CN115916902B

CN115916902B - Resin composition, film, optical filter, solid-state imaging element, image display device, resin, and compound

Info

Publication number: CN115916902B
Application number: CN202180044097.4A
Authority: CN
Inventors: 牧野雅臣; 川岛敬史
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-07-22
Filing date: 2021-07-19
Publication date: 2024-10-22
Anticipated expiration: 2041-07-19
Also published as: TW202208470A; JPWO2022019254A1; CN115916902A; JP2024124473A; KR20230016676A; JP7515592B2; WO2022019254A1

Abstract

A resin composition comprising a pigment-containing color material A, a resin B and a solvent C, wherein the resin B comprises a resin B-1 having a structure represented by the formula (1). Films, filters, solid-state imaging devices, image display devices, resins, and compounds obtained using the resin compositions. In the formula (1), X ¹ represents a 4-valent linking group, X ² represents a 2-valent linking group, R ¹¹、R¹²、R²¹、R²² and R ²³ each independently represent a hydrogen atom or a substituent, lp ¹ represents an n+1-valent linking group, lp ² represents a 2-valent linking group, P ¹ represents a polymer chain, and n represents an integer of 1 or more.

Description

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

Technical Field

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

Background

In recent years, with the popularization of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has increased greatly. A film containing a pigment such as a color filter is used for the solid-state imaging element. The film containing a color material such as a color filter is produced using a resin composition containing a pigment, a resin, and a solvent.

For example, patent document 1 describes an invention related to a resin composition containing a pigment, a dispersant, a binder resin, an epoxy compound and a solvent, and containing the following dispersant (X): the dispersant has a polyester part X1 'having a carboxyl group and obtained by reacting an acid anhydride group in at least one acid anhydride (b) selected from the group consisting of tetracarboxylic acid anhydride (b 1) and tricarboxylic acid anhydride (b 2) with a hydroxyl group in the hydroxyl group-containing compound (a), and a vinyl polymer part X2' having a thermally crosslinkable functional group and obtained by radical polymerization of the ethylenically unsaturated monomer (c), wherein the thermally crosslinkable functional group is at least 1 selected from the group consisting of hydroxyl group, oxetanyl group, t-butyl group, blocked isocyanate group and (meth) acryl group.

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication 2016-170325

Disclosure of Invention

Technical problem to be solved by the invention

In the resin composition containing the pigment, the resin and the solvent, the dispersibility of the pigment is preferably good. If the dispersibility of the pigment is insufficient, the pigment is aggregated in the resin composition and becomes coarse or the viscosity of the resin composition is liable to become high. Further, even if the viscosity of the resin composition immediately after production is low, the viscosity may increase with the lapse of time.

According to the studies of the present inventors, it has been found that the resin composition described in patent document 1 is insufficient in pigment dispersibility, and there is room for further improvement.

Accordingly, an object of the present invention is to provide a resin composition excellent in pigment dispersibility. The present invention also provides a film, a filter, a solid-state imaging element, and an image display device each using the resin composition. The present invention also provides a resin and a compound.

Means for solving the technical problems

Examples of representative embodiments of the present invention are shown below.

<1> A resin composition comprising a pigment-containing color material A, a resin B and a solvent C,

The resin B contains a resin B-1 having a structure represented by the formula (1),

A resin composition;

[ chemical formula 1]

In the formula (1), X1 represents a 4-valent linking group,

X2 represents a 2-valent linking group,

R11, R12, R21, R22 and R23 each independently represent a hydrogen atom or a substituent,

Lp1 represents an n+1 valent linking group,

Lp2 represents a 2-valent linking group,

P1 represents a polymer chain and is represented by,

N represents an integer of 1 or more.

<2> The resin composition according to <1>, wherein,

Lp2 in the above formula (1) is-O-or-S-.

<3> The resin composition according to <1> or <2>, wherein,

X1 in the formula (1) is a group containing an aromatic hydrocarbon ring.

<4> The resin composition according to any one of <1> to <3>, wherein,

X2 in the formula (1) is a group containing a fluorine atom and an aromatic hydrocarbon ring.

<5> The resin composition according to any one of <1> to <4>, wherein,

The polymer chain represented by P1 contains a repeating unit of at least 1 structure selected from the group consisting of a poly (meth) acrylic structure, a polystyrene structure, a polyether structure and a polyester structure.

<6> The resin composition according to any one of <1> to <4>, wherein,

The polymer chain represented by the above formula P1 contains a repeating unit represented by any one of the formulae (P1-1) to (P1-6),

[ Chemical formula 2]

Wherein RG1 and RG2 each represent an alkylene group,

RG3 represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a hydroxymethyl group,

QG1 represents-O-or-NRq-, rq represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

LG1 represents a single bond or arylene group,

LG2 represents a single bond or a 2-valent linking group,

RG4 represents a hydrogen atom or a substituent,

RG5 represents a hydrogen atom or a methyl group, and RG6 represents an aryl group.

<7> The resin composition according to <6>, wherein,

The substituent represented by RG4 is at least 1 selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group and a t-butyl group.

<8> The resin composition according to any one of <1> to <7>, wherein,

The structure represented by the above formula (1) is a structure represented by the formula (1-1),

[ Chemical formula 3]

In the formula (1-1), X1 represents a 4-valent linking group,

X2 represents a 2-valent linking group,

Rp11 represents a substituent, m Rp11 may be the same or different,

Lp11 represents an n+1 valent linking group,

Lp2 represents a 2-valent linking group,

P1 represents a polymer chain and is represented by,

N represents an integer of 1 or more,

M represents an integer of 0 to 4.

<9> The resin composition according to any one of <1> to <8>, wherein,

The solvent C contains at least 1 selected from the group consisting of ester solvents, ether solvents, alcohol solvents and ketone solvents.

<10> The resin composition according to any one of <1> to <9>, wherein,

The color material A contains at least 1 selected from diketopyrrolopyrrole pigments and phthalocyanine pigments.

<11> The resin composition according to any one of <1> to <10>, further comprising a polymerizable monomer.

<12> The resin composition according to any one of <1> to <11>, further comprising a photopolymerization initiator.

<13> A film obtained using the resin composition of any one of <1> to <12 >.

<14> An optical filter having the film of <13 >.

<15> A solid-state imaging element having the film of <13 >.

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

<17> A resin comprising a structure represented by the formula (1),

[ Chemical formula 4]

In the formula (1), X1 represents a 4-valent linking group,

X2 represents a 2-valent linking group,

Lp1 represents an n+1 valent linking group,

Lp2 represents a 2-valent linking group,

P1 represents a polymer chain and is represented by,

N represents an integer of 1 or more.

<18> A compound represented by the formula (EDM 1),

[ Chemical formula 5]

In the formula (EDM 1), RED1 represents an acid anhydride group,

LpED1 < 1 > represents an n+1-valent group, wherein the n+1-valent group is a hydrocarbon group or a group having a structure in which a hydrocarbon group is combined with at least 1 group selected from the group consisting of-NRpED < 1 >, -N <, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRpED < 1 > CO-and-CONRpED < 1 >,

RpED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

LpED2 represents-O-or-S-,

PED1 represents a polymer chain comprising a repeating unit represented by any one of the formulas (P1-1) to (P1-4),

N represents an integer of 1 to 4,

[ Chemical formula 6]

In the formulae (P1-1) to (P1-4), RG1 and RG2 each represent an alkylene group.

<19> The compound according to <18>, wherein,

The compound represented by the above formula (EDM 1) is a compound represented by the formula (EDM 2),

[ Chemical formula 7]

In the formula (EDM 2), RED12 represents a halogen atom, an alkyl group, a carboxyl group or a hydroxyl group,

LpED a represents an n+1-valent group, wherein the n+1-valent group is a hydrocarbon group or a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group, the above-mentioned linking group is-NRpED < 1 > -SO-, -SO2-, -CO- >, -O-, -COO-, -OCO-, -S-, -NRpED CO-or-CONRpED 1,

LpED2 represents-O-or-S-,

PED1 represents a polymer chain comprising a repeating unit represented by any of the above formulas (P1-1) to (P1-4),

R represents an integer of 0 to 3,

N represents an integer of 1 to 4.

Effects of the invention

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

Detailed Description

Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiments.

In the present specification, "to" is used in a meaning including values described before and after the values as a lower limit value and an upper limit value.

In the labeling of groups (radicals) in the present specification, the label which is not labeled with a substituted or unsubstituted includes a group (radical) having no substituent and includes a group (radical) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, unless otherwise specified, "exposure" includes not only exposure using light but also painting using a particle beam such as an electron beam or an ion beam. The light used for exposure includes an open line spectrum of a mercury lamp, and actinic rays or radiation such as extreme ultraviolet rays (EUV light), X-rays, and electron beams, which are represented by excimer laser light.

In the present specification, (meth) allyl represents either or both of allyl and methallyl, "(meth) acrylate" represents either or both of acrylate and methacrylate, "(meth) acrylic acid" represents either or both of acrylic acid and methacrylic acid, and "(meth) acryl" represents either or both of acryl and methacryl.

In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).

In the present specification, near infrared refers to light having a wavelength of 700 to 2500 nm.

In the present specification, the total solid component means the total mass of components from which the solvent is removed from all components of the composition.

In the present specification, the term "process" includes not only an independent process but also the term if the intended function of the process is achieved even if the process cannot be clearly distinguished from other processes.

In the present specification, the pigment means a compound which is not easily dissolved in a solvent.

In the present specification, the symbol (e.g., a or the like) appended before or after the name is a term used for distinguishing the constituent elements, and the types of the constituent elements, the number of the constituent elements, and the advantages and disadvantages of the constituent elements are not limited.

< Resin composition >

The resin composition of the present invention is characterized by comprising a pigment-containing color material A, a resin B and a solvent C, wherein the resin B comprises a resin B-1 (hereinafter also referred to as a specific resin) having a structure represented by formula (1).

The resin composition of the present invention is excellent in pigment dispersibility. The detailed reasons for obtaining such effects are not clear, but are presumed as follows: since the specific resin has a structure in which an amide group (-C (=o) -NR21-, -C (=o) -NR 22-) is bonded to X1 as a 4-valent linking group, adsorption of the specific resin to the pigment surface is promoted, and since the specific resin has the polymer chain P1, the polymer chain P1 becomes a steric repulsion group, aggregation of pigments and the like can be suppressed, and as a result, the resin composition can be used as a resin composition excellent in pigment dispersibility.

Further, by using the resin composition of the present invention, a film having excellent heat resistance, which is less likely to be decomposed even at high temperature and is less likely to shrink even after heat treatment at high temperature, can be formed. Therefore, even if the obtained film is subjected to a high-temperature (for example, 300 ℃ or higher) heat treatment after the film is formed using the resin composition of the present invention, shrinkage of the film is suppressed, and even when another film such as an inorganic film is formed on the film, occurrence of cracks or the like in the other film can be suppressed. Therefore, according to the resin composition of the present invention, the process window of the process after the film is manufactured can be enlarged.

When a film having a thickness of 0.60 μm is formed by heating the resin composition of the present invention at 200℃for 30 minutes, the thickness of the film after the film is heated at 300℃for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more of the thickness of the film before the heat treatment.

The thickness of the film after the film is heated at 350 ℃ for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more of the thickness of the film before the heat treatment.

The thickness of the film after the film is heated at 400 ℃ for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more of the thickness of the film before the heat treatment.

The above physical properties can be achieved by adjusting the type, content, etc. of the specific resin used.

When a film having a thickness of 0.60 μm is formed by heating the resin composition of the present invention at 200℃for 30 minutes, the change rate DeltaA of absorbance represented by the following formula (A1) of the film after heat treatment is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, and particularly preferably 35% or less, when the film is heat-treated at 300℃for 5 hours in a nitrogen atmosphere.

ΔA(％)＝|100-(A2/A1)×100|······(A1)

Δa is the rate of change of absorbance of the film after heat treatment,

A1 is the maximum value of absorbance of the film before heat treatment in the wavelength range of 400 to 1100nm,

A2 is the absorbance of the film after the heat treatment, and is the absorbance at a wavelength at which the film before the heat treatment exhibits the maximum value of absorbance in the range of 400 to 1100 nm.

When a film having a thickness of 0.60 μm is formed by heating the resin composition of the present invention at 200℃for 30 minutes, the absolute value of the difference between the wavelength λ1 at which the film exhibits the maximum value of absorbance in the range of 400 to 1100nm and the wavelength λ2 at which the film exhibits the maximum value of absorbance after heating the film at 300℃for 5 hours in a nitrogen atmosphere is preferably 50nm or less, more preferably 45nm or less, and still more preferably 40nm or less.

When the resin composition of the present invention is used to form a film having a thickness of 0.60. Mu.m, the maximum value of the absorbance change rate DeltaA lambda of the film after heat treatment in the wavelength range of 400 to 1100nm is preferably 30% or less, more preferably 27% or less, and even more preferably 25% or less, when the film is heat-treated at 300℃for 5 hours in a nitrogen atmosphere. The rate of change in absorbance is a value calculated according to the following formula (2).

ΔAλ＝|100-(A2λ/A1λ)×100|······(2)

Δaλ is the rate of change of absorbance at wavelength λ of the film after heat treatment,

A1λ is absorbance of the film before heat treatment at wavelength λ,

A2λ is the absorbance of the film after heat treatment at wavelength λ.

The resin composition of the present invention can be preferably used as a resin composition for an optical filter. The filter may be a color filter, a near infrared ray transmission filter, a near infrared ray cut filter, or the like, and is preferably a color filter. The resin composition of the present invention can be preferably used as a resin composition for a solid-state imaging device, and can be preferably used as a resin composition for forming pixels of an optical filter used for a solid-state imaging device.

The color filter may be a filter having a colored pixel transmitting light of a specific wavelength, and preferably a filter having at least 1 colored pixel selected from the group consisting of a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel. The color filter can be formed using a resin composition containing a color material.

Examples of the near infrared cut filter include filters having a maximum absorption wavelength in the range of 700 to 1800 nm. The near infrared cut filter preferably has a maximum absorption wavelength in the range of 700 to 1300nm, and more preferably has a wavelength in the range of 700 to 1100 nm. The transmittance of the near infrared cut filter in all the wavelength ranges from 400 to 650nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Further, the transmittance at least 1 in the wavelength range of 700 to 1800nm is preferably 20% or less. The ratio of absorbance Amax at the maximum absorption wavelength to absorbance a550 at the wavelength of 550nm, that is, the ratio of absorbance Amax/absorbance a550, of the near infrared cut filter 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 ray cut filter can be formed using a resin composition containing a near infrared ray absorbing color material.

The near infrared ray transmission filter is a filter that transmits at least a part of near infrared rays. The near infrared ray transmission filter is preferably a filter that shields at least a part of visible light but transmits at least a part of near infrared rays. The near infrared ray transmission filter is preferably a filter that satisfies the spectral characteristics that the maximum value of the transmittance in the wavelength range of 400 to 640nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1300nm is 70% or more (preferably 75% or more, more preferably 80% or more). The near infrared ray transmission filter is preferably a filter satisfying any one of the spectral characteristics (1) to (5) below.

(1): A filter having a maximum value of transmittance in a wavelength range of 400 to 640nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 800 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(2): A filter having a maximum value of transmittance in a wavelength range of 400 to 750nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 900 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(3): A filter having a maximum value of transmittance in a wavelength range of 400 to 830nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1000 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(4): A filter having a maximum value of transmittance in a wavelength range of 400 to 950nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1100 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(5): A filter having a maximum value of transmittance in a wavelength range of 400 to 1050nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1200 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

As a preferable mode of the spectroscopic characteristics of the resin composition of the present invention, the following modes are given: when a film having a thickness of 5 μm is formed using the resin composition, the spectral characteristics are satisfied in which the maximum value of the transmittance in the thickness direction of the film in the wavelength range of 360 to 700nm is 50% or more. The resin composition satisfying such spectroscopic characteristics can be preferably used as a resin composition for forming pixels of a color filter. Specifically, the resin composition can be preferably used as a resin composition for forming colored pixels selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels.

The resin composition having the spectral characteristics preferably contains a color material. For example, a resin composition containing a red color material and a yellow color material can be preferably used as the resin composition for red pixel formation. Further, a resin composition containing a blue color material and a violet color material can be preferably used as the resin composition for forming a blue pixel. Further, a resin composition containing a green color material can be preferably used as a resin composition for forming green or cyan pixels. When the resin composition is used as a green pixel-forming resin composition, it is preferable to further contain a yellow color material in addition to the green color material.

Another preferable mode of the spectroscopic characteristics of the resin composition of the present invention is a mode satisfying the spectroscopic characteristics that the ratio of the minimum absorbance Amin at a wavelength of 400 to 640nm to the absorbance B at a wavelength of 1500nm, i.e., amin/B is 5 or more. The resin composition satisfying such spectroscopic characteristics can be preferably used as a resin composition for forming a near infrared ray transmission filter. The absorbance ratio, i.e., amin/B, is preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more.

Here, the absorbance aλ at the wavelength λ is defined according to the following formula (λ1).

Aλ＝-log(Tλ/100)······(λ1)

Aλ is absorbance at wavelength λ, and tλ is transmittance (%) at wavelength λ.

In the present invention, the absorbance may be measured in a solution state or a film formed by using the composition. When absorbance is measured in a state of a film, the following film is preferably used for measurement: the composition is coated on a glass substrate by spin coating or the like, and dried at 100℃for 120 seconds using a heating plate or the like to obtain a film.

The resin composition of the present invention preferably satisfies any one of the following spectroscopic characteristics (IrJ) to (Ir 5).

(Ir 1): the ratio of the minimum absorbance A1 in the wavelength range of 400 to 640nm to the maximum absorbance B1 in the wavelength range of 800 to 1500nm, that is, the value of A1/B1, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more. According to this aspect, a film that shields light having a wavelength in the range of 400 to 640nm and transmits light having a wavelength greater than 750nm can be formed.

(Ir 2): the ratio of the minimum absorbance A2 in the wavelength range of 400 to 750nm to the maximum absorbance B2 in the wavelength range of 900 to 1500nm, that is, the value of A2/B2, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more. According to this aspect, a film that shields light having a wavelength in the range of 400 to 750nm and transmits light having a wavelength greater than 850nm can be formed.

(Ir 3): the ratio of the minimum absorbance A3 in the wavelength range of 400 to 830nm to the maximum absorbance B3 in the wavelength range of 1000 to 1500nm, that is, the value of A3/B3, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more. According to this aspect, a film that shields light in the wavelength range of 400 to 830nm and transmits light having a wavelength of more than 950nm can be formed.

(Ir 4): the ratio of the minimum absorbance A4 in the wavelength range of 400 to 950nm to the maximum absorbance B4 in the wavelength range of 1100 to 1500nm, that is, the value of A4/B4, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more. According to this aspect, a film that shields light having a wavelength in the range of 400 to 950nm and transmits light having a wavelength greater than 1050nm can be formed.

(Ir 5): the ratio of the minimum absorbance A5 in the wavelength range of 400 to 1050nm to the maximum absorbance B5 in the wavelength range of 1200 to 1500nm, that is, the value of A5/B5, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and even more preferably 30 or more. According to this aspect, a film that shields light having a wavelength in the range of 400 to 1050nm and transmits light having a wavelength greater than 1150nm can be formed.

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

The resin composition of the present invention can also be used as a resin composition for forming a black matrix and a resin composition for forming a light shielding film.

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

< 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 color material include white color material, black color material, color material, and near infrared ray absorbing color material. In the present invention, the white color material includes not only pure white but also a color material of bright gray (for example, off-white, thin gray, or the like) close to white.

The color material preferably contains at least 1 selected from the group consisting of a color material, a black color material, and a near infrared ray absorbing color material, more preferably contains at least 1 selected from the group consisting of a color material and a near infrared ray absorbing color material, still more preferably contains a color material, and still more preferably contains at least 1 selected from the group consisting of a red color material, a yellow color material, a blue color material, and a violet color material.

The color material preferably includes a color material and a near infrared ray absorbing color material, and also preferably includes 2 or more color materials and a near infrared ray absorbing color material. Further, black may be formed by a combination of 2 or more kinds of color materials. The color material preferably includes a black color material and a near infrared absorbing color material. According to these aspects, the resin composition of the present invention can be preferably used as a near infrared ray transmission filter forming resin composition. For the combination of the black color materials formed by the combination of 2 or more kinds of color materials, reference can be made to japanese patent application laid-open publication No. 2013-077009, japanese patent application laid-open publication No. 2014-130338, international publication No. 2015/166779, and the like.

The color material contained in the coloring composition of the present invention may be a color material containing a pigment. The pigment may be any of an inorganic pigment and an organic pigment, and is preferably an organic pigment from the viewpoints of a large number of color changes, ease of dispersion, safety, and the like. The pigment preferably includes at least 1 selected from the group consisting of color pigments and near infrared absorbing pigments, and more preferably includes color pigments.

The pigment preferably contains at least 1 selected from the group consisting of phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments and quinoline yellow pigments, more preferably contains at least 1 selected from the group consisting of phthalocyanine pigments, diketopyrrolopyrrole pigments and pyrrolopyrrole pigments, and still more preferably contains a phthalocyanine pigment or diketopyrrolopyrrole pigment. Further, the phthalocyanine pigment is preferably a phthalocyanine pigment having no central metal or a phthalocyanine pigment having copper or zinc as a central metal, from the viewpoint of easy formation of a film whose spectroscopic characteristics are not easily changed even after heating to a high temperature (for example, 300 ℃ or higher).

The average primary particle diameter of the pigment is preferably 1 to 200nm. The lower limit is preferably 5nm or more, more preferably 10nm or more. The upper limit is preferably 180nm or less, more preferably 150nm or less, and still more preferably 100nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the resin composition is good. In the present invention, the primary particle diameter of the pigment can be obtained by observing the primary particles of the pigment with a transmission electron microscope and obtaining a photograph. 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 diameter in the present invention is an arithmetic average value of primary particle diameters of primary particles for 400 pigments. The primary particles of the pigment are independent particles which are not aggregated.

(Color Material)

Examples of the color material include a color material having a wavelength of maximum absorption in a wavelength range of 400 to 700 nm. Examples thereof include yellow, orange, red, green, violet, and blue. From the viewpoint of heat resistance, the color material is preferably a pigment (color pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and further preferably a red pigment and a blue pigment. Specific examples of the color pigment include the following color pigments.

C.I. pigment yellow 1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35：1、36、36：1、37、37：1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214、215、228、231、232( methines), 233 (quinolines), 234 (aminoketones), 235 (aminoketones), 236 (aminoketones) and the like (yellow pigments above),

C.i. pigment orange 2, 5, 13, 16, 17: 1. 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 and the like (above orange pigments),

C.i. pigment red 1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48：1、48：2、48：3、48：4、49、49：1、49：2、52：1、52：2、53：1、57：1、60：1、63：1、66、67、81：1、81：2、81：3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、269、270、272、279、291、294( tons, organo Ultramarine (organic group blue), bluish Red (blue red), 295 (monoazo), 296 (diazo), 297 (amino ketone) and the like (the above being red pigments),

C.I. pigments green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanines), 65 (phthalocyanines), 66 (phthalocyanines), etc. (above, green pigment),

C.i. pigment violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethanes), 61 (xanthenes), etc. (above, violet pigment),

C.i. pigment blue 1,2, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo type), 88 (methine type), etc. (blue pigment above).

Among these color pigments, c.i. pigment red 254, c.i. pigment red 264, c.i. pigment red 272, c.i. pigment red 122, and c.i. pigment red 177 are preferable from the viewpoint of easy formation of a film whose spectroscopic characteristics are not easily changed even after heating to a high temperature (for example, 300 ℃ or higher). Further, as the blue pigment, c.i. pigment blue 15: 3. c.i. pigment blue 15: 4. c.i. pigment blue 15: 6. c.i. pigment blue 16.

Further, as the green pigment, a zinc halide phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can be used. Specific examples thereof include the compounds described in Japanese patent application laid-open No. 2015/118720. Further, as the green pigment, a compound described in the specification of chinese patent application 106909027, a phthalocyanine compound having a phosphate as a ligand described in international publication No. 2012/102395, a phthalocyanine compound described in japanese patent application laid-open No. 2019-008014, a phthalocyanine compound described in japanese patent application laid-open No. 2018-180023, a compound described in japanese patent application laid-open No. 2019-038958, and the like can also be used.

Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include compounds described in paragraphs 0022 to 0030 of Japanese patent application laid-open No. 2012-247591 and paragraph 0047 of Japanese patent application laid-open No. 2011-157478.

Further, as the yellow pigment, a compound described in Japanese patent application laid-open No. 2017-201003, a compound described in Japanese patent application laid-open No. 2017-197719, a compound described in paragraphs 0011 to 0062 and 0137 to 0276 of Japanese patent application laid-open No. 2017-171912, a compound described in paragraphs 0010 to 0062 and 0138 to 0295 of Japanese patent application laid-open No. 2017-171913, a compound described in paragraphs 0011 to 0062 and 0139 to 0190 of Japanese patent application laid-open No. 2017-171914, a compound described in the following formula may be used, Compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of Japanese patent application laid-open No. 2017-171915, quinoline yellow compounds described in paragraphs 0011 to 0034 of Japanese patent application laid-open No. 2013-054339, quinoline yellow compounds described in paragraphs 0013 to 0058 of Japanese patent application laid-open No. 2014-026228, isoindoline compounds described in Japanese patent application laid-open No. 2018-062644, quinoline yellow compounds described in Japanese patent application laid-open No. 2018-203798, quinoline yellow compounds described in Japanese patent application laid-open No. 2018-062578, and, quinoline yellow compound described in Japanese patent application publication 6432076, quinoline yellow compound described in Japanese patent application laid-open No. 2018-155881, quinoline yellow compound described in Japanese patent application laid-open No. 2018-111757, quinoline yellow compound described in Japanese patent application laid-open No. 2018-040835, quinoline yellow compound described in Japanese patent application laid-open No. 2017-197640, quinoline yellow compound described in Japanese patent application laid-open No. 2016-145282, quinoline yellow compound described in Japanese patent application laid-open No. 2014-085565, quinoline yellow compound described in Japanese patent application laid-open No. 2014-021139, and, Quinoline yellow compound described in Japanese patent application laid-open No. 2013-209414, quinoline yellow compound described in Japanese patent application laid-open No. 2013-209435, quinoline yellow compound described in Japanese patent application laid-open No. 2013-181015, quinoline yellow compound described in Japanese patent application laid-open No. 2013-061622, quinoline yellow compound described in Japanese patent application laid-open No. 2013-03486, quinoline yellow compound described in Japanese patent application laid-open No. 2012-226110, quinoline yellow compound described in Japanese patent application laid-open No. 2008-074987, Quinoline yellow compound described in Japanese patent application laid-open No. 2008-081565, quinoline yellow compound described in Japanese patent application laid-open No. 2008-074986, quinoline yellow compound described in Japanese patent application laid-open No. 2008-074985, quinoline yellow compound described in Japanese patent application laid-open No. 2008-050420, quinoline yellow compound described in Japanese patent application laid-open No. 2008-031281, quinoline yellow compound described in Japanese patent application laid-open No. 48-032765, quinoline yellow compound described in Japanese patent application laid-open No. 2019-008014, and, Quinoline yellow compound described in japanese patent No. 6607427, compound described in korean laid-open patent No. 10-2014-0034963, compound described in japanese patent application laid-open No. 2017-095706, compound described in taiwan area patent application laid-open No. 201920495, compound described in japanese patent No. 6607427, quinoline yellow dimer described in japanese patent laid-open No. 2020-033521, compound represented by the following formula (QP 1), compound represented by the following formula (QP 2). From the viewpoint of improving the color value, it is also preferable to use a method of multimerizing these compounds.

[ Chemical formula 8]

In the formula (QP 1), X1 to X16 each independently represent a hydrogen atom or a halogen atom, and Z1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP 1) include a compound described in paragraph 0016 of japanese patent No. 6443711.

[ Chemical formula 9]

In the formula (QP 2), Y1 to Y3 each independently represent a halogen atom. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or more. Specific examples of the compound represented by the formula (QP 2) include compounds described in paragraphs 0047 to 0048 of Japanese patent 6432077.

As the red pigment, a diketopyrrolopyrrole compound having a structure substituted with at least one bromine atom described in japanese patent application laid-open No. 2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of japanese patent No. 6248838, a diketopyrrolopyrrole compound described in international publication No. 2012/102399, a diketopyrrolopyrrole compound described in international publication No. 2012/117965, a naphthol azo compound described in japanese patent application laid-open No. 2012-229344, a naphthol azo compound described in japanese patent No. 6516119, a compound described in japanese patent No. 6525101, and the like can also be used. As the red color material, a compound having the following structure can also be used: an aromatic hydrocarbon ring group having a group to which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to the diketopyrrolopyrrole skeleton. As such a compound, a compound represented by the formula (DPP 1) is preferable, and a compound represented by the formula (DPP 2) is more preferable.

[ Chemical formula 10]

In the above formula, R11 and R13 each independently represent a substituent, R12 and R14 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n11 and n13 each independently represent an integer of 0 to 4, X12 and X14 each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, m12 represents 1 when X12 is an oxygen atom or a sulfur atom, m12 represents 2 when X12 is a nitrogen atom, m14 represents 1 when X14 is an oxygen atom or a sulfur atom, and m14 represents 2 when X14 is a nitrogen atom. The substituents represented by R11 and R13 include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, amide groups, cyano groups, nitro groups, trifluoromethyl groups, sulfoxide groups, sulfo groups, and the like, as preferred specific examples.

For each pigment having a diffraction angle preferable, reference can be made to japanese patent No. 6561862, japanese patent No. 6413872, and japanese patent No. 6281345, which are incorporated herein by reference.

Examples of the color dye include pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridine compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azo methine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyrrole methylene compounds. The methine dye described in Japanese patent application laid-open No. 2019-073695, the methine dye described in Japanese patent application laid-open No. 2019-073696, the methine dye described in Japanese patent application laid-open No. 2019-073697, and the methine dye described in Japanese patent application laid-open No. 2019-073698 may also be used.

The color material may be used in combination of 2 or more kinds. When 2 or more color materials are used in combination, black can be formed by a combination of 2 or more color materials. Examples of such combinations include the following modes (1) to (7). When 2 or more color materials are contained in the resin composition and black is represented by a combination of 2 or more color materials, the resin composition of the present invention can be preferably used as a resin composition for forming a near infrared ray transmission filter.

(1) And a red color material and a blue color material.

(2) And a red color material, a blue color material and a yellow color material.

(3) And a red color material, a blue color material, a yellow color material, and a violet color material.

(4) And a red color material, a blue color material, a yellow color material, a violet color material, and a green color material.

(5) And a red color material, a blue color material, a yellow color material, and a green color material.

(6) And a red color material, a blue color material and a green color material.

(7) And a yellow color material and a violet color material.

(White color Material)

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

The white pigment may be titanium oxide described in "titanium oxide physical properties and application technique Qing Kogyo, pages 13 to 45, 1991, 6 and 25, technical report house publication and release".

The white pigment may be composed of not only a single inorganic substance but also particles in which other materials are compounded. For example, it is preferable to use particles having voids and other materials inside, particles in which a plurality of inorganic particles are attached to a core particle, or core and shell composite particles including a core particle composed of polymer particles and a shell layer composed of inorganic nanoparticles. As the core-shell composite particles comprising the core particles composed of the polymer particles and the shell layers composed of the inorganic nanoparticles, for example, the disclosure of paragraphs 0012 to 0042 of jp 2015-047520 a can be referred to, and this disclosure is incorporated herein.

Hollow inorganic particles can also be used as the white pigment. The hollow inorganic particles mean inorganic particles having a hollow structure inside and represent inorganic particles having a hollow surrounded by a shell. Examples of the hollow inorganic particles include hollow inorganic particles described in Japanese patent application laid-open No. 2011-075786, international publication No. 2013/061621, japanese patent application laid-open No. 2015-164881, and the like, which are incorporated in the present specification.

(Black color Material)

The black material is not particularly limited, and a known black material can be used. For example, as the inorganic black color material, there may be mentioned inorganic pigments (black pigments) such as carbon black, titanium black, and graphite, preferably carbon black and titanium black, and more preferably titanium black. Titanium black is black particles containing titanium atoms, preferably titanium suboxide or titanium oxynitride. The titanium black may be surface-modified as needed for the purpose of improving dispersibility, suppressing aggregation, and the like. For example, the surface of the titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a treatment using a water repellent substance as described in japanese patent laid-open No. 2007-302836 can also be performed. Examples of the black pigment include pigment blacks 1 and 7 having a color index (c.i.). The titanium black preferably has a small primary particle diameter and a small average primary particle diameter. Specifically, the average primary particle diameter is preferably 10 to 45nm. Titanium black can also be used as a dispersion. For example, the following dispersions are mentioned: and a dispersion in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to be in the range of 0.20 to 0.50. The above-mentioned dispersion can be described in paragraphs 0020 to 0105 of Japanese patent application laid-open No. 2012-169556, incorporated herein by reference. Examples of the commercial products of titanium black include titanium black 10S, 12S, 13R, 13M-C, 13R-N, 13M-T (product name: mitsubishiMaterials Corporation), tilack D (product name: akoKasei Co., ltd.), and the like.

Examples of the organic black material include bis-benzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of the bis-benzofuranone compound include compounds described in japanese patent application laid-open publication No. 2010-534726, japanese patent application laid-open publication No. 2012-515233, japanese patent application laid-open publication No. 2012-515234, and the like, and are available as "Irgaphor Black" manufactured by BASF corporation. Examples of the perylene compound include compounds described in paragraphs 0016 to 0020 of JP-A2017-226821, C.I. pigment blacks 31 and 32, and the like. Examples of the azomethine compound include compounds described in Japanese patent application laid-open No. Hei 01-170601 and Japanese patent application laid-open No. Hei 02-034664, and are available as DAINICHISEIKA COLOR & Chemicals mfg.Co., ltd. "CHROMO FINE BLACK A" for example.

The color material used in the resin composition of the present invention may be only the black color material or may further include a color material. According to this aspect, a film excellent in light shielding property in the visible region can be easily obtained. When a black material and a color material are used as the color material, the mass ratio of the two is preferably the black material: color material=100: 10 to 300, more preferably 100:20 to 200. Further, a black pigment is preferably used as the black material, and a color pigment is preferably used as the color material.

Preferable combinations of the black color material and the color material are, for example, the following.

(A-1) an organic black material and a blue material.

The method (A-2) comprises an organic black material, a blue material and a yellow material.

(A-3) an organic black material, a blue material, a yellow material, and a red material.

(A-4) an organic black material, a blue material, a yellow material, and a violet material.

In the embodiment (a-1), the mass ratio of the organic black material to the blue material is preferably the organic black material: blue color material=100: 1 to 70, more preferably 100:5 to 60, more preferably 100:10 to 50 percent.

In the embodiment (a-2), the mass ratio of the organic black material, the blue material, and the yellow material is preferably the organic black material: blue color material: yellow color material = 100:10 to 90:10 to 90, more preferably 100: 15-85: 15 to 80, more preferably 100: 20-80: 20 to 70.

In the embodiment (a-3), the mass ratio of the organic black material, the blue material, the yellow material, and the red material is preferably the organic black material: blue color material: yellow color material: red color material = 100: 20-150: 1 to 60:10 to 100, more preferably 100: 30-130: 5-50: 20 to 90, more preferably 100: 40-120: 10 to 40: 30-80.

In the embodiment (a-4), the mass ratio of the organic black material, the blue material, the yellow material, and the violet material is preferably the organic black material: blue color material: yellow color material: purple color material = 100: 20-150: 1 to 60:10 to 100, more preferably 100: 30-130: 5-50: 20 to 90, more preferably 100: 40-120: 10 to 40: 30-80.

(Near infrared ray absorbing color Material)

The near infrared absorbing color material is preferably a pigment, more preferably an organic pigment. The near-infrared absorbing color material preferably has a maximum absorption wavelength in a range of from 700nm to 1400 nm. The maximum absorption wavelength of the near infrared ray absorbing color material is preferably 1200nm or less, more preferably 1000nm or less, and even more preferably 950nm or less. In the near-infrared absorbing color material, the ratio of absorbance a550 at a wavelength of 550nm to absorbance Amax at a maximum absorption wavelength, that is, a550/Amax is preferably 0.1 or less, more preferably 0.05 or less, still more preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, and may be, for example, 0.0001 or more, or 0.0005 or more. When the absorbance ratio is within the above range, the near-infrared absorbing color material can be used which is excellent in visible light transparency and near-infrared shielding property. In the present invention, the value of the absorbance of the near-infrared absorbing color material at the maximum absorption wavelength and at each wavelength is a value obtained from the absorption spectrum of a film formed using a resin composition containing the near-infrared absorbing color material.

The near infrared absorbing color material is not particularly limited, and examples thereof include pyrrolopyrrole compounds, cyanine compounds, squaric acid compounds, phthalocyanine compounds, naphthalocyanine compounds, quartilene (quaternine) compounds, merocyanine compounds, ketone onium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and dithiol metal complexes. Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP 2009-263614, compounds described in paragraphs 0037 to 0052 of JP 2011-068731, and compounds described in paragraphs 0010 to 0033 of International publication No. 2015/166873. examples of the squaric acid compound include compounds described in paragraphs 0044 to 0049 of JP 2011-208101, compounds described in paragraphs 0060 to 0061 of JP 6065169, compounds described in paragraph 0040 of International publication 2016/181987, compounds described in JP 2015-176046, compounds described in paragraph 0072 of International publication 2016/190162, compounds described in paragraphs 0196 to 0228 of JP 2016-074649, and, the compounds described in paragraph 0124 of JP-A2017-067963, the compounds described in International publication No. 2017/135359, the compounds described in JP-A2017-114956, the compounds described in JP-A6197940, the compounds described in International publication No. 2016/120166, etc. Examples of the cyanine compound include a compound described in paragraphs 0044 to 0045 of JP-A2009-108267, a compound described in paragraphs 0026 to 0030 of JP-A2002-194040, a compound described in JP-A2015-17204, a compound described in JP-A2015-172102, a compound described in JP-A2008-088426, a compound described in 0090 of International publication 2016/190162, and a compound described in JP-A2017-031394. Examples of the Ketone onium compound include those described in Japanese patent application laid-open No. 2017-081029. Examples of the ammonium compound include a compound described in japanese patent application laid-open publication No. 2008-528706, a compound described in japanese patent application laid-open publication No. 2012-012999, a compound described in japanese patent application laid-open publication No. 2007-092060, and a compound described in paragraphs 0048 to 0063 of international publication No. 2018/043564. Examples of the phthalocyanine compound include a compound described in paragraph 0093 of JP 2012-077153, oxytitanium phthalocyanine described in JP 2006-343631, a compound described in paragraphs 0013 to 0029 of JP 2013-195480, a vanadium phthalocyanine compound described in JP 6081771, and a compound described in International publication 2020/071470. examples of the naphthalocyanine compound include a compound described in paragraph 0093 of Japanese patent application laid-open No. 2012-077153. Examples of the dithiolene metal complex include compounds described in japanese patent No. 5733804.

And, as the near infrared ray absorbing color material, the squaric acid compound described in Japanese patent application laid-open No. 2017-197437, the squaric acid compound described in Japanese patent application laid-open No. 2017-025311, the squaric acid compound described in International publication No. 2016/154782, the squaric acid compound described in Japanese patent application No. 5884953, the squaric acid compound described in Japanese patent application No. 6036689, the squaric acid compound described in Japanese patent application No. 5810604, the squaric acid compound described in paragraph 0090 to 0107 of International publication No. 2017/213047, the pyrrole-containing compound described in paragraph 0019 to 0075 of Japanese patent application laid-open No. 2018-054760, the pyrrole-containing compound described in paragraph 0078 to 0082 of Japanese patent application laid-open No. 2018-040955, the pyrrole-containing compound described in paragraph 0043 to 0069 of Japanese patent application laid-open No. 2018-002773, the pyrrole-containing compound a squaric acid compound having an aromatic ring at the α -position of an amide described in paragraphs 0024 to 0086 of Japanese patent application laid-open No. 2018-0411, an amide-linked squaric acid compound described in Japanese patent application laid-open No. 2017-179131, a compound having a pyrrole-bis-squaric acid skeleton or a Ketone onium skeleton described in Japanese patent application laid-open No. 2017-141215, a dihydrocarbazole-bis-squaric acid compound described in Japanese patent application laid-open No. 2017-081029, an asymmetric compound described in paragraphs 0027 to 0114 of Japanese patent application laid-open No. 2017-068120, a pyrrole-containing compound (carbazole type) described in Japanese patent application laid-open No. 2017-067963, a phthalocyanine compound described in Japanese patent application laid-open No. 6251530, japanese patent application laid-open No. 2013-077009, a Japanese patent application laid-open No. 2014-130338, the color material described in International publication No. 2015/166779, or a combination of color materials described in these documents, or the like.

The content of the color material in the total solid content of the resin composition is preferably 20 to 90 mass%. The lower limit is preferably 30 mass% or more, more preferably 40 mass% or more, and still more preferably 50 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less.

The content of the pigment in the total solid content of the resin composition is preferably 20 to 90 mass%. The lower limit is preferably 30 mass% or more, more preferably 40 mass% or more, and still more preferably 50 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less.

The content of the dye in the color material is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

Further, the resin composition of the present invention preferably contains substantially no dye, from the viewpoint of more effectively suppressing the change in film thickness when the obtained film is heated to a high temperature. When the resin composition of the present invention contains substantially no dye, the content of the dye in the total solid content of the resin composition of the present invention is preferably 0.1 mass% or less, more preferably 0.05 mass% or less, and particularly preferably no dye.

< Resin B >

(Specific resin (resin b-1))

The resin composition of the present invention contains a resin B (hereinafter, also referred to as a resin). The resin contained in the resin composition includes a resin b-1 (hereinafter, also referred to as a specific resin) having a structure represented by formula (1). The specific resin is also a resin of the present invention.

[ Chemical formula 11]

In the formula (1), X1 represents a 4-valent linking group,

X2 represents a 2-valent linking group,

Lp1 represents an n+1 valent linking group,

Lp2 represents a 2-valent linking group,

P1 represents a polymer chain and is represented by,

N represents an integer of 1 or more.

[n]

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

[X1]

In the formula (1), the 4-valent linking group represented by X1 is preferably a group containing a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include substituent T described below.

Examples of the above-mentioned hydrocarbon group-containing group include a hydrocarbon group, a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group, and the like.

As the above-mentioned linking group for linking 2 or more hydrocarbon groups, examples include-NRX 1-, -SO-, -SO 2-; -CO-, -O-, -COO-; -OCO-, -S-, -NRX1CO-, -CONRX 1-and-C (CF 3) 2-. RX1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

The 4-valent linking group represented by X1 is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, more preferably a group containing an aromatic hydrocarbon ring. Further, the 4-valent linking group represented by X1 is preferably a group containing a fluorine atom or a sulfonyl group (-SO 2-) from the viewpoint of improving the solubility of the specific resin in a solvent. Among them, the 4-valent linking group represented by X1 is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring, from the viewpoint of being capable of forming a film excellent in solubility of a specific resin in a solvent and excellent in heat resistance. The group containing a fluorine atom and an aromatic hydrocarbon ring is preferably a group in which 2 or more aromatic hydrocarbon groups are bonded via a linking group and the linking group is a linking group containing a fluorine atom, or a group in which 2 or more aromatic hydrocarbon groups are bonded via a single bond or a linking group and the aromatic hydrocarbon groups are substituted with a group containing a fluorine atom. As the above-mentioned linking group containing a fluorine atom, there may be mentioned-C (CF 3) 2-and the like. The group containing a fluorine atom is preferably a fluorinated alkyl group, and more preferably a trifluoromethyl group.

The 4-valent linking group represented by X1 is also preferably a group represented by any one of (D-1) to (D-3).

[ Chemical formula 12]

In the formulae (D-1) to (D-3), cy independently represents an aliphatic hydrocarbon ring, rd1 represents a linear or branched aliphatic hydrocarbon group, xd1 represents a single bond or a 2-valent linking group, and 1 to 4 each represent a linking bond.

The aliphatic hydrocarbon ring represented by Cy of the formulae (D-1) to (D-3) may be a single ring or a condensed ring. The aliphatic hydrocarbon ring may have a crosslinked structure. The aliphatic hydrocarbon ring represented by Cy is preferably a monocyclic aliphatic hydrocarbon ring or an aliphatic hydrocarbon ring having a crosslinked structure.

In formula (D-1), 1 and 2, 3 and 4 are preferably present in adjacent positions on the aliphatic hydrocarbon ring Cy.

Rd1 of formula (D-2) represents a linear or branched aliphatic hydrocarbon group, preferably a linear or branched aliphatic saturated hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 4, and still more preferably 2. In formula (D-2), 3 and 4 are preferably 1 each on adjacent carbon atoms on aliphatic hydrocarbyl Rd 1. In formula (D-2), 3 and 4 are preferably present in adjacent positions on the aliphatic hydrocarbon ring Cy.

In the formula (D-3), xd1 represents a single bond or a 2-valent linking group, and is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C (=O) -, -S (=O) 2-, -NHC (=O) -or a group formed by combining these 2 or more, more preferably a group selected from the group consisting of an alkylene group having 1 to 3 carbon atoms, -O-, -C (=O) -, -S-and-S (=O) 2-which may be substituted with a fluorine atom, and still more preferably-CH 2-, -O-, -S (=O) 2-, -C (CF 3) 2-and-C (CH 3) 2-.

The 4-valent linking group represented by X1 is also preferably a group represented by the formula (E-1).

[ Chemical formula 13]

In the formula (E-1), ar independently represents an aromatic hydrocarbon ring, xe1 represents a 2-valent linking group containing a fluorine atom, and 1 to 4 each represent a linking bond.

The number of carbon atoms of the aromatic hydrocarbon ring represented by Ar of the formula (E-1) is preferably 6 to 30, more preferably 6 to 20. The aromatic hydrocarbon ring represented by Ar is preferably a benzene ring.

Xe1 of the formula (E-1) is preferably an alkylene group having 1 to 10 carbon atoms substituted with a fluorine atom, more preferably an alkylene group having 1 to 5 carbon atoms substituted with a fluorine atom, further preferably-C (CF 3) 2-; -C (CF 3) (C2F 5) -or-C (C2F 5) 2-, particularly preferred is-C (CF 3) 2-. In formula (D-1), 1 and 2,3 and 4 are preferably present in adjacent positions on the aromatic ring structure Ar.

Specific examples of the 4-valent linking group represented by X1 include groups having structures represented by any of the formulas (I-1) to (I-28).

[ Chemical formula 14]

In the formulas (I-1) to (I-28), X1 to X3 represent a single bond or a 2-valent linking group, L represents-CH=CH-or-CH 2-, R1 and R2 each independently represent a hydrogen atom or a substituent, R1 and R2 may be bonded to form a ring, and represent a linking bond with other structures in the formula (1).

Examples of the 2-valent linking group represented by X1 to X3 include-C (Rx) 2- (Rx represents a hydrogen atom or a substituent, when Rx is a substituent, may be linked to each other to form a ring), -O-, -SO2-, -CO-, -S-, -NRN, phenylene, or a combination of these, when Rx represents a substituent, specific examples thereof include an alkyl group which may be substituted with a fluorine atom. RN represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

X1 to X3 are each independently a single bond, -SO2-, or-C (Rx) 2-, more preferably-SO 2-, or-C (Rx) 2-, and still more preferably-C (Rx) 2-. And, -C (Rx) 2-is preferably-C (CH 3) 2-or-C (CF 3) 2-, more preferably-C (CF 3) 2-.

L is preferably-ch=ch-.

R1 and R2 are each independently a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom.

[X2]

In formula (1), X2 represents a 2-valent linking group. Examples of the 2-valent linking group represented by X2 include a hydrocarbon group and a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include substituent T described below.

As the linking group linking 2 or more hydrocarbon groups, examples include-O-, -S-, -C (CH 3) 2-, -C (CF 3) 2-, -CO-, -SO2-, -SiR2- (R independently of one another represents a hydrocarbon radical, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group), a polysiloxane group (-Si (R) - (O-Si) n-, wherein R represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group n represents an integer of 1 or more, preferably 1 to 10), or the like.

The 2-valent linking group represented by X2 is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, more preferably a group containing an aromatic hydrocarbon ring. Further, the 2-valent linking group represented by X2 is preferably a group containing a fluorine atom or a sulfonyl group (-SO 2-) from the viewpoint of improving the solubility of the specific resin in a solvent. Among them, the 2-valent linking group represented by X2 is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring, from the viewpoint of being capable of forming a film excellent in solubility of a specific resin in a solvent and excellent in heat resistance. The group containing a fluorine atom and an aromatic hydrocarbon ring is preferably a group in which 2 or more aromatic hydrocarbon groups are bonded via a linking group and the linking group is a linking group containing a fluorine atom, or a group in which 2 or more aromatic hydrocarbon groups are bonded via a single bond or a linking group and the aromatic hydrocarbon groups are substituted with a group containing a fluorine atom. As the above-mentioned linking group containing a fluorine atom, there may be mentioned-C (CF 3) 2-and the like. The group containing a fluorine atom is preferably a fluorinated alkyl group, and more preferably a trifluoromethyl group. When the 2-valent linking group represented by X2 is a group containing a fluorine atom and an aromatic hydrocarbon ring, for example, the following structure is preferable.

[ Chemical formula 15]

In the above structure, the bonding site to other structure is represented.

The 2-valent linking group represented by X2 is preferably a group derived from the structure of a diamine compound. Examples of the diamine compound include the following compounds.

[ Chemical formula 16]

[ Chemical formula 17]

[ Chemical formula 18]

[ Chemical formula 19]

[ R11, R12, R21, R22 and R23]

In the formula (1), R11, R12, R21, R22 and R23 each independently represent a hydrogen atom or a substituent.

Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, still more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched, and more preferably linear. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-or 6-membered ring. Examples of the type of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include substituent T, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, a blocked isocyanate group, and the like, which will be described later.

In formula (1), R11 and R12 are preferably hydrogen atoms. Further, R21, R22 and R23 are preferably hydrogen atoms. And, a part may form carboxylate, amine salt.

[Lp1]

In formula (1), lp1 represents an n+1 valent linking group. Examples of the n+1-valent linking group include a hydrocarbon group, -NRp-, -N <, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRpCO-, -CONRp-and a group in which 2 or more of these are combined. Rp represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

Examples of the n+1-valent linking group include a group represented by the formula (Lp-1) and a group represented by the formula (Lp-2).

[ Chemical formula 20]

In the formula (Lp-1), rp1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and Lp1a represents a hydrocarbon group or a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group.

In the formula (Lp-2), lp1b represents a hydrocarbon group or a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group.

In the formula (Lp-1) and the formula (Lp-2), n represents an integer of 1 or more, 1 represents a bond to a carbonyl carbon in-NR 23 CO-of the formula (1), and 2 represents a bond to Lp2 of the formula (1).

Specific examples of the alkyl group, aryl group and heterocyclic group represented by Rp1 include those described in the items R11, R12, R21, R22 and R23.

Examples of the hydrocarbon group represented by Lp1a and Lp1b include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include substituent T described below.

As the linking group linking 2 or more hydrocarbon groups, examples thereof include-NRp b-, -SO-; -SO2-, -CO-, -O-, and-COO-, -OCO-, -S-, -NRp bCO-, -CONRp1b-. Rp1b represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

The n+1 valent linking group represented by Lp1 is preferably a group represented by the formula (Lp-10), more preferably a group represented by the formula (Lp-11).

[ Chemical formula 21]

In formula (Lp-10), lp11 represents a single bond or an n+1 valent linking group, rp11 represents a substituent, n represents an integer of 1 or more, m represents an integer of 0 to 4, x1 represents a bond to a carbonyl carbon in-NR 23 CO-of formula (1), and x2 represents a bond to Lp2 of formula (1). The m rps 11 may be the same or different.

In formula (Lp-11), lp12 represents a single bond or an n+1 valent linking group, rp11 represents a substituent, n represents an integer of 1 or more, m represents an integer of 0 to 4, x1 represents a bond to a carbonyl carbon in-NR 23 CO-of formula (1), and x2 represents a bond to Lp2 of formula (1). The m rps 11 may be the same or different.

Examples of the n+1-valent linking group represented by Lp11 of the formula (Lp-10) include a hydrocarbon group, -NRp12-, -N <, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp12CO-, -CONRp-, and a combination of 2 or more of these groups. Examples of the hydrocarbon group include the above groups. Rp12 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

The n+1-valent linking group represented by Lp12 of the formula (Lp-11) is preferably a hydrocarbon group or a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group. As the linking group linking 2 or more hydrocarbon groups, examples thereof include-NRp-, -SO-; -SO2-, -CO-, -O-, and-COO-, -OCO-, -S-, -NRp CO-and-CONRp 13-. Rp13 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

Examples of the substituent represented by Rp11 of the formula (Lp-10) and the formula (Lp-11) include a substituent T described below, which is preferably a carboxyl group, a halogen atom or a hydroxyl group, more preferably a carboxyl group.

N in the formulae (Lp-10) and (Lp-11) represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.

M of the formulae (Lp-10) and (Lp-11) represents an integer of 0 to 4, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and further preferably 1 or 2. At least 1 or more of m Rp11 are preferably carboxyl groups.

[Lp2]

In formula (1), lp2 represents a 2-valent linking group. Examples of the 2-valent linking group include a hydrocarbon group, -NRp-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp-CO-, -CONRp-, and a group in which 2 or more of these groups are combined. Rp21 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group and the like. The 2-valent linking group is preferably a group containing an oxygen atom or a sulfur atom, more preferably a group containing a sulfur atom, and further preferably a group containing-S-.

The 2-valent linking group represented by Lp2 is preferably-S-or-O-, more preferably-S-.

[P1]

In formula (1), P1 represents a polymer chain. The weight average molecular weight of P1 is preferably 500 to 50000. The lower limit is preferably 800 or more, more preferably 1000 or more. The upper limit is preferably 20000 or less, more preferably 10000 or less. When the weight average molecular weight of the polymer chain is within the above range, more excellent pigment dispersibility is easily obtained. The weight average molecular weight of the polymer chains can be determined by GPC (gel permeation chromatography). More specifically, the weight average molecular weight of the raw material monomer used for introducing the polymer chain can be calculated.

The polymer chain represented by P1 preferably contains a repeating unit of at least 1 structure selected from the group consisting of a poly (meth) acrylic acid structure, a polystyrene structure, a polyether structure and a polyester structure, more preferably contains a repeating unit of at least 1 structure selected from the group consisting of a poly (meth) acrylic acid structure and a polystyrene structure, and still more preferably contains a repeating unit of a poly (meth) acrylic acid structure from the viewpoints of dispersibility of pigments and heat resistance. The polymer chain represented by P1 also preferably comprises repeating units of a polyether structure or repeating units of a polyester structure. When the polymer chain represented by P1 contains a repeating unit of a polyether structure, the number of repeating units of the polyether structure is preferably 9 or more. When the polymer chain represented by P1 contains a repeating unit of a polyester structure, the number of repeating units of the polyester structure is preferably 5 or more.

The polymer chain represented by P1 may have a crosslinkable group. Examples of the crosslinkable group include a group containing an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryl group, a cyclic ether group such as an epoxy group and an oxetanyl group, and a blocked isocyanate group. In the present specification, the blocked isocyanate group means a group capable of generating an isocyanate group by heat, and for example, a blocking agent is preferably exemplified as a group capable of reacting with an isocyanate group to protect the isocyanate group. Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds, and imide compounds. Examples of the blocking agent include compounds described in 0115 to 0117 of JP-A2017-067930, which are incorporated herein by reference. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 260 ℃.

The polymer chain represented by P1 also preferably has a tertiary alkyl group. Examples of the tertiary alkyl group include a tertiary butyl group and the like.

The polymer chain represented by P1 preferably contains a repeating unit represented by any one of the formulae (P1-1) to (P1-6), more preferably contains a repeating unit represented by the formula (P1-5) or (P1-6), and still more preferably contains a repeating unit represented by the formula (P1-5). The polymer chain represented by P1 also preferably contains a repeating unit represented by any one of the formulae (P1-1) to (P1-4). When the polymer chain represented by P1 contains a repeating unit of the formula (P1-4), the number of repeating units of the formula (P1-4) is preferably 9 or more. When the polymer chain represented by P1 contains repeating units represented by the formulae (P1-1) to (P1-3), the number of repeating units of these structures is preferably 5 or more.

[ Chemical formula 22]

In the above formula, RG1 and RG2 each represent an alkylene group. The alkylene group represented by RG1 and RG2 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and still more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.

In the above formula, RG3 represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

In the above formula, QG1 represents-O-or-NRq, and Rq represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. QG1 is preferably-O-.

The number of carbon atoms of the alkyl group represented by Rq is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, still more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched, and more preferably linear.

The number of carbon atoms of the aryl group represented by Rq is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.

The heterocyclic group represented by Rq may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-or 6-membered ring. Examples of the type of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a single ring or a condensed ring.

The alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include substituent T described below.

In the above formula, LG1 represents a single bond or an arylene group, preferably a single bond.

In the above formula, LG2 represents a single bond or a 2-valent linking group. Examples of the 2-valent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NRLG < 1 >, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRLG < 1 > CO-, -CONRLG-and a group in which 2 or more of these are combined, and preferably an alkylene group or an arylene group is included. RLG1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include substituent T described below.

In the above formula, RG4 represents a hydrogen atom or a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl sulfide group, an aryl sulfide group, a heterocyclic sulfide group, a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a blocked isocyanate group. RG4 is preferably at least 1 selected from the group consisting of an alkyl group, an aryl group, a group containing an ethylenic unsaturated bond, an epoxy group, and an oxetanyl group, and more preferably at least 1 selected from the group consisting of a group containing an ethylenic unsaturated bond, an epoxy group, an oxetanyl group, and a tert-butyl group.

In the above formula, RG5 represents a hydrogen atom or a methyl group, and RG6 represents an aryl group. The number of carbon atoms of the aryl group represented by RG6 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group represented by RG6 may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl sulfide group, an aryl sulfide group, a heterocyclic sulfide group, a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a blocked isocyanate group.

The polymer chain represented by P1 may contain 2 or more repeating units.

(Substituent T)

Alkyl (preferably alkyl group having 1 to 30 carbon atoms), alkenyl (preferably alkenyl group having 2 to 30 carbon atoms), alkynyl (preferably alkynyl group having 2 to 30 carbon atoms), aryl (preferably aryl group having 6 to 30 carbon atoms), amino (preferably amino group having 0 to 30 carbon atoms), alkoxy (preferably alkoxy group having 1 to 30 carbon atoms), aryloxy (preferably aryloxy group having 6 to 30 carbon atoms), heteroaryloxy (preferably heteroaryloxy group having 1 to 30 carbon atoms), acyl (preferably acyl group having 2 to 30 carbon atoms), alkoxycarbonyl (preferably alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), acyloxy (preferably acyloxy group having 2 to 30 carbon atoms), acylamino (preferably acylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino (preferably alkoxycarbonylamino having 2 to 30 carbon atoms), aryloxycarbonyl amino (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), aryloxycarbonyl amino (preferably sulfonylamino having 1 to 30 carbon atoms), arylthio (preferably thioamino having 1 to 30 carbon atoms) having 1 to 30 carbon atoms An alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably a heteroarylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably a heteroarylsulfinyl group having 1 to 30 carbon atoms), a ureido group (preferably a ureido group having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably a phosphoric acid amide group having 1 to 30 carbon atoms), a hydroxyl group, a mercapto group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom or the like), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfinyl group, a hydrazino group, an imino group or a heterocyclic group. When these groups are groups which can be further substituted, they may further have a substituent. Examples of the further substituent include those described for the substituent T.

Among the specific resins, the structure represented by the above formula (1) is preferably a structure represented by the formula (1-1).

[ Chemical formula 23]

In the formula (1-1), X1 represents a 4-valent linking group,

X2 represents a 2-valent linking group,

Rp11 represents a substituent, m Rp11 may be the same or different,

Lp11 represents an n+1 valent linking group,

Lp2 represents a 2-valent linking group,

P1 represents a polymer chain and is represented by,

N represents an integer of 1 or more,

M represents an integer of 0 to 4.

X1, X2, R11, R12, R21, R22, R23, lp2, P1 and n in the formula (1-1) have the same meanings as X1, X2, R11, R12, R21, R22, R23, lp2, P1 and n in the formula (1).

Lp11, rp11 and m of formula (1-1) have the same meanings as Lp11, rp11 and m of formula (Lp-10).

The specific resin may contain an imide cyclized structure of the structure represented by the above formula (1).

The special case resin may further contain a structure represented by formula (100). According to this aspect, more excellent dispersibility can be obtained.

[ Chemical formula 24]

In the formula (100), X101 represents a 4+q-valent linking group,

X102 represents a 2-valent linking group,

R111, R112, R121 and R122 each independently represent a hydrogen atom or a substituent,

Lp101 represents a 2-valent linking group,

P101 represents a polymer chain and,

Q represents an integer of 1 or more.

R111, R112, R121, R122 and P101 in the formula (100) have the same meanings as those of R11, R12, R21, R22 and P1 in the formula (1).

In the formula (100), q represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.

The 2-valent linking group represented by X102 of formula (100) includes the 2-valent linking group described in X2 of formula (1), and the preferable ranges are also the same.

In the formula (100), the 4+q-valent linking group represented by X101 is preferably a group containing a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T.

As the above-mentioned linking group for linking 2 or more hydrocarbon groups, examples include-NRx 101-, -N < -SO-; -SO2-, -CO-, -O-, -COO-, and-OCO-, -S-, -NRx101CO-, -CONRx 101-and-C (CF 3) 2-. Rx101 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. Preferably, the carbon atom of X101 is bonded to Lp 101. Further, it is also preferable that the nitrogen atom of X101 is bonded to Lp 101.

The 4+q valent linking group represented by X101 is preferably a group containing an aromatic hydrocarbon ring because of its strong affinity for pigments and the difficulty of foreign matter generation. Examples of the group containing an aromatic hydrocarbon ring include a group represented by the formula (X-1).

[ Chemical formula 25]

In the formula (X-1), 1 represents a bond to P101 of the formula (100), 2 represents a bond to-CO-bonded to X101 of the formula (100), rx1 and Rx2 each independently represent a substituent, m1 represents an integer of 0 to 3, m2 represents an integer of 0 to 3, n represents an integer of 1 or more, and X100 represents a 2+n-valent linking group.

As the 2+n valent linking group represented by X100, examples of the group include a hydrocarbon group, -NRx101-, -N <, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRx101CO-, -CONRx101-, -C (CF 3) 2-, and a combination of 2 or more of them. Examples of the hydrocarbon group include the above groups. Rx101 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

The substituents represented by Rx1 and Rx2 include the substituent T described above. Specific examples thereof include a halogen atom, an alkyl group, a carboxyl group, and the like.

M1 and m2 are each independently an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

In formula (100), lp101 represents a 2-valent linking group. Examples of the 2-valent linking group include a hydrocarbon group, -NRL1-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRL1CO-, -CONRL 1-and a group in which 2 or more of these groups are combined. RL1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. The 2-valent linking group is preferably a group containing an oxygen atom or a sulfur atom, more preferably a group containing a sulfur atom, and further preferably a group containing-S-.

The 2-valent linking group represented by Lp101 is preferably a group represented by the formula (Lp-101) or the formula (Lp-201), more preferably a group represented by the formula (Lp-101).

[ Chemical formula 26]

In the formula (Lp-101) and the formula (Lp-102), lp111 represents a single bond or a 2-valent linking group, 1 represents a bond with X101 of the formula (100), and 2 represents a bond with P101 of the formula (100).

Examples of the 2-valent linking group represented by Lp111 include a hydrocarbon group and a group having a structure in which 2 or more hydrocarbon groups are bonded to each other by a single bond or a linking group. As a linking group, a group may be used, examples thereof include-NRL 1-, -SO-; -SO2-, -CO-, -O-, and-COO-, -OCO-, -S-, -NRL1 CO-and-CONRL-respectively. RL1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

The specific resin may contain an imide cyclized structure of the structure represented by the above formula (100).

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

The weight average molecular weight (Mw) of the specific resin is preferably 2000 to 200000, more preferably 2500 to 100000, and even more preferably 3000 to 50000.

The 5% mass reduction temperature of the specific resin in TG/DTA (thermal mass measurement/thermal differential measurement) based on a nitrogen atmosphere is preferably 280 ℃ or higher, more preferably 300 ℃ or higher, still more preferably 320 ℃ or higher. The upper limit of the 5% mass reduction temperature is not particularly limited, and may be, for example, 1,000 ℃ or lower. The above 5% mass reduction temperature can be obtained by a known TG/DTA measurement method as a temperature at which the mass reduction rate becomes 5% when left standing for 5 hours at a specific temperature in a nitrogen atmosphere.

The mass reduction rate of the specific resin when left to stand at 300 ℃ for 5 hours in a nitrogen atmosphere is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less. The lower limit of the mass reduction rate is not particularly limited, and may be 0% or more.

The mass reduction ratio is a value calculated as a ratio of mass reduction in the specific resin before and after standing at 300 ℃ for 5 hours under a nitrogen atmosphere.

For example, a specific resin can be synthesized by reacting an acid dianhydride with a diamine compound to synthesize a polyamic acid, and then reacting with a capping agent (capping agent macromer) having a group that reacts with the terminal amine portion of the polyamic acid and a polymer chain, respectively. Capping agents other than the capping agent macromer (other capping agents) may be further used as desired. Examples of the other blocking agent include monoamines, anhydrides, monocarboxylic acids, monocarboxylic acid chlorides, monocarboxylic acid halide compounds, and monocarboxylic acid active esters.

The molar ratio of the acid dianhydride to the diamine compound is preferably 0.5 to 1.5 moles, more preferably 0.7 to 1.3 moles, and even more preferably 0.9 to 1.1 moles, relative to 1 mole of the diamine compound. The molar ratio of the diamine compound to the blocking agent macromer is preferably 0.1 to 2 moles, more preferably 0.2 to 1.5 moles, and even more preferably 0.5 to 1.2 moles, based on 1 mole of the diamine compound.

Examples of the blocking agent macromer include compounds represented by the formula (EDM).

[ Chemical formula 27]

In the formula (EDM), RED represents an acid anhydride group, a halogenated acyl group or an isocyanate group,

LpED1 represents an n+1 valent group,

The n+1-valent group is a hydrocarbon group or a group having a structure in which a hydrocarbon group is combined with at least 1 group selected from the group consisting of-NRpED 1-, -N <, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRpED CO-and-CONRpED-,

LpED2 represents-O-or-S-,

PED1 represents a polymer chain which,

N represents an integer of 1 to 4.

The acid anhydride group represented by RED of the formula (EDM) is preferably a cyclic acid anhydride group. The acid anhydride group represented by RED is preferably a group represented by the formulae (RED 1-11) to (RED 1-13), more preferably a group represented by the formulae (RED 1-13). Further, the halogenated acyl group is preferably a group represented by the formula (RED 1-21).

[ Chemical formula 28]

In the above formula, RED11 represents a hydrogen atom or a substituent, RED12 represents a substituent, RED21 represents a halogen atom, r represents an integer of 0 to 3, and r represents a bond to LpED 1.

The substituent represented by RED11 and RED12 may be the substituent T, but is preferably a halogen atom, a carboxyl group, an alkyl group or a hydroxyl group, and more preferably a carboxyl group.

The halogen atom represented by RED21 is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

R is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

Examples of the hydrocarbon group in LpED of the formula (EDM) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The cyclic aliphatic hydrocarbon group may be a single ring or a condensed ring. Also, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T.

LpED of the formula (EDM) represents-O-or-S-, preferably-S-.

The polymer chain represented by PED1 of formula (EDM) has the same meaning as the polymer chain represented by P1 of formula (1).

N of the formula (EDM) is preferably 1 or 2.

The capping agent macromer is preferably a compound having an acid anhydride group, more preferably a compound represented by the formula (EDM 1), and still more preferably a compound represented by the formula (EDM 2). The compound represented by the formula (EDM 1) and the compound represented by the formula (EDM 2) are the compounds of the present invention.

[ Chemical formula 29]

In the formula (EDM 1), RED1 represents an acid anhydride group,

LpED1 represents an n+1 valent group,

LpED2 represents-O-or-S-,

N represents an integer of 1 to 4.

[ Chemical formula 30]

LpED1a represents an n+1 valent group,

The n+1-valent group is a hydrocarbon group or a group in which 2 or more hydrocarbon groups are bonded via a single bond or a linking group,

The above-mentioned linking group is-NRpED 1-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRpED1 CO-or-CONRpED 1,

LpED2 represents-O-or-S-,

R represents an integer of 0 to 3,

N represents an integer of 1 to 4.

[ Chemical formula 31]

In the formulae (P1-1) to (P1-4), RG1 and RG2 each represent an alkylene group.

The acid anhydride group represented by RED1 of the formula (EDM 1) has the same meaning as the acid anhydride group described in RED of the formula (EDM).

The details of the polymer chain represented by PED1 of the formula (EDM 1) are the same as those described for the polymer chain represented by P1 of the formula (1).

LpED1, lpED and n of the formula (EDM 1) have the same meaning as LpED, lpED and n of the formula (EDM).

R of the formula (EDM 2) is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

The hydrocarbon group in LpED a of the formula (EDM 2) has the same meaning as the hydrocarbon group described in the formula (EDM). The n+1 valent group represented by LpED a of the formula (EDM 2) is preferably a hydrocarbon group.

The details of the polymer chain represented by PED1 of the formula (EI) M2) are the same as those described for the polymer chain represented by P1 of the formula (1).

LpED2 and n of formula (EDM 2) have the same meaning as LpED and n of formula (EDM).

Specific examples of the blocking agent macromer include the blocking agent macromers EDM-1 to EDM-40 described in examples described below.

For example, the capping agent macromer can be synthesized by the following method.

(1) A method of synthesizing a macromer obtained by radical-polymerizing a radical-polymerizable compound using a chain transfer agent having 1 hydroxyl group, 1 or 2 mercapto groups, by esterification reaction with an acid anhydride or acid anhydride chloride.

(2) A method comprising reacting a compound having 2 mercapto groups with an acid anhydride having an ethylenically unsaturated bond, and then ring-opening polymerizing the lactone.

(3) A method in which a macromer obtained by radical-polymerizing a radical-polymerizable compound with a chain transfer agent having 1 hydroxyl group, 1 or 2 mercapto groups is synthesized by coupling reaction with an acid anhydride having a halogen atom.

(4) A method of synthesizing a compound having 1 acid anhydride group, carboxyl group or halogenated acyl group by reacting with a polymer having a hydroxyl group or amino group at the terminal. The compound having 1 acid anhydride group and carboxyl group or halogenated acyl group used in the synthesis is preferably trimellitic anhydride or trimellitic anhydride chloride from the viewpoint of being capable of synthesizing a macromonomer with high purity and high yield.

(5) A method of synthesizing a macromonomer obtained by radical-polymerizing a radical-polymerizable compound using a chain transfer agent having 1 carboxyl group and 1 mercapto group (for example, mercaptopropionic acid or the like), by acid chlorination.

(6) A method in which a macromer obtained by ring-opening polymerization of a lactone with a compound having 1 or 2 hydroxyl groups and 1 mercapto group (for example, mercaptoethanol, mercaptopropanol, mercaptohexanol, mercaptoglycerol, etc.) is synthesized by subjecting the macromer to an ene-thiol reaction with a compound having an isocyanate group and a group containing an unsaturated bond.

If hydrochloric acid remains, the blocking agent macromer may cause deterioration and corrosion, and is therefore preferably removed. When an acid anhydride chloride is used as the starting material, it is preferable to synthesize the acid anhydride chloride by mixing the starting materials in the presence of a base and then separating the hydrochloride produced. The alkali may be an organic alkali or an inorganic alkali. In the case of the organic base, tertiary alkylamine, aromatic tertiary amine, heterocyclic aromatic amine, and the like are used. Examples thereof include triethylamine, diisopropylethylamine, tributylamine, diethylaniline, pyridine, 4-dimethylaminopyridine, 2-methylpyridine, 2, 6-dimethylpyridine, imidazole, 1-methylimidazole, 1-ethylimidazole, triazole, tetrazole and the like. Examples of the separation method include a method of filtering (natural filtration, pressure reduction filtration, centrifugal filtration) using a filter, a method of separating a liquid into an organic layer and an aqueous layer, a method of performing centrifugal separation, and a method of performing adsorption (silica gel column, activated carbon, etc.).

(Other resins)

The resin composition of the present invention may contain, as a resin, other resins than the above-mentioned specific resins. Examples of the other resin include a resin having alkali developability and a resin serving as a dispersant. Further, the resin composition may contain a decomposition product of a blocking agent macromonomer, a reaction product of a diamine and a blocking agent macromonomer, and the like as by-products in the synthesis of a specific resin.

[ Resin having alkali developability ]

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

Examples of the resin having alkali developability include (meth) acrylic resins, polyimide resins, polyether resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyimide resins, and the like, and (meth) acrylic resins and polyimide resins are preferable, and (meth) acrylic resins are more preferable. As the other resin, the resins described in paragraphs 0041 to 0060 of japanese patent application laid-open publication No. 2017-206689, the resins described in paragraphs 0022 to 0071 of japanese patent application laid-open publication No. 2018-010856, the resins described in japanese patent application laid-open publication No. 2017-057265, the resins described in japanese patent application laid-open publication No. 2017-032585, the resins described in japanese patent application laid-open publication No. 2017-075248, and the resins described in japanese patent application laid-open publication No. 2017-066240 may be used.

As the resin having alkali developability, a resin having an acid group is preferably used. According to this aspect, the developability of the resin composition can be further improved. Examples of the acid group include phenolic hydroxyl group, carboxyl group, sulfo group, phosphate group, phosphonate group, active imide group, and sulfonamide group, and preferably carboxyl group. As the resin having an acid group, a resin in which an acid anhydride is reacted with a hydroxyl group generated in ring opening of an epoxy to introduce an acid group may be used. As such a resin, the resin described in japanese patent No. 6349629 is exemplified. For example, a resin having an acid group can be used as the alkali-soluble resin.

The resin having alkali developability preferably contains a repeating unit having an acid group in a side chain, and more preferably contains 1 to 70 mol% of the repeating unit having an acid group in a side chain, out of all the repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 40 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 2 mol% or more, more preferably 5 mol% or more.

The acid value of the resin having alkali developability is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 120mgKOH/g or less, and particularly preferably 100mgKOH/g or less. The acid value of the resin having an acid group is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, and still more preferably 20mgKOH/g or more.

The resin having alkali developability also preferably further has a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, and a (meth) acryloyl group, and are preferably an allyl group and a (meth) acryloyl group, and more preferably a (meth) acryloyl group.

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

The resin having alkali developability preferably contains a repeating unit derived from a monomer component containing a compound represented by the following formula (ED 1) and/or a compound represented by the following formula (ED 2) (hereinafter, these compounds are also referred to as "ether dimers").

[ Chemical formula 32]

In the formula (ED 1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[ Chemical formula 33]

In the formula (ED 2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED 2), reference may be made to the description of Japanese patent application laid-open No. 2010-16889, which is incorporated herein.

As a specific example of the ether dimer, for example, reference can be made to paragraph 0317 of japanese patent application laid-open No. 2013-029760, which is incorporated herein.

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

[ Chemical formula 34]

In the formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, and R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

Examples of the resin having alkali developability include resins having the following structures. In the following structural formula, me represents a methyl group.

[ Chemical formula 35]

[ Dispersant ]

The resin composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) means a resin having an amount of acid groups larger than an amount of base groups. When the total amount of the acid groups and the base groups is 100 mol%, the acid dispersant (acid resin) is preferably a resin having an acid group content of 70 mol% or more, and more preferably a resin substantially consisting of only acid groups. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105mgKOH/g, more preferably 50 to 105mgKOH/g, still more preferably 60 to 105mgKOH/g. The basic dispersant (basic resin) is a resin having a larger amount of base than acid groups. When the total amount of the acid group and the base group is 100 mol% in the basic dispersant (basic resin), a resin having a base group amount exceeding 50 mol% is preferable. The basic group of the basic dispersant is preferably an amino group.

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

The resin used as the dispersant is also preferably a graft polymer. Examples of the graft polymer include resins described in paragraphs 0025 to 0094 of Japanese patent application laid-open No. 2012-255128, which are incorporated herein by reference.

The resin used as the dispersant is also preferably a polyimide-based dispersant (polyimide resin) containing a nitrogen atom in at least one of the main chain and the side chain. The polyimide-based dispersant is preferably a resin having a main chain and a side chain, at least one of the main chain and the side chain having a basic nitrogen atom, the main chain having a partial structure having a functional group with a pKa of 14 or less, and the number of atoms of the side chain being 40 to 10000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Examples of the polyimide-based dispersant include resins described in paragraphs 0102 to 0166 of Japanese patent application laid-open No. 2012-255128, which are incorporated herein by reference.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A2013-043962.

The dispersant may be commercially available, and specific examples thereof include the DISPERBYK series (for example, DISPERBYK-111, 161, etc.) manufactured by BYK-Chemie GmbH, the Solsperse series (for example, solsperse 36000, etc.) manufactured by Lubrizol, and the like. The pigment dispersant described in paragraphs 0041 to 0130 of JP-A2014-130338, incorporated herein by reference, can also be used. As the dispersant, there may be used compounds described in Japanese patent application laid-open No. 2018-150498, japanese patent application laid-open No. 2017-100116, japanese patent application laid-open No. 2017-100115, japanese patent application laid-open No. 2016-108520, japanese patent application laid-open No. 2016-108519 and Japanese patent application laid-open No. 2015-232105.

The resin described as the dispersant can be used for applications other than the dispersant. For example, it can also be used as an adhesive.

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

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

The content of the specific resin is preferably 10 to 80 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

The resin composition of the present invention preferably contains 20 mass% or more of a specific resin, more preferably 30 mass% or more, and even more preferably 40 mass% or more of a component for removing a coloring material from the total solid content of the resin composition. The upper limit may be set to 100 mass%, 90 mass% or less, or 85 mass% or less. When the content of the specific resin is within the above range, a film excellent in heat resistance is easily formed, and shrinkage of the film after heating and the like are more easily suppressed. In addition, when an inorganic film is formed on the surface of a film obtained using the resin composition of the present invention, the occurrence of cracks or the like in the inorganic film can be suppressed even when the laminate is exposed to high temperatures.

The total content of the color material and the specific resin in the total solid content of the resin composition is preferably 25 to 100 mass%. The lower limit is more preferably 30 mass% or more, and still more preferably 40 mass% or more. The upper limit is more preferably 90 mass% or less, and still more preferably 80 mass% or less.

In the resin composition, the content of the other resin is preferably 230 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less, based on 100 parts by mass of the specific resin. The lower limit may be 0 part by mass, or may be 5 parts by mass or more, or may be 10 parts by mass or more. Further, it is also preferable that the resin composition contains substantially no other resin. According to this embodiment, a film excellent in heat resistance is easily formed. The case where the other resin is substantially not included means that the content of the other resin in the total solid content of the resin composition is 0.1 mass% or less, preferably 0.05 mass% or less, and more preferably no content.

< Solvent C >

The resin composition of the present invention contains a solvent C (hereinafter, referred to as a solvent). The solvent is not particularly limited as long as the solubility of each component and the coatability of the resin composition are satisfied. The solvent is preferably an organic solvent. The organic solvent includes an ester solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ether solvent, a hydrocarbon solvent, and the like, and preferably at least 1 selected from the group consisting of an ester solvent, an ether solvent, an alcohol solvent, and a ketone solvent. For details of these, reference can be made to paragraph 0223 of International publication No. 2015/166779, which is incorporated herein. Also, a cyclic alkyl substituted ester solvent or a cyclic alkyl substituted ketone solvent can be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl sirtuin acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ -butyrolactone, sulfolane, anisole, and the like. However, for environmental reasons, it is preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent (for example, 50 mass ppm (parts per million: parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent).

In the present invention, an organic solvent having a small metal content is preferably used, and the metal content of the organic solvent is preferably, for example, 10 ppb by mass (parts per billion:part per billion). Organic solvents of the quality ppt (parts per trillion: megaminutes) grade, such as provided by Toyo Gosei co., ltd (chemical industry journal, 2015, 11, 13) may be used as desired. Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further 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). The isomer may be contained in 1 or more kinds.

The content of the peroxide in the organic solvent is preferably 0.8mmol/L or less, and more preferably substantially no peroxide is contained.

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

< Pigment derivative >

The resin composition of the present invention preferably contains a pigment derivative. Examples of the pigment derivative include a compound having a structure in which a part of a color-forming group is substituted with an acid group, a base group, or a phthalimidomethyl group. Examples of the color-forming groups constituting the pigment derivative include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, viol skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinoline yellow skeleton, reducing skeleton, metal complex skeleton, and the like, preferably quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, quinoline Huang Gujia, isoindoline skeleton, and phthalocyanine skeleton, more preferably azo skeleton and benzimidazolone skeleton. The acid group of the pigment derivative is preferably a sulfo group or a carboxyl group, and more preferably a sulfo group. The base of the pigment derivative is preferably an amino group, and more preferably a tertiary amino group.

As the pigment derivative, a pigment derivative having excellent transparency to visible light (hereinafter, also referred to as a transparent pigment derivative) can be used. The maximum value (εmax) of the molar absorptivity of the transparent pigment derivative in the wavelength region of 400-700 nm is preferably 3000L/mol-1/cm-1 or less, more preferably 1000L/mol-1/cm-1 or less, and still more preferably 100L/mol-1/cm-1 or less. For example, εmax may have a lower limit of 1L/mol-1/cm-1 or more, or may have a lower limit of 10L/mol-1/cm-1 or more.

As a specific example of the pigment derivative, there is provided, examples thereof include Japanese patent application laid-open No. 56-118462, japanese patent application laid-open No. 63-264674, japanese patent application laid-open No. 01-217077, japanese patent application laid-open No. 03-009961, japanese patent application laid-open No. 03-153780, japanese patent application laid-open No. 03-045662, japanese patent application laid-open No. 04-285669, japanese patent application laid-open No. 06-145546, japanese patent application laid-open No. 06-212088, japanese patent application laid-open No. 06-240158, japanese patent application laid-open No. 10-030063, japanese patent application laid-open No. 10-195326, japanese patent application laid-open No. 201I/024896, japanese patent application laid-open No. 0086-0098, japanese patent application laid-open No. 0063-0094, japanese patent application laid-open No. 2017/038252, japanese patent application laid-open No. 2015, japanese patent application laid-open No. 20152-0162-373, japanese patent application laid-open No. 2-9738, japanese patent application laid-open No. 2015-2015, 20155-20135, 20135-20135, and 20155-2015, 2015-2015.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the pigment. The pigment derivative may be used alone or in combination of 2 or more kinds.

< Polymerizable monomer >

The resin composition of the present invention preferably contains a polymerizable monomer. As the polymerizable monomer, for example, a known compound which can be crosslinked by a radical, an acid, or heat can be used. Examples of the polymerizable monomer include a compound having a group containing an ethylenically unsaturated bond, a compound having a cyclic ether group, and the like, and a compound having a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. A compound having a group containing an ethylenically unsaturated bond can be preferably used as the radical polymerizable monomer. Further, a compound having a cyclic ether group can be preferably used as the cationically polymerizable monomer. The polymerizable monomer is preferably a polyfunctional polymerizable monomer. That is, the polymerizable monomer is preferably a monomer having 2 or more polymerizable groups such as a group having an ethylenically unsaturated bond or a cyclic ether group.

The molecular weight of the polymerizable monomer is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and still more preferably 1500 or less. The lower limit is more preferably 150 or more, and still more preferably 250 or more.

(Compound having a group containing an ethylenically unsaturated bond)

As the compound having a group containing an ethylenically unsaturated bond used as the polymerizable monomer, a polyfunctional compound is preferable. That is, a compound containing 2 or more ethylenically unsaturated bond-containing groups is preferable, a compound containing 3 or more ethylenically unsaturated bond-containing groups is more preferable, a compound containing 3 to 15 ethylenically unsaturated bond-containing groups is more preferable, and a compound containing 3 to 6 ethylenically unsaturated bond-containing groups is still more preferable. The compound having an ethylenically unsaturated bond-containing group is preferably a3 to 15 functional (meth) acrylate compound, more preferably a3 to 6 functional (meth) acrylate compound. Specific examples of the compound having a group containing an ethylenically unsaturated bond include compounds described in paragraphs 0095 to 0108 of JP-A2009-288705, paragraph 0227 of JP-A2013-029760, paragraphs 0254 to 0257 of JP-A2008-29292970, paragraphs 0034 to 0038 of JP-A2013-253224, paragraph 0477 of JP-A2012-208494, japanese patent publication 2017-048367, japanese patent publication 6057891, japanese patent publication 6031807, and Japanese patent publication 2017-194662, which are incorporated into the present specification.

As the compound having a group containing an ethylenically unsaturated bond, dipentaerythritol tri (meth) acrylate (as a commercially available product, manufactured by KAYARAD D-330;Nippon Kayaku Co, ltd.), dipentaerythritol tetra (meth) acrylate (as a commercially available product, manufactured by KAYARAD D-320;Nippon Kayaku Co, ltd.), dipentaerythritol penta (meth) acrylate (as a commercially available product, manufactured by KAYARAD D-310;Nippon Kayaku Co, ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; nippon Kayaku Co., ltd., NK ESTER A-DPH-12E; shin-Nakamura Chemica Co., ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454, SR499, commercially available by SARTOMER Company, inc.) are preferable. Further, as the compound having a group containing an ethylenically unsaturated bond, diglycerol EO (ethylene oxide) -modified (meth) acrylate (as a commercially available product, M-460; TOAGOSEI CO., ltd.), neopentyltetraol tetraacrylate (Shin Nakamura Chemical Co., ltd., NK ESTER A-TMMT), 1, 6-hexanediol diacrylate (Nippon Kayaku Co., ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., ltd.), ARONIX TO-2349 (TOAGOSEI CO., ltd.), NK Oligo UA-7200 (Shin Nakamura Chemical Co., ltd.), 8UH-1006, 8-1012 (TAISEI FINE CHEMICAL Co., ltd.), LIGHT ACRYLATE B-AO (KYOEISHA CHEMICAL Co., LTD.), and the like can also be used.

As the compound having an ethylenically unsaturated bond-containing group, a 3-functional (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, or neopentyl tetraol tri (meth) acrylate is also preferably used. Examples of THE commercial products of THE 3-functional (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 (TOAGOSEI CO., manufactured by LTD. )、NK ESTER A9300、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、TMPT(Shin-Nakamura Chemical Co.,Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., ltd.), and THE like.

Compounds having a group containing an ethylenically unsaturated bond can also be used as the compound having an acid group. By using a compound having an acid group, development residue generation can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable. Examples of commercially available polymerizable monomers having an acid group include ARONIX M-305, M-510, M-520, ARONIX T0-2349 (TOAGOSEI CO., LTD.). The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40mgKOH/g, more preferably 5 to 30mgKOH/g. When the acid value of the polymerizable compound is 0.1mgKOH/g or more, the solubility in a developer is good, and when it is 40mgKOH/g or less, the production and handling are advantageous.

Compounds having a group containing an ethylenically unsaturated bond are also preferred as compounds having a caprolactone structure. As the compound having a caprolactone structure, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., ltd.

Compounds having a group containing an ethylenically unsaturated bond can also be used as the compound having an alkyleneoxy group. The compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and still more preferably a 3-6 functional (meth) acrylate compound having 4-20 ethyleneoxy groups. Examples of the commercially available polymerizable compound having an alkyleneoxy group include SR-494, which is a 4-functional (meth) acrylate having 4 ethyleneoxy groups, KAYARAD TPA-330, which is a 3-functional (meth) acrylate having 3 isobutyloxy groups, which is produced by SARTOMER Company, inc.

Compounds having a group containing an ethylenically unsaturated bond can also be used as compounds having a fluorene skeleton. Examples of commercial products of the fluorene skeleton-containing compound include OGSOL FA-0200 and FA-0300 (Osaka GAS CHEMICALS Co., ltd., (meth) acrylate monomers having a fluorene skeleton).

As the compound having a group containing an ethylenically unsaturated bond, a compound substantially free of an environmental control substance such as toluene is also preferably used. Commercially available products of such compounds include KAYARAD DPHALT, KAYARAD DPEA-12 and LT (Nippon Kayaku Co., ltd.).

As the compound having a group containing an ethylenically unsaturated bond, urethane compounds having an ethylene oxide skeleton described in Japanese patent application laid-open No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, japanese patent application laid-open No. 02-016765, japanese patent application laid-open No. 58-049860, japanese patent application laid-open No. 56-017654, japanese patent application laid-open No. 62-039417, and Japanese patent application laid-open No. 62-039418 are also preferred. Further, a compound having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 is also preferably used. Further, commercially available products such as UA-7200 (Shin-Nakamura Chemical Co., ltd.), DPHA-40H (Nippon Kayaku Co., ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (KYOEISHA CHEMICAL Co., LTD.) and the like can be used as the polymerizable compound.

(Compound having a cyclic ether group)

Examples of the compound having a cyclic ether group used as the polymerizable monomer include a compound having an epoxy group (hereinafter, also referred to as an epoxy compound) and a compound having an oxetanyl group (hereinafter, also referred to as an oxetane compound). The epoxy compound is preferably a multifunctional epoxy compound. That is, the epoxy compound is preferably a compound having 2 or more epoxy groups. The upper limit of the number of epoxy groups is preferably 20 or less, more preferably 10 or less. The oxetane compound is preferably a polyfunctional oxetane compound. That is, the oxetane compound is preferably a compound having 2 or more oxetanyl groups. The upper limit of the oxetane base number is preferably 20 or less, more preferably 10 or less.

Examples of the commercial products of the epoxy compounds include JER828, JER1007, JER S70 (manufactured by Mitsubishi Chemical Corporation), JER S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and the like, and those described in paragraph 0189 of Japanese patent application laid-open No. 2011-221494. Examples of other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA CORPORATION above), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA CORPORATION and )、DENACOL EX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、DLC-301、DLC-402、EX-111,EX-121、EX-141、EX-145、EX-146、EX-147、EX-171、EX-192( above Nagase ChemteX Corporation above), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by NIPPON STEEL & SUMIKIN MATERIALS CO above), LTD. CELLOXIDE P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, SERVINERS B0134, B0177 (manufactured by Daicel Corporation), TETRAD-X (manufactured by MITSUBISHI GAS CHEMICAL PANY, INC).

Examples of commercial products of oxetane compounds include OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ TX-100, (TOAGOSEI CO., LTD. Co., ltd.).

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

When a compound having a group containing an ethylenically unsaturated bond is used as the polymerizable monomer, the content of the compound having a group containing an ethylenically unsaturated bond as the polymerizable monomer is preferably 1 to 50 parts by mass per 100 parts by mass of the specific resin. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

When a compound having a cyclic ether group is used as the polymerizable monomer, the content of the compound having a cyclic ether group as the polymerizable monomer is preferably 1 to 50 parts by mass per 100 parts by mass of the specific resin. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

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

< Photopolymerization initiator >

The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photo radical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton and an imidazole skeleton), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α -hydroxyketone compounds, and α -aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a biimidazole compound, a benzyldimethyl ketal compound, an α -hydroxyketone compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from the group consisting of biimidazole compounds, oxime compounds, α -hydroxyketone compounds, α -aminoketone compounds, and acylphosphine compounds, and further preferably an oxime compound. Examples of the photopolymerization initiator include a compound described in paragraphs 0065 to 0111 of Japanese patent application laid-open No. 2014-130173, a compound described in Japanese patent application laid-open No. 6301489, MATERIAL STAGE to 60p, vol.19, no.3, and 2019, a peroxide-based photopolymerization initiator described in International publication No. 2018/221177, a photopolymerization initiator described in International publication No. 2018/110179, a photopolymerization initiator described in Japanese patent application laid-open No. 2019-043864, a photopolymerization initiator described in Japanese patent application laid-open No. 2019-044030, and a peroxide-based initiator described in Japanese patent application laid-open No. 2019-313, and these are incorporated into the present specification.

Examples of the bisimidazole compound include 2, 2-bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole, 2' -bis (o-chlorophenyl) -4,4',5, 5-tetrakis (3, 4, 5-trimethoxyphenyl) -1,2' -biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenyl biimidazole, 2' -bis (o-chlorophenyl) -4, 5' -tetraphenyl-1, 2' -biimidazole, and the like. Examples of the commercial products of the α -hydroxyketone compounds include Omnirad 184, omnirad 1173, omnirad 2959, omnirad 127 (manufactured by IGM RESINS b.v. company, above), irgacure 184, irgacure 1173, irgacure 2959, irgacure 127 (manufactured by BASF company, above), and the like. Examples of the commercial products of the α -aminoketone compound include Omnirad 907, omnirad 369E, omnirad 379EG (manufactured by IGM RESINS b.v. company, above), irgacure 907, irgacure 369E, irgacure 379EG (manufactured by BASF company, above), and the like. Examples of commercial products of the acylphosphine compound include Omnirad 819, omnirad TPO (manufactured by IGM RESINS b.v. company, above), irgacure 819, irgacure TPO (manufactured by BASF company, above), and the like.

Examples of the oxime compound include a compound described in Japanese patent application laid-open No. 2001-233846, a compound described in Japanese patent application laid-open No. 2000-080068, a compound described in Japanese patent application laid-open No. 2006-342166, a compound described in J.C.S. Perkin II (1979, pages 1653-1660), a compound described in J.C.S. Perkin II (1979, pages 156-162), a compound described in Journal of Photopolymer SCIENCE AND Technology (1995, pages 202-232), a compound described in Japanese patent application laid-open No. 2000-066385, a compound described in Japanese patent application laid-open No. 1672004-534797, a compound described in Japanese patent application laid-open No. 2006-342166, a compound described in Japanese patent application laid-open No. 6065596, a compound described in International publication No. 152153, a compound described in International publication No. 2017/680, a compound described in International publication No. 2015-2015, a publication No. 2015, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxyimino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino1-phenylpropane-1-one. As commercial products, irgacure-OXE01, irgacure-OXE02, irgacure-OXE03, irgacure-OXE04 (manufactured by BASF corporation, above), TR-PBG-304 (Changzhou Tronly New Electronic Materials CO., LTD., manufactured by LTD.), adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) may be mentioned. Furthermore, as the oxime compound, a compound which is free from coloring or a compound which is highly transparent and hardly discolored is preferably used. Commercially available products include ADEKA ARKLS NCI-730, NCI-831, NCI-930 (manufactured by ADEKA CORPORATION above), and the like.

As photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include those described in JP-A2014-137466.

Further, 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 be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include a compound described in JP 2010-26261028A, compounds 24, 36 to 40 described in JP 2014-500852A, and compound (C-3) described in JP 2013-164471A.

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

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably provided as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

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

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

[ Chemical formula 36]

[ Chemical formula 37]

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

As the photopolymerization initiator, a 2-functional or 3-functional or more photo radical polymerization initiator can be used. By using such a photo radical polymerization initiator, 2 or more radicals are generated from one molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent or the like is increased, and deposition becomes difficult with the passage of time, whereby the stability of the resin composition with time can be improved. Specific examples of the 2-functional or 3-functional or more photo-radical polymerization initiator include the photoinitiators of oxime esters described in Japanese patent application publication No. 2010-527339, japanese patent application publication No. 2011-524436, the photoinitiators described in Japanese patent application publication No. 2015/004565, the dimers of oxime compounds described in Japanese patent application publication No. 0407-0412, the paragraphs 0039-0055, the compounds (E) and (G) described in Japanese patent application publication No. 2013-522445, the Cmpd 1-7 described in Japanese patent application publication No. 2016/034963, the photoinitiators of oxime esters described in Japanese patent application publication No. 2017-523465 in paragraph 0007, the photoinitiators described in Japanese patent application publication No. 0020-0033, the photoinitiators described in Japanese patent application publication No. 2017-151342, the photoinitiators described in paragraphs 0017-0026, and the oxime compounds described in Japanese patent application publication No. 6469669, and the like.

The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 30 mass%. The lower limit is preferably 0.5 mass% or more, more preferably 1 mass% or more. The upper limit is preferably 20 mass% or less, more preferably 15 mass% or less. The photopolymerization initiator may be used in an amount of 1 or 2 or more.

< Silane coupling agent >

The resin composition of the present invention may contain a silane coupling agent. In the present specification, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. The hydrolyzable group is a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxy silane group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryl group, a mercapto group, an epoxy group, a amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, and the like, and amino groups, a (meth) acryl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A2009-288703 and compounds described in paragraphs 0056 to 0066 of JP-A2009-242604, which are incorporated herein by reference.

The content of the silane coupling agent in the total solid content of the resin composition is preferably 0.1 to 5 mass%. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less. The lower limit is preferably 0.5 mass% or more, more preferably 1 mass% or more. The silane coupling agent may be 1 or 2 or more.

< Curing accelerator >

The resin composition of the present invention may further contain a curing accelerator for the purpose of accelerating the reaction of the resin and the polymerizable compound or reducing the curing temperature. As the curing accelerator, a hydroxymethyl compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of japanese patent application laid-open No. 2015-034963), an amine, a phosphonium salt, an amidine salt, an amide compound (for example, a curing agent described in paragraph 0186 of japanese patent application laid-open No. 2013-041115), an alkali generator (for example, an ionic compound described in japanese patent application laid-open No. 2014-055114), a cyanate ester compound (for example, a compound described in paragraph 0071 of japanese patent application laid-open No. 2012-150180), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in japanese patent application laid-open No. 2011-253054), an onium salt compound (for example, a compound exemplified as an acid generator in paragraph 0216 of japanese patent application laid-open No. 2015-034963, a compound described in japanese patent application laid-open No. 2009-180949) and the like can be used.

When the resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9 mass%, more preferably 0.8 to 6.4 mass% based on the total solid content of the resin composition.

< Polymerization inhibitor >

The resin composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, gallphenol, t-butylcatechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, first cerium salts, and the like). Among them, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.

< Surfactant >

The resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Examples of the surfactant include those described in paragraphs 0238 to 0245 of International publication No. 2015/166779, which are incorporated herein by reference.

The surfactant is preferably a fluorine-based surfactant. By containing the fluorine-based surfactant in the resin composition, the liquid properties (particularly, fluidity) are further improved, and the liquid saving property can be further improved. Further, a film with less thickness unevenness can be formed.

The fluorine content of 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. The fluorine-containing surfactant having a fluorine content within this range is effective in uniformity of thickness of the coating film and liquid saving property, and has good solubility in the resin composition.

Examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of JP 2014-04318 (corresponding to paragraphs 0060 to 0064 of International publication No. 2014/017669), surfactants described in paragraphs 0117 to 0132 of JP 2011-132503, and surfactants described in JP 2020-008634, the contents of which are incorporated herein by reference. Examples of the commercially available fluorine-based surfactant include DIC CORPORATION MEGAFACE F-171、F-172、F-173、F-176、F-177、F-141、F-142、F-143、F-144、F-437、F-475、F-477、F-479、F-482、F-554、F-555-A、F-556、F-557、F-558、F-559、F-560、F-561、F-565、F-563、F-568、F-575、F-780、EXP、MFS-330、R-41、R-41-LM、R-01、R-40、R-40-LM、RS-43、TF-1956、RS-90、R-94、RS-72-K、DS-21( or more, FLUORAD FC430, FC431, FC171 (Sumitomo 3M Limited) SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (AGC INC, above), polyFox PF636, PF656, PF6320, PF6520, PF7002 (OMNOVA SOLUTIONS INC, above), futurgent FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (NEOS COMPANY LIMITED, above), and the like.

In addition, as the fluorine-based surfactant, 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 is also preferably used. As such a fluorine-based surfactant, the description of japanese patent application laid-open publication 2016-216602, which is incorporated herein by reference, can be referred to.

The fluorine-based surfactant may be a block polymer. For example, a compound described in Japanese patent application laid-open No. 2011-089090 is mentioned. The fluorine-containing surfactant may preferably be a fluorine-containing polymer compound comprising: repeating units derived from a (meth) acrylate compound having a fluorine atom; and repeating units derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[ Chemical formula 38]

The weight average molecular weight of the above compound is preferably 3000 to 50000, for example 14000. In the above-mentioned compounds, the% representing the proportion of the repeating unit is mol%.

The fluorine-based surfactant may be a fluoropolymer having a group containing an ethylenically unsaturated bond in a side chain. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, for example, MEGAFACE RS-101, RS-102, RS-718K, RS-72-K and the like manufactured by DIC Corporation. The fluorine-based surfactant may be any of those described in paragraphs 0015 to 0158 of JP-A2015-117327.

The content of the surfactant in the total solid content of the resin composition is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass. The number of surfactants may be 1 or 2 or more. In the case of 2 or more, the total amount is preferably within the above range.

< Ultraviolet absorber >

The resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber can use conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, and the like. For details of these, reference is made to paragraphs 0052 to 0072 of JP 2012-208374, paragraphs 0317 to 0334 of JP 2013-068814, and paragraphs 0061 to 0080 of JP 2016-162946, which are incorporated herein by reference. Examples of the commercial product of the ultraviolet absorber include UV-503 (DAITO CHEMICAL CO., LTD.). As benzotriazole compounds, MIYOSHI OIL & FAT CO., LTD. MYUA series (Japanese chemical industry report, 2016, 2/1/month) are mentioned. The ultraviolet absorber may be any of those described in paragraphs 0049 to 0059 of Japanese patent No. 6268967. The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. The ultraviolet absorber may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.

< Antioxidant >

The photosensitive composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphorus acid ester compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenol antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphate group in the same molecule. In addition, a phosphorus antioxidant can be preferably used as the antioxidant. In addition, the antioxidant may be a compound described in Korean laid-open patent publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.

< Other ingredients >

The resin composition of the present invention may contain a sensitizer, a filler, a heat curing accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a perfume, a surface tension regulator, a chain transfer agent, and the like) as needed. By properly containing these components, properties such as film physical properties can be adjusted. For these components, for example, reference can be made to the descriptions of paragraphs 0183 and later of Japanese patent application laid-open No. 2012-003225 (paragraph 0237 of the specification of corresponding U.S. patent application publication No. 2013/0034812), and the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and the like, which are incorporated herein by reference. Further, the resin composition may contain a latent antioxidant as needed. As potential antioxidants, the following compounds may be mentioned: a compound in which a site functioning as an antioxidant is protected with a protecting group, and the protecting group is detached by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst and functions as an antioxidant. Examples of the latent antioxidant include compounds described in Japanese patent laid-open publication Nos. 2014/021023 and 2017/030005, and Japanese patent laid-open publication No. 2017-008219. Commercially available products include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

The resin composition of the present invention may contain a metal oxide to adjust the refractive index of the obtained film. Examples of the metal oxide include TiO ₂、ZrO₂、Al₂O₃、SiO₂. The primary particle diameter of the metal oxide is preferably 1 to 100nm, more preferably 3 to 70nm, and still more preferably 5 to 50nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

The resin composition of the present invention may contain a light resistance improver. As an agent for improving the light resistance, examples thereof include the compounds described in paragraphs 0036 to 0037 of Japanese patent application laid-open No. 2017-198787, the compounds described in paragraphs 0029 to 0034 of Japanese patent application laid-open No. 2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of Japanese patent application laid-open No. 2017-129774, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of Japanese patent application laid-open No. 2017-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of Japanese patent application laid-open No. 2017-122803, the compounds described in paragraphs 0025 to 0039 of International publication No. 2017/164127, the compounds described in paragraphs 0034 to 0047 of Japanese patent application laid-open No. 2017-186546, and the like the compounds described in paragraphs 0019 to 0041 of Japanese patent application laid-open No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese patent application laid-open No. 2012-145604, the compounds described in paragraphs 0018 to 0021 of Japanese patent application laid-open No. 2012-1034975, the compounds described in paragraphs 0015 to 0018 of Japanese patent application laid-open No. 2011-257591, the compounds described in paragraphs 0017 to 0021 of Japanese patent application laid-open No. 2011-191483, the compounds described in paragraphs 0108 to 0116 of Japanese patent application laid-open No. 2011-145668, and the compounds described in paragraphs 0103 to 0153 of Japanese patent application laid-open No. 2011-253174.

The content of the free metal not bonded to or coordinated with the pigment or the like in the resin composition of the present invention is preferably 100ppm or less, more preferably 50ppm or less, still more preferably 1Oppm or less, and particularly preferably substantially none. According to this aspect, effects such as stabilization of pigment dispersibility (suppression of aggregation), improvement of spectroscopic characteristics with an increase in dispersibility, stabilization of curable components, suppression of variation in conductivity accompanying elution of metal atoms/metal ions, and improvement of display characteristics can be expected. Further, the effects described in Japanese patent application laid-open No. 2012-153796, japanese patent application laid-open No. 2000-345085, japanese patent application laid-open No. 2005-200560, japanese patent application laid-open No. 08-043620, japanese patent application laid-open No. 2004-145078, japanese patent application laid-open No. 2014-119487, japanese patent application laid-open No. 2010-083997, japanese patent application laid-open No. 2017-090930, japanese patent application laid-open No. 2018-025612, japanese patent application laid-open No. 2018-025797, japanese patent application laid-open No. 2017-155228, japanese patent application laid-open No. 2018-036521 and the like can be obtained. The type of the free metal may be Na, K, ca, sc, ti, mn, cu, zn, fe, cr, co, mg, al, sn, zr, ga, ge, ag, au, pt, cs, ni, cd, pb, bi. The content of free halogen not bonded to or coordinated with the pigment or the like in the resin composition of the present invention is preferably 100ppm or less, more preferably 50ppm or less, still more preferably 10ppm or less, and particularly preferably substantially no halogen. As the halogen, F, cl, br, I and anions thereof are mentioned. Examples of the method for reducing free metal and halogen in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, purification with ion-exchange resin, and the like.

From the viewpoint of environmental regulations, the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof, is sometimes regulated. In the resin composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of the perfluoroalkylsulfonic acid (particularly, the perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt and the perfluoroalkylcarboxylic acid (particularly, the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt are preferably in the range of 0.01ppb to 1,000 ppb, more preferably in the range of 0.05ppb to 500ppb, still more preferably in the range of 0.1ppb to 300ppb, relative to the total solid content of the resin composition. The resin composition of the present invention may contain substantially no perfluoroalkylsulfonic acid or salt thereof, and no perfluoroalkylcarboxylic acid or salt thereof. For example, by using a compound capable of becoming a substitute for a perfluoroalkylsulfonic acid and a salt thereof and a compound capable of becoming a substitute for a perfluoroalkylcarboxylic acid and a salt thereof, a resin composition containing substantially no perfluoroalkylsulfonic acid and salt thereof and no perfluoroalkylcarboxylic acid and salt thereof can be selected. Examples of the compound that can be a substitute for the controlled compound include compounds that are excluded from the controlled object according to the difference in the number of carbon atoms of 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 contain a perfluoroalkylsulfonic acid and a salt thereof, and a perfluoroalkylcarboxylic acid and a salt thereof within a maximum allowable range.

The resin composition of the present invention also preferably contains substantially no terephthalate. The term "substantially free" as used herein means that the content of terephthalic acid ester in the total amount of the resin composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

< Storage Container >

The container for the resin composition is not particularly limited, and a known container can be used. In addition, as the storage container, a multilayer bottle having 6 kinds of 6 layers of resins constituting the inner wall of the container and a bottle having 6 kinds of resins in a 7-layer structure are preferably used in order to suppress the mixing of impurities into the raw material and the resin composition. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351. The inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing elution of metal from the inner wall of the container, improving the storage stability of the resin composition, suppressing deterioration of components, or the like.

< Method for producing resin composition >

The resin composition of the present invention can be prepared by mixing the components. In the preparation of the resin composition, all the components may be dissolved and/or dispersed in a solvent at the same time to prepare the resin composition, or the components may be appropriately divided into 2 parts or more of a solution or a dispersion as required, and these may be mixed at the time of use (at the time of coating) to prepare the resin composition.

Also, in preparing the resin composition, a pigment dispersing process is preferably included. In the pigment dispersion process, examples of the mechanical force for dispersing the pigment include compression, extrusion, impact, shearing, cavitation, and the like. Specific examples of these processes include bead milling, sand milling, roll milling, ball milling, paint stirring, micro-jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, in grinding a pigment in a sand mill (bead mill), it is preferable to perform the treatment under a condition that the grinding efficiency is improved by using microbeads having a small diameter, increasing the filling rate of the microbeads, or the like. Further, it is preferable to remove coarse particles by filtration, centrifugal separation, or the like after the pulverization treatment. The pigment dispersion process and the dispersing machine can be preferably used as the "general collection of dispersing techniques, JOHOKIKO co., ltd. Release, 7/15 th month of 2005" or "integrated data set of dispersing techniques and practical applications in industry centered on a suspension (solid/liquid dispersion system), release by the department of business development center, 10/10 th month of 1978, and the process and dispersing machine described in paragraph 0022 of japanese patent application laid-open No. 2015-157893. In the pigment dispersion process, the fine particle size reduction treatment can be performed by a salt milling process. For example, the materials, equipment, process conditions, etc. used in the salt milling step can be described in Japanese patent application laid-open No. 2015-194521 and Japanese patent application laid-open No. 2012-046629.

In the preparation of the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing impurities, reducing defects, and the like. The filter is not particularly limited as long as it is a filter conventionally used for filtration and the like. Examples of the filter include filters using a material such as a fluororesin such as Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), a polyamide resin such as nylon (for example, nylon-6 or nylon-6, 6), a polyolefin resin such as polyethylene or polypropylene (PP) (including a high-density and ultrahigh-molecular-weight polyolefin resin). 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. Mu.m, more preferably 0.01 to 3.0. Mu.m, still more preferably 0.05 to 0.5. Mu.m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. As regards the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by NIHON PALL Corporat ion (DFA 4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), advantec Toyo Kaisha, ltd, nihon Entegris k.k. (Formerly Nippon Mykrolis Corporation), KITZ MICROFILTER Corporation, etc. can be used.

Also, as the filter, a fibrous filter medium is preferably used. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include ROKI TECHNO co., ltd. SBP type series (SBP 008, etc.), TPR type series (TPR 002, TPR005, etc.), SHPX type series (SHPX 003, etc.).

When filters are used, different filters (e.g., filter 1 and filter 2, etc.) may be combined. In this case, the filtration using each filter may be performed only 1 time, or may be performed 2 times or more. Also, filters of different pore diameters may be combined within the above range. The filtration using the 1 st filter is performed only on the dispersion liquid, and the filtration using the 2 nd filter may be performed after mixing other components. The filter can be appropriately selected according to the hydrophilicity and hydrophobicity of the resin composition.

(Film)

The film of the present invention is a film obtained from the above-described resin composition of the present invention. The film of the present invention can be used for filters such as color filters, near infrared ray transmission filters, near infrared ray cut-off filters, and the like. The film of the present invention can also be used for a black matrix, a light shielding film, and the like.

The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further 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 hue of green, red, blue, cyan, magenta, or yellow. Further, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of the coloring pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

When the film of the present invention is used as a near infrared cut filter, the film of the present invention preferably has a maximum absorption wavelength in the range of 700 to 1800nm, more preferably in the range of 700 to 1300nm, and even more preferably in the range of 700 to 1100 nm. The transmittance of the film in all the wavelength ranges from 400 to 650nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance of the film at least 1 in the wavelength range of 700 to 1800nm is preferably 20% or less. The ratio of absorbance Amax at the maximum absorption wavelength to absorbance a550 at the wavelength 550nm, that is, 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.

When the film of the present invention is used as a near infrared ray transmission filter, the film of the present invention preferably has any one of the following spectroscopic characteristics (i 1) to (i 5), for example.

(I1) : a filter having a maximum value of transmittance in a wavelength range of 400 to 640nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 800 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more). The film having such spectroscopic characteristics shields light having a wavelength in the range of 400 to 640nm and transmits light having a wavelength of more than 750 nm.

(I2) : a filter having a maximum value of transmittance in a wavelength range of 400 to 750nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 900 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectroscopic properties shields light in the wavelength range of 400 to 750nm and transmits light having a wavelength of more than 850 nm.

(I3) : a filter having a maximum value of transmittance in a wavelength range of 400 to 830nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1000 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectroscopic properties shields light in the wavelength range of 400 to 830nm and transmits light having a wavelength of more than 950 nm.

(I4) : a filter having a maximum value of transmittance in a wavelength range of 400 to 950nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1100 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectroscopic properties shields light in the wavelength range of 400 to 950nm and transmits light having a wavelength greater than 1050 nm.

(I5) : a filter having a maximum value of transmittance in a wavelength range of 400 to 1050nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1200 to 1500nm of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectroscopic properties shields light in the wavelength range of 400 to 1050nm and transmits light having a wavelength of more than 1150 nm.

The thickness of the film after heat treatment at 300 ℃ for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, still more preferably 95% or more, and particularly preferably 99% or more of the thickness of the film before heat treatment.

The thickness of the film after the film is heated at 350 ℃ for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, still more preferably 95% or more, and particularly preferably 99% or more of the thickness of the film before the heat treatment.

The thickness of the film after the film is heated at 400 ℃ for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, still more preferably 95% or more, and particularly preferably 99% or more of the thickness of the film before the heat treatment.

< Method for producing film >

The film of the present invention can be produced by a process of applying the resin composition of the present invention to a support. The method for producing a film of the present invention preferably further includes a step of forming a pattern (pixel). As a method for forming a pattern (pixel), photolithography and dry etching are mentioned, and photolithography is preferable.

(Photolithography)

First, a case where a film is manufactured by patterning by photolithography will be described. The patterning by photolithography preferably includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer in a pattern, and a step of developing and removing an unexposed portion of the resin composition layer to form a pattern (pixel). A step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided as needed.

In the step of forming the resin composition layer, the resin composition of the present invention is used to form the resin composition layer on the support. The support is not particularly limited, and may be appropriately selected according to the application. For example, a glass substrate, a silicon substrate, or the like is given, and a silicon substrate is preferable. Further, 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, a black matrix (black matrix) may be formed on the silicon substrate to isolate each pixel. In order to improve adhesion to the upper layer, prevent diffusion of substances, and planarize the substrate surface, a base layer may be provided on the silicon substrate. The surface contact angle of the underlayer is preferably 20 to 70 ° when measured with diiodomethane. And, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the wettability of the resin composition is good. For example, the surface contact angle of the base layer can be adjusted by adding a surfactant or the like.

As a method for applying the resin composition, a known method can be used. For example, a dropping method (drop casting) is mentioned; a slit coating method; spraying; roll coating; spin coating (spin coating); a casting coating method; slit spin coating; prewet (for example, a method described in japanese patent application laid-open No. 2009-145395); inkjet (e.g., on-demand, piezo, thermal), jet printing such as nozzle jetting, flexography, screen printing, gravure, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; nanoimprint method, etc. The method for applying the ink jet is not particularly limited, and examples thereof include the methods described in "unlimited possibility in ink jet development and use-patent", release by month 2 2005, sumitbe Techon Research co., ltd. "and the methods described in (especially pages 115 to 133) and japanese patent application laid-open nos. 2003-262626716, 2003-185831, 2003-261827, 2012-126830, 2006-169325, and the like. The method of applying the resin composition may be any method described in International publication Nos. 2017/030174 and 2017/018419, which are incorporated herein by reference.

The resin composition layer formed on the support may be dried (prebaked). When the film is manufactured by a low temperature process, the pre-baking may not be performed. In the case of performing the prebaking, the prebaking temperature is preferably 150℃or less, more preferably 120℃or less, and further preferably 110℃or less. The lower limit may be, for example, 50℃or higher, or 80℃or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. The pre-baking can be performed using a hot plate, an oven, or the like.

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

Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Light having a wavelength of 300nm or less (preferably, light having a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. Further, a light source having a long wavelength of 300nm or more can be used.

In the exposure, light may be continuously irradiated to perform exposure, or pulse irradiation may be performed to perform exposure (pulse exposure). The pulse exposure is an exposure method in which light is repeatedly irradiated and suspended for a short period of time (for example, in the order of milliseconds or less) to perform exposure. In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, and may be 1 femtosecond (fs) or more, or may be 10 femtoseconds or more. The frequency is preferably 1kHz or more, more preferably 2kHz or more, and still more preferably 4kHz or more. The upper limit of the frequency is preferably 50kHz or less, more preferably 20kHz or less, and still more preferably 10kHz or less. The maximum instantaneous illuminance is preferably 50000000W/m ² or more, more preferably 100000000W/m ² or more, and still more preferably 200000000W/m ² or more. The upper limit of the maximum instantaneous illuminance is preferably 1000000000W/m ² or less, more preferably 800000000W/m ² or less, and even more preferably 500000000W/m ² or less. The pulse width refers to the time of light irradiation in the pulse period. And, the frequency refers to the number of pulse periods per 1 second. The maximum instantaneous illuminance means an average illuminance of light in a pulse period during the irradiation time. The pulse period is a period in which irradiation and suspension of light during pulse exposure are 1 period.

For example, the irradiation amount (exposure amount) is preferably 0.03 to 2.5J/cm ², more preferably 0.05 to 1.0J/cm ². The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the exposure to the atmosphere, for example, exposure may be performed in a low oxygen atmosphere (for example, 15 vol%, 5 vol%, or substantially no oxygen) having an oxygen concentration of 19 vol% or less, or exposure may be performed in a high oxygen atmosphere (for example, 22 vol%, 30 vol%, or 50 vol%) having an oxygen concentration of more than 21 vol%. The exposure illuminance can be set appropriately, and can be generally selected from a range of 1000W/m ²～100000W/m² (for example, 5000W/m ²、15000W/m² or 35000W/m ²). The conditions of the oxygen concentration and the exposure illuminance may be appropriately combined, and for example, the oxygen concentration may be 10% by volume and the illuminance 10000W/m ², the oxygen concentration may be 35% by volume and the illuminance 20000W/m ², or the like.

Next, the unexposed portions of the resin composition layer are removed by development to form a pattern (pixel). The development and removal of the unexposed portion of the resin composition layer can be performed using a developer. Thus, the resin composition in the unexposed portion in the exposure step dissolves out into the developer, leaving only the photo-cured portion. For example, the temperature of the developer is preferably 20 to 30 ℃. The development time is preferably 20 to 180 seconds. In order to improve the residue removal performance, the following steps may be repeated several times: and a step of throwing off the developer every 60 seconds and supplying a new developer.

The developer may be an organic solvent, an alkali developer, or the like, and an alkali developer is preferably used. As the alkali developer, an alkali aqueous solution (alkali developer) obtained by diluting an alkali agent with pure water is preferable. Examples of the alkaline agent include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diethyleneglycol amine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethyl bis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1, 8-diazabicyclo [5.4.0] -7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight from the viewpoint of environmental aspects and safety aspects. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, nonionic surfactants are preferred. From the viewpoint of convenience in transportation, storage, and the like, the developer may be first prepared as a concentrated solution and diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, and can be set in a range of 1.5 to 100 times, for example. Further, it is also preferable to perform washing (rinsing) with pure water after development. And, the flushing is preferably performed as follows: the rinse liquid is supplied to the developed resin composition layer while rotating the support on which the developed resin composition layer is formed. Further, it is also preferable that the cleaning liquid is discharged by moving the nozzle from the center portion of the support body to the peripheral portion of the support body. In this case, when the nozzle is moved from the center portion to the peripheral portion of the support body, the nozzle can be moved while gradually reducing the moving speed. By performing the flushing in this manner, in-plane unevenness of flushing can be suppressed. The same effect can be obtained by gradually decreasing the rotation speed of the support body while moving the nozzle from the center portion to the peripheral portion of the support body.

After development, it is preferable to perform additional exposure treatment and heat treatment (post baking) after drying. The post-exposure treatment and post-baking are post-development curing treatments for complete curing. For example, the heating temperature in post baking is preferably 100 to 240 ℃, more preferably 200 to 240 ℃. The film after development can be post-baked continuously or intermittently using a heating mechanism such as a hot plate, a convection oven (heated air circulation dryer), or a high-frequency heater so as to satisfy the above conditions. In the case of performing the additional exposure treatment, the light used for exposure is preferably light having a wavelength of 400nm or less. The additional exposure treatment may be performed by the method described in korean laid-open patent No. 10-2017-012130.

(Dry etching method)

The patterning by the dry etching method preferably includes the steps of: the method for producing a resin composition comprises the steps of forming a resin composition layer on a support using the resin composition of the present invention, curing the resin composition layer as a whole to form a cured product layer, forming a resist layer on the cured product layer, exposing the resist layer in a pattern, developing the resist layer to form a resist pattern, and dry etching the cured product layer with an etching gas using the resist pattern as a mask. When forming the resist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming the resist layer, a method of performing a post-exposure heat treatment and a post-development heat treatment (post-baking treatment) is preferable. For the patterning by the dry etching method, reference can be made to the descriptions in paragraphs 0010 to 0067 of Japanese patent application laid-open No. 2013-064993, which is incorporated herein by reference.

< Filter >

The optical filter of the present invention has the film of the present invention described above. The type of the filter includes a color filter, a near infrared ray transmission filter, a near infrared ray cut filter, and the like, and is preferably a color filter. As the color filter, a colored pixel having the film of the present invention as the color filter is preferable. The optical filter of the present invention can be used for a solid-state imaging element such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.

In the optical filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 5 μm or less, more preferably 1 μm or less, and still more preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

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

It is preferable that each pixel included in the filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100nm or less, more preferably 40nm or less, and further preferably 15nm or less. The lower limit is not limited, but is preferably 0.1nm or more, for example. The surface roughness of the pixel can be measured by using, for example, AFM (atomic force microscope) Dimension3100 manufactured by Veeco corporation. The water contact angle at the pixel can be set to a suitable value, and is usually in the range of 50 to 110 °. For example, the contact angle can be measured using a contact angle meter type CV-DT.A (manufactured by Kyowa INTERFACE SCIENCE Co., LTD.). The volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, and more preferably 10 ¹¹ Ω·cm or more. The upper limit is not limited, and is preferably 10 ¹⁴ Ω·cm or less, for example. For example, the volume resistance value of a pixel can be measured using the ultra-high resistance meter 5410 (ADVANTEST CORPORATION).

In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, various functions such as oxidation resistance, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, and the like) can be imparted. The thickness of the protective layer is preferably 0.01 to 10. Mu.m, more preferably 0.1 to 5. Mu.m. Examples of the method for forming the protective layer include a method of forming a protective layer by applying a resin composition for forming a protective layer dissolved in an organic solvent, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive material. Examples of the component constituting the protective layer include (meth) acrylic resin, alkene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polystyrene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, polyurethane resin, aromatic polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, si, C, W, al ₂O₃、Mo、SiO₂、Si₂N₄ and the like, and two or more of these components may be contained. For example, in the case of a protective layer for oxidation resistance, the protective layer preferably contains a polyol resin, siO ₂, and Si ₂N₄. In the case of a protective layer for the purpose of low reflection, the protective layer preferably contains a (meth) acrylic resin and a fluororesin.

In the case of forming the protective layer by applying the resin composition for forming the protective layer, a known method such as spin coating, casting, screen printing, or ink jet can be used as a method for applying the resin composition for forming the protective layer. The organic solvent contained in the resin composition for forming a protective layer may be any known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When the protective layer is formed by a chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) can be used as the chemical vapor deposition method.

The protective layer may contain organic/inorganic fine particles, an absorber of light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjuster, an antioxidant, an adhesive, a surfactant, and other additives as needed. Examples of the organic/inorganic fine particles include polymer fine particles (e.g., silicone fine particles, polystyrene fine particles, melamine fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, calcium carbonate, barium sulfate, and the like. The absorber for light of a specific wavelength can be a known absorber. The content of these additives can be appropriately adjusted, and is preferably 0.1 to 70 mass%, more preferably 1 to 60 mass%, relative to the total mass of the protective layer. Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of Japanese patent application laid-open No. 2017-151176 can be used.

The filter may also have the following structure: for example, each pixel is embedded in a space divided into a square by a partition wall. The resin composition of the present invention can be preferably used for the pixel structure described in international publication No. 2019/102887.

< Solid-state imaging element >

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

That is, a transfer electrode composed of a plurality of photodiodes and polysilicon or the like constituting a light receiving region of a solid-state imaging element (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide film semiconductor) image sensor or the like) is provided on a substrate, a light shielding film having only a light receiving portion opening of the photodiode is provided on the photodiodes and the transfer electrode, a device protection film composed of silicon nitride or the like is provided on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiodes, and a color filter is provided on the device protection film. The device protection film may have a light condensing mechanism (e.g., a microlens, etc. hereinafter, the same applies) on the lower side (side close to the substrate) of the color filter, or may have a light condensing mechanism on the color filter. The color filter may have the following structure: for example, each colored pixel is embedded in a space divided into a square by a partition wall. The refractive index of the partition wall at this time is preferably lower than that of each colored pixel. Examples of imaging devices having such a structure include those described in japanese patent application laid-open publication No. 2012-227478, japanese patent application laid-open publication No. 2014-179577, international publication No. 2018/043654, and U.S. patent application laid-open publication No. 2018/0040656. Further, as described in japanese patent application laid-open No. 2019-211559, an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance. The imaging device including the solid-state imaging element of the present invention can be used as a digital camera, an electronic device (such as a mobile phone) having an imaging function, an in-vehicle camera, and a monitoring camera. The solid-state imaging device incorporating the color filter of the present invention may incorporate other color filters, near infrared cut filters, organic photoelectric conversion films, and the like in addition to the color filter of the present invention.

< Image display device >

The image display device of the present invention has the film of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescent display device. The definition of the image display device and the details of each image display device are described in, for example, "electronic display device (zozuo zhaofu, kogyo Chosakai Publishing co., ltd., release in 1990)", "display device (isb, sangyo Tosho Publishing co., ltd., release in 1989)", and the like. The liquid crystal display device is described in, for example, "next-generation liquid crystal display technology (edited in Tian Longnan, kogyo Chosakai Publishing co., ltd., release 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

Examples

The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

< Measurement of weight average molecular weight (Mw) of sample >

The weight average molecular weight of the sample was measured by Gel Permeation Chromatography (GPC) under the following conditions.

Type of column: tubular column for connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000

Developing solvent: tetrahydrofuran (THF)

Column temperature: 40 DEG C

Flow rate (sample injection amount): 1.0. Mu.L (sample concentration: 0.1% by mass)

Device name: tosoh Corporation HLC-8230 GPC

A detector: RI (refractive index) detector

Calibration curve matrix resin: polystyrene resin

< Measurement of acid value of sample >

The acid value of the sample represents the mass of potassium hydroxide required for neutralizing the acidic component per 1g of the solid component in the sample. The acid value of the sample was measured as follows. Specifically, the measurement sample was dissolved in a tetrahydrofuran/water=9/1 (mass ratio) mixed solvent, and the obtained solution was subjected to neutralization titration with a 0.1mol/L aqueous potassium hydroxide solution AT 25℃using a potential difference titration apparatus (product name: AT-510,KYOTO ELECTRONICS MANUFACTURING CO, LTD.). The acid value was calculated from the following equation with the point of inflection of the titration pH curve as the titration end point.

A＝56.11×Vs×0.5×f/w

A: acid value (mgKOH/g)

Vs: the amount of 0.1mol/L aqueous potassium hydroxide solution (mL) required for titration

F: titration amount of 0.1mol/L aqueous potassium hydroxide solution

W: mass (g) of sample (solid content conversion)

< Synthesis of blocking agent macromer >

Synthesis example 1-1 Synthesis example of end-capping agent macromer EDM-1

2.3G of 2-mercaptoethanol, 35g of epsilon-caprolactone and 0.5g of monobutyl tin oxide were added to a three-necked flask replaced with nitrogen gas, and the mixture was heated and stirred at 90℃for 2 hours and 120℃for 6 hours, whereby a polymer having SH groups and 0H groups at both ends of the polyester was obtained. After cooling to 5 ℃,0.5 g of acetyl chloride was added and further stirred for 2 hours, thereby sealing the end of OH group to obtain a polymer having a single-end SH group. Next, 4.1g of 2-acryloyloxyethyl isocyanate (manufactured by Karenz AOI, SHOWA DENKO K.K.) and 0.3g of a polymerization initiator (manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation) were added, and the mixture was heated and stirred at 80℃for 2 hours to effect an ene-thiol reaction, thereby obtaining a blocking agent macromonomer EDM-1.

Synthesis examples 1-2 and 1-3 of end capping agent macromers EDM-2 and EDM-3

In the same manner as in Synthesis example 1-1, end-capping agent macromers EDM-2 and EDM-3 were synthesized.

Synthesis examples 1-4 Synthesis example of end-capping agent macromer EDM-4

Into a three-necked flask replaced with nitrogen gas, 181.3g of methyl methacrylate and 200.2g of butyl acrylate were added, and the flask was diluted with 590g of propylene glycol monomethyl ether acetate. It was warmed to 75 ℃ under nitrogen. Then, 9.2g of 3-mercaptopropionic acid and 2.2g of a polymerization initiator (manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation) were added thereto, and the mixture was heated and stirred at 75℃for 8 hours under a nitrogen atmosphere. To the resulting polymer solution, 7.3g of thionyl chloride was added, and the mixture was further heated and stirred at 75℃for 2 hours. The weight average molecular weight of the resulting capping agent macromer EDM-4 was 7400.

Synthesis examples 1-5 Synthesis examples of end-capping agent macromer EDM-5

In the same manner as in Synthesis examples 1-4, an end-capping agent macromer EDM-5 was synthesized.

Synthesis examples 1-6 Synthesis example of end-capping agent macromer EDM-6

Into a three-necked flask replaced with nitrogen gas, 181.3g of methyl methacrylate and 200.2g of butyl acrylate were added, and the flask was diluted with 590g of propylene glycol monomethyl ether acetate. It was warmed to 75 ℃ under nitrogen. Then, 19.9g of 6-mercaptohexanol and 2.2g of a polymerization initiator (manufactured by V-601,FUJIFILM Wako Pure Chemica]Corporation) were added thereto, and the mixture was heated and stirred at 75℃for 8 hours under a nitrogen atmosphere. To the resulting polymer solution, 37.3g of pyromellitic anhydride was added, and the mixture was further heated and stirred at 75℃for 2 hours. Unreacted pyromellitic anhydride was removed as insoluble matter by filtration. The resulting capping reagent macromer EDM-6 had a weight average molecular weight of 2400.

Synthesis examples 1-7 Synthesis example of end-capping agent macromer EDM-7

In the same manner as in Synthesis examples 1-6, an end-capping agent macromer EDM-7 was synthesized.

Synthesis examples 1-8 Synthesis example of end-capping agent macromer EDM-8

6.1G of 6-mercaptohexanol, 35g of epsilon-caprolactone and 0.5g of monobutyl tin oxide were added to a three-necked flask replaced with nitrogen gas, and the mixture was heated and stirred at 90℃for 2 hours and 120℃for 6 hours, thereby obtaining a polymer having SH groups and 0H groups at both ends of the polyester. After cooling to 5 ℃, 0.5g of acetyl chloride was added and stirred for a further 2 hours, thereby sealing the OH ends to obtain a polymer having a single end SH. Next, 5.5g of itaconic anhydride and 0.3g of a polymerization initiator (manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation) were added, and the mixture was heated and stirred at 80℃for 2 hours to effect an ene-thiol reaction, thereby obtaining a blocking agent macromer EDM-8.

Synthesis examples 1-9 to 1-15 blocking agent macromers EDM-9 to EDM-15

In the same manner as in Synthesis examples 1 to 8, end-capping agent macromers EDM-9 to EDM-15 were synthesized.

Synthesis examples 1 to 16 blocking agent macromer EDM-16

To a three-necked flask replaced with nitrogen gas were added 281.3g of methyl methacrylate and 100.2g of butyl acrylate, and the mixture was diluted with 590g of propylene glycol monomethyl ether acetate. It was warmed to 75 ℃ under nitrogen. Then, 13.9g of a chain transfer agent (AAA-1) and 2.5g of a polymerization initiator (manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation) were added thereto, and the mixture was heated and stirred at 75℃for 8 hours under a nitrogen atmosphere. The resulting capping reagent macromer EDM-16 had a weight average molecular weight of 7400.

[ Chemical formula 39]

Synthesis examples 1-17 to 1-20 blocking agent macromers EDM-17 to EDM-20

In the same manner as in Synthesis examples 1 to 16, end-capping agent macromers EDM-17 to EDM-20 were synthesized.

Synthesis examples 1 to 21 blocking agent macromer EDM-21

In a three-necked flask replaced with nitrogen gas, 151.3g of methyl methacrylate and 230.2g of butyl acrylate were added, and the flask was diluted with 590g of propylene glycol monomethyl ether acetate. It was warmed to 75 ℃ under nitrogen. Then, 20.9g of 6-mercaptohexanol and 2.0g of a polymerization initiator (manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation) were added thereto, and the mixture was heated and stirred at 75℃for 8 hours under a nitrogen atmosphere. The obtained polymer solution having terminal hydroxyl groups was cooled to 5℃and 32.1g of trimellitic anhydride chloride was added thereto, and 15.3g of pyridine was added dropwise over 6 hours. Stirring was continued for a further 24 hours at room temperature, and insoluble materials were filtered off. The weight average molecular weight of the resulting capping agent macromer EDM-21 was 7800.

Synthesis examples 1-22 to 1-40 blocking agent macromers EDM-22 to EDM-40

In the same manner as in Synthesis examples 1-21, end-capping agent macromers EDM-22 to EDM-40 were synthesized.

The structure and weight average molecular weight (Mw) of the capping agent macromers EDM-1 to EDM-40 are shown below. In Poly, the numbers of repeating units labeled with EDM-1 to EDM-3, EDM-8 to EDM-15, and EDM-27 to EDM-29 represent the number of repeating units, and the numbers of repeating units labeled with EDM-4, EDM-6, EDM-16, EDM-19 to EDM-21, EDM-24 to EDM-26, EDM-30, EDM-33 to EDM-36, EDM-39, and EDM-40 represent the molar ratio of repeating units. The structure described in Poly is P ¹ of formula (1).

TABLE 1

TABLE 2

TABLE 3

< Synthetic example of resin >

Synthesis of resin B-1 (Synthesis example 2-1)

3.3G of 1, 3-phenylenediamine (diamine DA-1:Tokyo Chemical Industry Co, manufactured by ltd.) was added to a three-necked flask replaced with nitrogen, 10g of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 40 ℃. To this was added 2.2g of pyromellitic anhydride (acid dianhydride AA-1:Tokyo Chemical Industry Co, manufactured by ltd. And manufactured by koku corporation), and stirred at 40 ℃ for 6 hours, thereby obtaining an amic acid prepolymer having amino groups at both ends. To this prepolymer solution was added 19g (in terms of solid content) of a capping agent macromonomer EDM-1, and the mixture was heated and stirred at 40℃for 2 hours, thereby obtaining a 30% propylene glycol monomethyl ether acetate solution of resin B-1. The weight average molecular weight of the obtained resin B-1 was 20600 and the acid value was 55mgKOH/g.

Synthesis of resins B-2 to B-93 (Synthesis examples 2-2 to 2-93)

Resins B-2 to B-93 were synthesized in the same manner as in Synthesis example 2-1 except that the acid dianhydride, diamine, blocking agent macromer, and blocking agent were changed to the types and the amounts added as shown in the following tables. The weight average molecular weight (Mw) and the acid value of each resin are collectively shown in the following table.

TABLE 4

TABLE 5

TABLE 6

The end-capping agent macromers EDM-1 to EDM-40 are respectively compounds with the structures. The acid dianhydrides AA-1 to AA-8, diamines DA-1 to DA-7 and end-capping agents ED-1 to ED-3 are each compounds having the structures shown below.

[ Chemical formula 40]

[ Chemical formula 41]

[ Chemical formula 42]

< Preparation of Dispersion liquid >

After the mixed solution obtained by mixing the raw materials described in the following table was mixed and dispersed for 3 hours by a bead mill (using 0.3mm diameter zirconium dioxide beads), the mixture was further dispersed by a high-pressure dispersing machine NANO-3000-10 (manufactured by Japan BEE Co., ltd.) equipped with a pressure reducing mechanism at a flow rate of 500 g/min under a pressure of 2000 MPa. This dispersion treatment was repeated 10 times to obtain each dispersion.

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

The numerical values described in the above tables are in parts by mass. Of the raw materials shown in the above table, the raw materials expressed by abbreviations are described in detail below.

[ Color material ]

PR264: c.i. pigment red 264 (red pigment, diketopyrrolopyrrole pigment)

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

PR179: c.i. pigment Red 179

PB15:6: c.i. pigment blue 15:6 (blue pigment, phthalocyanine pigment)

PB16: c.i. pigment blue 16 (blue pigment, phthalocyanine pigment)

PG7: c.i. pigment green 7

PG36: c.i. pigment green 36

PG58: c.i. pigment green 58

PY129: c.i. pigment yellow 129

PY185: C.I. pigment yellow 185

PY215: c.i. pigment yellow 215

PV23: c.i. pigment violet 23

IRGAPHORE: irgaphor Black S0100 CF (Compound of the following Structure, lactam pigment manufactured by BASF Co.)

[ Chemical formula 43]

PBk32: C.I. pigment Black 32 (Compound of the following Structure, perylene pigment)

[ Chemical formula 44]

[ Pigment derivative ]

Derivative 1: compounds of the structure

[ Chemical formula 45]

Derivative 2: compounds of the structure

[ Chemical formula 46]

[ Resin (dispersant) ]

(Specific resin)

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

(Comparative resin)

CB-1: the resin having the following structure (wherein the weight average molecular weight is 10885, the acid value is 74mgKOH/g. "Polym" means that the repeating unit of the structure represented by "Polym" is bonded to the sulfur atom (S) by the number of the attached number.)

[ Chemical formula 47]

[ Solvent ]

C-1: propylene glycol monomethyl ether acetate

C-2: propylene glycol monomethyl ether

C-3: cyclohexanone

< Production of resin composition >

Resin compositions of examples and comparative examples were prepared by mixing the raw materials described in the following table.

TABLE 15

TABLE 16

TABLE 17

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

[ Dispersion liquid ]

Dispersions R1 to R26, B1 to B25, G1 to G27, bk1 to Bk20, CR1, CB1, CG1, CBk1 to 3: the above dispersion

[ Resin ]

Ba-1: the resin having the following structure (the number indicated in the main chain is a molar ratio, the weight average molecular weight is 11000)

[ Chemical formula 48]

Ba-2: the resin of the following structure (the number marked in the main chain is molar ratio, weight average molecular weight is 15000)

[ Chemical formula 49]

Ba-3: the resin having the following structure (the number noted in the main chain is the molar ratio. The sum of x, y and z is 50. Mw=15000)

[ Chemical formula 50]

Bb-1: the resin having the following structure (the number indicated in the main chain is the molar ratio, the weight average molecular weight is 13000)

[ Chemical formula 51]

[ Polymerizable monomer ]

D-1: acrylic acid ester compound (KAYARAD DPHA, nippon Kayaku co., ltd. Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

D-2: epoxy compound (tetra D-X, MITSUBISHI GAS CHEMICAL COMPANY, manufactured by INC. Co., ltd., N, N, N ', N' -tetraepoxypropyl-m-xylylenediamine)

D-3: oxycyclobutane compounds (OXT-221, TOAGOSEI CP., LTD. Manufactured by LTD, 3-ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetan)

D-4: oxycyclobutane compounds (OX-SQ TX-100, TOAGOSEI CO., LTD.)

[ Photopolymerization initiator ]

E-1: omnirad 379EG (IGM RESINS B.V. Co., ltd., 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one)

E-2: irgacure OXE01 (oxime Compound manufactured by BASF Co., ltd.)

E-3: compounds of the structure

[ Chemical formula 52]

[ Solvent ]

C-1: propylene glycol monomethyl ether acetate

C-2: propylene glycol monomethyl ether

C-3: cyclohexanone

< Evaluation >

[ Evaluation of dispersibility ]

(Storage stability)

In each of examples and comparative examples, the viscosity (mpa·s) of the resin composition was measured by "RE-85L" manufactured by Toki Sangyo Co., ltd. After the above measurement, the resin composition was allowed to stand at 45℃under light-shielding conditions for 3 days, and the viscosity (mPas) was measured again. The storage stability was evaluated based on the difference in viscosity (Δvis) before and after leaving to stand, according to the following evaluation criteria. It can be said that the smaller the value of the viscosity difference (. DELTA.Vis), the better the storage stability of the resin composition and the better the dispersibility of the pigment. The viscosity measurements were carried out in a laboratory in which the temperature and humidity were controlled at 22.+ -. 5 ℃ and 60.+ -. 20% and the temperature of the resin composition was adjusted to 25 ℃.

Evaluation criterion-

A: ΔVis is 0.5 mPas or less.

B: ΔVis is greater than 0.5 mPas and less than 1.0 mPas.

C: ΔVis is greater than 1.0 mPas and less than 2.0 mPas.

D: ΔVis is greater than 2.0 mPas and less than 2.5 mPas.

E: ΔVis is greater than 2.5 mPas.

(Particle size)

The method according to JIS8826:2005 (HORIBA, manufactured by ltd. Under LB-500), the resin composition obtained above was packaged in 20ml sample bottles, and diluted with propylene glycol monomethyl ether acetate to adjust the solid content to 0.2 mass%. The data of the above-mentioned diluted solution were read 50 times at a temperature of 25℃using a 2ml quartz cell for measurement, and the arithmetic average particle diameter (number average particle diameter) of the obtained number-based pigment was obtained. The smaller the value of the number average particle diameter of the pigment, the better the dispersibility of the pigment can be said.

Evaluation criterion-

A: the number average particle diameter of the pigment is 0.05 μm or less.

B: the number average particle diameter of the pigment is more than 0.05 μm and less than 0.10 μm.

C: the number average particle diameter of the pigment is more than 0.10 μm and less than 0.20 μm.

D: the number average particle diameter of the pigment is more than 0.20 μm and less than 0.50 μm.

E: the number average particle size of the pigment is greater than 0.50. Mu.m.

[ Evaluation of film shrinkage ]

In each of examples and comparative examples, the resin composition was coated on a glass substrate by spin coating, dried at 100℃for 120 seconds (pre-baking) using a heating plate, and then heated at 200℃for 30 minutes (post-baking) using an oven, thereby producing a film having a thickness of 0.60. Mu.m. Regarding the film thickness, a part of the film was removed to expose the surface of the glass substrate, and the difference in height between the surface of the glass substrate and the coating film (film thickness of the coating film) was measured by a stylus type height difference meter (DektakXT, bruker Corporation). Next, the obtained film was heat-treated at 300℃for 5 hours under a nitrogen atmosphere. The film thickness of the film after the heat treatment was measured in the same manner, and the film shrinkage was determined according to the following formula, and the film shrinkage was evaluated according to the following evaluation criteria. The following T ₀ and T ₁ were measured in a laboratory in which the temperature and humidity were controlled at 22.+ -. 5 ℃ and 60.+ -. 20% and the substrate temperature was adjusted to 25 ℃. It can be said that the smaller the film shrinkage, the more suppressed the film shrinkage, which is a preferable result.

Film shrinkage (%) = (1- (T ₁/T₀)) ×100

T ₀: film thickness of film immediately after production (=0.60 μm)

T ₁: film thickness after heat treatment at 300℃for 5 hours under nitrogen atmosphere

Evaluation criterion-

A: the film shrinkage is 1% or less.

B: the film shrinkage is greater than 1% and less than 5%.

C: the film shrinkage is more than 5% and less than 10%.

D: the shrinkage of the film is more than 10% and less than 30%.

E: the film shrinkage is greater than 30%.

[ Evaluation of crack ]

In each of examples and comparative examples, the resin composition was coated on a glass substrate by spin coating, dried at 100℃for 120 seconds (pre-baking) using a heating plate, and then heated at 200℃for 30 minutes (post-baking) using an oven, thereby producing a film having a thickness of 0.60. Mu.m. Next, an inorganic film was formed by laminating 200nm SiO ₂ on the surface of the obtained film by a sputtering method. The film having the inorganic film formed on the surface was heat-treated at 300℃for 5 hours under a nitrogen atmosphere. The surface of the heat-treated inorganic film was observed with an optical microscope, and the number of cracks per 1cm ² was counted, and the presence or absence of cracks was evaluated according to the following evaluation criteria.

Evaluation criterion-

A: the number of cracks per 1cm ² was 0.

B: the number of cracks per 1cm ² is 1-10.

C: the number of cracks per 1cm ² is 11 to 50.

D: the number of cracks per 1cm ² is 51 to 100.

E: the number of cracks per 1cm ² is 101 or more.

TABLE 18

TABLE 19

TABLE 20

When the resin composition of example was used, the storage stability and the evaluation of particle diameter were both excellent, and the dispersibility of pigment was excellent, as compared with the case of using the resin composition of comparative example. In addition, when the resin composition of example was used, the film shrinkage was smaller than that of the resin composition of comparative example, and the occurrence of cracks was suppressed. Therefore, it can be said that the process window in the process after the film is manufactured can be enlarged as compared with the resin composition of the comparative example.

(Example 1000 patterning by photolithography)

The resin composition of example 1 was spin-coated on a silicon wafer, and after drying at 100℃for 120 seconds (pre-baking) using a heating plate, heating at 200℃for 30 minutes (post-baking) using an oven, thereby producing a resin composition layer having a thickness of 0.60. Mu.m. Next, a mask pattern having 1 side of a 1.1 μm square non-mask portion arranged in a 4mm X3 mm region was used to expose the resin composition layer by irradiation with light having a wavelength of 365nm at an exposure dose of 500mJ/cm ² using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.). Next, the silicon wafer on which the resin composition after exposure was formed was placed on a horizontal turntable of a rotary/shower developing machine (DW-30 model, CHEMITRONICS co., ltd.) and subjected to puddle development at 23 ℃ for 60 seconds using a developing solution (CD-2000,FUJIFILM F1ectronic Materials Co, ltd.). Next, the silicon wafer was rotated at 50rpm, and pure water was supplied in a shower-like manner from above the rotation center thereof by a discharge nozzle to perform a rinsing process, followed by spray drying, thereby forming a pattern (pixels).

The fabricated silicon wafer with pixels was divided into 2 pieces, and 1 piece of the silicon wafer was heat-treated at 300℃for 5 hours under a nitrogen atmosphere (hereinafter, 1 piece was used as a 300℃heat-treated substrate, and the other was used as a 300℃heat-treated substrate). As a result of evaluating the cross sections of the pixels formed on the substrate before and after 300 ℃ heat treatment by a Scanning Electron Microscope (SEM), the height (thickness) of the pixels formed on the substrate after 300 ℃ heat treatment was 97% of the height (thickness) of the pixels formed on the substrate before 300 ℃ heat treatment.

Claims

1. A resin composition comprising a pigment-containing color material A, a resin B and a solvent C,

The resin B comprises a resin B-1 having a structure represented by the formula (1),

In formula (1), X ¹ represents a 4-valent linking group,

X ² represents a 2-valent linking group,

R ¹¹、R¹²、R²¹、R²² and R ²³ each independently represent a hydrogen atom or a substituent,

Lp ¹ represents an n+1 valent linking group,

Lp ² represents a 2-valent linking group,

P ¹ represents a polymer chain, the polymer chain represented by P ¹ comprises a repeating unit represented by any one of the formulas (P1-1) to (P1-5),

N represents an integer of 1 or more,

Wherein R ^G1 and R ^G2 each represent an alkylene group,

R ^G3 represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a hydroxymethyl group,

Q ^G1 represents-O-or-NR ^q-,R^q represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

L ^G1 represents a single bond or arylene,

L ^G2 represents a single bond or a 2-valent linking group,

R ^G4 represents a hydrogen atom or a substituent.

2. The resin composition according to claim 1, wherein,

Lp ² of the formula (1) is-O-or-S-.

3. The resin composition according to claim 1 or 2, wherein,

X ¹ in the formula (1) is a group containing an aromatic hydrocarbon ring.

4. The resin composition according to claim 1 or 2, wherein,

X ² in the formula (1) is a group containing a fluorine atom and an aromatic hydrocarbon ring.

5. The resin composition according to claim 1, wherein,

The substituent represented by R ^G4 is at least 1 selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group and a t-butyl group.

6. The resin composition according to claim 1 or 2, wherein,

The structure represented by the formula (1) is a structure represented by the formula (1-1),

In the formula (1-1), X ¹ represents a 4-valent linking group,

X ² represents a 2-valent linking group,

Rp ¹¹ represents a substituent, m Rp ¹¹ are the same or different,

Lp ¹¹ represents an n+1 valent linking group,

Lp ² represents a 2-valent linking group,

P ¹ represents a polymer chain, the polymer chain represented by P ¹ comprises a repeating unit represented by any one of the formulae (P1-1) to (P1-5),

N represents an integer of 1 or more,

M represents an integer of 0 to 4.

7. The resin composition according to claim 1 or 2, wherein,

8. The resin composition according to claim 1 or 2, wherein,

9. The resin composition according to claim 1 or 2, further comprising a polymerizable monomer.

10. The resin composition according to claim 1 or 2, further comprising a photopolymerization initiator.

11. A film obtained using the resin composition according to claim 1 or 2.

12. A filter having the film of claim 11.

13. A solid-state imaging element having the film according to claim 11.

14. An image display device having the film of claim 11.

15. A resin comprising a structure represented by formula (1),

In formula (1), X ¹ represents a 4-valent linking group,

X ² represents a 2-valent linking group,

Lp ¹ represents an n+1 valent linking group,

Lp ² represents a 2-valent linking group,

N represents an integer of 1 or more,

Wherein R ^G1 and R ^G2 each represent an alkylene group,

Q ^G1 represents-O-or-NR ^q-,R^q represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, L ^G1 represents a single bond or an arylene group,

L ^G2 represents a single bond or a 2-valent linking group,

R ^G4 represents a hydrogen atom or a substituent.