KR20230016676A - Resin composition, film, optical filter, solid-state imaging device, image display device, resin and compound - Google Patents

Abstract

식 (1) 중, X¹은 4가의 연결기를 나타내고, X²는 2가의 연결기를 나타내며, R¹¹, R¹², R²¹, R²² 및 R²³은, 각각 독립적으로 수소 원자 또는 치환기를 나타내고, Lp¹은 n+1가의 연결기를 나타내며, Lp²는 2가의 연결기를 나타내고, P¹은 폴리머쇄를 나타내며, n은 1 이상의 정수를 나타낸다.The resin composition containing color material A containing a pigment, resin B, and solvent C, and resin B containing resin b-1 containing the structure represented by Formula (1). A film obtained by using the resin composition, an optical filter, a solid-state imaging device, an image display device, a resin, and a compound.

In formula (1), X ¹ represents a tetravalent linking group, X ² represents a divalent linking group, R ¹¹ , R ¹² , R ²¹ , R ²² 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 divalent linking group, P ¹ represents a polymer chain, and n represents an integer greater than or equal to 1.

Description

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

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

BACKGROUND OF THE INVENTION [0002] In recent years, demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased due to the spread of digital cameras, camera-equipped mobile phones, and the like. A film containing a pigment such as a color filter is used for a solid-state imaging device. A film containing a color material such as a color filter is manufactured using, for example, a resin composition containing a pigment, a resin, and a solvent.

For example, in Patent Document 1, as a resin composition containing a pigment, a dispersant, a binder resin, an epoxy compound, and a solvent, the dispersant is at least one selected from tetracarboxylic anhydride (b1) and tricarboxylic acid anhydride (b2). Formed by radical polymerization of the polyester moiety X1' having a carboxyl group, which is formed by reacting the acid anhydride group in the acid anhydride group with the hydroxyl group in the hydroxyl group-containing compound (a), and the ethylenically unsaturated monomer (c), and also a thermal crosslinkable functional group A dispersing agent having a vinyl polymer portion X2' having a thermal crosslinkable functional group, which is at least one member selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a block isocyanate group, and a (meth)acryloyl group. An invention relating to a resin composition containing (X) is described.

Patent Document 1: Japanese Unexamined Patent Publication No. 2016-170325

In the resin composition containing a pigment, a resin, and a solvent, it is preferable that the dispersibility of the pigment is good. If the dispersibility of the pigment is insufficient, the pigment aggregates and becomes coarse in the resin composition, or the viscosity of the resin composition tends to increase. Moreover, even if the viscosity of the resin composition immediately after manufacture is low, the viscosity may increase with time.

According to the study of the present inventors, it was found that even in the resin composition described in Patent Document 1, the dispersibility of the pigment is not sufficient, and there is room for further improvement.

Accordingly, an object of the present invention is to provide a resin composition having excellent pigment dispersibility. Moreover, the objective of this invention is providing the film|membrane using a resin composition, an optical filter, a solid-state image sensor, and an image display apparatus. Moreover, the objective of this invention is providing resin and a compound.

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

<1> A color material A containing a pigment;

Resin B,

Contains solvent C,

The said resin B contains resin b-1 containing the structure represented by Formula (1),

resin composition;

[Formula 1]

In Formula (1), X ¹ represents a tetravalent linking group;

X ² represents a divalent linking group;

R ¹¹ , R ¹² , R ²¹ , R ²² 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 divalent linking group;

P ¹ represents a polymer chain,

n represents an integer greater than or equal to 1;

<2> The resin composition according to <1>, wherein Lp ² in Formula (1) is -O- or -S-.

<3> The resin composition according to <1> or <2>, wherein X ¹ 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 X ² in the formula (1) is a group containing a fluorine atom and an aromatic hydrocarbon ring.

<5> The polymer chain represented by P ¹ contains repeating units of at least one structure selected from a poly(meth)acrylic structure, a polystyrene structure, a polyether structure, and a polyester structure, from <1> to < The resin composition described in any one of 4>.

<6> The resin composition according to any one of <1> to <4>, wherein the polymer chain represented by P ¹ includes a repeating unit represented by any one of formulas (P1-1) to (P1-6);

[Formula 2]

In the formula, 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 an arylene group;

L ^G2 represents a single bond or a divalent linking group;

R ^G4 represents a hydrogen atom or a substituent;

R ^G5 represents a hydrogen atom or a methyl group, and R ^G6 represents an aryl group.

<7> The resin composition according to <6>, wherein the substituent represented by R ^G4 is at least one selected from an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a t-butyl group.

<8> resin composition according to any one of <1> to <7>, wherein the structure represented by formula (1) is a structure represented by formula (1-1);

[Formula 3]

In formula (1-1), X ¹ represents a tetravalent linking group;

X ² represents a divalent linking group;

R ¹¹ , R ¹² , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a substituent;

Rp ¹¹ represents a substituent, m Rp ¹¹ may be the same or different,

Lp ¹¹ represents an n+1 valent linking group;

Lp ² represents a divalent linking group;

P ¹ represents a polymer chain;

n represents an integer greater than or equal to 1;

m represents an integer from 0 to 4;

<9> The resin composition according to any one of <1> to <8>, wherein the solvent C contains at least one selected from ester solvents, ether solvents, alcohol solvents, and ketone solvents.

<10> The resin composition according to any one of <1> to <9>, in which the color material A contains at least one 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 by using the resin composition according to any one of <1> to <12>.

<14> An optical filter having the film according to <13>.

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

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

<17> Resin containing the structure represented by Formula (1);

[Formula 4]

In Formula (1), X ¹ represents a tetravalent linking group;

X ² represents a divalent linking group;

R ¹¹ , R ¹² , R ²¹ , R ²² 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 divalent linking group;

P ¹ represents a polymer chain,

n represents an integer greater than or equal to 1;

<18> A compound represented by formula (EDM1);

[Formula 5]

In formula (EDM1), R ^ED1 represents an acid anhydride group;

Lp ^ED1 represents an n+1 valent group, and the n+1 valent group is a hydrocarbon group, or a hydrocarbon group and -NRp ^ED1 -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ^ED1 CO- and -CONRp ^ED1 - is a group having a structure combining at least one group selected from,

Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;

Lp ^ED2 represents -O- or -S-;

P ^ED1 represents a polymer chain containing a repeating unit represented by any one of formulas (P1-1) to (P1-4);

n represents an integer of 1 to 4;

[Formula 6]

In formulas (P1-1) to (P1-4), R ^G1 and R ^G2 each represent an alkylene group.

<19> The compound represented by the formula (EDM1) is the compound described in <18>, which is a compound represented by the formula (EDM2);

[Formula 7]

In formula (EDM2), R ^ED12 represents a halogen atom, an alkyl group, a carboxy group or a hydroxy group;

Lp ^ED1a represents an n+1 valent group, wherein the n+1 valent group is a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded together with a single bond or a linking group, and the linking group is -NRp ^ED1 -, -SO -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ^ED1 CO- or -CONRp ^ED1 ;

Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;

Lp ^ED2 represents -O- or -S-;

P ^ED1 represents a polymer chain containing a repeating unit represented by any one of the formulas (P1-1) to (P1-4);

r represents an integer from 0 to 3,

n represents the integer of 1-4.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in the dispersibility of a pigment can be provided. Moreover, a film|membrane, an optical filter, a solid-state image sensor, and an image display apparatus using a resin composition can be provided. In addition, resins and compounds can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the main embodiment of this invention is described. However, the present invention is not limited to the specific embodiments.

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

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

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

In the present specification, the (meth)allyl group represents either or both of allyl and methallyl, and "(meth)acrylate" represents both or either of acrylate and methacrylate, “(Meth)acryl” represents either or both of acryl and methacryl, and “(meth)acryloyl” represents both or either of acryloyl and methacryloyl.

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

In this specification, near-infrared rays refer to light with a wavelength of 700 to 2500 nm.

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

In this specification, the word "process" does not refer only to an independent process, and even if it cannot be clearly distinguished from other processes, if the intended action of the process is achieved, it is included in the term.

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

In this specification, a symbol (for example, A, etc.) added before or after a name is a term used to distinguish components, and the type of components, the number of components, and do not limit the superiority or inferiority of components.

<Resin composition>

The resin composition of the present invention includes a color material A containing a pigment, a resin B, and a solvent C, and the resin B contains a structure represented by formula (1). Resin b-1 (hereinafter also referred to as a specific resin) It is characterized by including).

The resin composition of the present invention is excellent in pigment dispersibility. Although the detailed reason why such an effect is obtained is unknown, in a specific resin, an amide group (-C(=O)-NR ²¹ -, -C(=O)-NR ²² -) is bonded to X ¹ , which is a tetravalent linking group. Since it has such a structure, adsorption of a specific resin to the surface of the pigment is promoted, and since this specific resin has a polymer chain P ¹ , the polymer chain P ¹ becomes a steric repulsion group, such as aggregation of pigments. can be suppressed, and as a result, it is estimated that a resin composition with excellent pigment dispersibility was able to be obtained.

In addition, by using the resin composition of the present invention, it is possible to form a film having excellent heat resistance that is difficult to decompose even at a high temperature and hardly causes film shrinkage even after heat treatment at a high temperature. For this reason, after forming a film using the resin composition of the present invention, even if the obtained film is heat treated at a high temperature (for example, 300° C. or higher), film shrinkage is suppressed and another film such as an inorganic film is formed on the film. Even in the case of forming such a film, it is possible to suppress the occurrence of cracks or the like in other films. For this reason, according to the resin composition of this invention, the process window of the process after manufacturing a film|membrane can be widened.

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

In addition, the thickness of the film after heat treatment at 350 ° C. 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 heat treatment.

Further, the thickness of the film after heat treatment at 400 ° C. 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 heat treatment.

The above physical properties can be achieved by methods such as adjusting the type or content of the specific resin used.

In addition, when a film having a thickness of 0.60 μm was formed by heating at 200° C. for 30 minutes using the resin composition of the present invention, when the film was heat-treated at 300° C. for 5 hours in a nitrogen atmosphere, the following formula (A1 ) is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, and particularly preferably 35% or less.

ΔA(%)=|100-(A2/A1)×100|... (A1)

ΔA is the rate of change in absorbance of the film after heat treatment;

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

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

The above physical properties can be achieved by methods such as adjusting the type or content of the specific resin used.

In addition, when a film having a thickness of 0.60 μm is formed by heating at 200° C. for 30 minutes using the resin composition of the present invention, the wavelength λ1 representing the maximum value of absorbance in the wavelength range of 400 to 1100 nm of the film and nitrogen nitrogen for the film The absolute value of the difference between the wavelengths λ2 representing the maximum absorbance value of the film after heat treatment at 300° C. for 5 hours in an atmosphere is preferably 50 nm or less, more preferably 45 nm or less, and still more preferably 40 nm or less.

The above physical properties can be achieved by methods such as adjusting the type or content of the specific resin used.

In addition, when a film having a thickness of 0.60 μm was formed by heating at 200° C. for 30 minutes using the resin composition of the present invention, when the film was heat-treated at 300° C. for 5 hours in a nitrogen atmosphere, the wavelength of the film after heat treatment was 400 to 1100 nm. The maximum value of the absorbance change rate ΔA _λ in the range of is preferably 30% or less, more preferably 27% or less, and still more preferably 25% or less. In addition, the change rate of absorbance is a value computed from following formula (2).

ΔA _λ =|100-(A2 _λ /A1 _λ )×100|... (2)

ΔA _λ is the rate of change in absorbance at the wavelength λ of the film after heat treatment;

A1 _λ is the absorbance at the wavelength λ of the film before heat treatment;

A2 _λ is the absorbance at the wavelength λ of the film after heat treatment.

The above physical properties can be achieved by methods such as adjusting the type or content of the specific resin used.

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

Examples of the color filter include a filter having a colored pixel that transmits light of a specific wavelength, and at least one colored pixel selected from a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel. It is preferable that it is a filter with A color filter can be formed using the resin composition containing a chromatic color material.

As a near-infrared cutoff filter, the filter whose maximum absorption wavelength exists in the range of wavelength 700-1800nm is mentioned. The maximum absorption wavelength of the near-infrared cut filter preferably exists in a range of wavelengths of 700 to 1300 nm, and more preferably in a range of wavelengths of 700 to 1100 nm. In addition, the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Moreover, it is preferable that the transmittance|permeability at at least 1 point in the range of wavelength 700-1800nm is 20 % or less. Further, the absorbance Amax/absorbance A550, which is the ratio between the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter and the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500, and 70 More preferably ~ 450, particularly preferably 100 ~ 400. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing colorant.

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

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

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

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

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

(5): The maximum value of the transmittance in the range of wavelengths 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelengths 1200 to 1500 nm 70% or more (preferably 75% or more, more preferably 80% or more).

As a preferable aspect of the spectral characteristics of the resin composition of the present invention, when a film having a thickness of 5 μm is formed using the resin composition, the maximum value of the transmittance of light in the thickness direction of the film in the range of wavelength 360 to 700 nm is An aspect satisfying the spectral characteristics of 50% or more is exemplified. A resin composition satisfying such spectral characteristics can be suitably used as a resin composition for pixel formation of a color filter. Specifically, it 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 colors.

It is preferable that the resin composition provided with said spectral characteristic contains a chromatic color material. For example, a resin composition containing a red color material and a yellow color material can be preferably used as a resin composition for red pixel formation. In addition, a resin composition containing a blue color material and a purple color material can be preferably used as a resin composition for forming blue pixels. In addition, a resin composition containing a green color material can be suitably used as a resin composition for forming green or cyan color pixels. When using a resin composition as a resin composition for green pixel formation, it is also preferable to further contain a yellow color material other than a green color material.

As another preferred aspect of the spectral characteristics of the resin composition of the present invention, the spectral characteristics in which Amin/B, which is the ratio between the minimum absorbance value Amin in the wavelength range of 400 to 640 nm and the absorbance B in the wavelength range of 1500 nm, is 5 or more. conditions that are being satisfied. A resin composition that satisfies such spectral characteristics can be preferably used as a resin composition for forming a near-infrared transmission filter. The value of Amin/B, which is the ratio of absorbance, 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 by the following formula (λ1).

Aλ=-log(Tλ/100)… (λ1)

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

In the present invention, the absorbance value may be a value measured in a solution state or a value of a film formed using the composition. When the absorbance is measured in a film state, it is preferable to measure the absorbance using a film obtained by coating the composition on a glass substrate by a method such as spin coating and drying it at 100° C. for 120 seconds using a hot plate or the like.

The resin composition of the present invention preferably satisfies any one of the spectral characteristics of (Ir1) to (Ir5) below.

(Ir1): The value of A1 / B1, which is the ratio of the minimum absorbance A1 in the wavelength range of 400 to 640 nm and the maximum absorbance value B1 in the wavelength range of 800 to 1500 nm, is 4.5 or more, preferably 7.5 or more, It is more preferably 15 or more, and more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in a wavelength range of 400 to 640 nm and transmitting light exceeding a wavelength of 750 nm.

(Ir2): The value of A2/B2, which is the ratio of the minimum absorbance A2 in the wavelength range of 400 to 750 nm and the maximum absorbance value B2 in the wavelength range of 900 to 1500 nm, is 4.5 or more, preferably 7.5 or more, It is more preferably 15 or more, and more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in a wavelength range of 400 to 750 nm and transmitting light exceeding a wavelength of 850 nm.

(Ir3): The value of A3/B3, which is the ratio between the minimum absorbance value A3 in the wavelength range of 400 to 830 nm and the maximum absorbance value B3 in the wavelength range of 1000 to 1500 nm, is 4.5 or more, preferably 7.5 or more, It is more preferably 15 or more, and more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in a wavelength range of 400 to 830 nm and transmitting light exceeding a wavelength of 950 nm.

(Ir4): The value of A4/B4, which is the ratio between the minimum value of absorbance A4 in the range of wavelength 400 to 950 nm and the maximum value of absorbance B4 in the range of wavelength 1100 to 1500 nm, is 4.5 or more, preferably 7.5 or more, It is more preferably 15 or more, and more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in a wavelength range of 400 to 950 nm and transmitting light exceeding a wavelength of 1050 nm.

(Ir5): The value of A5 / B5, which is the ratio of the minimum value of absorbance A5 in the range of wavelength 400 to 1050 nm and the maximum value of absorbance B5 in the range of wavelength 1200 to 1500 nm, is 4.5 or more, preferably 7.5 or more, It is more preferably 15 or more, and more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in a wavelength range of 400 to 1050 nm and transmitting light exceeding a wavelength of 1150 nm.

It is also preferable that the resin composition of this invention is a resin composition for pattern formation by the photolithography method. According to this aspect, it is possible to easily form pixels of fine size. For this reason, it can use especially suitably as a resin composition for pixel formation of an optical filter used for a solid-state image sensor. For example, a resin composition containing a component having an ethylenically unsaturated bond-containing group (for example, a resin having an ethylenically unsaturated bond-containing group or a monomer having an ethylenically unsaturated bond-containing group) and a photopolymerization initiator is obtained by a photolithography method. It can be used suitably as a resin composition for pattern formation of. It is also preferable that the resin composition for pattern formation in the photolithography method 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 or a resin composition for forming a light shielding film.

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

<Coloring material A>

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

The colorant preferably contains at least one selected from the group consisting of a chromatic colorant, a black colorant, and a near-infrared absorbing colorant, and more preferably contains at least one selected from the group consisting of a chromatic colorant and a near-infrared absorbing colorant. It is more preferable to include a chromatic colorant, and more preferably to include at least one chromatic colorant selected from the group consisting of a red colorant, a yellow colorant, a blue colorant, and a purple colorant.

In addition, the color material preferably contains a chromatic color material and a near-infrared absorbing colorant, and preferably contains two or more types of chromatic colorant and a near-infrared absorbing colorant. Moreover, black color may be formed by the combination of 2 or more types of chromatic color material. Moreover, it is also preferable that the color material contains a black color material and a near-infrared absorbing color material. According to these aspects, the resin composition of the present invention can be suitably used as a resin composition for forming a near-infrared transmission filter. For a combination of colorants forming black by a combination of two or more chromatic colorants, Japanese Patent Laid-Open No. 2013-077009, Japanese Unexamined Patent Publication No. 2014-130338, International Publication No. 2015/166779, etc. can be referred to. .

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

In addition, the pigments include phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, and quinopes. It is preferably containing at least one selected from talon pigments, and more preferably containing at least one selected from phthalocyanine pigments, diketopyrrolopyrrole pigments and pyrrolopyrrole pigments, It is more preferable to include a phthalocyanine pigment or a diketopyrrolopyrrole pigment. In addition, for the reason that it is easy to form a film whose spectral characteristics do not fluctuate even after heating to a high temperature (eg, 300 ° C. or higher), a phthalocyanine pigment having no central metal or a central metal as a phthalocyanine pigment , phthalocyanine pigments with copper or zinc are preferred.

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

(chromatic coloring material)

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

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, 235 (amino ketone system), 236 (amino ketone system), etc. (above, yellow pigment),

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 light (ideal, orange pigment),

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 (xanthene, Organo Ultramarine, Bluish Red), 295 (monoazo), 296 (diazo), 297 (amino ketone), etc. (above, red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine-based), 65 (phthalocyanine-based), 66 (phthalocyanine-based), etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (above, purple pigment),

C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoa Crude), 88 (metane based), etc. (above, blue pigment).

Among these chromatic pigments, C. I. Pigment Red 254, C. I. Pigment Red 264, and C. I. Pigment are red pigments because they tend to form films whose spectral characteristics do not fluctuate even after heating at a high temperature (eg, 300° C. or higher). Red 272, C. I. Pigment Red 122, C. I. Pigment Red 177 are preferred. Moreover, as a blue pigment, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C. I. Pigment Blue 15:6, and C. I. Pigment Blue 16 are preferable.

In addition, as a green pigment, a halogenated zinc 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 also be used. there is. As a specific example, the compound of international publication 2015/118720 is mentioned. Further, as a green pigment, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric acid ester as a ligand described in International Publication No. 2012/102395, and a phthalocyanine described in Japanese Laid-Open Patent Publication No. 2019-008014 An anine compound, the phthalocyanine compound of Unexamined-Japanese-Patent No. 2018-180023, the compound of Unexamined-Japanese-Patent No. 2019-038958, etc. can also be used.

Moreover, as a blue pigment, the aluminum phthalocyanine compound which has a phosphorus atom can also be used. As a specific example, Paragraph No. 0022 of Unexamined-Japanese-Patent No. 2012-247591 - 0030, and the compound of Paragraph No. 0047 of Unexamined-Japanese-Patent No. 2011-157478 are mentioned.

Moreover, as a yellow pigment, the compound of Unexamined-Japanese-Patent No. 2017-201003, the compound of Unexamined-Japanese-Patent No. 2017-197719, the compound of Paragraph No. 0011-0062, 0137-0276 of Unexamined-Japanese-Patent No. 2017-171912 , Compounds described in Paragraph Nos. 0010 to 0062, 0138 to 0295 of Japanese Laid-open Patent Publication No. 2017-171913, Paragraph Nos. 0011 to 0062, 0139 to 0190 of Japanese Unexamined Patent Publication No. 2017-171914, Compounds described in Japanese Unexamined Patent Publication No. 2017-171915 Paragraph Nos. 0010 to 0065, 0142 to 0222, the compound described in Paragraph Nos. 0011 to 0034 of Japanese Patent Application Laid-Open No. 2013-054339, the quinophthalone compound described in Paragraph Nos. 0013 to 0058 of Unexamined-Japanese-Patent No. 2014-026228 A nophthalone compound, an isoindoline compound described in Japanese Unexamined Patent Publication No. 2018-062644, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2018-203798, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2018-062578, Japan A quinophthalone compound described in Patent Publication No. 6432076, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2018-155881, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2018-111757, Japanese Unexamined Patent Publication No. 2018-040835 A quinophthalone compound described in, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2017-197640, a quinophthalone compound described in Japanese Unexamined Patent Publication No. 2016-145282, a quinophthalone described in Japanese Unexamined Patent Publication No. 2014-085565 A compound, a quinophthalone compound described in Japanese Laid-Open Patent Publication No. 2014-021139, a quinophthalone compound described in Japanese Laid-Open Patent Publication No. 2013-209614, a quinophthalone compound described in Japanese Laid-Open Patent Publication No. 2013-209435, Japanese Laid-Open Patent A quinophthalone compound described in Publication No. 2013-181015, and Japanese Unexamined Patent Publication No. 2013-061622 The described quinophthalone compound, the quinophthalone compound described in Japanese Patent Laid-Open No. 2013-032486, the quinophthalone compound described in Japanese Patent Laid-Open No. 2012-226110, the quinophthalone compound described in Japanese Patent Laid-Open No. 2008-074987 , A quinophthalone compound described in Japanese Laid-Open Patent Publication No. 2008-081565, a quinophthalone compound described in Japanese Laid-Open Patent Publication No. 2008-074986, a quinophthalone compound described in Japanese Laid-Open Patent Publication No. 2008-074985, Japanese Laid-Open Patent Publication A quinophthalone compound described in Japanese Patent Laid-Open No. 2008-050420, a quinophthalone compound described in Japanese Patent Laid-Open No. 2008-031281, a quinophthalone compound described in Japanese Patent Publication No. 48-032765, Japanese Patent Laid-Open No. 2019-008014 A quinophthalone compound described in, a quinophthalone compound described in Japanese Patent Publication No. 6607427, a compound described in Korean Laid-Open Patent Publication No. 10-2014-0034963, a compound described in Japanese Unexamined Patent Publication No. 2017-095706, a Taiwanese patent application A compound described in Japanese Laid-open Publication No. 201920495, a compound described in Japanese Patent Publication No. 6607427, a quinophthalone dimer described in Japanese Unexamined Patent Publication No. 2020-033521, a compound represented by the following formula (QP1), and the following formula (QP2) The compound shown can also be used. Moreover, what multimerized these compounds is also used preferably from a viewpoint of color value improvement.

[Formula 8]

In Formula (QP1), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. As a specific example of the compound represented by Formula (QP1), the compound described in Paragraph No. 0016 of Japanese Patent Publication No. 6443711 is mentioned.

[Formula 9]

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

As a red pigment, the diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in Japanese Laid-open Patent Publication No. 2017-201384, and the diketopyrrolopyrrole compound described in paragraph Nos. 0016 to 0022 of Japanese Patent Publication 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 Laid-Open No. 2012-229344, Japan A compound described in Patent Publication No. 6516119, a compound described in Japanese Patent Publication No. 6525101, and the like can also be used. As the red pigment, a compound having a structure in which an aromatic hydrocarbon group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic hydrocarbon ring is introduced is bonded to a diketopyrrolopyrrole skeleton can also be used. As such a compound, it is preferable that it is a compound represented by formula (DPP1), and it is more preferable that it is a compound represented by formula (DPP2).

[Formula 10]

In the above formula, R ¹¹ and R ¹³ each independently represent a substituent, R ¹² and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n11 and n13 each independently represent 0 to 4 represents an integer, X ¹² and X ¹⁴ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, when X ¹² is an oxygen atom or a sulfur atom, m12 represents 1, and when X ¹² is a nitrogen atom, , m12 represents 2, m14 represents 1 when X ¹⁴ is an oxygen atom or a sulfur atom, and m14 represents 2 when X ¹⁴ is a nitrogen atom. Examples of the substituent represented by R ¹¹ and R ¹³ include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an amide group, a cyano group, a nitro group, and trifluoro. A romethyl group, a sulfoxide group, a sulfo group, etc. are mentioned as preferable specific examples.

Regarding the diffraction angle that various pigments preferably have, descriptions of Japanese Patent Publication No. 6561862, Japanese Patent Publication No. 6413872, and Japanese Patent Publication No. 6281345 can be referred to, and these contents are incorporated herein by reference.

As chromatic dyes, pyrazolazo compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazolazo compounds, pyridonazo compounds, An anine compound, a phenothiazine compound, a pyrrolopyrazole azomethane compound, a xanthene compound, a phthalocyanine compound, a benzopyran compound, an indigo compound, and a pyromethene compound are mentioned. In addition, the metamine dye described in Japanese Unexamined Patent Publication No. 2019-073695, the metamine dye described in Japanese Patent Application Laid-Open No. 2019-073696, the metamine dye described in Japanese Unexamined Patent Publication No. 2019-073697, and Japanese Unexamined Patent Publication 2019- It is also possible to use the methine dyes described in 073698.

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

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

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

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

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

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

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

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

(white color material)

As the white color material, 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 and inorganic pigments (white pigments) such as particles and zinc sulfide. The white pigment is preferably a particle having a titanium atom, and more preferably a titanium oxide. Moreover, it is preferable that the white pigment is a particle having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. It is preferable that it is 2.10-3.00, and, as for the refractive index mentioned above, it is more preferable that it is 2.50-2.75.

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

The white pigment is not only composed of a single inorganic substance, but may also be used in combination with other materials. For example, core and shell composite particles composed of particles having pores or other materials inside, particles in which many inorganic particles are adhered to core particles, core particles composed of polymer particles and shell layers composed of inorganic nanoparticles, It is preferable to use As the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles, for example, the description of paragraphs No. 0012 to 0042 of Japanese Unexamined Patent Publication No. 2015-047520 can be referred to, and this content is incorporated herein.

As the white pigment, hollow inorganic particles can also be used. The hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and refers to an inorganic particle having a cavity surrounded by an outer shell. As hollow inorganic particles, the hollow inorganic particles described in Unexamined-Japanese-Patent No. 2011-075786, International publication 2013/061621, Unexamined-Japanese-Patent No. 2015-164881 etc. are mentioned, These content is integrated in this specification.

(black color material)

It does not specifically limit as a black color material, A well-known thing can be used. For example, as an inorganic black colorant, inorganic pigments (black pigment), such as carbon black, titanium black, and graphite, are mentioned, Carbon black and titanium black are preferable, and titanium black is more preferable. Titanium black is a black particle containing a titanium atom, and low-order titanium oxide or oxynitride titanium is preferable. The surface of titanium black can be modified as needed for the purpose of improving dispersibility, suppressing aggregation, and the like. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Moreover, treatment with a water repellent substance as shown in Japanese Unexamined Patent Publication No. 2007-302836 is also possible. As a black pigment, color index (C.I.) Pigment Black 1, 7 etc. are mentioned. Titanium black preferably has a small primary particle diameter and an average primary particle diameter of individual particles. Specifically, it is preferable that the average primary particle size is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to the range of 0.20 to 0.50 is exemplified. About the said dispersion, Paragraph 0020 of Unexamined-Japanese-Patent No. 2012-169556 - description of 0105 can be considered into consideration, and this content is integrated in this specification. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (trade name: Ako Kasei Note) and the like.

Moreover, as an organic black color material, a bisbenzofuranone compound, an azo metaine compound, a perylene compound, an azo compound, etc. are mentioned. Examples of the bisbenzofuranone compound include compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc. For example, "Irgaphor Available as "Black". As a perylene compound, Paragraph No. 0016 of Unexamined-Japanese-Patent No. 2017-226821 - the compound of 0020, C. I. Pigment Black 31, 32, etc. are mentioned. Examples of the azometaine compound include compounds described in Japanese Unexamined Patent Publication No. Hei 01-170601, Japanese Unexamined Patent Publication No. Hei 02-034664, etc. For example, as "Chromofine Black A1103" manufactured by Dainichi Seika Co., Ltd. can be obtained

The color material used in the resin composition of the present invention may be only the black color material described above or may further contain a chromatic color material. According to this aspect, it is easy to obtain a resin composition capable of forming a film having excellent light-shielding properties in the visible region. When a black colorant and a chromatic colorant are used together as the colorant, the mass ratio of both is preferably black colorant:chromatic colorant = 100:10 to 300, and more preferably 100:20 to 200. Moreover, it is preferable to use a black pigment as said black color material, and it is preferable to use a chromatic color pigment as said chromatic color material.

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

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

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

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

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

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

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

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

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

(Near-infrared absorbing colorant)

The near-infrared absorbing colorant is preferably a pigment, and more preferably an organic pigment. Further, the near-infrared absorbing colorant preferably has a maximum absorption wavelength in a range of more than 700 nm and 1400 nm or less. Further, the maximum absorption wavelength of the near-infrared absorbing colorant is preferably 1200 nm or less, more preferably 1000 nm or less, and still more preferably 950 nm or less. In the near-infrared absorbing colorant, A ₅₅₀ /A _max , which is a ratio of absorbance A ₅₅₀ at a wavelength of 550 nm and absorbance A _max at a maximum absorption wavelength, is preferably 0.1 or less, more preferably 0.05 or less, and further preferably 0.03 or less. It is preferable, and it is especially preferable that it is 0.02 or less. The lower limit is not particularly limited, but may be, for example, 0.0001 or more, or 0.0005 or more. When the above-described absorbance ratio is within the above range, a near-infrared absorbing colorant having excellent visible light transparency and near-infrared ray shielding properties can be obtained. In the present invention, the maximum absorption wavelength of the near-infrared absorbing colorant and the absorbance value at each wavelength are values obtained from the absorption spectrum of a film formed using a resin composition containing the near-infrared absorbing colorant.

The near-infrared absorbing colorant is not particularly limited, but is pyrrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterrylene compound, merocyanine compound, croconium compound, iodine A nol compound, an iminium compound, a dithiol compound, a triarylmethane compound, a pyromethene compound, an azomethane compound, an anthraquinone compound, a dibenzofuranone compound, a dithiorene metal complex, etc. are mentioned. As a pyrrolopyrrole compound, the compound of Paragraph No. 0016 of Unexamined-Japanese-Patent No. 2009-263614 - 0058, the compound of Paragraph No. 0037 of Unexamined-Japanese-Patent No. 2011-068731 - 0052, Paragraph No. of International Publication No. 2015/166873 The compound of 0010-0033, etc. are mentioned. As a squarylium compound, the compound described in Paragraph Nos. 0044 to 0049 of Unexamined-Japanese-Patent No. 2011-208101, the compound described in Paragraph Nos. 0060 to 0061 of Japanese Patent Publication No. 6065169, and Paragraph No. 0040 of International Publication No. 2016/181987 The compound described, the compound described in Japanese Unexamined Patent Publication No. 2015-176046, the compound described in Paragraph No. 0072 of International Publication No. 2016/190162, the compound described in Paragraph Nos. A compound described in Paragraph No. 0124 of Publication No. 2017-067963, a compound described in International Publication No. 2017/135359, a compound described in Japanese Unexamined Patent Publication No. 2017-114956, a compound described in Japanese Patent Publication No. 6197940, International Publication No. 2016 /120166, etc. are mentioned. As a cyanine compound, the compound described in Paragraph No. 0044 of Unexamined-Japanese-Patent No. 2009-108267 - 0045, the compound of Paragraph No. 0026 - 0030 of Unexamined-Japanese-Patent No. 2002-194040, and the compound described in Unexamined-Japanese-Patent No. 2015-172004 , a compound described in Japanese Laid-open Patent Publication No. 2015-172102, a compound described in Japanese Unexamined Patent Publication No. 2008-088426, a compound described in International Publication No. 2016/190162, Paragraph No. 0090, and a compound described in Japanese Unexamined Patent Publication No. 2017-031394 A compound etc. are mentioned. As a croconium compound, the compound of Unexamined-Japanese-Patent No. 2017-082029 is mentioned. Examples of the iminium compound include a compound described in Japanese Laid-Open Patent Publication No. 2008-528706, a compound described in Unexamined-Japanese-Patent No. 2012-012399, a compound described in Japanese Unexamined Patent Publication No. 2007-092060, and International Publication No. 2018 /043564, Paragraph No. 0048 - the compound of 0063 is mentioned. As a phthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153, the oxytitanium phthalocyanine of Unexamined-Japanese-Patent No. 2006-343631, Paragraph No. 0013 of Unexamined-Japanese-Patent No. 2013-195480 The compound described in -0029, the vanadium phthalocyanine compound described in Japanese Patent Publication No. 6081771, and the compound described in International Publication No. 2020/071470 are exemplified. As a naphthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned. Examples of the dithiorene metal complex include compounds described in Japanese Patent Publication No. 5733804.

As a near-infrared absorbing colorant, a squarylium compound described in Japanese Unexamined Patent Publication No. 2017-197437, a squarylium compound described in Japanese Unexamined Patent Publication No. 2017-025311, and a squarylium described in International Publication No. 2016/154782 A compound, a squarylium compound described in Japanese Patent Publication No. 5884953, a squarylium compound described in Japanese Patent Publication No. 6036689, a squarylium compound described in Japanese Patent Publication No. 5810604, a paragraph in International Publication No. 2017/213047 The squarylium compound described in Nos. 0090 to 0107, the pyrrole ring-containing compound described in Paragraph Nos. 0019 to 0075 of Japanese Unexamined Patent Publication No. 2018-054760, and the pyrrole ring-containing compound described in Paragraph Nos. 0078 to 0082 of Japanese Unexamined Patent Publication No. 2018-040955 , a pyrrole ring-containing compound described in Paragraph Nos. 0043 to 0069 of Japanese Laid-open Patent Publication No. 2018-002773, a squarylium compound having an aromatic ring on the amide α described in Paragraph Nos. 0024 to 0086 of Japanese Laid-Open Patent Publication No. 2018-041047 An amide-linked squarylium compound described in Japanese Patent Publication No. 2017-179131, a compound having a pyrrolbis type squarylium skeleton or a croconium skeleton described in Japanese Unexamined Patent Publication No. 2017-141215, and a compound described in Japanese Unexamined Patent Publication No. 2017-082029 Dihydrocarbazole bis-type squarylium compounds, asymmetric compounds described in Paragraphs Nos. 0027 to 0114 of Japanese Unexamined Patent Publication No. 2017-068120, and pyrrole ring-containing compounds described in Japanese Unexamined Patent Publication No. 2017-067963 (carbazole type) , The phthalocyanine compound described in Japanese Patent Publication No. 6251530, the coloring material described in Japanese Unexamined Patent Publication No. 2013-077009, Japanese Unexamined Patent Publication No. 2014-130338, International Publication No. 2015/166779, or in these documents Combinations of the described colorants and the like can also be used.

It is preferable that content of the color material in the total solid content of a resin composition is 20-90 mass %. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. It is preferable that it is 80 mass % or less, and, as for an upper limit, it is more preferable that it is 70 mass % or less.

Moreover, it is preferable that content of the pigment in the total solid content of a resin composition is 20-90 mass %. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. It is preferable that it is 80 mass % or less, and, as for an upper limit, it is more preferable that it is 70 mass % or less.

Moreover, it is preferable that content of the dye in a color material is 50 mass % or less, it is more preferable that it is 40 mass % or less, and it is more preferable that it is 30 mass % or less.

Moreover, it is also preferable that the resin composition of this invention contains substantially no dye for the reason that it is easy to suppress the film thickness change when the film obtained is heated to high temperature more effectively. When the resin composition of the present invention does not substantially contain a dye, the content of the dye in the total solids of the resin composition of the present invention is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and does not contain is particularly preferred.

<Resin B>

(specific resin (resin b-1))

The resin composition of the present invention contains Resin B (hereinafter also referred to as Resin). Resin contained in a resin composition contains resin b-1 (henceforth also called a specific resin) containing the structure represented by Formula (1). Specific resin is also the resin of this invention.

[Formula 11]

In Formula (1), X ¹ represents a tetravalent linking group;

X ² represents a divalent linking group;

R ¹¹ , R ¹² , R ²¹ , R ²² 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 divalent linking group;

P ¹ represents a polymer chain,

n represents an integer greater than or equal to 1;

[n]

In Formula (1), n represents an integer greater than or equal to 1, and is preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.

[X ¹ ]

In formula (1), as the tetravalent linking group represented by X ¹ , a group containing a hydrocarbon group is preferable. As a hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group are mentioned. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. As a substituent, the substituent T mentioned later is mentioned.

As a group containing the said hydrocarbon group, the group etc. which bonded a hydrocarbon group and two or more hydrocarbon groups with a single bond or a linking group are mentioned.

As a linking group connecting two or more hydrocarbon groups, -NR ^X1 -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NR ^X1 CO- , -CONR ^X1 - and -C(CF ₃ ) ₂ -. R ^X1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

The tetravalent linking group represented by X ¹ is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and more preferably a group containing an aromatic hydrocarbon ring. In addition, the tetravalent linking group represented by X ¹ is preferably a group containing a fluorine atom or a sulfonyl group (-SO ₂ -) because it can improve the solubility of a specific resin in a solvent. Among them, the tetravalent linking group represented by X ¹ is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring for the reason that it has excellent solubility in the solvent of a specific resin and can form a film having excellent heat resistance. The group containing a fluorine atom and an aromatic hydrocarbon ring is a group in which two or more aromatic hydrocarbon groups are bonded with a linking group, and the linking group is a linking group containing a fluorine atom, or two or more aromatic hydrocarbon groups with a single bond or a linking group. It is a bonded group, and a group in which the aromatic hydrocarbon group is substituted with a group containing a fluorine atom is preferable. As a linking group containing the said fluorine atom, -C( _CF3 ) _2- etc. are mentioned. As a group containing the said fluorine atom, a fluorinated alkyl group is preferable and a trifluoromethyl group is more preferable.

In addition, the tetravalent linking group represented by X ¹ is also preferably a group represented by any one of (D-1) to formula (D-3).

[Formula 12]

In formulas (D-1) to (D-3), each Cy independently represents an aliphatic hydrocarbon ring, R ^d1 represents a linear or branched aliphatic hydrocarbon group, and X ^d1 represents a single bond or 2 A valent linking group is shown, and each of * ¹ to * ⁴ represents a linking hand.

The aliphatic hydrocarbon ring represented by Cy in formulas (D-1) to (D-3) may be a monocyclic ring or a condensed ring. Moreover, 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 cross-linked structure.

In formula (D-1), it is preferable that * ¹ and * ² , and * ³ and * ⁴ exist in the adjacent position in the aliphatic hydrocarbon ring Cy.

R ^d1 in the formula (D-2) represents a linear or branched aliphatic hydrocarbon group, and is preferably a linear or branched saturated aliphatic hydrocarbon group. As for carbon number of the said aliphatic hydrocarbon group, it is preferable that it is 2-10, it is more preferable that it is 2-4, and it is still more preferable that it is 2. In the formula (D-2), it is preferable that each of * ³ and * ⁴ is present at each adjacent carbon atom in the aliphatic hydrocarbon group ^Rd1 . In formula (D-2), it is preferable that * ³ and * ⁴ exist in adjacent positions in the aliphatic hydrocarbon ring Cy.

In formula (D-3), ^Xd1 represents a single bond or a divalent linking group, and represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O )-, -S-, -S(=O) ₂ -, -NHC(=O)-, or a group obtained by combining two or more thereof is preferable, and an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom; More preferably, a group selected from -O-, -C(=O)-, -S-, or -S(=O) ₂ -, -CH ₂ -, -O-, -S-, -S More preferably, it is (=0) ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.

The tetravalent linking group represented by X ¹ is also preferably a group represented by formula (E-1).

[Formula 13]

In formula (E-1), Ar each independently represents an aromatic hydrocarbon ring, X ^e1 represents a divalent linking group containing a fluorine atom, and * ¹ to * ⁴ each represent a linking hand.

6-30 are preferable and, as for carbon number of the aromatic hydrocarbon ring represented by Ar of Formula (E-1), 6-20 are more preferable. It is preferable that the aromatic hydrocarbon ring represented by Ar is a benzene ring.

X ^e1 in 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, and -C(CF ₃ ) ₂ - , -C(CF ₃ )(C ₂ F ₅ )- or -C(C ₂ F ₅ ) ₂ - is more preferable, and -C(CF ₃ ) ₂ - is particularly preferable. In Formula (D-1), it is preferable that * ¹ and * ² , and * ³ and * ⁴ exist in the adjacent position in aromatic ring structure Ar.

Specific examples of the tetravalent linking group represented by X ¹ include groups having a structure represented by any one of formulas (I-1) to (I-28).

[Formula 14]

In formulas (I-1) to (I-28), X ¹ to X ³ represent a single bond or a divalent linking group, L represents -CH=CH- or -CH ₂ -, R ¹ and R ² Each independently represents a hydrogen atom or a substituent, R ¹ and R ² may be bonded to form a ring structure, and * represents a connecting hand with another structure in Formula (1).

Examples of the divalent linking group represented by X ¹ to X ³ are -C(Rx) ₂ - (Rx represents a hydrogen atom or a substituent. When Rx is a substituent, they may be linked to each other to form a ring), -O-, - SO ₂ -, -CO-, -S-, -NR ^N -, a phenylene group, or a combination thereof, and when Rx represents a substituent, specific examples thereof include an alkyl group which may be substituted with a fluorine atom. there is. R ^N represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

X ¹ to X ³ are each independently a single bond, preferably -SO ₂ - or -C(Rx) ₂ -, more preferably -SO ₂ - or -C(Rx) ₂ -, and -C( Rx) ₂ - is more preferred. Moreover, -C(Rx) ₂ - is preferably -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -, and more preferably -C(CF ₃ ) ₂ -.

It is preferable that L is -CH=CH-.

R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom.

[X ² ]

In formula (1), X ² represents a divalent linking group. Examples of the divalent linking group represented by X ² include a hydrocarbon group and a group in which two or more hydrocarbon groups are bonded through a single bond or a linking group.

As a hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group are mentioned. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. As a substituent, the substituent T mentioned later is mentioned.

Examples of the linking group linking the above two or more hydrocarbon groups include -O-, -S-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CO-, -SO ₂ -, -SiR ₂ - (R each independently represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.), a polysiloxane group (-Si(R)-(O-Si) _n -, R represents a hydrocarbon group, , An alkyl group or a phenyl group having 1 to 4 carbon atoms is preferable, n represents an integer of 1 or more, and 1 to 10 are preferable).

The divalent linking group represented by X ² is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and more preferably a group containing an aromatic hydrocarbon ring. In addition, the divalent linking group represented by X ² is preferably a group containing a fluorine atom or a sulfonyl group (-SO ₂ -) because it can improve the solubility of a specific resin in a solvent. Among them, the divalent linking group represented by X ² is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring for the reason that it has excellent solubility in the solvent of a specific resin and can form a film having excellent heat resistance. The group containing a fluorine atom and an aromatic hydrocarbon ring is a group in which two or more aromatic hydrocarbon groups are bonded with a linking group, and the linking group is a linking group containing a fluorine atom, or two or more aromatic hydrocarbon groups with a single bond or a linking group. It is a bonded group, and a group in which the aromatic hydrocarbon group is substituted with a group containing a fluorine atom is preferable. As a linking group containing the said fluorine atom, -C( _CF3 ) _2- etc. are mentioned. As a group containing the said fluorine atom, a fluorinated alkyl group is preferable and a trifluoromethyl group is more preferable. When the divalent linking group represented by X ² is a group containing a fluorine atom and an aromatic hydrocarbon ring, for example, a group having the following structure is preferable.

[Formula 15]

In the above structure, * represents a binding site with another structure.

The divalent linking group represented by X ² is preferably a group having a structure induced by a diamine compound. As a diamine compound, the following compounds are mentioned, for example.

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[R ¹¹ , R ¹² , R ²¹ , R ²² and R ²³ ]

In formula (1), R ¹¹ , R ¹² , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a substituent.

As a substituent, an alkyl group, an aryl group, a heterocyclic group, etc. are mentioned. 1-30 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, 1-8 are more preferable, 1-5 are still more preferable, and 1-3 are especially preferable. The alkyl group may be straight-chain, branched or cyclic, preferably straight-chain or branched, and more preferably straight-chain. 6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are more preferable. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group has a preferable 5- or 6-membered ring. Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. As for the number of hetero atoms which comprise a heterocyclic group, 1-3 are preferable. The heterocyclic group may be a monocyclic or condensed ring. The above-mentioned alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include substituent T described later, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a block isocyanate group.

In Formula ( ¹ ), it is preferable that ^R11 and R12 are a hydrogen atom. Also, R ²¹ , R ²² and R ²³ are preferably hydrogen atoms. Moreover, a part may form carboxylate and amine salt.

[Lp ¹ ]

In formula (1), Lp ¹ represents an n+1 valent linking group. As the n+1 valent linking group, a hydrocarbon group, -NRp-, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRpCO -, -CONRp-, and a group formed by combining two or more thereof. Rp represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

As an n+1 valent linking group, the group represented by Formula (Lp-1) and the group represented by Formula (Lp-2) are mentioned.

[Formula 20]

In formula (Lp-1), Rp ¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and Lp ^1a represents a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded together by a single bond or a linking group.

In formula (Lp-2), Lp ^1b represents a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded together by a single bond or a linking group.

In formulas (Lp-1) and (Lp-2), n represents an integer greater than or equal to 1, *1 represents a linking hand with the carbonyl carbon in -NR ²³ CO- in formula (1), and * 2 represents a linking hand with Lp ² in Formula (1).

Details of the alkyl group, aryl group, and heterocyclic group represented by Rp ¹ include the groups described in the section for R ¹¹ , R ¹² , R ²¹ , R ²² and R ²³ .

Examples of the hydrocarbon group represented by Lp ^1a and Lp ^1b include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. As a substituent, the substituent T mentioned later is mentioned.

As a linking group connecting two or more hydrocarbon groups, -NRp ^1b -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ^1b CO-, -CONRp ^1b -. Rp ^1b represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

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

[Formula 21]

In formula (Lp-10), Lp ¹¹ represents a single bond or an n+1 valent linking group, Rp ¹¹ represents a substituent, n represents an integer greater than or equal to 1, m represents an integer of 0 to 4, *1 represents a linkage with the carbonyl carbon in -NR ²³ CO- in formula (1), and *2 represents a linkage with Lp ² in formula (1). m pieces of Rp ¹¹ may be the same or different.

In formula (Lp-11), Lp ¹² represents a single bond or an n+1 valent linking group, Rp ¹¹ represents a substituent, n represents an integer greater than or equal to 1, m represents an integer of 0 to 4, *1 represents a linkage with the carbonyl carbon in -NR ²³ CO- in formula (1), and *2 represents a linkage with Lp ² in formula (1). m pieces of Rp ¹¹ may be the same or different.

Examples of the n+1 valent linking group represented by Lp ¹¹ in formula (Lp-10) include a hydrocarbon group, -NRp ¹² -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO -, -OCO-, -S-, -NRp ¹² CO-, -CONRp ¹² -, and groups formed by combining two or more of these. As a hydrocarbon group, the thing mentioned above is mentioned. Rp ¹² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

The n+1 valent linking group represented by Lp ¹² in formula (Lp-11) is preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded together with a single bond or a linking group. Examples of linking groups connecting two or more hydrocarbon groups include -NRp ¹³ -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ¹³ CO- and -CONRp ¹³ -. Rp ¹³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

Examples of the substituent represented by Rp ¹¹ in formulas (Lp-10) and (Lp-11) include substituent T described below, preferably a carboxy group, a halogen atom or a hydroxy group, more preferably a carboxy group.

n in the formulas (Lp-10) and (Lp-11) represents an integer greater than or equal to 1, preferably an integer of 1 to 4, more preferably 1 or 2, still more preferably 1.

m in formulas (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, still more preferably 1 or 2 do. Moreover, it is preferable that at least 1 or more of m ^Rp11 is a carboxy group.

[LP ² ]

In formula (1), Lp ² represents a divalent linking group. As the divalent linking group, a hydrocarbon group, -NRp ²¹ -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ²¹ CO-, - CONRp ²¹ -, and a group formed by combining two or more thereof. Rp ²¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom. The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. A hydroxyl group etc. are mentioned as a substituent. The divalent linking group is preferably a group containing an oxygen atom or a sulfur atom, more preferably a group containing a sulfur atom, and still more preferably a group containing -S-.

The divalent linking group represented by Lp ² is preferably -S- or -O-, and more preferably -S-.

[P ¹ ]

In formula (1), P ¹ represents a polymer chain. ^As for the weight average molecular weight of P1, 500-50000 are preferable. It is preferable that it is 800 or more, and, as for a minimum, it is more preferable that it is 1000 or more. It is preferable that it is 20000 or less, and, as for an upper limit, it is more preferable that it is 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 chain can be measured by a GPC (Gel Permeation Chromatography) method. More specifically, it can be calculated from the weight average molecular weight of the raw material monomer used for introduction of the polymer chain.

The polymer chain represented by P ¹ preferably contains a repeating unit of at least one structure selected from a poly(meth)acrylic structure, a polystyrene structure, a polyether structure, and a polyester structure, and has a poly(meth)acrylic structure. and a polystyrene structure, and more preferably includes a repeating unit of at least one structure selected from a polystyrene structure, and from the viewpoint of pigment dispersibility and heat resistance, a repeating unit of a poly(meth)acryl structure is more preferable. It is also preferable that the polymer chain represented by P ¹ contains a repeating unit of a polyether structure or a repeating unit of a polyester structure. When the polymer chain represented by P ¹ contains repeating units of a polyether structure, the number of repeating units of a polyether structure is preferably nine or more. When the polymer chain represented by P ¹ contains repeating units of a polyester structure, the number of repeating units of a polyester structure is preferably five or more.

The polymer chain represented by P ¹ may have a crosslinkable group. Examples of the crosslinkable group include ethylenically unsaturated bond-containing groups such as vinyl, (meth)allyl, and (meth)acryloyl groups, cyclic ether groups such as epoxy groups and oxetane groups, and block isocyanate groups. . In addition, in this specification, a blocked isocyanate group is a group which can generate an isocyanate group by heat, and, for example, a group obtained by reacting a blocking agent with an isocyanate group to protect an isocyanate group is preferable. can be exemplified. Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. About blocking agent, Paragraph No. 0115 of Unexamined-Japanese-Patent No. 2017-067930 - the compound of 0117 are mentioned, This content is integrated in this specification. In addition, the block isocyanate group is preferably a group capable of generating an isocyanate group by heating at 90 to 260°C.

It is also preferable that the polymer chain represented by P ¹ has a tertiary alkyl group. As a tertiary alkyl group, t-butyl group etc. are mentioned.

The polymer chain represented by P ¹ preferably contains a repeating unit represented by any of formulas (P1-1) to (P1-6), and repeats represented by formula (P1-5) or formula (P1-6). It is more preferable to include a unit, and it is still more preferable to include a repeating unit represented by formula (P1-5). Moreover, it is also preferable that the polymer chain represented by P ¹ contains a repeating unit represented by any one of formulas (P1-1) to (P1-4). When the polymer chain represented by P ¹ contains a repeating unit of formula (P1-4), the number of repeating units of formula (P1-4) is preferably 9 or more. When the polymer chain represented by P ¹ contains repeating units of formulas (P1-1) to (P1-3), it is preferable that the number of repeating units of these structures is five or more.

[Formula 22]

In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 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 having 3 to 12 carbon atoms. It is more preferable that it is a linear or branched alkylene group of

In the above formula, R ^G3 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, Q ^G1 represents -O- or -NR ^q -, and R ^q represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Q ^G1 is preferably -O-.

The number of carbon atoms in the alkyl group represented by R ^q 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 straight-chain, branched or cyclic, preferably straight-chain or branched, and more preferably straight-chain.

The number of carbon atoms in the aryl group represented by R ^q is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 12.

The heterocyclic group represented by R ^q may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group has a preferable 5- or 6-membered ring. Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. As for the number of hetero atoms which comprise a heterocyclic group, 1-3 are preferable. The heterocyclic group may be a monocyclic or condensed ring.

The above-mentioned alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. As a substituent, the substituent T mentioned later is mentioned.

In the above formula, L ^G1 represents a single bond or an arylene group, and is preferably a single bond.

In the above formula, ^LG2 represents a single bond or a divalent linking group. Examples of the divalent 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), -NR ^LG1 -, -SO-, -SO ₂ -, - CO-, -O-, -COO-, -OCO-, -S-, -NR ^LG1 CO-, -CONR ^LG1- , and a group formed by combining two or more of these; an alkylene group or an arylene group; It is preferable that it is a group containing R ^LG1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom. The alkylene group and arylene described above may have a substituent or may be unsubstituted. As a substituent, the substituent T mentioned later is mentioned.

In the above formula, R ^G4 represents a hydrogen atom or a substituent. As the substituent, a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, an ethylenically unsaturated bond A containing group, an epoxy group, an oxetanyl group, and a block isocyanate group etc. are mentioned. R ^G4 is preferably at least one selected from an alkyl group, an aryl group, an ethylenically unsaturated bond-containing group, an epoxy group, and an oxetanyl group, and is selected from an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a t-butyl group. It is more preferable that it is at least 1 sort(s) chosen.

In the above formula, R ^G5 represents a hydrogen atom or a methyl group, and R ^G6 represents an aryl group. The number of carbon atoms in the aryl group represented by R ^G6 is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 12. The aryl group represented by R ^G6 may have a substituent. As the substituent, a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, an ethylenically unsaturated bond A containing group, an epoxy group, an oxetanyl group, and a block isocyanate group etc. are mentioned.

The polymer chain represented by P ¹ may contain two or more types of repeating units.

(substituent T)

An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an alkenyl group having 2 to 30 carbon atoms) is an aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably having 6 to 30 carbon atoms) aryloxy group), heteroaryloxy group (preferably a heteroaryloxy group having 1 to 30 carbon atoms), an acyl group (preferably an acyl group having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms) an alkoxycarbonyl group of), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably having 2 carbon atoms) 30 acylamino group), alkoxycarbonylamino group (preferably 2 to 30 carbon atoms alkoxycarbonylamino group), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms aryloxycarbonylamino group), sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an aryl group Ogi (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably heteroarylthio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 30 carbon atoms) , An arylsulfonyl group (preferably a C6-C30 arylsulfonyl group), a heteroarylsulfonyl group (preferably a C1-C30 heteroarylsulfonyl group), an alkylsulfinyl group (preferably a C1-C30 alkyl sulfinyl group), aryl sulfinyl group (preferably having 6 to 30 carbon atoms), heteroaryl sulfinyl group (preferably having 1 to 30 carbon atoms heteroaryl sulfinyl group), ureido group (preferably having 1 to 30 carbon atoms) A ureido group), 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, etc.), between Anogi, Sulfogroup, Car Double group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group. These groups may further have a substituent in the case of a substitutable group. As an additional substituent, the group described for substituent T above can be mentioned.

Specific resin WHEREIN: It is preferable that the structure represented by Formula (1) mentioned above is a structure represented by Formula (1-1).

[Formula 23]

In formula (1-1), X ¹ represents a tetravalent linking group;

X ² represents a divalent linking group;

R ¹¹ , R ¹² , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a substituent;

Rp ¹¹ represents a substituent, m Rp ¹¹ may be the same or different,

Lp ¹¹ represents an n+1 valent linking group;

Lp ² represents a divalent linking group;

P ¹ represents a polymer chain;

n represents an integer greater than or equal to 1;

m represents an integer from 0 to 4;

X ¹ , X ² , R ¹¹ , R ¹² , R ²¹ , R ²² , R ²³ , Lp ² , P ¹ and n in Formula (1-1) are X ¹ , X ² , R ¹¹ in Formula (1) , R ¹² , R ²¹ , R ²² , R ²³ , Lp ² , P ¹ and n have the same meaning.

Lp ¹¹ , Rp ¹¹ and m in formula (1-1) have the same meaning as Lp ¹¹ , Rp ¹¹ and m in formula (Lp-10).

Specific resin may contain the imide cyclization structure of the structure represented by Formula (1) mentioned above.

Exception resin may further contain the structure represented by Formula (100). According to this aspect, more excellent dispersibility is obtained.

[Formula 24]

In formula (100), X ¹⁰¹ represents a 4+q valent linking group;

X ¹⁰² represents a divalent linking group,

R ¹¹¹ , R ¹¹² , R ¹²¹ and R ¹²² each independently represent a hydrogen atom or a substituent;

Lp ¹⁰¹ represents a divalent linking group,

P ¹⁰¹ represents a polymer chain;

q represents an integer greater than or equal to 1;

R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² and P ¹⁰¹ in formula (100) have the same meaning as R ¹¹ , R ¹² , R ²¹ , R ²² and P ¹ in formula (1).

In Formula (100), q represents an integer greater than or equal to 1, and is preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.

Examples of the divalent linking group represented by X ¹⁰² in formula (100) include the divalent linking group described by X ² in formula (1), and the preferred range is also the same.

In formula (100), the 4+q valent linking group represented by X ¹⁰¹ is preferably a group containing a hydrocarbon group. As a hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group are mentioned. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. As a substituent, the substituent T mentioned above is mentioned.

As a group containing the said hydrocarbon group, the group etc. which bonded a hydrocarbon group and two or more hydrocarbon groups with a single bond or a linking group are mentioned.

As a linking group connecting two or more hydrocarbon groups, -NRx ¹⁰¹ -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, - NRx ¹⁰¹ CO-, -CONRx ¹⁰¹ - and -C(CF ₃ ) ₂ -. Rx ¹⁰¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom. It is preferable that the carbon atom of X ¹⁰¹ is bonded to Lp ¹⁰¹ . Moreover, it is also preferable that the nitrogen atom of X ¹⁰¹ is bonded to Lp ¹⁰¹ .

As the 4+q valent linking group represented by X ¹⁰¹ , a group containing an aromatic hydrocarbon ring is preferable because it has a strong affinity for pigments and hardly generates foreign substances. As a group containing an aromatic hydrocarbon ring, the group represented by Formula (X-1) is mentioned.

[Formula 25]

In formula (X-1), *1 represents a linking hand with P ¹⁰¹ in formula (100), *2 represents a linking hand with -CO- bonded to X ¹⁰¹ in formula (100), and Rx ¹ And Rx ² represents a substituent each independently, m1 represents an integer of 0 to 3, m2 represents an integer of 0 to 3, n represents an integer of 1 or more, X ¹⁰⁰ represents a 2+n valent linking group .

Examples of the 2+n valent linking group represented by X ¹⁰⁰ include a hydrocarbon group, -NRx ¹⁰¹ -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, - S-, -NRx ¹⁰¹ CO-, -CONRx ¹⁰¹ -, -C(CF ₃ ) ₂ -, and groups formed by combining two or more of these. As a hydrocarbon group, the thing mentioned above is mentioned. Rx ¹⁰¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

Examples of the substituent represented by Rx ¹ and Rx ² include the substituent T described above. As a specific example, a halogen atom, an alkyl group, a carboxy group, etc. are mentioned.

m1 and m2 are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

In formula (100), Lp ¹⁰¹ represents a divalent linking group. As the divalent linking group, a hydrocarbon group, -NR ^L1 -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NR ^L1 CO-, - CONR ^L1 -, and a group formed by combining two or more of these. R ^L1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom. The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. The divalent linking group is preferably a group containing an oxygen atom or a sulfur atom, more preferably a group containing a sulfur atom, and still more preferably a group containing -S-.

The divalent linking group represented by Lp ¹⁰¹ is preferably a group represented by formula (Lp-101) or formula (Lp-201), and more preferably a group represented by formula (Lp-101).

[Formula 26]

In the formulas, formulas (Lp-101) and (Lp-102), Lp ¹¹¹ represents a single bond or a divalent linking group, *1 is a linking hand with X ¹⁰¹ in formula (100), *2 is formula ( 100) is the connecting hand with P ¹⁰¹ .

Examples of the divalent linking group represented by Lp ¹¹¹ include a hydrocarbon group and a group having a structure in which two or more hydrocarbon groups are bonded through a single bond or a linking group. Examples of the linking group include -NR ^L1 -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NR ^L1 CO-, and -CONR ^L1 -. can R ^L1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

Specific resin may contain the imide cyclization structure of the structure represented by Formula (100) mentioned above.

As for the acid value of a specific resin, 10-150 mgKOH/g is preferable. 100 mgKOH/g or less is preferable and, as for an upper limit, 80 mgKOH/g or less is more preferable. 20 mgKOH/g or more is preferable and, as for a minimum, 30 mgKOH/g or more is more preferable.

2000-200000 are preferable, as for the weight average molecular weight (Mw) of specific resin, 2500-100000 are more preferable, and 3000-50000 are more preferable.

The specific resin has a 5% mass reduction temperature by TG/DTA (thermal mass measurement/differential thermal measurement) in a nitrogen atmosphere of preferably 280°C or higher, more preferably 300°C or higher, and still more preferably 320°C or higher. The upper limit of the 5% mass reduction temperature is not particularly limited, and may be, for example, 1,000°C or less. The 5% mass reduction temperature is a temperature at which the mass reduction rate when left still at a specific temperature for 5 hours in a nitrogen atmosphere becomes 5%, and is determined by a known TG/DTA measurement method.

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

The said mass decrease rate is a value computed as the ratio of the decrease of the mass in specific resin before and after leaving still at 300 degreeC for 5 hours in nitrogen atmosphere.

A specific resin is, for example, a polyamic acid synthesized by reacting an acid dianhydride with a diamine compound, and then an end-capping agent (end-capping macromonomer) each having a polymer chain and a group that reacts with the terminal amine moiety of polyamic acid. can be synthesized by reacting You may further use terminal blocking agents (other terminal blocking agents) other than terminal blocking agent macromonomer as needed. Examples of other terminal blockers include monoamines, acid 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 of the acid dianhydride per mole of the diamine compound. Further, the molar ratio of the diamine compound and the terminal blocking macromonomer is preferably 0.1 to 2 moles, more preferably 0.2 to 1.5 moles, and 0.5 to 1.2 moles of the terminal blocking macromonomer to 1 mole of the diamine compound. more preferable

As an end capping agent macromonomer, the compound represented by Formula (EDM) is mentioned.

[Formula 27]

In formula (EDM), R ^ED represents an acid anhydride group, an acid halide group or an isocyanate group;

Lp ^ED1 represents an n+1 valent group;

The n+1 valent group is a hydrocarbon group, or a hydrocarbon group and -NRp ^ED1 -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO- , -S-, -NRp ^ED1 CO- and -CONRp ^ED1 - is a group having a structure combining at least one group selected from,

Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;

Lp ^ED2 represents -O- or -S-;

P ^ED1 represents a polymer chain,

n represents the integer of 1-4.

The acid anhydride group represented by R ^ED in the formula (EDM) is preferably a cyclic acid anhydride group. The acid anhydride group represented by R ^ED is preferably a group represented by formulas (R ^ED1-11 ) to (R ^ED1-13 ), and more preferably a group represented by formula (R ^ED1-13 ). Moreover, it is preferable that an acid halide group is a group represented by formula (R ^ED1-21 ).

[Formula 28]

In the above formula, R ^ED11 represents a hydrogen atom or a substituent, R ^ED12 represents a substituent, R ^ED21 represents a halogen atom, r represents an integer from 0 to 3, and * represents a linking hand with Lp ^ED1 . .

Examples of the substituent represented by R ^ED11 and R ^ED12 include the substituent T described above, preferably a halogen atom, a carboxy group, an alkyl group or a hydroxy group, and more preferably a carboxy group.

The halogen atom represented by R ^ED21 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, still more preferably 0.

As a hydrocarbon group in Lp ^ED1 of Formula (EDM), an aliphatic hydrocarbon group and an aromatic hydrocarbon group are mentioned. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are more preferable. The aliphatic hydrocarbon group may be straight chain, branched or cyclic. In addition, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Moreover, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are more preferable. The hydrocarbon group may have a substituent. As a substituent, the substituent T mentioned above is mentioned.

Lp ^ED2 in the formula (EDM) represents -O- or -S-, and is preferably -S-.

The polymer chain represented by P ^ED1 in formula (EDM) has the same meaning as the polymer chain represented by P ¹ in formula (1).

It is preferable that n of formula (EDM) is 1 or 2.

The end capping agent macromonomer is preferably a compound having an acid anhydride group, more preferably a compound represented by formula (EDM1), and still more preferably a compound represented by formula (EDM2). The compound represented by the formula (EDM1) and the compound represented by the formula (EDM2) are the compounds of the present invention.

[Formula 29]

In formula (EDM1), R ^ED1 represents an acid anhydride group;

Lp ^ED1 represents an n+1 valent group;

The n+1 valent group is a hydrocarbon group, or a hydrocarbon group and -NRp ^ED1 -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO- , -S-, -NRp ^ED1 CO- and -CONRp ^ED1 - is a group having a structure combining at least one group selected from,

Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;

Lp ^ED2 represents -O- or -S-;

P ^ED1 represents a polymer chain containing a repeating unit represented by any one of formulas (P1-1) to (P1-4);

n represents the integer of 1-4.

[Formula 30]

In formula (EDM2), R ^ED12 represents a halogen atom, an alkyl group, a carboxy group or a hydroxy group;

Lp ^ED1a represents an n+1 valent group;

The n+1 valent group is a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded with a single bond or a linking group;

The linking group is -NRp ^ED1 -, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ^ED1 CO- or -CONRp ^ED1 ,

Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;

Lp ^ED2 represents -O- or -S-;

P ^ED1 represents a polymer chain containing a repeating unit represented by any one of formulas (P1-1) to (P1-4);

r represents an integer from 0 to 3,

n represents the integer of 1-4.

[Formula 31]

In formulas (P1-1) to (P1-4), R ^G1 and R ^G2 each represent an alkylene group.

The acid anhydride group represented by R ^ED1 in the formula (EDM1) has the same meaning as the acid anhydride group described by R ^ED in the formula (EDM).

Details of the polymer chain represented by P ^ED1 in formula (EDM1) are the same as those described for the polymer chain represented by P ¹ in formula (1).

Lp ^{ED1 , Lp ED2 and n in formula (EDM1) have the same meaning as Lp ED1 , Lp ED2} and n in formula (EDM).

r in Formula (EDM2) represents an integer of 0 to 3, and r is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

As a hydrocarbon group in Lp ^ED1a of formula (EDM2), it has the same meaning as the hydrocarbon group demonstrated by formula (EDM). The n+1 valent group represented by Lp ^ED1a in Formula (EDM2) is preferably a hydrocarbon group.

Details of the polymer chain represented by P ^ED1 in formula (EDM2) are the same as those described for the polymer chain represented by P ¹ in formula (1).

Lp ^{ED2 and n in Formula (EDM2) have the same meaning as Lp ED2 and} n in Formula (EDM).

As specific examples of the end capping agent macromonomer, the terminal capping agent macromonomers EDM-1 to EDM-40 described in the examples described below may be cited.

The end capping agent macromonomer can be synthesized, for example, by the following method.

(1) A method of synthesizing a macromonomer obtained by radical polymerization of a radically polymerizable compound using a chain transfer agent having one hydroxyl group and one or two mercapto groups by esterification reaction with an acid anhydride or an acid anhydride chloride.

(2) A method in which a compound having two mercapto groups is subjected to an en-thiol reaction with an acid anhydride having an ethylenically unsaturated bond-containing group, followed by ring-opening polymerization of a lactone to synthesize the compound.

(3) Coupling reaction of a macromonomer obtained by radical polymerization of a radically polymerizable compound using a chain transfer agent having one hydroxyl group and one or two mercapto groups with an acid anhydride having a halogen atom to synthesize method.

(4) A method of synthesizing by reacting a compound having one acid anhydride group and a carboxy group or an acid halide group with a polymer having a hydroxyl group or an amino group at the terminal. As the compound having one acid anhydride group and a carboxy group or an acid halide group used in this synthesis, trimellitic anhydride and trimellitic anhydride chloride are preferable because a macromonomer can be synthesized with high purity and high yield.

(5) A method of synthesizing a macromonomer obtained by radical polymerization of a radically polymerizable compound using a chain transfer agent having one carboxy group and one mercapto group (for example, mercaptopropionic acid, etc.) by acid chloride conversion.

(6) Ring-opening polymerization of lactones using a compound having one or two hydroxyl groups and one mercapto group (for example, mercaptoethanol, mercaptopropanol, mercaptohexanol, mercaptoglycerol, etc.) A method of synthesizing the obtained macromonomer by en-thiol reaction with a compound having an isocyanate group and an unsaturated bond-containing group.

It is preferable to exclude the terminal blocker macromonomer, since remaining hydrochloric acid will cause denaturation or corrosion. When acid anhydride chloride is used as a raw material, it is preferable to synthesize by separating the generated hydrochloride after mixing the raw materials in the presence of a base. As a base, an organic base or an inorganic base may be sufficient. In the case of organic bases, tertiary alkylamines, tertiary aromatic amines, heterocyclic aromatic amines and the like are used. For example, triethylamine, diisopropylethylamine, tributylamine, diethylaniline, pyridine, 4,4-dimethylaminopyridine, 2-picoline, 2,6-lutidine, imidazole, 1- Methylimidazole, 1-ethylimidazole, triazole, tetrazole, etc. are mentioned. As the separation method, filtration using a filter (natural filtration, pressure filtration, reduced pressure filtration, centrifugal filtration), separation into an organic layer and aqueous layer, centrifugal separation, adsorption (silica gel column, activated carbon, etc.) etc. can be mentioned.

(other resins)

The resin composition of the present invention may also contain resins other than the specific resins described above as resins. As another resin, resin which has alkali developability, or resin as a dispersing agent, etc. are mentioned, for example. Moreover, by-products at the time of synthesize|combining a specific resin, such as the decomposition product of terminal blocker macromonomer, and the reaction product of diamine and terminal blocker macromonomer, may be included.

[Resin having alkali developability]

As for the weight average molecular weight (Mw) of resin which has alkali developability, 3000-2000000 are preferable. As for an upper limit, 1000000 or less are more preferable, and 500000 or less are still more preferable. The lower limit is more preferably 4000 or more, and more preferably 5000 or more.

Examples of the resin having alkali developability include (meth)acrylic resins, polyimine resins, polyether resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyimide resins, and the like, and (meth) Acrylic resins and polyimine resins are preferred, and (meth)acrylic resins are more preferred. Moreover, as another resin, the resin described in Paragraph Nos. 0041 to 0060 of Unexamined-Japanese-Patent No. 2017-206689, the resin described in Paragraph No. 0022 to 0071 of Unexamined-Japanese-Patent no. You may use resin, resin of Unexamined-Japanese-Patent No. 2017-032685, resin of Unexamined-Japanese-Patent No. 2017-075248, and resin of Unexamined-Japanese-Patent No. 2017-066240.

Moreover, as resin which has alkali developability, it is preferable to use resin which has an acidic radical. According to this aspect, the developability of the resin composition can be further improved. Examples of the acid group include a phenolic hydroxyl group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an active imide group, and a sulfonamide group, with a carboxy group being preferable. As the resin having an acid group, a resin obtained by introducing an acid group by reacting an acid anhydride with a hydroxyl group generated by ring opening of the epoxy may be used. As such a resin, the resin described in Japanese Patent Publication No. 6349629 is exemplified. Resin having an acid group can be used as an alkali-soluble resin, for example.

The resin having alkali developability preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 1 to 70 mol% of the repeating unit having an acid group in the side chain of all repeating units of the resin. It is preferable that it is 50 mol% or less, and, as for the upper limit of content of the repeating unit which has an acidic radical in a side chain, it is more preferable that it is 40 mol% or less. It is preferable that it is 2 mol% or more, and, as for the lower limit of content of the repeating unit which has an acidic radical in a side chain, it is more preferable that it is 5 mol% or more.

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

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

The resin having an ethylenically unsaturated bond-containing group preferably contains a repeating unit having an ethylenically unsaturated bond-containing group in the side chain, and the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is 5 to 80 moles of the total repeating units of the resin It is more preferable to include %. It is preferable that it is 60 mol% or less, and, as for the upper limit of content of the repeating unit which has an ethylenically unsaturated bond-containing group in a side chain, it is more preferable that it is 40 mol% or less. It is preferable that it is 10 mol% or more, and, as for the lower limit of content of the repeating unit which has an ethylenically unsaturated bond-containing group in a side chain, it is more preferable that it is 15 mol% or more.

The resin having alkali developability is a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable to include a repeating unit derived from it.

[Formula 32]

In Formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[Formula 33]

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

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

It is also preferable that resin which has alkali developability contains the repeating unit derived from the compound represented by following formula (X).

[Formula 34]

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may include a benzene ring. indicate n represents the integer of 1-15.

As resin which has alkali developability, resin etc. of the following structure are mentioned, for example. In the structural formulas below, Me represents a methyl group.

[Formula 35]

[Dispersing agent]

The resin composition of this invention may also contain resin as a dispersing agent. As for a dispersing agent, an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin) are mentioned. Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and a resin substantially consisting only of acid groups is more preferable . The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. 40-105 mgKOH/g is preferable, as for the acid value of an acidic dispersing agent (acidic resin), 50-105 mgKOH/g is more preferable, and its 60-105 mgKOH/g is still more preferable. Moreover, a basic dispersing agent (basic resin) shows resin with more basic group quantities than acid group quantities. The basic dispersant (basic resin) is preferably a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the amount of the acid group and the amount of the basic group is 100 mol%. It is preferable that the basic group which a basic dispersing agent has is an amino group.

It is preferable that resin used as a dispersing agent contains the repeating unit which has an acidic radical.

It is also preferable that the resin used as a dispersing agent is a graft polymer. As a graft polymer, Paragraph No. 0025 of Unexamined-Japanese-Patent No. 2012-255128 - resin of 0094 are mentioned, This content is integrated in this specification.

It is also preferable that the resin used as a dispersing agent is a polyimine-based dispersing agent (polyimine resin) containing a nitrogen atom in at least one of the main chain and side chain. As the polyimine-based dispersant, a resin having a main chain having a partial structure having a functional group of pKa14 or less and a side chain having 40 to 10,000 atoms and having a basic nitrogen atom in at least one of the main chain and the side chain is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom showing basicity. As a polyimine type dispersing agent, Paragraph No. 0102 of Unexamined-Japanese-Patent No. 2012-255128 - resin of 0166 are mentioned, This content is integrated in this specification.

It is also preferable that the resin used as a dispersing agent is a resin having a structure in which a plurality of polymer chains are bonded to a core portion. As such a resin, a dendrimer (including a star-shaped polymer) is mentioned, for example. Moreover, as a specific example of a dendrimer, Paragraph No. 0196 of Unexamined-Japanese-Patent No. 2013-043962 - the high molecular compound C-1 - C-31 of 0209 etc. are mentioned.

The dispersant is also available as a commercial product, and specific examples thereof include the DISPERBYK series manufactured by BYK Chemie (eg, DISPERBYK-111, 161, etc.), and the Solsperse series manufactured by Lubrizol (eg, Solsperse 36000, etc.). can Moreover, Paragraph No. 0041 of Unexamined-Japanese-Patent No. 2014-130338 - the pigment dispersant of 0130 can also be used, This content is integrated in this specification. In addition, the dispersing agent is Japanese Patent Application Laid-open No. 2018-150498, Japanese Patent Laid-Open No. 2017-100116, Japanese Laid-Open Patent No. 2017-100115, Japanese Laid-Open Patent No. 2016-108520, Japanese Laid-Open Patent Publication 2016-108519, You may use the compound of Unexamined-Japanese-Patent No. 2015-232105.

In addition, the resin described as the dispersing agent can also be used for applications other than dispersing agents. For example, it can also be used as a binder.

As for content of resin in the total solid content of a resin composition, 5-60 mass % is preferable. 10 mass % or more is preferable and, as for a minimum, 15 mass % or more is more preferable. 50 mass % or less is preferable and, as for an upper limit, 40 mass % or less is more preferable.

As for content of the above-mentioned specific resin in the total solid content of a resin composition, 5-60 mass % is preferable. 10 mass % or more is preferable and, as for a minimum, 15 mass % or more is more preferable. 50 mass % or less is preferable and, as for an upper limit, 40 mass % or less is more preferable.

As for content of the above-mentioned specific resin, 10-80 mass parts is preferable with respect to 100 mass parts of pigments. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. The upper limit is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

In addition, the resin composition of the present invention preferably contains 20% by mass or more of the specific resin, more preferably 30% by mass or more, and contains 40% by mass or more of the specific resin among the components excluding the colorant from the total solid content of the resin composition. It is more desirable to The upper limit may be 100% by mass, 90% by mass or less, or 85% by mass or less. When the content of the specific resin is within the above range, it is easy to form a film having excellent heat resistance, and it is easy to more easily suppress film shrinkage or the like after heating. Furthermore, when an inorganic film or the like is formed on the surface of a film obtained using the resin composition of the present invention, generation of cracks or the like in the inorganic film can be suppressed even when this layered product is exposed to high temperatures.

Moreover, as for content of the total of the color material and the above-mentioned specific resin in the total solid content of a resin composition, 25-100 mass % is preferable. The lower limit is more preferably 30% by mass or more, and more preferably 40% by mass or more. As for an upper limit, 90 mass % or less is more preferable, and 80 mass % or less is still more preferable.

In the resin composition, the content of the above-mentioned 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 with respect to 100 parts by mass of the specific resin described above. The lower limit may be 0 parts by mass, 5 parts by mass or more, or 10 parts by mass or more. Moreover, it is also preferable that the resin composition does not substantially contain the other resin mentioned above. According to this aspect, it is easy to form a film more excellent in heat resistance. The case of substantially not containing other resin means that the content of other resin in the total solids of the resin composition is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably not contained.

<Solvent C>

The resin composition of the present invention contains solvent C (hereinafter referred to as a solvent). The solvent is basically not particularly limited as long as the solubility of each component and the coating properties of the resin composition are satisfied. It is preferable that a solvent is an organic solvent. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. It is preferable that it is at least 1 sort(s) selected. About these details, Paragraph No. 0223 of International Publication No. 2015/166779 can be referred, and this content is integrated in this specification. In addition, an ester-based solvent in which a cyclic alkyl group is substituted and a ketone-based solvent in which a cyclic alkyl group is substituted can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptane one, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, Anisole etc. are mentioned. However, there are cases where it is better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents for reasons such as environmental concerns (for example, 50 mass ppm relative to the total amount of organic solvents). (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In this invention, it is preferable to use the organic solvent with little metal content, and it is preferable that the metal content of an organic solvent is 10 mass ppb (parts per billion) or less, for example. If necessary, an organic solvent at a ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Kosei Co., Ltd. (Cagaku Kogyo Nippo, November 13, 2015). Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter. The filter hole diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

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

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

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

<Pigment derivative>

It is preferable that the resin composition of this invention contains a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimide methyl group. As the chromophore constituting the pigment derivative, quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perrinone skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, threne skeleton, and metal complex skeleton; A rolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable. As an acid group which a pigment derivative has, a sulfo group and a carboxy group are preferable, and a sulfo group is more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable.

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

As a specific example of a pigment derivative, Unexamined-Japanese-Patent No. 56-118462, Unexamined-Japanese-Patent No. 63-264674, Unexamined-Japanese-Patent No. 01-217077, Unexamined-Japanese-Patent No. 03-009961, Japanese Unexamined Patent Publication Hei 03-026767, Japanese Unexamined Patent Publication Hei 03-153780, Japanese Unexamined Patent Publication Hei 03-045662, Japanese Unexamined Patent Publication No. Hei 04-285669, Japanese Unexamined Patent Publication Hei 06-145546, Japanese Unexamined Patent Publication Hei 06-212088, Japanese Patent Laid-Open No. Hei 06-240158, Japanese Patent Laid-Open No. 10-030063, Japanese Patent Laid-Open No. Hei 10-195326, Paragraph Nos. 0086 to 0098 of International Publication No. 2011/024896; Paragraph No. 0063 to 0094 of International Publication No. 2012/102399, Paragraph No. 0082 of International Publication No. 2017/038252, Paragraph No. 0171 of Japanese Unexamined Patent Publication No. 2015-151530, Paragraph No. 0162 to No. 2011-252065 0183, Japanese Unexamined Patent Publication No. 2003-081972, Japanese Patent Publication No. 5299151, Japanese Unexamined Patent Publication No. 2015-172732, Japanese Unexamined Patent Publication No. 2014-199308, Japanese Unexamined Patent Publication No. 2014-085562, Japanese Unexamined Patent Publication 2014 -035351, Unexamined-Japanese-Patent No. 2008-081565, and the compound of Unexamined-Japanese-Patent No. 2019-109512 are mentioned.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. A pigment derivative may use only 1 type, and may use 2 or more types together.

<Polymeric monomer>

It is preferable that the resin composition of this invention contains a polymerizable monomer. As the polymerizable monomer, known compounds crosslinkable by, for example, radicals, acids or heat can be used. Examples of the polymerizable monomer include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, and the like, and a compound having an ethylenically unsaturated bond-containing group is preferable. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. As a cyclic ether group, an epoxy group, an oxetane group, etc. are mentioned. A compound having an ethylenically unsaturated bond-containing group can be preferably used as the radically polymerizable monomer. In addition, a compound having a cyclic ether group can be preferably used as a cationically polymerizable monomer. It is preferable that a polymerizable monomer is a polyfunctional polymerizable monomer. That is, it is preferable that a polymerizable monomer is a monomer which has two or more polymerizable groups, such as an ethylenically unsaturated bond-containing group and a cyclic ether group.

As for the molecular weight of a polymerizable monomer, 100-3000 are preferable. As for an upper limit, 2000 or less are more preferable, and 1500 or less are still more preferable. As for a lower limit, 150 or more are more preferable, and 250 or more are still more preferable.

(Compound having an ethylenically unsaturated bond-containing group)

As the compound having an ethylenically unsaturated bond-containing group used as the polymerizable monomer, it is preferable that it is a polyfunctional compound. That is, it is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and a compound containing 3 to 15 ethylenically unsaturated bond-containing groups It is more preferable that it is, and it is still more preferable that it is a compound containing 3-6 ethylenically unsaturated bond-containing groups. Moreover, it is preferable that it is a tri- to 15-functional (meth)acrylate compound, and, as for the compound which has an ethylenically unsaturated bond-containing group, it is more preferable that it is a tri- to hexafunctional (meth)acrylate compound. As specific examples of the compound having an ethylenically unsaturated bond-containing group, Paragraph Nos. 0095 to 0108 of Unexamined-Japanese-Patent No. 2009-288705, Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-029760, Paragraph Nos. 0254 to 0257 of Unexamined-Japanese-Patent No. 2008-292970 , Paragraph Nos. 0034 to 0038 of Japanese Laid-Open Patent Publication No. 2013-253224, Paragraph No. 0477 of Unexamined-Japanese-Patent No. 2012-208494, Japanese Unexamined Patent Publication No. 2017-048367, Japanese Patent Publication No. 6057891, Japanese Patent Publication No. 6031807, The compound described in Unexamined-Japanese-Patent No. 2017-194662 is mentioned, These content is integrated in this specification.

As the compound having an ethylenically unsaturated bond-containing group, dipentaerythritol tri(meth)acrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate rate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth)acryloyl groups are ethylene glycol and/or A compound having a structure bonded via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer) is preferred. In addition, as a compound having an ethylenically unsaturated bond-containing group, diglycerin EO (ethylene oxide) modified (meth)acrylate (M-460 as a commercial product; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin Nakamura Chemical Industry Co., Ltd.) Co., Ltd., NK Ester A-TMMT), 1,6-Hexanedioldiacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toa Kosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) or the like can also be used.

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

As the compound having an ethylenically unsaturated bond-containing group, a compound having an acid group can also be used. By using a compound having an acid group, generation of development residue can be suppressed. Examples of the acid group include a carboxy group, a sulfo group, and a phosphoric acid group, with a carboxy group being preferable. Examples of commercially available polymerizable monomers having an acid group include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). A preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, solubility in a developing solution is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.

It is also preferable that the compound having an ethylenically unsaturated bond-containing group is a compound having a caprolactone structure. Compounds having a caprolactone structure are commercially available as the KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

As the compound having an ethylenically unsaturated bond-containing group, a compound having an alkyleneoxy group can also be used. 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 a tri-hexafunctional (meth)acrylate having 4 to 20 ethyleneoxy groups. compounds are more preferred. As a commercial product of the compound having an alkyleneoxy group, for example, SR-494, which is a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth)acrylate having three isobutyleneoxy groups. Phosphorus KAYARAD TPA-330 etc. are mentioned.

As the compound having an ethylenically unsaturated bond-containing group, a compound having a fluorene skeleton may be used. As a commercial item of the compound which has a fluorene skeleton, Ogsol EA-0200, EA-0300 (Osaka Gas Chemical Co., Ltd. product, (meth)acrylate monomer which has a fluorene skeleton), etc. are mentioned.

As the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound that does not substantially contain environmental regulating substances such as toluene. As a commercial item of such a compound, KAYARAD DPHA LT, KAYARAD DPEA-12 LT (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

As a compound having an ethylenically unsaturated bond-containing group, Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. Hei 02-032293, Japanese Patent Publication No. Hei 02-016765 Urethane acrylates as described, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418 The urethane compounds having an ethylene oxide-based skeleton described in No. 2 are also suitable. Moreover, it is also preferable to use the polymeric compound which has an amino structure or a sulfide structure in a molecule|numerator of Unexamined-Japanese-Patent No. 63-277653, Unexamined-Japanese-Patent No. 63-260909, and Unexamined-Japanese-Patent No. 01-105238. . In addition, the polymerizable compound is UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 , T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), or other commercially available products can also be used.

(Compound having a cyclic ether group)

Examples of compounds having a cyclic ether group that are also used as polymerizable monomers include compounds having an epoxy group (hereinafter also referred to as epoxy compounds) and compounds having an oxetane group (hereinafter also referred to as oxetane compounds). It is preferable that an epoxy compound is a polyfunctional epoxy compound. That is, it is preferable that an epoxy compound is a compound which has 2 or more epoxy groups. 20 or less are preferable and, as for the upper limit of the number of epoxy groups, 10 or less are more preferable. Moreover, it is preferable that an oxetane compound is a polyfunctional oxetane compound. That is, it is preferable that an oxetane compound is a compound which has 2 or more oxetane groups. 20 or less are preferable and, as for the upper limit of the number of oxetane groups, 10 or less are more preferable.

As a commercial item of an epoxy compound, the commercial item of Unexamined-Japanese-Patent No. 2011-221494, Paragraph 0189, such as JER828, JER1007, JER157S70 (made by Mitsubishi Chemical Co., Ltd.), and JER157S65 (made by Mitsubishi Chemical Holdings Co., Ltd.), etc. are mentioned. . As other commercially available products, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Co., Ltd.), NC-2000, NC-3000, NC-7300, XD-1000, EPPN- 501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), 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 made by Nagase Chemtex), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), Celloxide 2021P, 2081 .

As commercially available products of the oxetane compound, OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ TX-100 (above, manufactured by Toagosei Co., Ltd.), etc. can be used. can

It is preferable that content of the polymerizable monomer in the total solid content of a resin composition is 0.1-40 mass %. 0.5 mass % or more is preferable and, as for a minimum, 1 mass % or more is more preferable. 30 mass % or less is preferable and, as for an upper limit, 20 mass % or less is more preferable.

When using a compound having an ethylenically unsaturated bond-containing group as the polymerizable monomer, the content of the compound having an ethylenically unsaturated bond-containing group as the polymerizable monomer is preferably 1 to 50 parts by mass relative to 100 parts by mass of the above-mentioned specific resin. . It is preferable that it is 3 mass parts or more, and, as for a minimum, it is more preferable that it is 5 mass parts or more. It is preferable that it is 40 mass parts or less, and, as for an upper limit, it is more preferable that it is 30 mass parts or less.

When using a compound having a cyclic ether group 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 with respect to 100 parts by mass of the specific resin described above. It is preferable that it is 3 mass parts or more, and, as for a minimum, it is more preferable that it is 5 mass parts or more. It is preferable that it is 40 mass parts or less, and, as for an upper limit, it is more preferable that it is 30 mass parts or less.

When a compound having an ethylenically unsaturated bond-containing group and a compound having a cyclic ether group are used as polymerizable monomers, the resin composition contains 10 to 10 parts of a compound having a cyclic ether group with respect to 100 parts by mass of the compound having an ethylenically unsaturated bond-containing group. It is preferable to contain 500 mass parts. It is preferable that it is 20 mass parts or more, and, as for a minimum, it is more preferable that it is 30 mass parts or more. It is preferable that it is 400 mass parts or less, and, as for an upper limit, it is more preferable that it is 300 mass parts or less. If the ratio of both is within the above range, a film having more excellent heat resistance (crack suppression and film shrinkage suppression) can be formed.

<Photoinitiator>

It is preferable that the resin composition of this invention contains a photoinitiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light rays in the visible range from the ultraviolet range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

As the photopolymerization initiator, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having an imidazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a biimidazole compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, and a phosphine oxide. compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and It is preferably a 3-aryl-substituted coumarin compound, more preferably a compound selected from biimidazole compounds, oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and oxime compounds It is more preferable to be Moreover, as a photoinitiator, the compound of Paragraph 0065 of Unexamined-Japanese-Patent No. 2014-130173 - 0111, the compound of Unexamined-Japanese-Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, no. 3, a peroxide-based photopolymerization initiator described in 2019, a 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 Unexamined Patent Publication No. 2019-043864, The photoinitiator described in Unexamined-Japanese-Patent No. 2019-044030, and the peroxide-type initiator described in Unexamined-Japanese-Patent No. 2019-167313 are mentioned, These content is integrated in this specification.

As the biimidazole compound, 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4 ',5,5-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole; there is. Commercially available products of the α-hydroxyketone compound include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above, manufactured by BASF), and the like. can Commercially available products of α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (above, manufactured by BASF). there is. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (above, manufactured by BASF) and the like.

As an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2001-233842, the compound described in Unexamined-Japanese-Patent No. 2000-080068, the compound described in Unexamined-Japanese-Patent No. 2006-342166, J. C. S. Perkin II (1979, pp. 1653 -1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Unexamined Patent Publication 2000- A compound described in Japanese Patent Application Publication No. 066385, a compound described in Japanese Patent Publication No. 2004-534797, a compound described in Japanese Unexamined Patent Publication No. 2006-342166, a compound described in Japanese Unexamined Patent Publication No. 2017-019766, a compound described in Japanese Patent Publication No. 6065596 A compound, a compound described in International Publication No. 2015/152153, a compound described in International Publication No. 2017/051680, a compound described in Japanese Unexamined Patent Publication No. 2017-198865, Paragraph No. 0025 of International Publication No. 2017/164127 The compound of 0038, the compound of international publication 2013/167515, etc. are mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentan-3-one. , 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one etc. are mentioned. As commercially available products, Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), Adeka optomer N-1919 (made by ADEKA Co., Ltd., the photoinitiator 2 of Unexamined-Japanese-Patent No. 2012-014052) is mentioned. As the oxime compound, it is also preferable to use a compound having no colorability or a compound having high transparency and hardly discolored. As a commercial item, Adeka Akles NCI-730, NCI-831, NCI-930 (above, made by ADEKA Corporation), etc. are mentioned.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned.

Moreover, as a photoinitiator, the oxime compound which has the frame|skeleton which the at least 1 benzene ring of a carbazole ring turned into a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned.

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

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

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound which has a nitro group as a dimer. As specific examples of the oxime compound having a nitro group, the compounds described in Paragraph Nos. 0031 to 0047 of Unexamined-Japanese-Patent No. 2013-114249, Paragraph Nos. 0008 to 0012, and 0070 to 0079 of Unexamined-Japanese-Patent No. 2014-137466, Japanese Patent Publication The compound described in Paragraph No. 0007 - 0025 of 4223071, Adeka Akles NCI-831 (made by Adeka Co., Ltd.) is mentioned.

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

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

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

[Formula 36]

[Formula 37]

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

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. Since two or more radicals generate|occur|produce from one molecule of radical photopolymerization initiator by using such a radical photopolymerization initiator, favorable sensitivity is obtained. In addition, in the case of using a compound with an asymmetric structure, crystallinity is reduced, solubility in solvents and the like is improved, and it is difficult to precipitate over time, so that the stability over time of the resin composition can be improved. As a specific example of a bifunctional or trifunctional or more than trifunctional radical photopolymerization initiator, paragraphs of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, Japanese Patent Publication No. 2016-532675 Dimers of oxime compounds described in No. 0407 to 0412, Paragraph Nos. 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in Paragraph No. 0007 of Japanese Patent Publication No. 2017-523465, Paragraph Nos. 0020 to 0033 of Japanese Unexamined Patent Publication No. 2017-167399 The photoinitiator described in, the photoinitiator (A) described in Paragraph Nos. 0017-0026 of Unexamined-Japanese-Patent No. 2017-151342, the oxime compound described in Japanese Patent Publication No. 6469669, etc. are mentioned.

As for content of the photoinitiator in the total solid content of a resin composition, 0.1-30 mass % is preferable. 0.5 mass % or more is preferable and, as for a minimum, 1 mass % or more is more preferable. 20 mass % or less is preferable and, as for an upper limit, 15 mass % or less is more preferable. As for the photoinitiator, only 1 type may be used and 2 or more types may be used.

<Silane coupling agent>

The resin composition of the present invention may contain a silane coupling agent. In the present specification, a silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. In addition, a hydrolyzable group refers to a substituent that is directly connected to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, as a functional group other than a hydrolyzable group, a vinyl group, a (meth) allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group, for example These etc. are mentioned, An amino group, a (meth)acryloyl group, and an epoxy group are preferable. As a specific example of a silane coupling agent, the compound of Paragraph No. 0018 of Unexamined-Japanese-Patent No. 2009-288703 - 0036, and the compound of Paragraph No. 0056 of Unexamined-Japanese-Patent No. 2009-242604 - 0066 are mentioned, The content of these is this incorporated into the specification.

As for content of the silane coupling agent in the total solid content of a resin composition, 0.1-5 mass % is preferable. 3 mass % or less is preferable and, as for an upper limit, 2 mass % or less is more preferable. 0.5 mass % or more is preferable and, as for a minimum, 1 mass % or more is more preferable. 1 type of silane coupling agent may be sufficient as it, and 2 or more types may be sufficient as it.

<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 or polymerizable compound or lowering the curing temperature. The curing accelerator is a methylol-based compound (for example, a compound exemplified as a crosslinking agent in Paragraph No. 0246 of Unexamined-Japanese-Patent No. 2015-034963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, A curing agent described in Paragraph No. 0186 of Japanese Unexamined Patent Publication No. 2013-041165), a base generator (eg, an ionic compound described in Japanese Unexamined Patent Publication No. 2014-055114), a cyanate compound (eg, Japanese Unexamined Patent Publication) A compound described in Paragraph No. 0071 of Patent Publication No. 2012-150180), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in Japanese Unexamined Patent Publication No. 2011-253054), an onium salt compound (for example, A compound exemplified as an acid generator in Paragraph No. 0216 of Unexamined-Japanese-Patent No. 2015-034963, a compound described in Unexamined-Japanese-Patent No. 2009-180949), etc. can also 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% by mass, and more preferably 0.8 to 6.4% by mass in the total solid content of the resin composition.

<Polymerization inhibitor>

The resin composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6 -tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salt, cerium salt, etc.). . Among them, p-methoxyphenol is preferred. As for content of the polymerization inhibitor in the total solid content of a resin composition, 0.0001-5 mass % is preferable.

<Surfactant>

The resin composition of the present invention may contain a surfactant. As surfactant, various surfactants, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, anionic surfactant, and a silicone type surfactant, can be used. About surfactant, Paragraph No. 0238 of International Publication No. 2015/166779 - surfactant of 0245 are mentioned, This content is integrated in this specification.

It is preferable that surfactant is a fluorochemical surfactant. By incorporating a fluorine-based surfactant into the resin composition, the liquid properties (particularly, fluidity) can be further improved and the liquid saving property can be further improved. In addition, a film having a small unevenness in thickness can be formed.

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

As a fluorochemical surfactant, the surfactant described in Paragraph No. 0060 - 0064 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph No. 0060 - 0064 of corresponding International Publication No. 2014/017669) etc., Paragraph No. 2011-132503 The surfactant of 0117-0132 and the surfactant of Unexamined-Japanese-Patent No. 2020-008634 are mentioned, These content is integrated in this specification. As commercially available products of fluorine-based surfactants, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F -437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F -561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40 -LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Fluorad FC430, FC431, FC171 (above, Sumitomo 3M manufactured by Suffron Co., Ltd.), Suffron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, OMNOVA Co., Ltd.), Prgent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (above, NEOS Co., Ltd.), etc. can be heard

Moreover, it is also preferable to use the polymer of the vinyl ether compound containing a fluorine atom which has a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound as a fluorochemical surfactant. Description of Unexamined-Japanese-Patent No. 2016-216602 can be considered into consideration for such a fluorochemical surfactant, and this content is integrated in this specification.

A block polymer can also be used for a fluorochemical surfactant. For example, the compound of Unexamined-Japanese-Patent No. 2011-089090 is mentioned. The fluorine-based surfactant is a (meth)acrylate compound having 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group). ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 38]

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

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

0.001 mass % - 5.0 mass % are preferable, and, as for content of surfactant in the total solid content of a resin composition, 0.005-3.0 mass % is more preferable. 1 type may be sufficient as surfactant, and 2 or more types may be sufficient as it. In the case of 2 or more types, it is preferable that the total amount becomes the said range.

<Ultraviolet absorber>

The resin composition of the present invention may contain a UV absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like may be used. can For these details, refer to Paragraph Nos. 0052 to 0072 of Japanese Laid-Open Patent Publication No. 2012-208374, Paragraph Nos. 0317 to 0334 of Unexamined-Japanese-Patent No. 2013-068814, and Paragraph Nos. 0061 to 0080 of Unexamined-Japanese-Patent No. 2016-162946. Reference may be made, the contents of which are incorporated herein. As a commercial item of a ultraviolet absorber, UV-503 (Daito Chemical Co., Ltd. product) etc. are mentioned, for example. Moreover, as a benzotriazole compound, the MYUA series by Miyoshi Yushi Co., Ltd. (Kagaku Kogyo Nippo, February 1, 2016) is mentioned. Moreover, the compound of Paragraph No. 0049 - 0059 of Unexamined-Japanese-Patent No. 6268967 can also be used as a ultraviolet absorber. 0.01-10 mass % is preferable and, as for content of the ultraviolet absorber in the total solid content of a resin composition, 0.01-5 mass % is more preferable. Only 1 type may be used for a ultraviolet absorber, and 2 or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Antioxidant>

The resin composition of the present invention may contain an antioxidant. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the substituent described above, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Moreover, a phosphorus antioxidant can also be used suitably as an antioxidant. Moreover, as an antioxidant, the compound described in Korean Unexamined Patent Publication No. 10-2019-0059371 can also be used. It is preferable that it is 0.01-20 mass %, and, as for content of the antioxidant in the total solid content of a resin composition, it is more preferable that it is 0.3-15 mass %. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Other ingredients>

The resin composition of the present invention, if necessary, a sensitizer, a filler, a heat curing accelerator, a plasticizer, and other auxiliary agents (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, exfoliation accelerators, fragrance, surface tension adjusting agent, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film properties can be adjusted. These components are, for example, described in paragraph No. 0183 of Japanese Laid-open Patent Publication No. 2012-003225 (paragraph No. 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph No. 2008-250074 Reference can be made to descriptions of 0101 to 0104 and 0107 to 0109, the contents of which are incorporated herein by reference. Moreover, the resin composition may contain a latent antioxidant as needed. The latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and the protective group is released by heating at 100 to 250° C. or at 80 to 200° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219. As a commercial item, Adeka Akles GPA-5001 (made by ADEKA Co., Ltd.) etc. are mentioned.

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

The resin composition of the present invention may also contain a light fastness improver. As a light fastness improver, the compound of Paragraph No. 0036 of Unexamined-Japanese-Patent No. 2017-198787 - the compound of 0037, Paragraph No. 0029 of Unexamined-Japanese-Patent No. 2017-146350 - the compound of 0034, Paragraph No. 0036 of Unexamined-Japanese-Patent No. 2017-129774 - 0037, a compound described in 0049 to 0052, a compound described in Paragraph Nos. 0031 to 0034, 0058 to 0059 of Unexamined-Japanese-Patent No. 2017-129674, a compound described in Paragraph Nos. 0036 to 0037, 0051 to 0054 of Unexamined-Japanese-Patent No. , Paragraph Nos. 0025 to 0039 of International Publication No. 2017/164127, a compound described in Paragraph Nos. 0034 to 0047 of Japanese Unexamined Patent Publication No. 2017-186546, and paragraph Nos. 0019 to 0041 of Japanese Unexamined Patent Publication No. 2015-025116 A compound described in Paragraph Nos. 0101 to 0125 of Unexamined-Japanese-Patent No. 2012-145604, a compound described in Paragraph Nos. 0018 to 0021 of Unexamined-Japanese-Patent No. 2012-103475, Paragraph Nos. 0015 to 0018 of Unexamined-Japanese-Patent No. 2011-257591 The compound described, the compound described in Paragraph Nos. 0017 to 0021 of Unexamined-Japanese-Patent No. 2011-191483, the compound described in Paragraph No. 0108 to 0116 of Unexamined-Japanese-Patent No. 2011-145668, Paragraph No. 0103 to 0153 of Unexamined-Japanese-Patent No. 2011-253174 The compounds described in , etc. are mentioned.

In the resin composition of the present invention, the content of a free metal that is not bonded or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, and not substantially contained. particularly preferred. According to this embodiment, effects such as stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of fluctuation in conductivity due to elution of metal atoms and metal ions, improvement of display characteristics, etc. can be expected Moreover, Japanese Unexamined Patent Publication No. 2012-153796, Japanese Unexamined Patent Publication No. 2000-345085, Japanese Unexamined Patent Publication No. 2005-200560, Japanese Unexamined Patent Publication No. 08-043620, Japanese Unexamined Patent Publication 2004-145078, Japanese Unexamined Patent Publication Patent Publication No. 2014-119487, Japanese Unexamined Patent Publication No. 2010-083997, Japanese Unexamined Patent Publication No. 2017-090930, Japanese Unexamined Patent Publication No. 2018-025612, Japanese Unexamined Patent Publication No. 2018-025797, Japanese Unexamined Patent Publication 2017-155228 , the effect described in Unexamined-Japanese-Patent No. 2018-036521, etc. is also acquired. As the type of metal of the above glass, 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 and the like. Further, in the resin composition of the present invention, the content of halogen in glass not bonded or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, and substantially not contained. particularly preferred. Examples of halogen include F, Cl, Br, I and anions thereof. Methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins can be cited as methods for reducing free metals and halogens in the resin composition.

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

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

<Container container>

There is no limitation in particular as a container for the resin composition, and a known container can be used. In addition, as a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 types of 6-layer resin or a bottle in which 6 types of resin are used in a 7-layer structure is used for the purpose of suppressing contamination of raw materials or impurities into the resin composition. is also desirable As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example. The inner wall of the container is also preferably made of glass or stainless steel for the purpose of preventing elution of metal from the inner wall of the container, enhancing the storage stability of the resin composition, or suppressing component deterioration.

<Preparation method of resin composition>

The resin composition of the present invention can be prepared by mixing the components described above. When preparing the resin composition, the resin composition may be prepared by simultaneously dissolving and/or dispersing all components in an organic solvent, and, if necessary, each component is appropriately prepared as a solution or dispersion of two or more, and at the time of use (at the time of application) ) and these may be mixed to prepare a resin composition.

Moreover, it is preferable to include the process of dispersing a pigment at the time of preparation of a resin composition. In the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, compression, impact, shear, cavitation, and the like. Specific examples of these processes include bead mill, sand mill, roll mill, ball mill, paint shaker, microfluidizer, high-speed impeller, sand grinder, float mixer, high-pressure wet atomization, ultrasonic dispersion, and the like. In addition, in pulverization of the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to treat under conditions in which the pulverization efficiency is increased by increasing the filling rate of the beads. In addition, it is preferable to remove coarse particles by filtration, centrifugation or the like after the crushing treatment. In addition, the process and disperser for dispersing the pigment are described in "Complete Collection of Dispersion Technology, published by Joho Kiko Co., Ltd., July 15, 2005" or "Dispersion Technology Centered on Suspension (High/Liquid Dispersion System) and Practice of Industrial Application" Comprehensive Data Collection, Keiei Kaihatsu Center Publishing, October 10, 1978", the process and disperser described in paragraph No. 0022 of Japanese Laid-open Patent Publication No. 2015-157893 can be suitably used. Further, in the process of dispersing the pigment, micronization of the particles may be performed in the salt milling step. For materials, equipment, processing conditions, and the like used in the salt milling process, descriptions of, for example, Japanese Unexamined Patent Publication No. 2015-194521 and Japanese Unexamined Patent Publication No. 2012-046629 can be referred.

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

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

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

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

(membrane)

The film of the present invention is a film obtained from the resin composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters, and near-infrared cutoff filters. Moreover, the film|membrane of this invention can also be used for a black matrix, a light shielding film, etc.

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

When the film of the present invention is used as a color filter, the film of the present invention preferably has a color of green, red, blue, cyan, magenta or yellow. Moreover, the film|membrane of this invention can be used suitably as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

When the film of the present invention is used as a near-infrared cut filter, the maximum absorption wavelength of the film of the present invention is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and in the range of 700 to 1300 nm. It is more preferably in the range of 1100 nm. In addition, the transmittance of the film in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Moreover, it is preferable that the transmittance|permeability at at least 1 point of the wavelength range of 700-1800 nm of a film|membrane is 20 % or less. Further, the absorbance Amax/absorbance A550, which is the ratio between the absorbance Amax at the maximum absorption wavelength and the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. It is more preferable, and it is especially preferable that it is 100 to 400.

When the film of the present invention is used as a near-infrared transmission filter, the film of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i5).

(i1): The maximum value of the transmittance in the range of wavelengths 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelengths 800 to 1500 nm 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 640 nm and transmit light exceeding a wavelength of 750 nm.

(i2): The maximum value of transmittance in the range of wavelength 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelength 900 to 1500 nm 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 750 nm and transmit light exceeding a wavelength of 850 nm.

(i3): The maximum value of transmittance in the range of wavelength 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelength 1000 to 1500 nm 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 830 nm and transmit light exceeding a wavelength of 950 nm.

(i4): The maximum value of the transmittance in the range of wavelengths 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelengths 1100 to 1500 nm 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 950 nm and transmit light exceeding a wavelength of 1050 nm.

(i5): The maximum value of the transmittance in the range of wavelengths 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the range of wavelengths 1200 to 1500 nm 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 1050 nm and transmit light exceeding a wavelength of 1150 nm.

In the film of the present invention, the thickness of the film after heat treatment at 300 ° C. 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 heat treatment, It is even more preferable that it is 95% or more, and it is particularly preferable that it is 99% or more.

In addition, the thickness of the film after heat treatment at 350 ° C. for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, 95% or more of the thickness of the film before heat treatment. It is even more preferable that it is % or more, and it is particularly preferable that it is 99% or more.

Further, the thickness of the film after heat treatment at 400° C. for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and 95% or more of the thickness of the film before heat treatment. It is even more preferable that it is % or more, and it is particularly preferable that it is 99% or more.

<Method for producing membrane>

The film of the present invention can be produced through a step of applying the resin composition of the present invention described above onto a support. In the film production method of the present invention, it is preferable to further include a step of forming a pattern (pixel). Examples of the pattern (pixel) formation method include a photolithography method and a dry etching method, and the photolithography method is preferable.

(Photolithography method)

First, a case where a film is produced by forming a pattern by a photolithography method will be described. Pattern formation by the photolithography method includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer in a pattern shape, and developing and removing the unexposed portion of the resin composition layer. It is preferable to include a process of forming a pattern (pixel) by using If necessary, you may provide a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step).

In the step of forming the resin composition layer, the resin composition layer is formed on the support using the resin composition of the present invention. As a support body, there is no limitation in particular, It can select suitably according to a use. For example, a glass substrate, a silicon substrate, etc. are mentioned, and it is preferable that it is a silicon substrate. In addition, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, in some cases, a black matrix isolating each pixel is formed on the silicon substrate. In addition, a base layer may be provided on the silicon substrate for the purpose of improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. Moreover, it is preferable that it is 30-80 degrees when measured with water. When the surface contact angle of the base layer is within the above range, the coating properties of the resin composition are good. Adjustment of the surface contact angle of the base layer can be performed, for example, by adding a surfactant or the like.

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

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

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

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

Moreover, at the time of exposure, you may expose by irradiating light continuously, and you may expose by irradiating and exposing light pulsewise (pulse exposure). Further, pulse exposure is an exposure method of a system in which light irradiation and pause are repeatedly exposed in cycles of a short time (eg, millisecond level or less). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and still more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 femt second (fs) or more, and may be 10 femt second or more. The frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, and still more preferably 4 kHz or higher. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 50000000 W/m ² or more, more preferably 100000000 W/m ² or more, and even more preferably 200000000 W/m ² or more. The upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m ² or less, more preferably 800000000 W/m ² or less, and still more preferably 500000000 W/m ² or less. In addition, the pulse width is the time during which light is irradiated in the pulse period. Incidentally, the frequency is the number of pulse cycles per second. Moreover, the maximum instantaneous illuminance is the average illuminance within the time during which the light in the pulse period is irradiated. In addition, the pulse period is a period in which light irradiation and pause in pulse exposure are regarded as one cycle.

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

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

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

It is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying after development. Additional exposure treatment and post-baking are curing treatments after development to complete curing. The heating temperature in post-baking is preferably 100 to 240°C, for example, and more preferably 200 to 240°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film meets the above conditions. When performing additional exposure processing, it is preferable that the light used for exposure is light with a wavelength of 400 nm or less. Moreover, you may perform additional exposure processing by the method described in Korean Unexamined Patent Publication No. 10-2017-0122130.

(Dry etching method)

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

<Optical filter>

The optical filter of the present invention has the film of the present invention described above. As the type of optical filter, a color filter, a near-infrared transmission filter, a near-infrared cutoff filter, etc. are mentioned as an optical filter, and it is preferable that it is a color filter. As the color filter, it is preferable to have the film of the present invention as a colored pixel of the color filter. The optical filter of the present invention can be used for a solid-state imaging device such as a charge-coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), image display device, or the like.

In the optical filter, 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.

It is preferable that the width of the pixel included in the optical filter is 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. Moreover, it is preferable that it is 0.5-20 GPa, and, as for the Young's modulus of a pixel, 2.5-15 GPa is more preferable.

Each pixel included in the optical filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, still more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using AFM (atomic force microscope) Dimension3100 by Veeco, for example. Moreover, although the contact angle of water on a pixel can be suitably set to a desirable value, it is typically in the range of 50 to 110 degrees. The contact angle can be measured using, for example, a contact angle meter CV-DT/A type (manufactured by Kyowa Gamemen Chemical Co., Ltd.). In addition, it is preferable that the volume resistance value of the pixel is 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. Although the upper limit is not specified, it is preferable that it is, for example, 10 ¹⁴ Ω·cm or less. The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).

In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilic hydration, and shielding of light (ultraviolet rays, near infrared rays, etc.) of a specific wavelength can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying and forming a resin composition for forming a protective layer dissolved in an organic solvent, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. As components constituting the protective layer, (meth)acrylic resin, enethiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, poly Arylene etherphosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, Aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine resin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ etc. are mentioned, You may contain 2 or more types of these components. For example, in the case of a protective layer for the purpose of blocking oxygen, the protective layer preferably contains a polyol resin, SiO ₂ and Si ₂ N ₄ . In addition, in the case of a protective layer aimed at low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

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

The protective layer may contain additives such as organic/inorganic fine particles, an absorber for light of a specific wavelength (eg, ultraviolet rays, near infrared rays, etc.), a refractive index modifier, an antioxidant, an adhesive agent, and a surfactant, if necessary. Examples of organic/inorganic fine particles include, for example, polymer fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and oxynitride. Titanium, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, etc. are mentioned. As an absorber of light of a specific wavelength, a known absorber can be used. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer. Moreover, as a protective layer, the protective layer of Paragraph No. 0073 of Unexamined-Japanese-Patent No. 2017-151176 - 0092 can also be used.

The optical filter may have a structure in which each pixel is embedded in a space partitioned in a lattice shape, for example, by barrier ribs. Moreover, the resin composition of this invention can be used suitably also for the pixel structure described in international publication 2019/102887.

<Solid-state imaging device>

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

On a substrate, a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon, etc., On the photodiode and the transfer electrode, there is a light blocking film in which only the light receiving portion of the photodiode is opened, and a device protective film made of silicon nitride or the like formed to cover the entire surface of the light blocking film and the light receiving portion of the photodiode is formed on the light blocking film, and a color filter is provided on the device protective film. It is a composition with Further, a structure having a light concentrating means (for example, a microlens, etc., hereinafter the same) on the device protective film and below the color filter (on the side close to the substrate), or a constitution having a light concentrating means on the color filter may be used. Further, the color filter may have a structure in which each color pixel is embedded in a space partitioned in a lattice shape, for example, by barrier ribs. It is preferable that the partition in this case has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in Japanese Laid-open Patent Publication No. 2012-227478, Japanese Laid-Open Patent Publication No. 2014-179577, International Publication No. 2018/043654, and United States Patent Application Publication No. 2018/0040656 can be heard Moreover, as in Japanese Unexamined Patent Publication No. 2019-211559, an ultraviolet ray absorbing layer may be provided in the structure of the solid-state imaging device to improve light resistance. The imaging device provided with the solid-state imaging element of the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an imaging function, but also for in-vehicle cameras and surveillance cameras. In addition to the color filter of the present invention, a solid-state imaging device incorporating the color filter of the present invention may also incorporate another color filter, a near-infrared cut filter, an organic photoelectric conversion film, or the like.

<Image Display Device>

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

Example

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

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

The weight average molecular weight of the sample was measured under the following conditions by gel permeation chromatography (GPC).

Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 connected columns

Developing solvent: tetrahydrofuran

Column temperature: 40°C

Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)

Device name: Tosoh HLC-8220GPC

Detector: RI (Refractive Index) Detector

Calibration curve base resin: polystyrene resin

<Measurement of acid value of sample>

The acid value of the sample represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of solid content in the sample. The acid value of the sample was measured as follows. That is, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the obtained solution was 25° C. using a potentiometric titration device (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). Neutralization titration was performed with a 0.1 mol/L potassium hydroxide aqueous solution. The acid value was calculated by the following formula, using the inflection point of the titration pH curve as the titration end point.

A=56.11×Vs×0.5×f/w

A: acid value (mgKOH/g)

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

f: Potency of 0.1 mol/L aqueous solution of potassium hydroxide

w: mass of sample (g) (converted to solid content)

<Synthesis of end capping agent macromonomer>

(Synthesis Example 1-1) Synthesis example of terminal blocker macromonomer EDM-1

2.3 g of 2-mercaptoethanol, 35 g of ε-caprolactone, and 0.5 g of monobutyl tin oxide were added to a three-necked flask purged with nitrogen, and heated and stirred at 90°C for 2 hours and at 120°C for 6 hours to make polyester at both ends. A polymer having an SH group and an OH group was obtained. After cooling to 5 deg. C, 0.5 g of acetyl chloride was added and further stirred for 2 hours to seal the OH group terminal to obtain a polymer having SH groups at one end. Next, 4.1 g of 2-acryloyloxyethyl isocyanate (Karenz AOI, Showa Denko Co., Ltd.) and 0.3 g of polymerization initiator (V-601, Fujifilm Wako Junyaku Co., Ltd.) was added, and an enethiol reaction was carried out with heating and stirring at 80°C for 2 hours to obtain end capping agent macromonomer EDM-1.

(Synthesis Examples 1-2 and 1-3) Synthesis Examples of End Capping Agent Macromonomers EDM-2 and EDM-3

End capping agent macromonomers EDM-2 and EDM-3 were synthesized in the same manner as in Synthesis Example 1-1.

(Synthesis Example 1-4) Synthesis example of terminal blocker macromonomer EDM-4

181.3 g of methyl methacrylate and 200.2 g of butyl acrylate were added to a three-necked flask purged with nitrogen, and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated at 75°C under a nitrogen atmosphere. Next, 9.2 g of 3-mercaptopropionic acid and 2.2 g of polymerization initiator (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and heating and stirring were performed at 75° C. for 8 hours in a nitrogen atmosphere. 7.3 g of thionyl chloride was added to the obtained polymer solution, and further heating was stirred at 75°C for 2 hours. The weight average molecular weight of the obtained terminal blocker macromonomer EDM-4 was 7400.

(Synthesis Example 1-5) Synthesis example of terminal blocker macromonomer EDM-5

End capping agent macromonomer EDM-5 was synthesized in the same manner as in Synthesis Example 1-4.

(Synthesis Example 1-6) Synthesis example of terminal blocker macromonomer EDM-6

181.3 g of methyl methacrylate and 200.2 g of butyl acrylate were added to a three-necked flask purged with nitrogen, and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated at 75°C under a nitrogen atmosphere. Next, 19.9 g of 6-mercaptohexanol and 2.2 g of a polymerization initiator (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 75° C. for 8 hours in a nitrogen atmosphere. 37.3 g of pyromellitic anhydride was added to the obtained polymer solution, and the mixture was heated and stirred at 75°C for 2 hours. Unreacted pyromellitic anhydride was removed by filtration as an insoluble matter. The weight average molecular weight of the obtained terminal blocker macromonomer EDM-6 was 2400.

(Synthesis Example 1-7) Synthesis example of terminal blocker macromonomer EDM-7

End capping agent macromonomer EDM-7 was synthesized in the same manner as in Synthesis Example 1-6.

(Synthesis Example 1-8) Synthesis example of terminal blocker macromonomer EDM-8

6.1 g of 6-mercaptohexanol, 35 g of ε-caprolactone, and 0.5 g of monobutyl tin oxide were added to a three-necked flask purged with nitrogen, and heated and stirred at 90°C for 2 hours and at 120°C for 6 hours to obtain polyester A polymer having an SH group and an OH group at the terminal was obtained. After cooling to 5 deg. Next, 5.5 g of itaconic anhydride and 0.3 g of a polymerization initiator (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, heated and stirred at 80° C. for 2 hours to carry out an ene-thiol reaction, and an end capping agent was obtained. A macromonomer EDM-8 was obtained.

(Synthesis Examples 1-9 to 1-15) Synthesis Examples of End Capping Agent Macromonomers EDM-9 to EDM-15

End capping agent macromonomers EDM-9 to EDM-15 were synthesized in the same manner as in Synthesis Example 1-8.

(Synthesis Example 1-16) Synthesis example of terminal blocker macromonomer EDM-16

281.3 g of methyl methacrylate and 100.2 g of butyl acrylate were added to a three-necked flask purged with nitrogen, and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated at 75°C under a nitrogen atmosphere. Next, 13.9 g of chain transfer agent (AAA-1) and 2.5 g of polymerization initiator (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and heating and stirring were performed at 75° C. for 8 hours in a nitrogen atmosphere. The weight average molecular weight of the obtained terminal blocker macromonomer EDM-16 was 7400.

[Formula 39]

(Synthesis Examples 1-17 to 1-20) Synthesis examples of terminal capping agent macromonomers EDM-17 to EDM-20

End capping agent macromonomers EDM-17 to EDM-20 were synthesized in the same manner as in Synthesis Example 1-16.

(Synthesis Example 1-21) Synthesis example of terminal blocker macromonomer EDM-21

151.3 g of methyl methacrylate and 230.2 g of butyl acrylate were added to a three-necked flask purged with nitrogen, and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated at 75°C under a nitrogen atmosphere. Next, 20.9 g of 6-mercaptohexanol and 2.0 g of a polymerization initiator (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and heating and stirring were performed at 75° C. for 8 hours in a nitrogen atmosphere. The obtained polymer solution of the terminal hydroxy group was cooled to 5°C, 32.1 g of trimellitic acid chloride anhydride was added, and 15.3 g of pyridine was added dropwise over 6 hours. Furthermore, it stirred at room temperature for 24 hours, and filtered and removed the insoluble matter. The weight average molecular weight of the obtained terminal blocker macromonomer EDM-21 was 7800.

(Synthesis Examples 1-22 to 1-40) Synthesis Examples of Terminal Capping Agent Macromonomers EDM-22 to EDM-40

End capping agent macromonomers EDM-22 to EDM-40 were synthesized in the same manner as in Synthesis Example 1-21.

The structure and weight average molecular weight (Mw) of terminal blocker macromonomer EDM-1 - EDM-40 are shown below. In addition, in Poly, the numerical values added to the repeating units of EDM-1 to EDM-3, EDM-8 to EDM-15, and EDM-27 to EDM-29 represent the number of repeating units, and 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, EDM-40 repeat units Indicates the mole ratio of units. Moreover, the structure described by Poly is P1 of Formula ( ¹ ).

[Table 1]

[Table 2]

[Table 3]

<Synthesis example of resin>

(Synthesis Example 2-1) Synthesis of Resin B-1

3.3 g of 1,3-phenylenediamine (diamine DA-1: manufactured by Tokyo Kasei) was added to a three-necked flask purged with nitrogen, 10 g of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 40°C. . To this, 2.2 g of pyromellitic anhydride (acid dianhydride AA-1: manufactured by Tokyo Kasei) was added and heated and stirred at 40°C for 6 hours to obtain an amino acid prepolymer having amino groups at both ends. A 30% propylene glycol monomethyl ether acetate solution of Resin B-1 was obtained by adding 19 g (in terms of solid content) of the terminal blocker macromonomer EDM-1 to this prepolymer solution and heating and stirring at 40°C for 2 hours. The weight average molecular weight of obtained Resin B-1 was 20600, and the acid value was 55 mgKOH/g.

(Synthesis Examples 2-2 to 2-93) Synthesis of resins B-2 to B-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, end-capping agent macromonomer, and end-capping agent were changed to the types and amounts charged in the table below. . The weight average molecular weight (Mw) and acid value of each resin are listed together in the table below.

[Table 4]

[Table 5]

[Table 6]

End capping agent macromonomers EDM-1 to EDM-40 are compounds each having the structure described above. In addition, acid dianhydrides AA-1 to AA-8, diamines DA-1 to DA-7, and terminal blockers ED-1 to ED-3 are compounds having structures shown below, respectively.

[Formula 40]

[Formula 41]

[Formula 42]

<Preparation of dispersion>

After mixing and dispersing the mixture of the raw materials listed in the table below for 3 hours using a bead mill (using zirconia beads with a diameter of 0.3 mm), a high-pressure disperser NANO-3000-10 (Nippon BEE ( The dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 MPa using Co.). 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 units of numerical values in the table above are parts by mass. Among the raw materials shown in the table above, the details of the abbreviated raw materials are as follows.

[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 S 0100 CF (manufactured by BASF, compound with the following structure, lactam pigment)

[Formula 43]

PBk32: C. I. Pigment Black 32 (compound of the following structure, perylene pigment)

[Formula 44]

[Pigment Derivative]

Derivative 1: a compound of the structure

[Formula 45]

Derivative 2: a compound of the structure

[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: Resin having the following structure (weight average molecular weight is 10885, acid value is 74 mgKOH/g. The base material of "Polym" is a polymer chain having a structure in which repeating units of the structure represented by "Polym" are bonded by the number of subscripts. It shows that it is bonded to the sulfur atom (S).)

[Formula 47]

〔solvent〕

C-1: propylene glycol monomethyl ether acetate

C-2: propylene glycol monomethyl ether

C-3: cyclohexanone

<Preparation of resin composition>

Resin compositions of Examples and Comparative Examples were prepared by mixing the raw materials listed in the table below.

[Table 15]

[Table 16]

[Table 17]

Among the raw materials listed in the table above, details of the abbreviated raw materials 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 dispersions described above

〔profit〕

Ba-1: resin having the following structure (the numerical value added to the main chain is a molar ratio. Weight average molecular weight 11000)

[Formula 48]

Ba-2: resin having the following structure (the numerical value added to the main chain is a molar ratio. Weight average molecular weight 15000)

[Formula 49]

Ba-3: resin having the following structure (the numerical value added to the main chain is a molar ratio. The sum of x, y, and z is 50. Mw = 15000)

[Formula 50]

Bb-1: resin having the following structure (the numerical value added to the main chain is a molar ratio. Weight average molecular weight 13000)

[Formula 51]

[Polymeric monomer]

D-1: Acrylate compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

D-2: Epoxy compound (TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd., N,N,N',N'-tetraglycidyl-m-xylylenediamine)

D-3: oxetane compound (OXT-221, manufactured by Toagosei Co., Ltd., 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane)

D-4: Oxetane compound (OX-SQ TX-100, manufactured by Toagosei Co., Ltd.)

[Photoinitiator]

E-1: Omnirad 379EG (manufactured by IGM Resins B.V., 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one)

E-2: Irgacure OXE01 (manufactured by BASF, oxime compound)

E-3: a compound having the following structure

[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 Example and Comparative Example, the viscosity (mPa·s) of each resin composition was measured with "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the said measurement, the resin composition was left still at 45 degreeC, light-shielding, and 3-day conditions, and the viscosity (mPa*s) was measured again. The storage stability was evaluated according to the following evaluation criteria from the viscosity difference (ΔVis) before and after the said stationary. It can be said that the smaller the numerical value of the difference in viscosity (ΔVis), the better the storage stability of the resin composition and the better the dispersibility of the pigment. All of the above viscosity measurements were measured in a laboratory where the temperature and humidity were controlled at 22±5° C. and 60±20%, in a state where the temperature of the resin composition was adjusted to 25° C.

-Evaluation standard-

A: ΔVis was 0.5 mPa·s or less.

B: ΔVis was more than 0.5 mPa·s and 1.0 mPa·s or less.

C: ΔVis was more than 1.0 mPa·s and 2.0 mPa·s or less.

D: ΔVis was more than 2.0 mPa·s and 2.5 mPa·s or less.

E: ΔVis exceeded 2.5 mPa·s.

(particle diameter)

Using a dynamic light scattering type particle size distribution analyzer (LB-500, manufactured by Horiba Seisakusho Co., Ltd.) in accordance with JIS8826:2005, the resin composition obtained above was fractionated into a 20 ml sample bottle and mixed with propylene glycol monomethyl ether acetate. Dilution was adjusted so that the solid content concentration would be 0.2% by mass. Using a 2 ml measuring quartz cell at a temperature of 25°C, the diluted solution data was extracted 50 times, and the arithmetic mean particle diameter (number average particle diameter) of the obtained number-based pigment was determined. It can be said that the dispersibility of the pigment is so good that the value of the number average particle diameter of the pigment is small.

-Evaluation standard-

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

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

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

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

E: The number average particle diameter of the pigment exceeded 0.50 µm.

[Evaluation of film shrinkage rate]

In each of Examples and Comparative Examples, each resin composition was applied by spin coating on a glass substrate, dried (prebaked) at 100° C. for 120 seconds using a hot plate, and then baked at 200° C. for 30 minutes using an oven. It heated (postbaked) to prepare a film with a thickness of 0.60 μm. For the film thickness, a part of the film was shaved to expose the surface of the glass substrate, and the difference in level between the surface of the glass substrate and the coating film (film thickness of the coating film) was measured using a stylus level meter (DektakXT, manufactured by BRUKER). Next, the obtained film was subjected to heat treatment at 300°C for 5 hours in a nitrogen atmosphere. The film thickness of the film after the heat treatment was measured in the same manner, the film shrinkage rate was obtained from the following formula, and the film shrinkage rate was evaluated according to the following evaluation criteria. The following T ₀ and T ₁ were all measured in a laboratory where the temperature and humidity were controlled at 22±5° C. and 60±20%, and the substrate temperature was adjusted to 25° C. It can be said that the smaller the film shrinkage rate is, the more the film shrinkage is suppressed, which is a preferable result.

Film shrinkage rate (%)=(1-(T ₁ /T ₀ ))×100

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

T ₁ : Film thickness after heat treatment at 300 ° C. for 5 hours in a nitrogen atmosphere

-Evaluation standard-

A: The film shrinkage rate was 1% or less.

B: The film shrinkage rate was more than 1% and 5% or less.

C: The film shrinkage rate was more than 5% and 10% or less.

D: The film shrinkage rate was more than 10% and 30% or less.

E: The film shrinkage rate exceeded 30%.

[Evaluation of cracks]

In each of Examples and Comparative Examples, each resin composition was applied by spin coating on a glass substrate, dried (prebaked) at 100° C. for 120 seconds using a hot plate, and then baked at 200° C. for 30 minutes using an oven. It heated (postbaked) to prepare a film with a thickness of 0.60 μm. Subsequently, 200 nm of SiO ₂ was laminated on the surface of the obtained film by a sputtering method to form an inorganic film. The film on which the inorganic film was formed was subjected to heat treatment at 300°C for 5 hours in a nitrogen atmosphere. The surface of the inorganic film after heat treatment was observed with an optical microscope, the number of cracks per 1 cm ² was counted, and the presence or absence of cracks was evaluated according to the following evaluation criteria.

-Evaluation standard-

A: The number of cracks per 1 cm ² was zero.

B: The number of cracks per 1 cm ² was 1 to 10.

C: The number of cracks per 1 cm ² was 11 to 50.

D: The number of cracks per 1 cm ² was 51 to 100.

E: The number of cracks per 1 cm ² was 101 or more.

[Table 18]

[Table 19]

[Table 20]

In the case of using the resin composition of Examples, compared to the case of using the resin composition of Comparative Example, all of them were excellent in evaluation of storage stability and particle size, and excellent in pigment dispersibility. Furthermore, when the resin compositions of Examples were used, compared to the case where the resin compositions of Comparative Examples were used, the film shrinkage rates were small in all cases, and generation of cracks was suppressed. For this reason, it can be said that it is possible to aim at expanding the process window in the process after film|membrane production compared with the resin composition of a comparative example.

(Example 1000: Pattern formation by photolithography method)

On a silicon wafer, the resin composition of Example 1 was applied by spin coating, dried using a hot plate at 100° C. for 120 seconds (pre-baking), and then heated using an oven at 200° C. for 30 minutes (post-baking). Thus, a resin composition layer having a thickness of 0.60 μm was formed. Next, with respect to this resin composition layer, an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.) was used to pass through a mask pattern in which square unmasked portions with a side of 1.1 μm were arranged in an area of 4 mm × 3 mm. It was exposed by irradiating light with a wavelength of 365 nm at an exposure amount of 500 mJ/cm ² . Next, the silicon wafer on which the resin composition layer after exposure is formed is placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and a developer (CD-2000, Fujifilm Electronic Material Puddle development was carried out at 23 ° C. for 60 seconds using Next, while rotating the silicon wafer at a rotational speed of 50 rpm, pure water was supplied from the ejection nozzle onto the shower from above the center of rotation to perform a rinse treatment, and then spray drying was performed to form a pattern (pixel).

The produced silicon wafer with pixels was divided into two, and one side was heat-processed at 300°C for 5 hours in a nitrogen atmosphere (hereinafter, one side is referred to as a substrate before 300°C heat treatment and the other side is referred to as a substrate after 300°C heat treatment). As a result of evaluating cross sections of the substrate before the 300 ° C heat treatment and the pixel formed on the substrate after the 300 ° C heat treatment with a scanning electron microscope (SEM), the height (thickness) of the pixel formed on the substrate after the 300 ° C heat treatment ) was 97% of the height (thickness) of the pixel formed on the substrate before the 300°C heat treatment.

Claims (19)

A color material A containing a pigment;
Resin B,
Contains solvent C,
Resin composition in which the said resin B contains resin b-1 containing the structure represented by Formula (1);
[Formula 1]

In Formula (1), X ¹ represents a tetravalent linking group;
X ² represents a divalent linking group;
R ¹¹ , R ¹² , R ²¹ , R ²² 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 divalent linking group;
P ¹ represents a polymer chain,
n represents an integer greater than or equal to 1; The method of claim 1,
The resin composition in which Lp2 of Formula ( ¹ ) is -O- or -S-. According to claim 1 or claim 2,
A resin composition in which X ¹ in the formula (1) is a group containing an aromatic hydrocarbon ring. The method according to any one of claims 1 to 3,
A resin composition in which X ² in the formula (1) is a group containing a fluorine atom and an aromatic hydrocarbon ring. The method according to any one of claims 1 to 4,
The resin composition in which the polymer chain represented by P ¹ includes a repeating unit of at least one structure selected from a poly(meth)acrylic structure, a polystyrene structure, a polyether structure, and a polyester structure. The method according to any one of claims 1 to 4,
A resin composition in which the polymer chain represented by P ¹ includes a repeating unit represented by any one of formulas (P1-1) to (P1-6);
[Formula 2]

In the formula, 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 an arylene group;
L ^G2 represents a single bond or a divalent linking group;
R ^G4 represents a hydrogen atom or a substituent;
R ^G5 represents a hydrogen atom or a methyl group, and R ^G6 represents an aryl group. The method of claim 6,
The resin composition in which the substituent represented by R ^G4 is at least one selected from an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a t-butyl group. According to any one of claims 1 to 7,
A resin composition in which the structure represented by the formula (1) is a structure represented by the formula (1-1);
[Formula 3]

In formula (1-1), X ¹ represents a tetravalent linking group;
X ² represents a divalent linking group;
R ¹¹ , R ¹² , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a substituent;
Rp ¹¹ represents a substituent, m Rp ¹¹ may be the same or different,
Lp ¹¹ represents an n+1 valent linking group;
Lp ² represents a divalent linking group;
P ¹ represents a polymer chain;
n represents an integer greater than or equal to 1;
m represents an integer from 0 to 4; The method according to any one of claims 1 to 8,
The resin composition in which the said solvent C contains at least 1 sort(s) selected from ester type solvent, ether type solvent, alcohol type solvent, and ketone type solvent. The method according to any one of claims 1 to 9,
The resin composition in which the said color material A contains at least 1 sort(s) chosen from a diketopyrrolopyrrole pigment and a phthalocyanine pigment. The method according to any one of claims 1 to 10,
A resin composition further comprising a polymerizable monomer. According to any one of claims 1 to 11,
A resin composition further comprising a photopolymerization initiator. A film obtained by using the resin composition according to any one of claims 1 to 12. An optical filter having the film according to claim 13. A solid-state imaging device having the film according to claim 13. An image display device having the film according to claim 13. Resin containing the structure represented by Formula (1);
[Formula 4]

In Formula (1), X ¹ represents a tetravalent linking group;
X ² represents a divalent linking group;
R ¹¹ , R ¹² , R ²¹ , R ²² 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 divalent linking group;
P ¹ represents a polymer chain,
n represents an integer greater than or equal to 1; a compound represented by formula (EDM1);
[Formula 5]

In formula (EDM1), R ^ED1 represents an acid anhydride group;
Lp ^ED1 represents an n+1 valent group, and the n+1 valent group is a hydrocarbon group, or a hydrocarbon group and -NRp ^ED1 -, -N<, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ^ED1 CO- and -CONRp ^ED1 - is a group having a structure combining at least one group selected from,
Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
Lp ^ED2 represents -O- or -S-;
P ^ED1 represents a polymer chain containing a repeating unit represented by any one of formulas (P1-1) to (P1-4);
n represents an integer of 1 to 4;
[Formula 6]

In formulas (P1-1) to (P1-4), R ^G1 and R ^G2 each represent an alkylene group. The method of claim 18
The compound represented by the formula (EDM1) is a compound represented by the formula (EDM2);
[Formula 7]

In formula (EDM2), R ^ED12 represents a halogen atom, an alkyl group, a carboxy group or a hydroxy group;
Lp ^ED1a represents an n+1 valent group, wherein the n+1 valent group is a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded together with a single bond or a linking group, and the linking group is -NRp ^ED1 -, -SO -, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ^ED1 CO- or -CONRp ^ED1 ;
Rp ^ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
Lp ^ED2 represents -O- or -S-;
P ^ED1 represents a polymer chain containing a repeating unit represented by any one of the formulas (P1-1) to (P1-4);
r represents an integer from 0 to 3,
n represents the integer of 1-4.