JP-A-10-0 30063, a compound described in Japanese Patent Application Laid-Open No. 10-195326, a compound described in International Publication No. 2011/024896, Paragraph No. 0086 to 0098, a compound described in International Publication No. 2012/102399, Paragraph No. 0063 to 0094, International Publication No. 2017/038252, Paragraph No. 0082 A compound described in, a compound described in Paragraph No. 0171 of Unexamined-Japanese-Patent No. 2015-151530, a compound described in Paragraph Nos. 0162 to 0183 of Unexamined-Japanese-Patent No. 2011-252065, a compound described in Unexamined-Japanese-Patent No. 2003-081972, a compound described in Japanese Unexamined Patent Publication No. 5299151, Japanese Unexamined Patent Publication No. 2015-1727 32, a compound described in JP-A-2014-199308, a compound described in JP-A-2014-085562, a compound described in JP-A-2014-035351, a compound described in JP-A-2008-081565, a compound described in JP-A-2019-109512, and JP-A-2019 The compound described in 2019-133154, the diketopyrrolopyrrole compound having a thiol linking group described in International Publication No. 2020/002106, the benzimidazolone compound described in Japanese Unexamined Patent Publication No. 2018-168244, or salts thereof, and the like.

The content of the colorant in the total solids of the resin composition is 55% by mass or more, preferably 57.5% by mass or more, more preferably 60% by mass or more, and still more preferably 62.5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and still more preferably 75% by mass or less.

It is preferable that it is 30 mass % or more, as for content of the pigment in the total solid content of a resin composition, it is more preferable that it is 45 mass % or more, and it is still more preferable that it is 55 mass % or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and still 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, since a film with color unevenness suppressed can be formed, the effect of the present invention appears more remarkably when the content of the pigment is high.

It is preferable that it is 20-100 mass %, as for content of the pigment in a color material, it is more preferable that it is 50-100 mass %, and it is more preferable that it is 70-100 mass %. In addition, the total content of the pigment and the pigment derivative in the color material is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 75 to 100% by mass.

<<Resin B>>

The resin composition of the present invention contains a resin (hereinafter referred to as a resin). The resin is blended for, for example, a use for dispersing a pigment or the like in a resin composition or a use for a binder. In addition, a resin mainly used for dispersing a pigment or the like in a resin composition is also referred to as a dispersing agent. However, such a use of the resin is an example, and the resin may be used for purposes other than such a use.

(specific resin)

The resin contained in the resin composition of the present invention includes a repeating unit b1-1 having an acid group, a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring, and a resin b1 (hereinafter also referred to as a specific resin) containing a repeating unit b1-3 other than repeating unit b1-1 and repeating unit b1-2.

[repeat unit b1-1]

Specific resin contains the repeating unit b1-1 (henceforth also called repeating unit b1-1) which has an acidic radical. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxyl group, and a carboxy group is preferred.

The number of acid groups contained in the repeating unit b1-1 may be one or two or more. The number of acid groups contained in repeating unit b1-1 is preferably 1 to 4, and more preferably 1 or 2.

As repeating unit b1-1, the repeating unit represented by the following formula (bb-1) is mentioned.

[Formula 4]

R ^b1 to R ^b3 in the formula (bb-1) each independently represent a hydrogen atom or an alkyl group. As for carbon number of the alkyl group represented by ^Rb1 - ^Rb3 , 1-10 are preferable, 1-3 are more preferable, and 1 is still more preferable.

L ^b1 in formula (bb-1) represents a single bond or an n1+1 valent linking group. However, when n1 is 2 or more, L ^b1 is an n1+1 valent linking group.

Examples of the n1+1-valent linking group represented by L ^b1 include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, and -S-, and groups formed by combining two or more of these. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

A ^b1 in the formula (bb-1) represents an acid group. Examples of the acid group represented by A ^b1 include a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, and a carboxy group is preferred.

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

As a specific example of repeating unit b1-1, the repeating unit of the structure shown below is mentioned.

[Formula 5]

The content of the repeating unit b1-1 in the specific resin is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 10 to 35% by mass. 12 mass % or more is preferable and, as for a minimum, 14 mass % or more is more preferable.

[repeat unit b1-2]

The specific resin contains a repeating unit b1-2 (hereinafter also referred to as repeating unit b1-2) having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring.

The functional group b of the repeating unit b1-2 is preferably a group containing a ketone structure. If the functional group b is a group containing a ketone structure, when a phthalocyanine pigment is used as a coloring material, a film with more suppressed color unevenness can be formed.

Moreover, it is also preferable that the functional group b is a group having 2 to 4 ring structures. In this aspect, it is preferable that the number of ring structures contained in functional group b is 2-3.

Moreover, it is also preferable that the functional group b is a group containing 2 to 5 heteroatoms. In this aspect, it is preferable that the number of heteroatoms contained in functional group b is 2-4.

Among them, the functional group b is preferably a group having a ring structure of 2 to 4 and containing 2 to 5 hetero atoms, and more preferably a group having a ring structure of 2 to 3 and containing 2 to 4 hetero atoms. In particular, the functional group b is a group containing a ketone structure, has a 2 to 4 ring structure (preferably 2 to 3 ring structures), and has 2 to 5 heteroatoms (preferably 2 to 4). It is preferable to be a group containing. By using a group having such a structure as the functional group b, when a phthalocyanine pigment is used as a color material, a film with more suppressed color unevenness can be formed.

Functional group b is a naphthalimide structure, acridone structure, thioxanthone structure, xanthone structure, anthrone structure, benzimidazole structure, benzothiazole structure, benzoxazole structure, benzotriazole structure, benzothiadiazole structure, benzothiadiazole structure, benzothiazine structure, benzoxazine structure, benzorain urea structure, isothiazolinone structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxacyine 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, quinoline structure Nolinone structure, thiochromanone structure, chromane 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, barbiturate It is preferably a group containing an acid structure, a perylene structure, a perrinone 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, benzothiadiazole structure, benzothiadiazole structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxacyne structure, dibenzopyran structure, carbazole structure, carboline structure, dibenzoxa Iophene 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, chromane structure, phthalimide structure, naphthalene-2,3-dicarboximide structure, pyrazole structure, pyrazolone structure, child It is more preferably a group containing a soindoline structure, an isoindolinone structure, an anthraquinone structure, a tetrazole structure, a benzophenone structure, a triazine structure, an azobenzene structure, a benzalaniline structure, a phenazine structure, a barbituric acid structure, a perylene structure, a perrinone 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, benzothiadiazole structure, benzothiadiazole structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxacyne structure, dibenzopyran structure, carboline structure, dibenzothiophene structure, It is more preferably a group containing a dibenzofuran structure, a pyrimidine structure, a pyrazine structure, a quinazoline structure, a quinoxaline structure, a thiochromanone structure, a chromane structure, a phthalimide structure, a pyrazolone structure, an isoindolinone structure, a tetrazole structure, 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, phenoxacyine structure, phthalimide structure, pyrazolone structure, tetrazole structure, benzothiazolone structure or benzoxazole More preferably, it is a group containing a linone structure,

It is more preferably 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 phenoxacyine structure, a phthalimide structure, a pyrazolone structure, or a tetrazole structure,

Particularly preferred is a group containing a naphthalimide structure or an acridone structure for the reason that it is easy to form a film with more suppressed color unevenness.

Specific examples of the functional group b include groups with structures shown below and groups with structures in which substituents bonded to these groups. As a substituent, the group mentioned as the substituent T mentioned later is mentioned. In the formulas below, * represents a connecting hand, and R represents a hydrogen atom or a substituent. As a substituent, the group mentioned as the substituent T mentioned later is mentioned.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

As the substituent T described above, the following groups are exemplified. A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heterocyclic group (preferably is a heterocyclic group having 1 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 30 carbon atoms), an acyl group (preferably an acyl group having 2 to 30 carbon atoms), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a heterocyclic oxycarbonyl group (preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably a carbon atom group) acylamino group having 2 to 30 carbon atoms), aminocarbonylamino group (preferably an 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 sulfa having 0 to 30 carbon atoms) moyl group), sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heterocyclic thio group (preferably having 1 to 30 carbon atoms) heterocyclic thio group), alkyl sulfonyl group (preferably C1-30 alkylsulfonyl group), alkylsulfonylamino group (preferably C1-30 alkylsulfonylamino group), arylsulfonyl group (preferably C6-30 arylsulfonyl group), arylsulfonylamino group (preferably C6-30 arylsulfonylamino group), heterocyclic sulfonyl group (preferably C6-30 arylsulfonylamino group) Specifically, 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 sulfinic group having 1 to 30 carbon atoms) diyl), ureido group (preferably 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, alkyl sulfino group, aryl sulfino group, arylazo group, heterocyclic azo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imine anger. These groups may further have a substituent in the case of a group capable of being further substituted.

As repeating unit b1-2, the repeating unit represented by the following formula (bb-2) is mentioned.

[Formula 10]

R ^b11 to R ^b13 in the formula (bb-2) each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by ^Rb11 to ^Rb13 is preferably 1 to 10, more preferably 1 to 3, still more preferably 1.

L ^b11 in formula (bb-2) represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ^b11 include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more thereof. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

A ^b11 in the formula (bb-2) represents the functional group b.

Specific examples of the repeating unit b1-2 include repeating units A-1 to A-57 described in Examples described later.

The content of the repeating unit b1-2 in the specific resin is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 10 to 35% by mass. 12 mass % or more is preferable and, as for a minimum, 14 mass % or more is more preferable.

[repeat unit b1-3]

Specific resin contains repeating unit b1-3 other than repeating unit b1-1 and repeating unit b1-2.

Examples of the repeating unit b1-3 include a repeating unit having a crosslinkable group (hereinafter also referred to as repeating unit b1-3a), a repeating unit having a graft chain (hereinafter also referred to as repeating unit b1-3b), a repeating unit having an acid group, a crosslinkable group, and a functional group other than the aforementioned functional group b (hereinafter also referred to as other functional groups) (hereinafter also referred to as other functional groups), and the like. It is also preferable that the repeating unit b1-3 is a repeating unit having a urea structure.

Examples of the crosslinkable group of the repeating unit b1-3a include an ethylenically unsaturated bond-containing group and a cyclic ether group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group. As a cyclic ether group, an epoxy group, oxetanyl group, etc. are mentioned, and an epoxy group is preferable. The epoxy group may be an alicyclic epoxy group. In addition, an 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 repeating unit b1-3a, the repeating unit represented by the following formula (bb-3a) is mentioned.

[Formula 11]

R ^b21 to R ^b23 in the formula (bb-3a) 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, still more preferably 1.

L ^b21 in formula (bb-3a) represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ^b21 include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, and -S-, and groups formed by combining two or more of these groups. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

^Ab21 in the formula (bb-3a) represents a crosslinkable group.

As a specific example of repeating unit b1-3a, the repeating unit of the structure shown below is mentioned.

[Formula 12]

Examples of the graft chain of the repeating unit b1-3b include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure. From the viewpoint that a film with more color unevenness can be formed and generation of coarse particles can be more effectively suppressed, it is preferably a graft chain of a polyester structure or a polyether structure, and more preferably a graft chain of a polyester structure.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. As a substituent, an alkyl group, an alkoxy group, an alkylthio ether group, etc. are mentioned. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsive effect is preferable, and an alkyl group or alkoxy group having 5 to 30 carbon atoms is preferable. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched.

In addition, the graft chain means a molecular chain branched from the main chain. In addition, a main chain means the molecular chain with the most branch points.

The weight average molecular weight of the graft chain is preferably 500 to 30000, more preferably 1000 to 20000, still more preferably 2000 to 10000.

As repeating unit b1-3b, the repeating unit represented by the following formula (bb-3b) is mentioned.

[Formula 13]

R ^b31 to R ^b33 in the formula (bb-3b) 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, still more preferably 1.

L ^b31 in the formula (bb-3b) represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ^b31 include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these groups. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

^Ab31 in formula (bb-3b) represents a graft chain. The graft chain represented by A ^b31 is preferably a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure and a poly(meth)acrylic structure, and more preferably a graft chain having a polyester structure or a polyether structure. Preferred ranges of the graft chain are the same as those described above.

As a specific example of repeating unit b1-3b, the repeating unit of the structure shown below is mentioned.

[Formula 14]

Examples of other functional groups included in the repeating unit b1-3c include an alkyl group, a phenyl group, an amino group, a hydroxyl group, and a cyano group.

As repeating unit b1-3c, the repeating unit represented by the following formula (bb-3c) is mentioned.

[Formula 15]

R ^b41 to R ^b43 in the formula (bb-3c) 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, still more preferably 1.

L ^b41 in the formula (bb-3c) represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ^b41 include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, and -S-, and groups formed by combining two or more of these groups. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

^Ab41 in the formula (bb-3c) represents another functional group. Examples of other functional groups include an alkyl group, a phenyl group, an amino group, a hydroxyl group, and a cyano group.

As a specific example of repeating unit b1-3c, the repeating unit of the structure shown below is mentioned.

[Formula 16]

Specific examples of repeating unit b1-3 include repeating units F-1 to F-7 described in Examples described later.

Specific resin may contain only 1 type of repeating unit b1-3, and may contain 2 or more types.

As one of the preferable aspects of a specific resin, the aspect containing the repeating unit (repeating unit b1-3b) which has a graft chain as repeating unit b1-3 is mentioned. According to this aspect, it is possible to form a film in which color non-uniformity is further suppressed. Furthermore, generation of coarse particles can be suppressed or stability over time of the resin composition can be further improved. In this aspect, the repeating unit b1-3b is preferably a repeating unit having a graft chain of a polyester structure or a polyether structure, and more preferably a repeating unit having a graft chain of a polyester structure.

As another preferred aspect of the specific resin, an aspect not containing a repeating unit having a graft chain (repeating unit b1-3b) as the repeating unit b1-3 is exemplified. In this aspect, it is preferable to further use a resin other than the specific resin (another resin described later), and it is more preferable to use at least one selected from graft polymers, molding polymers, block copolymers, and resins in which at least one end of the polymer chain is sealed with an acid group. Even with this aspect, a film with more suppressed color non-uniformity can be formed. Furthermore, generation of coarse particles can be suppressed or stability over time of the resin composition can be further improved.

It is preferable that content of repeating unit b1-3 in a specific resin is 10-85 mass %. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. It is preferable that it is 15 mass % or more, and, as for a minimum, it is more preferable that it is 20 mass % or more.

When the specific resin contains a repeating unit having a crosslinkable group (repeating unit b1-3a) as the repeating unit b1-3, the content of the repeating unit b1-3a in the specific resin is preferably 1 to 30% by mass. It is preferable that it is 25 mass % or less, and, as for an upper limit, it is more preferable that it is 15 mass % or less. It is preferable that it is 3 mass % or more, and, as for a minimum, it is more preferable that it is 5 mass % or more.

When the specific resin contains a repeating unit (repeating unit b1-3b) having a graft chain as the repeating unit b1-3, the content of the repeating unit b1-3b in the specific resin is preferably 1 to 80% by mass. It is preferable that it is 70 mass % or less, and, as for an upper limit, it is more preferable that it is 60 mass % or less. It is preferable that it is 3 mass % or more, and, as for a minimum, it is more preferable that it is 5 mass % or more.

When the specific resin contains a repeating unit (repeating unit b1-3c) having another functional group as the repeating unit b1-3, the content of the repeating unit b1-3c in the specific resin is preferably 1 to 80% by mass. It is preferable that it is 70 mass % or less, and, as for an upper limit, it is more preferable that it is 60 mass % or less. It is preferable that it is 3 mass % or more, and, as for a minimum, it is more preferable that it is 5 mass % or more.

[Specific examples of specific resins]

Specific examples of the specific resin include resins P1 to P188, PP1, PP2, and PP101 to PP136 shown in Examples described later.

[Physical properties of specific resin]

It is preferable that the acid value of specific resin is 10-250 mgKOH/g. It is preferable that it is 220 mgKOH/g or less, and, as for an upper limit, it is more preferable that it is 200 mgKOH/g or less. It is preferable that it is 30 mgKOH/g or more, and, as for a minimum, it is more preferable that it is 50 mgKOH/g or more. When the acid value of the specific resin is within the above range, the dispersibility of the pigment in the resin composition is good, and a film in which color nonuniformity is further suppressed can be formed. Furthermore, generation of coarse particles in the resin composition and the like can be more effectively suppressed. Moreover, when pattern formation is performed by the photolithography method, generation of development residues can be more effectively suppressed.

It is preferable that the weight average molecular weight of specific resin is 1000-100000. It is preferable that it is 2000 or more, and, as for a minimum, it is more preferable that it is 4000 or more. It is preferable that it is 60000 or less, and, as for an upper limit, it is more preferable that it is 40000 or less. When the weight average molecular weight of the specific resin is within the above range, a film with more suppressed color unevenness can be formed. Furthermore, the aging stability of the resin composition can be further improved. Moreover, when pattern formation is performed by the photolithography method, generation of development residues can be more effectively suppressed.

The specific absorbance represented by the following formula (A _λ ) of the specific resin is preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less.

E=A/(c×l)… (A _λ )

In the formula (A _λ ), E represents the specific absorbance of a specific resin at the maximum absorption wavelength in the wavelength range of 400 to 800 nm,

A represents the absorbance of a specific resin at the maximum absorption wavelength in the wavelength range of 400 to 800 nm,

l represents the cell length in cm,

c represents the concentration of the specific resin in the solution, expressed in mg/ml.

When specific resin has a crosslinkable group, it is preferable that the amount of crosslinkable groups of specific resin is 0.01-2.5 mmol/g. It is preferable that it is 0.2 mmol/g or more, and, as for a minimum, it is more preferable that it is 0.5 mmol/g or more. It is preferable that it is 2 mmol/g or less, and, as for an upper limit, it is more preferable that it is 1.5 mmol/g or less. When the crosslinkable group amount of specific resin is within the above range, the dispersibility of the pigment in the resin composition and the curability of the resin composition are good. In addition, the crosslinkable group amount of a specific resin is a numerical value showing the molar amount of the crosslinkable group per 1 g of solid content of the specific resin.

(other resins)

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

Examples of other resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, n-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Moreover, as resin, resin described in the Example of International Publication No. 2016/088645, resin described in Unexamined-Japanese-Patent No. 2017-057265, resin described in Unexamined-Japanese-Patent No. 2017-032685, resin described in Unexamined-Japanese-Patent No. 2017-075248, resin described in Unexamined-Japanese-Patent No. 2017-066240, Japanese Unexamined Patent Publication Resin described in Japanese Patent Laid-Open No. 2017-167513, resin described in Japanese Laid-Open Patent Publication No. 2017-173787, resin described in Paragraph Nos. 0041 to 0060 of Unexamined-Japanese-Patent No. 2017-206689, resin described in Paragraph Nos. The block polyisocyanate resin described in No. 891, the resin described in Japanese Laid-open Patent Publication No. 2020-122052, the resin described in Japanese Patent Laid-Open No. 2020-111656, the resin described in Japanese Patent Laid-Open No. 2020-139021, and the structural unit having a ring structure in the main chain and the structural unit having a biphenyl group in the side chain described in Japanese Patent Laid-Open No. 2017-138503 Resin, the resin described in paragraphs 0199 to 0233 of Unexamined-Japanese-Patent No. 2020-186373, the alkali-soluble resin described in Unexamined-Japanese-Patent No. 2020-186325, and the resin represented by formula 1 described in Korean Unexamined Patent Publication No. 10-2020-0078339 can also be used.

As for the weight average molecular weight (Mw) of other resin, 3000-2000000 are preferable. 1000000 or less are preferable and, as for an upper limit, 500000 or less are more preferable. 4000 or more are preferable and, as for a minimum, 5000 or more are more preferable.

As another resin, it is preferable to use resin which has an acidic radical. As an acidic group, a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example. The kind of acid group which other resin has may be the same as or different from the acid group which the specific resin mentioned above has. For the reason that the aging stability of the resin composition can be further improved, the other resin preferably includes a resin having an acid group having a pKa smaller than that of the specific resin (hereinafter, also referred to as resin X). Further, the difference between the pKa of the acid group of the specific resin and the pKa of the acid group of the resin X (pKa of the acid group of the specific resin - pKa of the resin X) is preferably 1.0 or more, more preferably 1.5 or more, and still more preferably 2.0 or more. A preferable combination of the acid group of the specific resin and the acid group of the resin X is a combination in which the acid group of the specific resin is a carboxyl group and the acid group of the resin X is a sulfo group or a phosphoric acid group (preferably a phosphoric acid group).

As for the acid value of resin which has an acid group, 30-500 mgKOH/g is preferable. As for a lower limit, 40 mgKOH/g or more is more preferable, and 50 mgKOH/g or more is especially preferable. The upper limit is more preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. 5000-100000 are preferable and, as for the weight average molecular weight (Mw) of resin which has an acidic radical, 5000-50000 are more preferable. Moreover, as for the number average molecular weight (Mn) of resin which has an acidic radical, 1000-20000 are preferable.

The resin having an acid group preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70% by mol of a repeating unit having an acid group on a side chain, out of all the repeating units of the resin. It is preferable that it is 50 mol% or less, and, as for the upper limit of content of the repeating unit which has an acid group in a side chain, it is more preferable that it is 30 mol% or less. It is preferable that it is 10 mol% or more, and, as for the lower limit of content of the repeating unit which has an acid group in a side chain, it is more preferable that it is 20 mol% or more.

Regarding the resin having an acid group, reference can be made to paragraph numbers 0558 to 0571 of Japanese Laid-open Patent Publication No. 2012-208494 (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) and paragraph numbers 0076 to 0099 of Japanese Laid-Open Patent Publication No. 2012-198408. incorporated herein by reference. Moreover, a commercial item can also be used for resin which has an acidic radical. Further, the method for introducing an acid group into the resin is not particularly limited, but examples thereof include the method described in Japanese Patent Publication No. 6349629. Moreover, as a method of introducing an acid group into the resin, a method of introducing an acid group by reacting an acid anhydride with a hydroxyl group generated by a ring-opening reaction of an epoxy group is also exemplified.

As another resin, resin which has a basic group can also be used. The resin having a basic group is preferably a resin containing a repeating unit having a basic group on its side chain, more preferably a copolymer having a repeating unit having a basic group on its side chain and a repeating unit not containing a basic group, and more preferably a block copolymer having a repeating unit having a basic group on its side chain and a repeating unit not containing a basic group. Resin having a basic group can also be used as a dispersing agent. As for the amine titer of resin which has a basic group, 5-300 mgKOH/g is preferable. 10 mgKOH/g or more is preferable and, as for a minimum, 20 mgKOH/g or more is more preferable. 200 mgKOH/g or less is preferable and, as for an upper limit, 100 mgKOH/g or less is more preferable.

Examples of commercially available resins having a basic group include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919. (above, manufactured by Big Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 3750 0, 38500, 39000, 53095, 56000, 7100 (above, manufactured by Nippon Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (above, manufactured by BASF), and the like. In addition, the resin having a basic group is a block copolymer (B) described in Paragraph Nos. 0063 to 0112 of Unexamined-Japanese-Patent No. 2014-219665, a block copolymer A1 described in Paragraph Nos. 0046 to 0076 of Unexamined-Japanese-Patent No. 2018-156021, and a base described in Paragraph Nos. Vinyl resin having a sexual group can also be used, and these content is integrated in this specification.

It is also preferable to use resin which has an acidic group and resin which has a basic group as another resin. According to this aspect, the aging stability of the resin composition can be further improved. When a resin having an acid group and a resin having a basic group are used together, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and still more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the resin having an acid group.

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

[Formula 17]

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.

[Formula 18]

In Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. About the detail of Formula (ED2), description of Unexamined-Japanese-Patent No. 2010-168539 can be considered into consideration, and this content is integrated in this specification.

As a specific example of an ether dimer, description of Paragraph No. 0317 of Unexamined-Japanese-Patent No. 2013-029760 can be considered into consideration, and this content is integrated in this specification, for example.

As another resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X).

[Formula 19]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represents an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by R ²¹ and R ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 3.

As a compound represented by Formula (X), ethylene oxide or propylene oxide modified (meth)acrylate of paracumyl phenol, etc. are mentioned. As a commercial item, Aronix M-110 (Toagosei Co., Ltd. product) etc. are mentioned.

As another resin, it is also preferable to use a resin having a crosslinkable group. Examples of the crosslinkable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group. As a cyclic ether group, an epoxy group, oxetanyl group, etc. are mentioned, and an epoxy group is preferable. The epoxy group may be an alicyclic epoxy group. In addition, an 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). Resin Ac WHEREIN: The aromatic carboxy group may be contained in the main chain of a repeating unit, and may be contained in the side chain of a repeating unit. It is preferable that the aromatic carboxy group is contained in the main chain of the repeating unit. In addition, in the present 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 to 4, and more preferably 1 to 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).

[Formula 20]

In formula (Ac-1), Ar ¹ represents a group containing an aromatic carboxy group, L ¹ represents -COO- or -CONH-, and L ² represents a divalent linking group.

In formula (Ac-2), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, and P ¹⁰ represents a polymer chain.

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

[Formula 21]

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

[Formula 22]

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, and more preferably an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxyl 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).

[Formula 23]

In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, 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, still more preferably 1. However, at least one of n3 and n4 is an integer greater than or equal to 1.

In formula (Ar-13), Q ¹ represents a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, a group represented by the formula (Q-1) or a group represented by the formula (Q-2).

In formulas (Ar-11) to (Ar-13), *1 represents a bonding position with L ¹ .

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

Examples of the divalent linking group represented by L ² in the formula (Ac-1) include an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a group combining two or more of these groups. 1-30 are preferable, as for carbon number of an alkylene group, 1-20 are more preferable, and 1-15 are more preferable. The alkylene group may be straight-chain, branched or cyclic. 6-30 are preferable, as for carbon number of an arylene group, 6-20 are more preferable, and 6-10 are more preferable. The alkylene group and the arylene group may have a substituent. A hydroxyl 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; Arylene group; Group combining an alkylene group and an arylene group; groups obtained by combining at least one selected from an alkylene group and an arylene group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-; and the like, preferably an alkylene group. 1-30 are preferable, as for carbon number of an alkylene group, 1-20 are more preferable, and 1-15 are more preferable. The alkylene group may be straight-chain, branched or cyclic. The alkylene group and the arylene group may have a substituent. A hydroxyl group etc. are mentioned as a substituent.

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

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

Examples of the trivalent linking group represented by L ¹² in the formula (Ac-2) include a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and groups combining two or more of these. The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. A hydroxyl group etc. are mentioned as a substituent. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).

[Formula 24]

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents a bonding position with L ¹¹ in formula (Ac-2), and *2 represents a bonding position with P ¹⁰ in formula (Ac-2). Examples of the trivalent linking group represented by L ^12b include a hydrocarbon group; and a group obtained by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a group obtained by combining a hydrocarbon group or a hydrocarbon group with -O- is preferable.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents a bonding position with L ¹¹ in formula (Ac-2), and *2 represents a bonding position with P ¹⁰ in formula (Ac-2). Examples of the trivalent linking group represented by L ^12c include a hydrocarbon group; and a group obtained by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group is preferable.

In the formula (Ac-2), P ¹⁰ represents a polymer chain. The polymer chain represented by P ¹⁰ preferably has at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acryl structure. As for the weight average molecular weight of polymer chain ^P10 , 500-20000 are preferable. As for a lower limit, 1000 or more are preferable. The upper limit is preferably 10000 or less, more preferably 5000 or less, and still more preferably 3000 or less. When the weight average molecular weight of P ¹⁰ is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersing agent.

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

As another resin, it is preferable to use at least one selected from graft polymers, molding polymers, block copolymers, and resins in which at least one end of the polymer chain is sealed with an acid group. Such a resin is preferably used as a dispersing agent.

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 formula (Ac-2) described above. Examples of the graft chain include graft chains containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acryl structure. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. As a substituent, an alkyl group, an alkoxy group, an alkylthio ether group, etc. are mentioned. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsive effect is preferable, and an alkyl group or alkoxy group having 5 to 30 carbon atoms is preferable. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched.

As a specific example of a graft polymer, Paragraph No. 0025-0094 of Unexamined-Japanese-Patent No. 2012-255128, Paragraph No. 0022-0097 of Unexamined-Japanese-Patent No. 2009-203462, Paragraph No. 0102-0166 of Unexamined-Japanese-Patent No. 2012-255128 Resin is mentioned.

As the molding polymer, a resin having a structure in which a plurality of polymer chains are bonded to a core portion is exemplified. As a specific example of a molding polymer, Paragraph No. 0196 of Unexamined-Japanese-Patent No. 2013-043962 - the high molecular compound C-1 - C-31 of 0209 etc. are mentioned.

As the block copolymer, a block of a polymer having a repeating unit containing an acidic or basic group (hereinafter also referred to as block A) and a block of a polymer having a repeating unit not containing an acidic or basic group (hereinafter, also referred to as block B) is preferably a block copolymer. As the block copolymer, block copolymer A1 described in Paragraph Nos. 0063 to 0112 of Unexamined-Japanese-Patent No. 2014-219665 and Paragraph Nos. 0046 to 0076 of Unexamined-Japanese-Patent No. 2018-156021 may be used, and these contents are incorporated herein by reference.

Examples of the resin in which at least one end of the polymer chain is sealed with an acid group include a resin having a structure in which at least one end of a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure is sealed with an acid group. Examples of the acid group that seals the end of the polymer chain include a carboxyl group, a sulfo group, and a phosphoric acid group.

Resin as a dispersing agent can also be used for another resin. As a dispersing agent, an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin) are mentioned. Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. As an acidic dispersing agent (acidic resin), when the total amount of the quantity of an acidic group and the quantity of a basic group is 100 mol%, resin whose amount of acidic groups is 70 mol% or more is preferable. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. As for the acid value of an acidic dispersing agent (acidic resin), 10-105 mgKOH/g is preferable. Moreover, a basic dispersing agent (basic resin) shows resin with more basic group quantities than acid group quantities. As the basic dispersant (basic resin), a resin in which the amount of the basic group exceeds 50 mol% is preferable when the total amount of the amount of the acid group and the amount of the basic group is 100 mol%. The basic group of the basic dispersing agent is preferably an amino group.

The dispersant is also available as a commercial product, and specific examples thereof include the Disperbyk series manufactured by Big Chemie Co., Ltd. (eg, Disperbyk-111, 161, 2001, etc.), the Solsperse series manufactured by Lubrizol Co., Ltd. (eg, Solsperse 20000, 76500, etc.), the Ajisper series manufactured by Ajinomoto Fine Techno, A208F (Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (Daiichi Kogyo Seiyaku Co., Ltd. product), Sandet ET (Sanyo Kasei Kogyo Co., Ltd. product), etc. are mentioned. Moreover, the product of Paragraph No. 0129 of Unexamined-Japanese-Patent No. 2012-137564, and the product of Paragraph No. 0235 of Unexamined-Japanese-Patent No. 2017-194662 can also be used as a dispersing agent.

It is preferable that content of resin in the total solid content of a resin composition is 1-50 mass %. It is preferable that it is 40 mass % or less, and, as for an upper limit, it is more preferable that it is 30 mass % or less. It is preferable that it is 5 mass % or more, and, as for a minimum, it is more preferable that it is 10 mass % or more.

It is preferable that content of specific resin in the total solid content of a resin composition is 1-50 mass %. It is preferable that it is 40 mass % or less, and, as for an upper limit, it is more preferable that it is 30 mass % or less. It is preferable that it is 5 mass % or more, and, as for a minimum, it is more preferable that it is 10 mass % or more.

It is preferable that it is 10-100 mass %, as for content of specific resin in resin contained in a resin composition, it is more preferable that it is 25-100 mass %, and it is more preferable that it is 45-100 mass %.

The resin composition of this invention may contain only 1 type of resin, and may contain 2 or more types. When containing 2 or more types of resin, it is preferable that their total amount becomes the said range.

<<Polymeric compound>>

It is preferable that the resin composition of this invention contains a polymeric compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

As a polymeric compound, any of chemical forms, such as a monomer, a prepolymer, and an oligomer, may be sufficient, but a monomer is preferable. As for the molecular weight of a polymeric compound, 100-2500 are preferable. 2000 or less are preferable and, as for an upper limit, 1500 or less are more preferable. 150 or more are preferable and, as for a minimum, 250 or more are more preferable.

It is preferable that the ethylenically unsaturated bond-containing group of the polymerizable compound (hereinafter referred to as C=C value) is 2 to 14 mmol/g from the viewpoint of the aging stability of the resin composition. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and still 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 still 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 three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four or more ethylenically unsaturated bond-containing groups. The upper limit of the number of ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, still more preferably 6 or less, from the viewpoint of the stability over time of the resin composition. The polymerizable compound is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional or more functional (meth)acrylate compound, more preferably a trifunctional to hexafunctional (meth)acrylate compound, and particularly preferably a trifunctional to hexafunctional (meth)acrylate compound. As a specific example of a polymeric compound, Paragraph No. 0095-0108 of Unexamined-Japanese-Patent No. 2009-288705, Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-029760, Paragraph No. 0254-0257 of Unexamined-Japanese-Patent No. 2008-292970, Paragraph No. 00 of Unexamined-Japanese-Patent No. 2013-253224 34-0038, Paragraph No. 0477 of Unexamined-Japanese-Patent No. 2012-208494, Unexamined-Japanese-Patent No. 2017-048367, Unexamined-Japanese-Patent No. 6057891, and the compound described in Unexamined-Japanese-Patent No. 6031807 are mentioned, These content is integrated in this specification.

Examples of the polymerizable compound include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds. As a modified body, the compound of the structure in which the (meth)acryloyl group of said compound is couple|bonded through the alkyleneoxy group, such as ethoxylated dipentaerythritol hexa (meth)acrylate, etc. are mentioned. As a specific example, the compound represented by the formula (Z-4), the compound represented by the formula (Z-5), etc. are mentioned.

[Formula 25]

In formulas (Z-4) and (Z-5), E each independently represents -((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 X each 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, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In formula (Z-4), m has a preferable integer of 0-6, and a more preferable integer of 0-4. Moreover, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In Formula (Z-5), n has a preferable integer of 0-6, and the integer of 0-4 is more preferable. Moreover, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

Further, E in formula (Z-4) or formula (Z-5), namely -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ ) O)-, is preferably in a form in which the terminal on the oxygen atom side is bonded to X.

Moreover, polypentaerythritol poly (meth)acrylate as shown by following formula (Z-6) can also be used as a polymeric compound.

[Formula 26]

In formula (Z-6), X ¹ to X ⁶ each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1 to 10. However, at least one of X ¹ to X ⁶ is a (meth)acryloyl group.

The polymerizable compound used in the present invention is preferably 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. Examples of commercially available products include KAYARAD D-310, DPHA, DPEA-12 (above, manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, and TPOA-50 (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.).

Moreover, as a polymeric compound, diglycerol EO (ethylene oxide) modified (meth)acrylate (M-460 as a commercial product; Toagosei make), pentaerythritol tetra(meth)acrylate (Shin-Nakamura Chemical Industry Co., Ltd. product, NK ester A-TMMT), 1, 6-hexanediol diacrylate (Nippon Kayaku Co., Ltd. product, KAYARAD HDDA), RP-10 40 (Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toa Kosei Co., Ltd.), NK Oligo UA-7200 (Shin-Nakamura Kagaku Kogyo Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.), EBECRYL8 0 (manufactured by Daicel Allnex Co., Ltd., amine-containing tetrafunctional acrylate) or the like can also be used.

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

Moreover, as a polymeric compound, the compound which has acid groups, such as a carboxyl group, a sulfo group, and a phosphoric acid group, can also be used. As a commercial item of such a compound, Aronix M-305, M-510, M-520, Aronix TO-2349 (made by Toagosei Co., Ltd.), etc. are mentioned.

Moreover, as a polymeric compound, the compound which has a caprolactone structure can also be used. About the compound which has a caprolactone structure, Paragraph 0042 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0045 can be considered into consideration, and this content is integrated in this specification. Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120 commercially available as the KAYARAD DPCA series from Nippon Kayaku Co., Ltd.

Moreover, as a polymeric compound, the polymeric compound which has a fluorene backbone can also be used. As a commercial item, Ogsol EA-0200, EA-0300 (Osaka Gas Chemical Co., Ltd. product, (meth)acrylate monomer which has a fluorene skeleton), etc. are mentioned.

Moreover, as a polymeric compound, it is also preferable to use the compound which does not substantially contain environmental regulation substances, such as toluene. As a commercial item of such a compound, KAYARAD DPHA LT, KAYARAD DPEA-12 LT (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

Moreover, as a polymeric compound, the urethane acrylates as described in Japanese Patent Publication No. 48-041708, Unexamined-Japanese-Patent No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Publication No. 02-016765, Japanese Publication No. 58-049860, Japanese Patent Publication No. 56-01 7654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418, urethane compounds having an ethylene oxide-based skeleton are also suitable. Moreover, it is also preferable to use the polymeric compound which has an amino structure or a sulfide structure in a molecule|numerator of Unexamined-Japanese-Patent No. 63-277653, Unexamined-Japanese-Patent No. 63-260909, and Unexamined-Japanese-Patent No. 01-105238. In addition, the polymerized compounds include the UA-7200 (Shinna Kamura Kagaku High School), DPHA-40H (Nippon Gayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-2002ua You can also use the breeding.

It is preferable that content of the polymeric compound in the total solid content of a resin composition is 1-35 mass %. It is preferable that it is 30 mass % or less, and, as for an upper limit, it is more preferable that it is 25 mass % or less. It is preferable that it is 2 mass % or more, and, as for a minimum, it is more preferable that it is 5 mass % or more. The resin composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When 2 or more types of polymeric compounds are included, it is preferable that those total amounts become the said range.

<<Photoinitiator>>

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

Examples of the photopolymerization initiator 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-amino ketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, hexaarylbiimidazole compound, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyl It is preferably an oxadiazole compound and a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-amino ketone compound, and an acylphosphine compound, and even more preferably an oxime compound. Moreover, as a photoinitiator, the compound described in Paragraph 0065 - 0111 of Unexamined-Japanese-Patent No. 2014-130173, the compound described in Japanese Patent Publication No. 6301489, the peroxide-type photoinitiator described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, the photopolymerization described in International Publication No. 2018/221177 Initiator, photopolymerization initiator described in International Publication No. 2018/110179, photopolymerization initiator described in Japanese Laid-Open Patent Publication No. 2019-043864, photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-044030, peroxide-based initiator described in Japanese Laid-Open Patent Publication No. 2019-167313, Japanese Laid-Open Patent Publication 2020-0559 An aminoacetophenone-based initiator having an oxazolidine group described in No. 92, an oxime-based photopolymerization initiator described in Unexamined-Japanese-Patent No. 2013-190459, a polymer described in Japanese Unexamined Patent Publication No. 2020-172619, and a compound represented by Formula 1 described in International Publication No. 2020/152120, etc., the contents of which are incorporated herein by reference.

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

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

As an oxime compound, the compound described in Japanese Unexamined Patent Publication No. 2001-233842, the compound described in Japanese Unexamined Patent Publication No. 2000-080068, the compound described in Japanese Unexamined Patent Publication No. 2006-342166, the compound described in J.C.S.Perkin II (1979, pp.1653-1660), J.C.S.Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp.202-232), a compound described in Japanese Patent Application Laid-Open No. 2000-066385, a compound described in Japanese Patent Publication No. 2004-534797, a compound described in Japanese Unexamined Patent Publication No. 2006-342166, Japanese Unexamined Patent Publication No. 2017-019 766, a compound described in Japanese Patent Publication No. 6065596, a compound described in International Publication No. 2015/152153, a compound described in International Publication No. 2017/051680, a compound described in Japanese Unexamined Patent Publication No. 2017-198865, a compound described in International Publication No. 2017/164127 Paragraph Nos. 0025 to 0038; The compound of international publication 2013/167515, etc. are mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, and 3-(4). -Toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), etc. are mentioned. As commercially available products, Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, made by BASF), TR-PBG-304, TR-PBG-327 (made by Tronley), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., Japanese Patent Laid-Open No. 2012-014052 The photopolymerization initiator 2) described in can be mentioned. As the oxime compound, it is also preferable to use a compound having no colorability or a compound having high transparency and hardly discolored. As a commercial item, Adeka Akles NCI-730, NCI-831, NCI-930 (above, made by ADEKA Corporation), etc. are mentioned.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466, the compound of Unexamined-Japanese-Patent No. 6636081, and the compound of Korean Unexamined-Japanese-Patent No. 10-2016-0109444 are mentioned.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. As a specific example of the oxime compound which has a fluorine atom, the compound of Unexamined-Japanese-Patent No. 2010-262028, the compounds 24 and 36-40 of Unexamined-Japanese-Patent No. 2014-500852, the compound (C-3) of Unexamined-Japanese-Patent No. 2013-164471, etc. are mentioned.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound which has a nitro group as a dimer. As specific examples of the oxime compound having a nitro group, the compounds described in Paragraph Nos. 0031 to 0047 of Japanese Unexamined Patent Publication No. 2013-114249, Paragraph Nos. 0008 to 0012, 0070 to 0079 of Japanese Unexamined Patent Publication No. 2014-137466, and Paragraph Nos. A compound, Adeka Akles NCI-831 (made by ADEKA Corporation) is mentioned.

As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. As a specific example, OE-01 described in international publication 2015/036910 - OE-75 is mentioned.

As the photopolymerization initiator, an oxime compound having a substituent having a hydroxyl group bonded to a carbazole skeleton can also be used. As such a photoinitiator, the compound of international publication 2019/088055, etc. are mentioned.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also 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, preferably an acyl group and a nitro group, more preferably an acyl group, and still more preferably a benzoyl group. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. It is more preferably a koxy group, an alkylsulfanyl group or an amino group.

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

[Formula 27]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl 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 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl 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.

Examples of the electron withdrawing group 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, preferably an acyl group and a nitro group, more preferably an acyl group, and still more preferably a benzoyl group.

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

As a specific example of oxime compound OX, the compound of Paragraph No. 0083 of Japanese Patent Publication 4600600 - 0105 is mentioned.

Although the specific example of the oxime compound preferably used in this invention is shown below, this invention is not limited to these.

[Formula 28]

[Formula 29]

[Formula 30]

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. In addition, 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, more preferably 2000 to 300000, and particularly preferably 5000 to 200000. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

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

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. Since two or more radicals generate|occur|produce from one molecule of radical photopolymerization initiator by using such a radical photopolymerization initiator, favorable sensitivity is obtained. In addition, in the case of using a compound with an asymmetric structure, crystallinity is reduced, solubility in solvents and the like is improved, and it is difficult to precipitate over time, so that the stability over time of the resin composition can be improved. As a specific example of a difunctional or trifunctional or more photoradical polymerization initiator, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, Paragraph No. 0407 to 0412 of Japanese Patent Publication No. 2016-532675, International Publication No. 2017/ A dimer of an oxime compound described in Paragraph Nos. 0039 to 0055 of Japanese Patent No. 033680, a compound (E) and a compound (G) described in Japanese Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, and Paragraph No. 0007 of Japanese Patent Publication No. 2017-523465 The oxime ester photoinitiator described, the photoinitiator described in paragraph numbers 0020 to 0033 of Japanese Laid-open Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraph numbers 0017 to 0026 of Japanese Patent Laid-Open No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent Publication No. can be heard

As for content of the photoinitiator in the total solid content of a resin composition, 0.1-30 mass % is preferable. 0.5 mass % or more is preferable and, as for a minimum, 1 mass % or more is more preferable. 20 mass % or less is preferable and, as for an upper limit, 15 mass % or less is more preferable. 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 using 2 or more types, it is preferable that those total amounts become the said range.

<<solvent>>

It is preferable that the resin composition of this invention contains a solvent. As a solvent, an organic solvent is mentioned. The type of solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. About these details, Paragraph No. 0223 of International Publication No. 2015/166779 can be referred, and this content is integrated in this specification. In addition, an ester-based solvent in which a cyclic alkyl group is substituted and a ketone-based solvent in which a cyclic alkyl group is substituted can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, Cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropaneamide , 3-butoxy-N,N-dimethylpropaneamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone Alcohol (as another name, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol, etc. are mentioned. However, there are cases where it is better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents for environmental reasons and the like (for example, with respect to the total amount of organic solvents, 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

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

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

The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be contained in an isomer, and plural types may be included.

It is preferable that the content rate of the peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the peroxide is not substantially contained.

It is preferable that it is 10-95 mass %, as for content of the solvent in a resin composition, it is more preferable that it is 20-90 mass %, and it is more preferable that it is 30-90 mass %.

Moreover, it is preferable that the resin composition of this invention contains substantially no environmental regulating substance from a viewpoint of environmental regulation. Further, in the present invention, substantially not containing an environmental regulating substance means that the content of the environmental regulating substance in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmentally regulated substances include, for example, benzene; Alkylbenzenes, such as toluene and xylene; Halogenated benzenes, such as chlorobenzene, etc. are mentioned. These are registered as environmentally regulated substances based on REACH (Registration Evaluation Authorization and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) laws, VOC (Volatile Organic Compounds) regulations, etc., and usage and handling methods are strictly regulated. These compounds may be used as a solvent when producing each component used in the resin composition and the like, and may be mixed in the resin composition as a residual solvent. From the viewpoint of human safety and consideration for the environment, it is desirable to reduce these substances as much as possible. As a method of reducing the environmental regulating substance, a method of reducing the environment regulating substance by heating or reducing the pressure in the system to a boiling point or higher and distilling the environmental regulating substance out of the system is exemplified. In addition, in the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having the same boiling point as the solvent in order to increase the efficiency. In the case of containing a compound having radical polymerization, it may be distilled off under reduced pressure by adding a polymerization inhibitor or the like in order to prevent radical polymerization reaction from proceeding and crosslinking between molecules during distillation under reduced pressure. These distillation methods can be performed at any stage, such as the stage of raw materials, the stage of reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or the stage of resin composition produced by mixing these compounds.

<<Heat Curing Agent>>

The resin composition of the present invention may contain a thermosetting agent as components other than the above-described resin and polymerizable compound. As a thermosetting agent, the compound which has a cyclic ether group is mentioned. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned. The epoxy group may be an alicyclic epoxy group. In addition, an 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). As an epoxy compound, the compound which has 1 or more epoxy groups in 1 molecule is mentioned, The compound which has 2 or more epoxy groups is preferable. It is preferable that an epoxy compound is a compound which has 1-100 epoxy groups in 1 molecule. The upper limit of the epoxy groups contained in the epoxy compound may be, for example, 10 or less, and may be 5 or less. As for the lower limit of the epoxy group contained in an epoxy compound, two or more are preferable. As an epoxy compound, Paragraph No. 0034-0036 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph No. 0147-0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph No. 0085-0092 of Unexamined-Japanese-Patent No. 2014-089408, The compound of Unexamined-Japanese-Patent No. 2017-179172 The compounds described can also be used. These contents are incorporated in this specification.

The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 2000, and furthermore, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). 200-100000 are preferable and, as for the weight average molecular weight of the compound which has a cyclic ether group, 500-50000 are more preferable. As for the upper limit of a weight average molecular weight, 10000 or less are more preferable, 5000 or less are especially preferable, and 3000 or less are still more preferable.

Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), Maproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G- 01100, G-01758 (above, Nichiyu Co., Ltd. product, epoxy group-containing polymer), etc. are mentioned. In addition, as the compound having a cyclic ether group, the compounds described in Examples described later can also be used.

As for content of the thermosetting agent in the total solid content of a resin composition, 0.1-20 mass % is preferable. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more, for example. As for an upper limit, 15 mass % or less is more preferable, for example, 10 mass % or less is still more preferable. Only 1 type may be used for a thermosetting agent, and 2 or more types may be used. When using 2 or more types, it is preferable that those total amounts become the said range.

<<Polyalkyleneimine>>

The resin composition of the present invention may contain polyalkyleneimine. Polyalkyleneimine is used, for example, as a pigment dispersion aid. A dispersing aid is a material for improving the dispersibility of color materials such as pigments in a resin composition. A polyalkyleneimine is a polymer obtained by ring-opening polymerization of an 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. As for carbon number of an alkyleneimine, 2-6 are preferable, 2-4 are more preferable, it is more preferable that it is 2 or 3, and it is especially preferable that it is 2.

It is preferable that it is 200 or more, and, as for the molecular weight of polyalkyleneimine, it is more preferable that it is 250 or more. The upper limit is preferably 100000 or less, more preferably 50000 or less, still more preferably 10000 or less, and particularly preferably 2000 or less. In addition, regarding the value of the molecular weight of 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 a 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 rising method is used. In addition, when it cannot be measured even by the boiling point rising method or when measurement is difficult, the value of the number average molecular weight measured by the viscosity method is used. In addition, if it cannot be measured by the viscosity method or if it is difficult to measure by the viscosity method, 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 still more preferably 15 mmol/g or more.

Specific examples of the alkylenimine include ethyleneimine, propyleneimine, 1,2-butylenimine, and 2,3-butyleneimine, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. As for polyalkyleneimine, it is especially preferable that it is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% or more with respect to the total of the primary amino group, the secondary amino group, and the tertiary amino group. As a commercial item of polyethyleneimine, Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (above, manufactured by Nippon Shokubai Co., Ltd.), etc. are mentioned.

It is preferable that content of the polyalkyleneimine in the total solid content of a resin composition is 0.1-5 mass %. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and still 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 still more preferably 3% by mass or less. Moreover, it is preferable that content of polyalkylene imine is 0.5-20 mass parts with respect to 100 mass parts of pigments. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more. It is preferable that it is 10 parts by mass or less, and, as for an upper limit, it is more preferable that it is 8 parts by mass or less. As for polyalkylene imine, only 1 type may be used and 2 or more types may be used. When using 2 or more types, it is preferable that their total amount is the said range.

<<Curing Accelerator>>

The resin composition of the present invention may also contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, and onium salt compounds. As specific examples of the curing accelerator, the compounds described in Paragraph Nos. 0094 to 0097 of International Publication No. 2018/056189, the compounds described in Paragraph Nos. 0246 to 0253 of Unexamined-Japanese-Patent No. 2015-034963, the compounds described in Paragraph Nos. The ionic compound described in Japanese Patent Laid-Open No. 055114, the compound described in Paragraph Nos. 0071 to 0080 of Unexamined-Japanese-Patent No. 2012-150180, the alkoxysilane compound having an epoxy group described in Unexamined-Japanese-Patent No. 2011-253054, the compound described in Paragraph Nos. and the epoxy curing agent containing a carboxy group described in No. 79. 0.3-8.9 mass % is preferable and, as for content of the hardening accelerator in the total solid content of a resin composition, 0.8-6.4 mass % is more preferable.

<<UV absorber>>

The resin composition of the present invention may contain a UV absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. As a specific example of such a compound, Paragraph Nos. 0038-0052 of Unexamined-Japanese-Patent No. 2009-217221, Paragraph No. 0052-0072 of Unexamined-Japanese-Patent No. 2012-208374, Paragraph No. 0317-0334 of Unexamined-Japanese-Patent No. 2013-068814, and Unexamined-Japanese-Patent No. 2016-162946 The compound of Paragraph No. 0061 - 0080 of is mentioned, These content is integrated in this specification. Specific examples of the ultraviolet absorber include compounds having the following structure. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), BASF Tinuvin series, Uvinul series, and Sumisorb series manufactured by Sumika ChemteX Co., Ltd. Moreover, as a benzotriazole compound, the MYUA series by Miyoshi Yushi Co., Ltd. (Kagaku Kogyo Nippo, February 1, 2016) is mentioned. Further, as the ultraviolet absorber, a compound described in paragraphs 0049 to 0059 of Japanese Patent Publication No. 6268967, a compound described in paragraphs 0059 to 0076 of international publication 2016/181987, and a thioaryl group-substituted benzotriazole type ultraviolet absorber described in international publication 2020/137819 can also be used.

[Formula 31]

0.01-10 mass % is preferable and, as for content of the ultraviolet absorber in the total solid content of a resin composition, 0.01-5 mass % is more preferable. In this invention, only 1 type of ultraviolet absorber may be used, and 2 or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Polymerization Inhibitor>>

The resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salt, cerium salt, etc.) there is Among them, p-methoxyphenol is preferable. As for content of the polymerization inhibitor in the total solid content of a resin composition, 0.0001-5 mass % is preferable. One type of polymerization inhibitor may be sufficient as it, and two or more types may be sufficient as it. In the case of two or more types, it is preferable that the total amount be within the above range.

<<Silane coupling agent>>

The resin composition of the present invention may contain a silane coupling agent. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. In addition, a hydrolyzable group refers to a substituent that is directly connected to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl, (meth)allyl, (meth)acryloyl, mercapto, epoxy, oxetanyl, amino, ureido, sulfide, isocyanate, phenyl and the like, with amino, (meth)acryloyl and epoxy groups being 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-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Kogyo Co., Ltd. product, trade name KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd. product, trade name KBM-903), γ-aminopropyl triethoxysilane (Shin-Etsu Chemical Industry Co., Ltd. product, trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd. product, brand name KBM-502), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd. product, brand name KBM-503), and the like. Moreover, about the specific example of a silane coupling agent, the compound of Paragraph No. 0018 of Unexamined-Japanese-Patent No. 2009-288703 - 0036, Paragraph No. 0056 of Unexamined-Japanese-Patent No. 2009-242604 - The compound of 0066 are mentioned, These content is integrated in this specification. 0.01-15.0 mass % is preferable, and, as for content of the silane coupling agent in the total solid content of a resin composition, 0.05-10.0 mass % is more preferable. One type of silane coupling agent may be sufficient as it, and two or more types may be sufficient as it. In the case of two or more types, it is preferable that the total amount be within the above range.

<<surfactants>>

The resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorochemical 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. About surfactant, Paragraph No. 0238 of International Publication No. 2015/166779 - surfactant of 0245 can be considered into consideration, and this content is integrated in this specification.

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

As a fluorochemical surfactant, the surfactant described in Paragraph No. 0060-0064 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph No. 0060-0064 of corresponding International Publication No. 2014/017669) etc., the surfactant described in Paragraph No. 0117-0132 of Unexamined-Japanese-Patent No. 2011-132503, Japanese Unexamined Patent Publication 20 Surfactant of 20-008634 is mentioned, These content is integrated in this specification. Examples of commercially available fluorinated surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-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 (above, manufactured by DIC Co., Ltd.), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Suffron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (Above, manufactured by AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Progent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, and FTX-218 (above, manufactured by NEOS Co., Ltd.).

As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom and in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heated is also preferably used. As such a fluorine-type surfactant, DIC Co., Ltd. Megafac DS series (Gagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shinbun (February 23, 2016)), for example, Megafac DS-21 is mentioned.

As the fluorine-based surfactant, 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 for such a fluorochemical surfactant, the fluorochemical surfactant of Unexamined-Japanese-Patent No. 2016-216602 is mentioned, and this content is integrated in this specification.

A block polymer can also be used for a fluorochemical surfactant. As the fluorine-based surfactant, a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) can also be preferably used. Moreover, the fluorine-containing surfactant of Paragraph No. 0016 of Unexamined-Japanese-Patent No. 2010-032698 - 0037 and the following compound are also illustrated as a fluorochemical surfactant used by this invention.

[Formula 32]

The weight average molecular weight of the above compound is preferably 3000 to 50000, for example 14000. Among the above compounds, % representing the ratio of repeating units is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain may be used. As a specific example, Paragraph No. 0050-0090 of Unexamined-Japanese-Patent No. 2010-164965, and the compound of Paragraph No. 0289-0295, DIC Co., Ltd. Megafac RS-101, RS-102, RS-718K, RS-72-K, etc. are mentioned. Moreover, Paragraph No. 0015 of Unexamined-Japanese-Patent No. 2015-117327 - the compound of 0158 can also be used for a fluorochemical surfactant.

Moreover, it is also preferable from a viewpoint of environmental regulation to use the surfactant of international publication 2020/084854 as a substitute for the surfactant which has a C6 or more perfluoroalkyl group.

Moreover, it is also preferable to use the fluorine-containing imide salt compound represented by Formula (fi-1) as a surfactant.

[Formula 33]

In formula (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, a represents 1 or 2, and X ^a+ represents a valent metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH ₄ ⁺ .

As the nonionic surfactant, glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, 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 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW- 1001, NCW-1002 (manufactured by Fujifilm Wako Junyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

As the silicone surfactant, DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (above, manufactured by Dow-Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (above, manufactured by Big Chemistry) etc. can be mentioned.

Moreover, the compound of the following structure can also be used for silicone type surfactant.

[Formula 34]

0.001 mass % - 5.0 mass % are preferable, and, as for content of surfactant in the total solid content of a resin composition, 0.005-3.0 mass % is more preferable. One type of surfactant may be sufficient as it, and two or more types may be sufficient as it. In the case of two or more types, it is preferable that the total amount be within the above range.

<<Antioxidants>>

The resin composition of the present invention may contain an antioxidant. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. Phosphorus antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy] ethyl]amine, 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, Adekastab AO-330 (above, ADEKA Co., Ltd.) ) and the like. In addition, as an antioxidant, the compound described in Paragraph No. 0023-0048 of Patent Publication No. 6268967, the compound described in International Publication No. 2017/006600, the compound described in International Publication No. 2017/164024, and the compound described in Korean Unexamined Patent Publication No. 10-2019-0059371 can also be used. It is preferable that it is 0.01-20 mass %, and, as for content of the antioxidant in the total solid content of a resin composition, it is more preferable that it is 0.3-15 mass %. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Other Ingredients>>

The resin composition of the present invention, if necessary, may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (eg, conductive particles, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension regulator, a chain transfer agent, etc.). By appropriately containing these components, properties such as film properties can be adjusted. For these components, for example, the description of paragraph No. 0183 of Japanese Unexamined Patent Publication No. 2012-003225 (paragraph No. 0237 of the corresponding US Patent Application Publication No. 2013/0034812), the description of paragraph Nos. , these contents are incorporated herein by reference. Moreover, the resin composition of this invention may contain a latent antioxidant as needed. Examples of the latent antioxidant include a compound in which a site functioning as an antioxidant is protected with a protecting group, and the protecting group is released by heating at 100 to 250° C. or at 80 to 200° C. in the presence of an acid/base catalyst, and the compound functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219. As a commercial item of a latent antioxidant, Adeka Akles GPA-5001 (made by ADEKA Corporation) etc. are mentioned.

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

The resin composition of the present invention may also contain a light fastness improving agent. As a light fastness improver, the compound described in Paragraph No. 0036 of Unexamined-Japanese-Patent No. 2017-198787 - 0037, the compound of Paragraph No. 0029 - 0034 of Unexamined-Japanese-Patent No. 2017-146350, Paragraph No. 0036 - 0037, 0049 - 0052 of Unexamined-Japanese-Patent No. 2017-129774 A compound, a compound described in Paragraph Nos. 0031 to 0034, 0058 to 0059 of Japanese Unexamined Patent Publication No. 2017-129674, a compound described in Paragraph Nos. 0036 to 0037, 0051 to 0054 of Japanese Unexamined Patent Publication No. 2017-122803, Paragraph No. 0025 to 003 of International Publication No. 2017/164127 The compound described in No. 9, the compound described in Paragraph Nos. 0034 to 0047 of Unexamined-Japanese-Patent No. 2017-186546, the compound described in Paragraph Nos. 0019 to 0041 of Unexamined-Japanese-Patent No. 2015-025116, the compound described in Paragraph Nos. 3475, Paragraph Nos. 0018 to 0021, a compound described in Unexamined-Japanese-Patent No. 2011-257591, Paragraph Nos. 0015 to 0018, a compound described in Unexamined-Japanese-Patent No. 2011-191483, Paragraph Nos. 0017 to 0021, and Unexamined-Japanese-Patent No. 2011-145668, Paragraph Nos. 0108 to 0116 The compound described in, the compound of Paragraph No. 0103 of Unexamined-Japanese-Patent No. 2011-253174 - 0153, etc. are mentioned.

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

From the viewpoint of environmental regulations, the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof are regulated in some cases. In the resin composition of the present invention, when the content of the above compound is reduced, the content of perfluoroalkylsulfonic acid (particularly, perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt, and perfluoroalkylcarboxylic acid (particularly, perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt are in the range of 0.01 ppb to 1,000 ppb with respect to the total solid content of the resin composition. It is preferable, it is more preferable that it is the range of 0.05 ppb - 500 ppb, and it is still more preferable that it is the range of 0.1 ppb - 300 ppb. The resin composition of the present invention need not substantially contain perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. For example, by using a compound that can be substituted for perfluoroalkylsulfonic acid and its salt, and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, a resin composition that does not substantially contain perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt may be selected. Examples of the compound that can be substituted for the regulated compound include compounds excluded from the regulated subject depending on the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above does not prevent the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. The resin composition of the present invention may also contain perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt within the maximum permissible range.

The moisture content of the resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. Moisture 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 shape (flatness, etc.), adjusting the film thickness, and the like. Although the value of viscosity can be selected suitably as needed, for example, 0.3 mPa·s - 50 mPa·s are preferable at 25 degreeC, and 0.5 mPa·s - 20 mPa·s are more preferable. As a method for measuring the viscosity, it can be measured in a state where the temperature is adjusted at 25°C using, for example, a cone plate type viscometer.

<<retaining container>>

There is no limitation in particular as a container for the resin composition, and a known container can be used. In addition, it is also preferable to use a multi-layered bottle in which the inner wall of the container is composed of 6 types of 6-layer resin or a bottle in which 6 types of resins have a 7-layer structure for the purpose of suppressing the mixing of impurities into the raw material or resin composition as the containment container. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example. The inner wall of the container is also preferably made of glass or stainless steel for the purpose of preventing elution of metal from the inner wall of the container, enhancing the stability over time of the resin composition, or suppressing deterioration of components.

<Preparation method of resin composition>

The resin composition of the present invention can be prepared by mixing the components described above. When preparing the resin composition, the resin composition may be prepared by simultaneously dissolving and/or dispersing all the components in a solvent, and if necessary, each component may be appropriately prepared as two or more solutions or dispersions, and the resin composition may be prepared by mixing them during use (coating).

Moreover, it is preferable to include the process of dispersing a pigment at the time of preparation of a resin composition. In the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, compression, impact, shear, cavitation, and the like. Specific examples of these processes include bead mill, sand mill, roll mill, ball mill, paint shaker, microfluidizer, high-speed impeller, sand grinder, float mixer, high-pressure wet atomization, ultrasonic dispersion, and the like. In addition, in pulverization of the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to treat under conditions in which the pulverization efficiency is increased by increasing the filling rate of the beads. In addition, it is preferable to remove coarse particles by filtration, centrifugation or the like after the crushing treatment. In addition, the process and disperser for dispersing the pigment are "Complete Collection of Dispersion Technology, published by Joho Kiko Co., Ltd., July 15, 2005" or "Practical Comprehensive Data Collection of Dispersion Technology and Industrial Application Centering on Suspension (High/Liquid Dispersion System), Keiei Kaihatsu Center Publication, October 10, 1978", Paragraph No. 002 of Japanese Unexamined Patent Publication No. 2015-157893 The process and disperser described in 2 can be suitably used. Further, in the process of dispersing the pigment, micronization of the particles may be performed in the salt milling step. For materials, equipment, processing conditions, and the like used in the salt milling process, descriptions in Japanese Unexamined Patent Publication No. 2015-194521 and Japanese Unexamined Patent Publication No. 2012-046629 can be referred to, for example.

In preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign matter or reducing defects. As a filter, it can be used without particular limitation as long as it is a filter conventionally used for filtration purposes or the like. For example, filters using materials such as fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight polyolefin resins) are exemplified. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and still more preferably 0.05 to 0.5 μm. When the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the value of the pore diameter of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by Nihon Pole Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nihon Microlis Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used.

Moreover, it is also preferable to use a fibrous filter medium as a filter. As a fibrous filter medium, polypropylene fiber, nylon fiber, glass fiber etc. are mentioned, for example. Examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Rocky Techno.

When using a filter, you may combine different filters (for example, a 1st filter and a 2nd filter, etc.). In that case, filtration using each filter may be performed only once, or may be performed twice or more. Moreover, you may combine filters of different pore diameters within the above-mentioned range. In addition, filtration using the first filter may be performed only for the dispersion liquid, and after mixing other components, filtration may be performed with the second filter. Moreover, according to the hydrophilicity and hydrophobicity of a composition, a filter can be selected suitably.

<Act>

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 cutoff filters.

The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and still 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 still 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 color of green, red, blue, cyan, magenta or yellow, more preferably of green, blue or cyan, and still more preferably of green. Moreover, the film|membrane of this invention can be used suitably as a colored pixel of a color filter. Examples of the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels and the like, preferably green pixels, blue pixels or cyan pixels, more preferably green pixels.

<Method for producing membrane>

Next, the manufacturing method of the film|membrane of this invention is demonstrated. The film of the present invention can be produced through a step of applying the resin composition of the present invention. In the film manufacturing method, it is preferable to further include a step of forming a pattern (pixel). Examples of the pattern (pixel) formation method include a photolithography method and a dry etching method, and the photolithography method is preferable.

The pattern formation by the photolithography method preferably includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer in a pattern shape, and a step of developing and removing an unexposed portion of the resin composition layer to form a pattern (pixel). If necessary, you may provide a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step).

In the step of forming the resin composition layer, the resin composition layer is formed on the support using the resin composition of the present invention. As a support body, there is no limitation in particular, It can select suitably according to a use. For example, a glass substrate, a silicon substrate, etc. are mentioned, and it is preferable that it is a silicon substrate. In addition, 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. Further, in some cases, a black matrix isolating each pixel is formed on the silicon substrate. In addition, a base layer may be provided on the silicon substrate for the purpose of improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate. The base layer may be formed using a composition obtained by removing a colorant from the resin composition described in this specification, or a composition containing resin, polymerizable compound, surfactant, and the like described in this specification. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. Moreover, it is preferable that it is 30-80 degrees when measured with water.

As a method of applying the resin composition, a known method can be used. For example, the drop method (drop cast); slit coat method; spray method; roll coat method; spin coating (spin coating); casting method; slit and spin method; Pre-wet method (for example, the method described in Unexamined-Japanese-Patent No. 2009-145395); inkjet (eg, on demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, various printing methods such as metal mask printing; transfer method using a mold or the like; The nanoimprint method etc. are mentioned. The application method for inkjet is not particularly limited, and is, for example, the method shown in “Diffusion and Usable Inkjet -Infinite Possibilities as Seen from Patents-, February 2005, Sumibe Techno Research” (particularly pages 115 to 133), Japanese Unexamined Patent Publication No. 2003-262716, Japanese Unexamined Patent Publication No. 2003-185831, and Japanese Unexamined Patent Publication 200 The method described in 3-261827, Unexamined-Japanese-Patent No. 2012-126830, Unexamined-Japanese-Patent No. 2006-169325 etc. is mentioned. Moreover, about the coating method of a resin composition, international publication 2017/030174 and description of international publication 2017/018419 can be considered into consideration, and these content is integrated in this specification.

The resin composition layer formed on the support may be dried (prebaked). When manufacturing a film by a low-temperature process, it is not necessary to perform prebaking. In the case of prebaking, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, 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. In this way, the exposed portion can be cured.

Examples of the radiation (light) that can be used during exposure include g-ray and i-ray. Moreover, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength of 248 nm), ArF rays (wavelength of 193 nm), and the like, and KrF rays (wavelength of 248 nm) are preferable. In addition, a long-wave light source of 300 nm or more can also be used.

Moreover, at the time of exposure, you may expose by irradiating light continuously, and you may expose by irradiating and exposing light pulsewise (pulse exposure). Further, pulse exposure is an exposure method of a system in which light irradiation and pause are repeatedly exposed in cycles of a short time (eg, millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , and more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and exposure may be performed in a low-oxygen atmosphere in which the oxygen concentration is 19 vol% or less (for example, 15 vol%, 5 vol%, or substantially oxygen-free), in addition to performing under atmospheric conditions, or in a high-oxygen atmosphere in which the oxygen concentration exceeds 21 vol% (eg, 22 vol%, 30 vol%, or 50 vol%). You can shine. In addition, the exposure illuminance can be set appropriately, and can be selected from the range of usually 1000 W/m ² to 100000 W/m ² (eg 5000 W/m ² , 15000 W/m ² , or 35000 W/m ² ). Oxygen concentration and exposure illuminance may suitably combine conditions, and, for example, an oxygen concentration of 10 vol% and an illuminance of 10000 W/m ² , an oxygen concentration of 35 vol% and an illuminance of 20000 W/m ² , and the like.

Next, the unexposed portion of the resin composition layer is developed and removed to form a pattern (pixel). The development and removal of the unexposed portion of the resin composition layer can be performed using a developing solution. Thereby, the resin composition layer of the unexposed part in the exposure step is eluted to the developing solution, leaving only the photocured part. As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. As for developing time, 20 to 180 second is preferable. Further, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several more times.

Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As the alkali developing solution, an alkaline aqueous solution (alkali developing solution) obtained by diluting an alkali agent with pure water is preferable. Examples of the alkali agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, organic alkaline compounds such as piperidine and 1,8-diazabicyclo-[5.4.0]-7-undecene; and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight from the viewpoint of environment and safety. 0.001-10 mass % is preferable, and, as for the density|concentration of the alkali agent of alkaline aqueous solution, 0.01-1 mass % is more preferable. Moreover, the developing solution may further contain a surfactant. The developing solution may be once prepared as a concentrated solution and diluted to a concentration necessary for use from the viewpoint of transportation or storage convenience. Although the dilution factor is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. Moreover, it is also preferable to wash (rinse) with pure water after image development. Further, the rinse is preferably performed 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 rinse liquid from the center of the support to the periphery of the support. At this time, when the nozzle is moved from the central portion of the support body to the peripheral edge portion, the nozzle may be moved while gradually lowering the moving speed. By performing the rinse in this way, the in-plane variation of the rinse can be suppressed. Also, the same effect can be obtained by gradually lowering the rotational speed of the support while moving the nozzle from the center of the support to the periphery.

It is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying after development. Additional exposure treatment and post-baking are curing treatments after development to complete curing. The heating temperature in the post-baking is, for example, preferably 100 to 240°C, and more preferably 200 to 240°C. 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 meets the above conditions. When performing additional exposure processing, it is preferable that the light used for exposure is light with a wavelength of 400 nm or less. Moreover, you may perform additional exposure processing by the method described in Korean Unexamined Patent Publication No. 10-2017-0122130.

The pattern formation using the dry etching method preferably includes a step of forming a resin composition layer on a support using the resin composition of the present invention and curing the entire resin composition layer to form a cured product layer, a step of forming a photoresist layer on the cured product layer, a step of exposing the photoresist layer in a pattern shape and then developing a resist pattern, and a step of dry etching the cured product layer using an etching gas using the resist pattern as a mask. In formation of the photoresist layer, it is preferable to further perform a prebaking process. In particular, as the formation process of the photoresist layer, an embodiment in which heat treatment after exposure and heat treatment after development (post-bake treatment) are performed is preferable. About pattern formation using the dry etching method, Paragraph No. 0010 of Unexamined-Japanese-Patent No. 2013-064993 - description of 0067 can be considered into consideration, and this content is integrated in this specification.

<Optical filter>

The optical filter of the present invention has the film of the present invention described above. Types of optical filters include color filters, near-infrared cutoff filters and near-infrared transmission filters, etc., and color filters are preferred. The color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as a color pixel, and still more preferably has the film of the present invention as a green pixel.

In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilic hydration, and shielding of light (ultraviolet rays, near infrared rays, etc.) of a specific wavelength can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the protective layer formation method include a method of applying and forming a resin composition for forming a protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. 보호층을 구성하는 성분으로서는, (메트)아크릴 수지, 엔·싸이올 수지, 폴리카보네이트 수지, 폴리에터 수지, 폴리아릴레이트 수지, 폴리설폰 수지, 폴리에터설폰 수지, 폴리페닐렌 수지, 폴리아릴렌에터포스핀옥사이드 수지, 폴리이미드 수지, 폴리아마이드이미드 수지, 폴리올레핀 수지, 환상 올레핀 수지, 폴리에스터 수지, 스타이렌 수지, 폴리올 수지, 폴리 염화 바이닐리덴 수지, 멜라민 수지, 유레테인 수지, 아라미드 수지, 폴리아마이드 수지, 알키드 수지, 에폭시 수지, 변성 실리콘 수지, 불소 수지, 폴리카보네이트 수지, 폴리아크릴로나이트릴 수지, 셀룰로스 수지, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ 등을 들 수 있으며, 이들 성분을 2종 이상 함유해도 된다. For example, in the case of a protective layer for the purpose of blocking oxygen, the protective layer preferably contains a polyol resin, SiO ₂ and Si ₂ N ₄ . In addition, in the case of a protective layer aimed at low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

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

The protective layer may contain additives such as organic/inorganic fine particles, an absorber for light of a specific wavelength (eg, ultraviolet rays, near infrared rays, etc.), a refractive index modifier, an antioxidant, an adhesive agent, and a surfactant, if necessary. Examples of the organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. As an absorber of light of a specific wavelength, a known absorber can be used. 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.

Moreover, as a protective layer, the protective layer of Paragraph No. 0073 of Unexamined-Japanese-Patent No. 2017-151176 - 0092 can also be used.

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

<Solid-state imaging device>

The solid-state imaging device of the present invention has the film of the present invention described above. The configuration of the solid-state imaging device is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging device, but examples include the following configurations.

On a substrate, a plurality of photodiodes constituting a 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 transfer electrode made of polysilicon, and a light-shielding film in which only the light-receiving portion of the photodiode is opened on the photodiode and the transfer electrode, and a device protective film made of silicon nitride or the like formed on the light-shielding film to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. , It is a configuration having a color filter on the device protective film. Further, a structure having a light concentrating means (for example, a microlens, etc. hereinafter the same) on the device protective film and below the color filter (on the side close to the substrate) or a constitution having a light concentrating means on the color filter may be used. Further, the color filter may have a structure in which each color pixel is embedded in a space partitioned in a lattice shape, for example, by barrier ribs. It is preferable that the partition in this case has a lower refractive index than each color pixel. As an example of the imaging device which has such a structure, the apparatus of Unexamined-Japanese-Patent No. 2012-227478, Unexamined-Japanese-Patent No. 2014-179577, and International Publication No. 2018/043654 is mentioned. Moreover, as shown in Unexamined-Japanese-Patent No. 2019-211559, a ultraviolet ray absorbing layer may be provided in the structure of a solid-state imaging element to improve light resistance. The imaging device provided with the solid-state imaging element of the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an imaging function, but also for in-vehicle cameras and monitoring cameras.

<Image Display Device>

The image display device of the present invention has the film of the present invention described above. As an image display device, a liquid crystal display device, an organic electroluminescence display device, etc. are mentioned. The definition of an image display device and the details of each image display device are described, for example, in "Electronic Display Device (authored by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)" and "Display Device (authored by Sumiaki Ibuki, published in 1990 by Sangyo Tosho Co., Ltd.)" and the like. Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to liquid crystal display devices of various types described in the above "next-generation liquid crystal display technology".

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<About resin P1 to P188, PP1 to PP23, PP101 to PP136, CP1 to CP3>

Resins P1 to P188, PP1 to PP23, PP101 to PP136, and CP1 to CP3 are resins each containing a repeating unit shown in the table below. The acid value and weight average molecular weight (Mw) of the resin are also described. Resins P1 to P188, PP1, PP2, and PP101 to PP136 are specific resins described above.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[repeat unit 1]

A-1: repeating unit having the following structure (repeating unit having a naphthalimide structure)

A-2: repeating unit having the following structure (repeating unit having a naphthalimide structure)

A-3: repeating unit having the following structure (repeating unit having an acridone structure)

A-4: repeating unit having the following structure (repeating unit having a benzothiazole structure)

A-5: repeating unit having the following structure (repeating unit having a benzimidazole structure)

A-6: repeating unit having the following structure (repeating unit having a benzoxazole structure)

A-7: repeating unit having the following structure (repeating unit having a benzotriazole structure)

A-8: repeating unit having the following structure (repeating unit having a tetrazole structure)

A-9: repeating unit having the following structure (repeating unit having a phthalimide structure)

A-10: repeating unit having the following structure (repeating unit having a phthalimide structure)

A-11: repeating unit having the following structure (repeating unit having a carbazole structure)

A-12: repeating unit having the following structure (repeating unit having a fluorene structure)

A-13: repeating unit having the following structure (repeating unit having a benzimidazolone structure)

A-14: repeating unit having the following structure (repeating unit having an anthraquinone structure)

A-15: repeating unit having the following structure (repeating unit having a benzothiazine structure)

A-16: repeating unit having the following structure (repeating unit having a benzoxazine structure)

A-17: repeating unit having the following structure (repeating unit having a benzoleinurea structure)

A-18: repeating unit having the following structure (repeating unit having an isoindoline structure)

A-19: repeating unit having the following structure (repeating unit having an isoindolinone structure)

A-20: repeating unit having the following structure (repeating unit having a phenoxazine structure)

A-21: repeating unit having the following structure (repeating unit having a phenothiazine structure)

A-22: repeating unit having the following structure (repeating unit having a dihydroacridine structure)

A-23: repeating unit having the following structure (repeating unit having a benzothiazolone structure)

A-24: repeating unit having the following structure (repeating unit having a benzoxazolinone structure)

A-25: repeating unit having the following structure (repeating unit having an imidazole structure)

A-26: repeating unit having the following structure (repeating unit having a thiazole structure)

A-27: repeating unit having the following structure (repeating unit having a pyrimidine structure)

A-28: repeating unit having the following structure (repeating unit having a quinazoline structure)

A-29: repeating unit having the following structure (repeating unit having a pyrazine structure)

A-30: repeating unit having the following structure (repeating unit having a quinoxaline structure)

A-31: repeating unit having the following structure (repeating unit having a naphthalene-2,3-dicarboxyimide structure)

A-32: repeating unit having the following structure (repeating unit having a quinoline structure)

A-33: repeating unit having the following structure (repeating unit having a benzophenone structure)

A-34: repeating unit having the following structure (repeating unit having a triazine structure)

A-35: repeating unit having the following structure (repeating unit having a thioxanthone structure)

A-36: repeating unit having the following structure (repeating unit having a chromane structure)

A-37: repeating unit having the following structure (repeating unit having a thiochromanon structure)

A-38: repeating unit having the following structure (repeating unit having an azobenzene structure)

A-39: repeating unit having the following structure (repeating unit having a dibenzopyran structure)

A-40: repeating unit having the following structure (repeating unit having a benzalaniline structure)

A-41: repeating unit having the following structure (repeating unit having a phenazine structure)

A-42: repeating unit having the following structure (repeating unit having a barbituric acid structure)

A-43: repeating unit having the following structure (repeating unit having a xanthone structure)

A-44: repeating unit having the following structure (repeating unit having a saccharin structure)

A-45: repeating unit having the following structure (repeating unit having a phenoxacyine structure)

A-46: repeating unit having the following structure (repeating unit having a pyrazole structure)

A-47: repeating unit having the following structure (repeating unit having a pyrazolone structure)

A-48: repeating unit having the following structure (repeating unit having a caprolactam structure)

A-49: repeating unit having the following structure (repeating unit having an indole structure)

A-50: repeating unit having the following structure (repeating unit having a biphenyl structure)

A-51: repeating unit having the following structure (repeating unit having a benzothiophene structure)

A-52: repeating unit having the following structure (repeating unit having a carboline structure)

A-53: repeating unit having the following structure (repeating unit having a benzoxadiazole structure)

A-54: repeating unit having the following structure (repeating unit having a benzothiadiazole structure)

A-55: repeating unit having the following structure (repeating unit having a triarylbenzene structure)

A-56: repeating unit having the following structure (repeating unit having a triarylamine structure)

A-57: repeating unit having the following structure (repeating unit having an isothiazolinone structure)

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[repeat unit 2]

B-2, B-3, B-6, B-7, B-9, B-11, B-14: repeating units having the following structures (repeating units having acid groups)

[Formula 41]

[repeat unit 3]

C-1, C-3, C-5, C-7, C-9, C-10, C-12, C-13, C-14, C-17, C-18, C-19: repeating units of the following structure

[Formula 42]

[repeat unit 4]

D-1, D-3, D-5, D-7: repeating units having the following structures (repeating units having graft chains)

[Formula 43]

[repeat unit 5]

E-2, E-3, E-6: repeating units having the following structures (repeating units having a crosslinkable group)

[Formula 44]

[repeat unit 6]

F-1 to F-6: repeating units of the following structure

[Formula 45]

[repeat unit 7]

F-7: repeating unit of the following structure

[Formula 46]

<Preparation of Pigment Dispersion>

After mixing and dispersing the mixed solution of 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 NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g/min under a pressure of 2000 MPa. This dispersion treatment was repeated 10 times to obtain each pigment dispersion. Numerical values in the table below are values in parts by mass. The average particle diameter (nm) and viscosity value (mPa·s) of the pigment in each pigment dispersion are also described. The average particle diameter of the pigment was measured by a dynamic light scattering method using nanoSAQLA (manufactured by Otsuka Electronics Co., Ltd.). The viscosity of the pigment dispersion was measured by adjusting the temperature of the pigment dispersion to 25°C.

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

[Table 19]

[Table 20]

The details of the raw materials described in abbreviations in the table above are as follows.

(colorant)

PR254: C.I. Pigment Red 254 (diketopyrrolopyrrole compound, red pigment)

PR272: C.I. Pigment Red 272 (diketopyrrolopyrrole compound, red pigment)

PY139: C.I. Pigment Yellow 139 (isoindoline compound, yellow pigment)

PG36: C.I. Pigment Green 36 (phthalocyanine compound, green pigment)

PG58: C.I. Pigment Green 58 (phthalocyanine compound, green pigment)

PB15:6: C.I. Pigment Blue 15:6 (phthalocyanine compound, blue pigment)

PV23: C.I. Pigment Violet 23 (dioxazine compound, purple pigment)

PBk32: C.I. Pigment Black 32 (perylene compound, organic black pigment)

IR colorant 1: compound having the following structure (near infrared ray absorbing pigment)

[Formula 47]

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

[Formula 48]

(profit)

P1 to P188, PP1 to PP23, PP101 to PP136, CP1, CP2, CP3: the above resin

CP11: Flysurf A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a phosphoric acid group (pKa = about 2), terminal acid group type)

CP12: Flysurf H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a carboxyl group (pKa = about 4.5), terminal acid group type)

CP13: Resin having the following structure (resin having a sulfo group (pKa = about 2), terminal acid group type)

[Formula 49]

(solvent)

Solvent 1: Propylene glycol monomethyl ether acetate

Solvent 2: Cyclopentanone

Solvent 3: 1-methoxy-2-propanol

<Preparation of resin composition>

Each material was mixed in a ratio of formulations 1 to 7 shown below, and each resin composition was prepared by filtering with a nylon filter having a pore diameter of 0.45 µm (manufactured by Nippon Pole Co., Ltd.). In the following table, the value of the content of the color material in the total solid content of the resin composition is described in the column of "content of the color material".

(prescription 1)

The pigment dispersions listed in the table below … 520 mass parts

polymerizable compound 1 … 6.6 mass parts

polymerizable compound 2 … 12.6 mass parts

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 5 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 2 parts by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 2)

The pigment dispersions listed in the table below … 566.4 parts by mass

polymerizable compound 1 … 6.6 mass parts

polymerizable compound 2 … 6.1 parts by mass

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 5 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 2 parts by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 3)

The pigment dispersions listed in the table below … 603.6 mass parts

polymerizable compound 1 … 6.6 mass parts

polymerizable compound 2 … 1.9 parts by mass

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 4 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 2 parts by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 4)

The pigment dispersions listed in the table below … 650 parts by mass

polymerizable compound 1 … 6.6 mass parts

polymerizable compound 2 … 1.4 parts by mass

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 5 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 2 parts by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 5)

The pigment dispersions listed in the table below … 566.4 parts by mass

polymerizable compound 1 … 3.9 mass parts

polymerizable compound 2 … 15.9 mass parts

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 5 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 1 part by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 6)

The pigment dispersions listed in the table below … 371.4 parts by mass

dye 1 … 21 mass parts

polymerizable compound 1 … 6.6 mass parts

polymerizable compound 2 … 12.4 parts by mass

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 5 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 2 parts by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(Recipe 7)

The pigment dispersions listed in the table below … 566.4 parts by mass

polymerizable compound 1 … 3.9 mass parts

polymerizable compound 2 … 5.7 mass parts

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 3 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 1 part by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 8)

The pigment dispersions listed in the table below … 696.4 parts by mass

polymerizable compound 1 … 3.9 mass parts

polymerizable compound 2 … 1.1 parts by mass

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 3 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 1 part by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

(prescription 9)

The pigment dispersions listed in the table below … 464.3 parts by mass

polymerizable compound 1 … 6.6 mass parts

polymerizable compound 2 … 12.6 mass parts

resin solution 1 . . . 3 parts by mass

photopolymerization initiator 1 … 5 parts by mass

surfactant 1 … 0.1 parts by mass

heat curing agent 1 … 2 parts by mass

solvent 1 … 200 parts by mass

solvent 2 … 100 parts by mass

solvent 3 … 21.96 parts by mass

Dye 1: a compound having the following structure (m=3, n=3, weight average molecular weight 7000)

[Formula 50]

Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound 2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)

Resin solution 1: 30% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (weight average molecular weight: 9000, numerical values added to repeating units are mass ratios)

[Formula 51]

Photopolymerization initiator 1: Irgacure OXE01 (manufactured by BASF, oxime compound)

Surfactant 1: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant)

Heat Curing Agent 1: Compound T-1 having the following structure

[Formula 52]

Solvent 1: Propylene glycol monomethyl ether acetate

Solvent 2: Cyclopentanone

Solvent 3: 1-methoxy-2-propanol

<Performance evaluation>

(uneven color)

On a glass substrate, a composition for forming an underlayer (CT-4000, manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied by spin coating to a film thickness of 0.1 μm, and heated at 220° C. for 1 hour using a hot plate to form an underlayer. Each resin composition was applied on the glass substrate with a base layer by spin coating, and then heated at 100°C for 2 minutes using a hot plate to obtain a composition layer having a film thickness of 0.5 µm. The composition layer was exposed to light with a wavelength of 365 nm at an exposure amount of 500 mJ/cm ² using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.). The composition layer after exposure was subjected to puddle development at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Thereafter, it was rinsed using water in a spin shower, and further washed with pure water. Thereafter, water droplets were blown with high-pressure air to dry the glass substrate naturally, and then post-baking was performed at 220° C. for 300 seconds using a hot plate to form a film. Using the glass substrate (substrate for evaluation) on which this film was formed, the luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the number of pixels whose deviation from the average was ±10% or more.

A method for measuring the luminance distribution will be described. A substrate for evaluation was placed between the observation lens of an optical microscope and a light source, and light was irradiated toward the observation lens, and the state of the transmitted light was observed using an optical microscope MX-50 (manufactured by Olympus) equipped with a digital camera. Film surface imaging was performed on five randomly selected areas. The luminance of the photographed image was digitized and stored as a density distribution of 256 gradations from 0 to 255. The luminance distribution was analyzed from this image, and color unevenness was evaluated by the number of pixels whose deviation from the average exceeded ±10%. The evaluation criteria are as follows. If it is an evaluation of A to C, it is judged that there is no problem in practical use.

A: The number of pixels in which the deviation from the average exceeds ±10% is 1000 or less.

B: The number of pixels in which the deviation from the average exceeds ±10% is more than 1000 and 3000 or less.

C: The number of pixels in which the deviation from the average exceeds ±10% is more than 3000 and 5000 or less.

D: The number of pixels in which the deviation from the average exceeds ±10% exceeds 5000.

(coarse particles)

On a glass substrate, a composition for forming an underlayer (CT-4000, manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied using a spin coater to a thickness of 0.1 μm after post-baking, and heated at 220° C. for 300 seconds using a hot plate to form an underlayer, thereby obtaining a glass substrate (support) with an underlayer. Each resin composition was applied on the glass substrate with a base layer by spin coating, and then heated at 100°C for 2 minutes using a hot plate to form a film having a thickness of 0.5 µm. Foreign matter contained in this film was detected by a foreign matter evaluation device Complas III (manufactured by Applied Materials), foreign matter (coarse particles) having a maximum width of 1.0 μm or more was visually classified from all detected foreign matters, and the number of classified coarse particles having a maximum width of 1.0 μm or more (the number of coarse particles per 1 cm ² ) was counted.

A: The number of coarse particles per 1 cm ² of the film is less than 10

B: The number of coarse particles per 1 cm ² of the film is 10 or more and less than 30

C: The number of coarse particles per 1 cm ² of the film is 30 or more and less than 100

D: The number of coarse particles per 1 cm ² of the film is 100 or more

(developability)

On an 8-inch (20.32 cm) silicon wafer, a composition for forming a base layer (CT-4000, manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied using a spin coater to a thickness of 0.1 μm after post-baking, and heated at 220° C. for 300 seconds using a hot plate to form a base layer, thereby obtaining a silicon wafer (support) with a base layer. Next, each resin composition was applied by spin coating so that the film thickness after post-baking would be 0.62 μm. Next, it heated at 100 degreeC for 2 minutes using the hotplate. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.), light having a wavelength of 365 nm was exposed at an exposure amount of 1000 mJ/cm ² through a rectangular dot pattern mask with sides of 1.0 μm. Next, the silicon wafer on which the exposed coating film was formed was placed on a horizontal rotation table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and puddle development was performed at 23° C. for 60 seconds using a 60% dilution of CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.). While rotating at 0 rpm, pure water was supplied from the spray nozzle to the shower top from above the center of rotation to perform a rinse treatment, followed by spray drying. Furthermore, a heat treatment (post-bake) was performed for 300 seconds using a 200°C hot plate to form a pattern (pixel).

The silicon wafer on which pixels were formed was observed with a scanning electron microscope (SEM) (magnification: 10000 times), and developability was evaluated according to the following evaluation criteria.

A: No residue was observed outside the pixel formation area (unexposed area).

B: Very little residue was observed outside the pixel formation area (unexposed area), but there was no problem in practical use.

C: A few residues were observed outside the pixel formation area (unexposed area), but there was no problem in practical use.

D: Residues were significantly observed outside the pixel formation area (unexposed area)

(stability over time)

The viscosity (mPa·s) of the resin compositions of Examples and Comparative Examples was measured with "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the said measurement, the resin composition was left still at 45 degreeC, light-shielding, and 5-day conditions, and the viscosity (mPa*s) was measured again. Stability over time was evaluated according to the following evaluation criteria from the difference in viscosity (ΔVis) before and after the said stationary. It can be said that the aging stability of the resin composition is so good that the numerical value of the viscosity difference (ΔVis) is small. All of the above viscosity measurements were measured in a laboratory where the temperature and humidity were controlled at 22±5° C. and 60±20%, in a state where the temperature of the resin composition was adjusted to 25° C. All measurements were performed three times, and the average value was used.

A: ΔVis was 0.2 mPa·s or less.

B: ΔVis was more than 0.2 mPa·s and 0.3 mPa·s or less.

C: ΔVis was more than 0.3 mPa·s and 0.5 mPa·s or less.

D: ΔVis exceeded 0.5 mPa·s.

[Table 21]

[Table 22]

[Table 23]

[Table 24]

[Table 25]

[Table 26]

[Table 27]

[Table 28]

[Table 29]

[Table 30]

As shown in the table above, the resin compositions of Examples were able to form a film with color unevenness suppressed.

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

[Formula 53]

In Example 43, the same effect was obtained even when the photoinitiator 1 was changed to compounds I-2 to I-5 having structures shown below.

[Formula 54]

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

[Formula 55]

In Example 43, the same effect was obtained even when surfactant 1 was changed to a compound having a structure shown below (a weight average molecular weight of 14,000, a fluorine-based surfactant whose % numerical value representing the ratio of repeating units is mol%) or PolyFox PF6320 (manufactured by OMNOVA, a fluorine-based surfactant).

[Formula 56]

PG36 of Example 1, C.I. Pigment Green 7, C.I. Pigment Green 58 or C.I. The same result was obtained even if it replaced with Pigment Green 59.

<Manufacturing example of image sensor>

[Manufacture of composition for bulkhead]

After mixing each component so that it might become the composition of the following table|surface, after filtering with a filtration filter (Protego Plus PRL00S1S1, Entegris make), it further filtered with a filtration filter (DFA4201J006, Pall make), and obtained the composition for partition walls. The numerical value of the compounding quantity described in the following table|surface is a mass part. In addition, the mixing amount of the silica particle liquid is the value of SiO ₂ in the silica particle liquid. The numerical value of the compounding amount of the solvent is a numerical value obtained by summing the amount of the solvent contained in the silica particle liquid.

[Table 31]

The raw materials described in the table above are as follows.

(silica particle liquid)

P1: A solution of silica particles (beaded silica) in which a plurality of spherical silica particles having an average particle diameter of 10 nm are connected in a bead shape by a metal oxide-containing silica (linking material).

P2: Surulia 4110: manufactured by Nikki Shokubai Kasei Co., Ltd., a solution of silica particles (silica particles having a hollow structure) having an average particle diameter of 60 nm. Solid content concentration in terms of SiO ₂ 20% by mass

(Surfactants)

F1: Compound having the following structure (weight average molecular weight = 3000)

[Formula 57]

F2: Silwet L-7220 (manufactured by Momentive Performance Materials)

F3: Pionin B-111 (Takemoto Oil Co., Lauryl Trimethylammonium Chloride)

(additive)

A1: NOD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a compound having the following structure)

[Formula 58]

(solvent)

S1: 1,4-butanediol diacetate

S2: propylene glycol monomethyl ether acetate

S3: propylene glycol monomethyl ether

S4: Ethanol

S5: water

[Production of Image Sensor]

On a silicon wafer, barrier ribs 40 to 43 in FIG. 1 of Japanese Patent Laid-Open No. 2017-028241 were produced using the composition for barrier ribs prepared above using the composition for barrier ribs prepared above.

Next, a green pixel-forming composition, a red pixel-forming composition, and a blue pixel-forming composition were pattern-formed by photolithography in a region partitioned by barrier ribs on the silicon wafer to form green pixels, red pixels, and blue pixels, respectively, to manufacture an image sensor. The obtained image sensor was excellent in sensitivity.

In addition, the resin composition of Example 1 was used for the composition for forming a green pixel. In addition, the resin composition of Example 70 was used for the composition for forming red pixels. In addition, the resin composition of Example 76 was used for the composition for forming a blue pixel.

In the production of each partition wall composition, the same effect as described above was obtained even when filtration was performed using IonKleen SL (manufactured by Pall) instead of Protego Plus PRL00S1S1 (manufactured by Entegris) as a filtration filter.

Claims (16)

As a resin composition containing a color material A and a resin B,
The color material A includes a pigment,
The resin B contains a repeating unit b1-1 having an acid group, a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring, and a resin b1 containing a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2;
The resin composition in which content of the said color material A in the total solids of the said resin composition is 55 mass % or more. The method of claim 1,
The color material A is a resin composition containing a phthalocyanine pigment. According to claim 1 or claim 2,
The color material A further comprises a dye, the resin composition. The method according to any one of claims 1 to 3,
The functional group b is 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 benzothiadiazole structure, a benzothiadiazole structure, a benzothiazine structure, a benzoxazine structure, a benzorain urea structure, an isothiazolinone structure, a phenoxy photo structure, phenothiazine structure, dihydroacridine structure, phenoxacyine 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, chromane structure, benzimidazolone structure, phthalimide structure, naphthalene-2,3-dicarboxyimide structure, pyrazole structure, pyrazolone structure, isoindoline structure, isoindolinone structure, anthraquinone structure, tetrazole structure, benzophenone structure, triazine structure, azobenzene structure, benzalaniline structure, phenazine structure, barbiturate A resin composition comprising a ric acid structure, a perylene structure, a perrinone 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. The method according to any one of claims 1 to 3,
The functional group b is a naphthalimide structure, an acridone structure, a xanthone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a benzotriazole structure, a benzothiadiazole structure, a benzothiadiazole structure, a phenoxazine structure, a phenothiazine structure, a phenoxacyine structure, a phthalimide structure, a pyrazolone structure, a tetrazole structure, and a benzothiazolone. A resin composition comprising a structure or a benzoxazolinone structure. The method according to any one of claims 1 to 5,
The resin composition whose content of the said unit b1-2 in the said resin b1 is 10-35 mass %. The method according to any one of claims 1 to 6,
The resin composition, wherein the repeating unit b1-3 includes a repeating unit having a graft chain having a polyester structure or a polyether structure. According to any one of claims 1 to 7,
The resin composition, wherein the resin B further includes a resin b2 different from the resin b1. The method of claim 8,
The resin composition in which the said resin b2 contains resin which has a different acidic radical from the said resin b1. The method of claim 9,
The resin composition in which the said resin b2 has an acidic radical with a pKa smaller than the acidic radical which the said resin b1 has. The method according to any one of claims 8 to 10,
The resin composition according to claim 1 , wherein the resin b2 contains at least one selected from graft polymers, molding polymers, block copolymers, and resins in which at least one terminal of the polymer chain is sealed with an acid group. According to any one of claims 1 to 11,
A resin composition further comprising a polymerizable compound and a photopolymerization initiator. A film obtained from the resin composition according to any one of claims 1 to 12. 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.