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

Abstract

The resin composition includes a pigment-containing colorant A, a resin B, and a solvent C. The resin B includes a resin b-1 having a structure represented by formula (1). A film obtained using the resin composition, an optical filter, a solid-state imaging element, an image display device, a resin, and a compound. In formula (1), X1 represents a tetravalent linking group, X2 represents a divalent linking group, R11, R12, R21, R22, and R23 each independently represents a hydrogen atom or a substituent, Lp1 represents an n + 1 valent linking group, Lp2 represents a divalent linking group, P1 represents a polymer chain, and n represents an integer of 1 or more. # imgabs0 #

Description

[0001] This application is a divisional application of the application number 202180044097.4 filed by the applicant and the invention name is “resin composition, film, filter, solid-state imaging element, image display device, resin and compound”. The application date of the parent case is July 19, 2021, and the priority date is July 22, 2020. Technical Field

[0002] The present invention relates to a resin composition, a film, an optical filter, a solid-state imaging element, an image display device, a resin and a compound. Background Art

[0003] In recent years, with the popularization of digital cameras, mobile phones with cameras, etc., the demand for solid-state imaging elements such as charge coupled devices (CCD) image sensors has increased significantly. Films containing pigments such as color filters are used in solid-state imaging elements. Films containing color materials such as color filters are manufactured using resin compositions containing pigments, resins, and solvents.

[0004] For example, Patent Document 1 discloses an invention concerning a resin composition comprising a pigment, a dispersant, a binder resin, an epoxy compound and a solvent and comprising the following dispersant (X): the dispersant comprises a polyester portion X1' having a carboxyl group formed by reacting an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2) with a hydroxyl group in a hydroxyl-containing compound (a), and a vinyl polymer portion X2' having a thermally crosslinkable functional group formed by free radical polymerization of an ethylenically unsaturated monomer (c), wherein the thermally crosslinkable functional group is at least one selected from a hydroxyl group, an oxetane group, a tert-butyl group, a blocked isocyanate group and a (meth)acryloyl group.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2016-170325 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] In the resin composition comprising a pigment, a resin and a solvent, it is preferred that the dispersibility of the pigment is good. If the dispersibility of the pigment is insufficient, the pigment agglomerates in the resin composition and becomes coarse or the viscosity of the resin composition tends to increase. Furthermore, even if the viscosity of the resin composition is low immediately after manufacture, the viscosity may increase over time.

[0010] According to the research conducted by the present inventors, it has been found that the dispersibility of the pigment in the resin composition described in Patent Document 1 is also insufficient, and there is room for further improvement.

[0011] Therefore, the object of the present invention is to provide a resin composition having excellent pigment dispersibility. In addition, the object of the present invention is to provide a film, an optical filter, a solid-state imaging element, and an image display device using the resin composition. In addition, the object of the present invention is to provide a resin and a compound.

[0012] Means for solving technical problems

[0013] Hereinafter, examples of representative embodiments of the present invention will be described.

[0014] <1> A resin composition comprising a color material A containing a pigment, a resin B and a solvent C,

[0015] The above-mentioned resin B includes a resin b-1 having a structure represented by formula (1),

[0016] Resin composition;

[0017] [Chemical formula 1]

[0018]

[0019] In formula (1), X 1 represents a 4-valent linking group,

[0020] X 2 represents a divalent linking group,

[0021] R 11 , R 12 , R 21 , R 22 and R 23 each independently represents a hydrogen atom or a substituent,

[0022] Lp 1 represents an n+1 valent connecting group,

[0023] Lp 2 represents a divalent linking group,

[0024] P 1 represents the polymer chain,

[0025] n represents an integer of 1 or greater.

[0026] <2> according to <1> The resin composition, wherein

[0027] Lp in the above formula (1) 2 It is -O- or -S-.

[0028] <3> according to <1> or <2> The resin composition, wherein

[0029] X in the above formula (1) 1 It is a group containing an aromatic hydrocarbon ring.

[0030] <4> according to <1> to <3> The resin composition described in any one of the preceding claims, wherein

[0031] X in the above formula (1) 2 It is a group containing a fluorine atom and an aromatic hydrocarbon ring.

[0032] <5> according to <1> to <4> The resin composition described in any one of the preceding claims, wherein

[0033] The above P 1 The polymer chain represented includes a repeating unit of at least one structure selected from the group consisting of a poly(meth)acrylic acid structure, a polystyrene structure, a polyether structure, and a polyester structure.

[0034] <6> according to <1> to <4> The resin composition described in any one of the preceding claims, wherein

[0035] The above P 1 The polymer chain represented by includes a repeating unit represented by any of formula (P1-1) to formula (P1-6),

[0036] [Chemical formula 2]

[0037]

[0038] In the formula, R G1 and R G2 represent alkylene groups,

[0039] R G3 represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a hydroxymethyl group,

[0040] Q G1 Indicates -O- or -NR q -, R q represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

[0041] L G1 represents a single bond or an arylene group,

[0042] L G2 represents a single bond or a divalent connecting group,

[0043] R G4 represents a hydrogen atom or a substituent,

[0044] R G5 represents a hydrogen atom or a methyl group, R G6 It represents an aryl group.

[0045] <7> according to <6> The resin composition, wherein

[0046] By R G4 The substituent represented by is at least one selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a tert-butyl group.

[0047] <8> according to <1> to <7> The resin composition described in any one of the preceding claims, wherein

[0048] The structure represented by the above formula (1) is a structure represented by formula (1-1),

[0049] [Chemical formula 3]

[0050]

[0051] In formula (1-1), X 1 represents a 4-valent linking group,

[0052] X 2 represents a divalent linking group,

[0053] R 11 , R 12 , R 21 , R 22 and R 23 each independently represents a hydrogen atom or a substituent,

[0054] R 11 Represents a substituent, m Rp 11 Can be the same or different.

[0055] Lp 11 represents an n+1 valent connecting group,

[0056] Lp 2 represents a divalent linking group,

[0057] P 1 represents the polymer chain,

[0058] n represents an integer greater than 1,

[0059] m represents an integer of 0-4.

[0060] <9> according to <1> to <8> The resin composition described in any one of the preceding claims, wherein

[0061] The solvent C includes at least one selected from the group consisting of ester solvents, ether solvents, alcohol solvents, and ketone solvents.

[0062] <10> according to <1> to <9> The resin composition described in any one of the preceding claims, wherein

[0063] The color material A includes at least one selected from the group consisting of a diketopyrrolopyrrole pigment and a phthalocyanine pigment.

[0064] <11> according to <1> to <10> The resin composition described in any one of the preceding claims further comprises a polymerizable monomer.

[0065] <12> according to <1> to <11> The resin composition described above further comprises a photopolymerization initiator.

[0066] <13> A membrane, using <1> to <12> It can be obtained by using the resin composition described in any one of the above.

[0067] <14> A filter having <13> The membrane.

[0068] <15> A solid-state imaging element having <13> The membrane.

[0069] <16> An image display device having <13> The membrane.

[0070] <17> A resin comprising a structure represented by formula (1),

[0071] [Chemical formula 4]

[0072]

[0073] In formula (1), X 1 represents a 4-valent linking group,

[0074] X 2 represents a divalent linking group,

[0075] R 11 , R 12 , R 21 , R 22 and R 23 each independently represents a hydrogen atom or a substituent,

[0076] Lp 1 represents an n+1 valent connecting group,

[0077] Lp 2 represents a divalent linking group,

[0078] P 1 represents the polymer chain,

[0079] n represents an integer of 1 or greater.

[0080] <18> A compound represented by formula (EDM1),

[0081] [Chemical formula 5]

[0082]

[0083] In formula (EDM1), R ED1 represents anhydride group,

[0084] Lp ED1 represents an n+1 valent group, wherein the n+1 valent group is a hydrocarbon group or a hydrocarbon group and a group selected from -NRp ED1 -、-N<、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO- and -CONRp ED1 -a group of a structure composed of at least one group in combination,

[0085] R ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

[0086] Lp ED2 Indicates -O- or -S-,

[0087] P ED1 represents a polymer chain including a repeating unit represented by any of formula (P1-1) to formula (P1-4),

[0088] n represents an integer from 1 to 4,

[0089] [Chemical formula 6]

[0090]

[0091] In formula (P1-1) to formula (P1-4), R G1 and R G2 respectively represent an alkylene group.

[0092] <19> according to <18> The compound, wherein

[0093] The compound represented by the above formula (EDM1) is a compound represented by formula (EDM2),

[0094] [Chemical formula 7]

[0095]

[0096] In formula (EDM2), R ED12 represents a halogen atom, an alkyl group, a carboxyl group or a hydroxyl group,

[0097] 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 via a single bond or a linking group, the linking group being -NRp ED1 -、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRpED1 CO-or-CONRp ED1 ,

[0098] R ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

[0099] Lp ED2 Indicates -O- or -S-,

[0100] P ED1 represents a polymer chain including a repeating unit represented by any of the above formulas (P1-1) to (P1-4),

[0101] r represents an integer from 0 to 3,

[0102] n represents an integer of 1 to 4.

[0103] Effects of the Invention

[0104] According to the present invention, a resin composition having excellent pigment dispersibility can be provided. Also, a film, an optical filter, a solid-state imaging element, and an image display device using the resin composition can be provided. Also, a resin and a compound can be provided. DETAILED DESCRIPTION

[0105] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0106] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0107] In the marking of groups (atomic groups) in this specification, the marking not indicating substituted or unsubstituted includes groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0108] In this specification, "exposure" includes not only exposure using light, but also painting using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, examples of light used for exposure include bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other actinic rays or radiation.

[0109] In the present specification, (meth)allyl means both or either allyl and methallyl, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0110] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene conversion values ​​measured by GPC (gel permeation chromatography) method.

[0111] In this specification, near infrared rays refer to light with a wavelength of 700 to 2500 nm.

[0112] In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.

[0113] In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the expected effect of the step is achieved.

[0114] In this specification, a pigment refers to a compound that is not easily dissolved in a solvent.

[0115] In this specification, symbols (such as A) added before or after a name are used to distinguish components, and do not limit the type of components, the number of components, or the quality of components.

[0116] <Resin composition>

[0117] The resin composition of the present invention is characterized by comprising a color material A containing a pigment, a resin B and a solvent C, wherein the resin B comprises a resin b-1 (hereinafter also referred to as a specific resin) having a structure represented by formula (1).

[0118] The resin composition of the present invention has excellent pigment dispersibility. The detailed reason for obtaining such an effect is not clear, but it is presumed as follows: the specific resin has X as a tetravalent linking group. 1 The amide group (-C(=O)-NR 21 -、-C(=O)-NR 22 -) structure, so the adsorption of the specific resin to the pigment surface is promoted, and the specific resin has a polymer chain P 1 , the polymer chain P 1 The steric repelling group can suppress aggregation of pigments, and as a result, the resin composition can be excellent in pigment dispersibility.

[0119] Furthermore, by using the resin composition of the present invention, a film having excellent heat resistance that is not easily decomposed at high temperatures and is not easily shrunk after heat treatment at high temperatures can be formed. Therefore, after forming a film using the resin composition of the present invention, even if the obtained film is subjected to high temperature (for example, above 300° C.) heat treatment, the film shrinkage is suppressed, and even when other films such as inorganic films are formed on the film, cracks can be suppressed on other films. Therefore, according to the resin composition of the present invention, the process window of the process after the film is manufactured can be expanded.

[0120] When the resin composition of the present invention is heated at 200°C for 30 minutes to form a film with a thickness of 0.60 μm, the thickness of the film after heat treatment at 300°C for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before the heat treatment, more preferably 80% or more, and further preferably 90% or more.

[0121] Furthermore, the thickness of the film after heat treatment at 350° C. for 5 hours in a nitrogen atmosphere is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0122] Furthermore, the thickness of the film after heat treatment at 400° C. for 5 hours in a nitrogen atmosphere is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0123] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin used.

[0124] Furthermore, when the resin composition of the present invention is used and heated at 200°C for 30 minutes to form a film with a thickness of 0.60 μm, and the above-mentioned film is heat-treated at 300°C for 5 hours in a nitrogen environment, the rate of change ΔA of the absorbance represented by the following formula (A1) of the film after heat treatment is preferably 50% or less, more preferably 45% or less, further preferably 40% or less, and especially preferably 35% or less.

[0125] ΔA(%)=|100-(A2 / A1)×100|······(A1)

[0126] ΔA is the rate of change of absorbance of the film after heating treatment,

[0127] A1 is the maximum absorbance of the film before heat treatment in the wavelength range of 400 to 1100 nm.

[0128] A2 is the absorbance of the film after the heat treatment, and is the absorbance at a wavelength at which the film before the heat treatment shows the maximum absorbance in the range of wavelengths from 400 to 1100 nm.

[0129] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin used.

[0130] Furthermore, when the resin composition of the present invention is used and heated at 200°C for 30 minutes to form a film with a thickness of 0.60 μm, the absolute value of the difference between the wavelength λ1 of the maximum absorbance shown by the above film in the wavelength range of 400 to 1100 nm and the wavelength λ2 of the maximum absorbance shown by the film after heating the above film at 300°C for 5 hours in a nitrogen environment is preferably 50 nm or less, more preferably 45 nm or less, and further preferably 40 nm or less.

[0131] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin used.

[0132] Furthermore, when the resin composition of the present invention is used to form a film having a thickness of 0.60 μm by heating at 200° C. for 30 minutes, and the film is then heat-treated at 300° C. for 5 hours in a nitrogen atmosphere, the rate of change ΔA of the absorbance of the film after the heat treatment in the wavelength range of 400 to 1100 nm is λ The maximum value of is preferably 30% or less, more preferably 27% or less, and further preferably 25% or less. The rate of change in absorbance is a value calculated according to the following formula (2).

[0133] ΔA λ =|100-(A2 λ / A1 λ )×100|······(2)

[0134] ΔA λ is the rate of change of absorbance of the film at wavelength λ after heating,

[0135] A1 λ is the absorbance of the film at wavelength λ before heating treatment,

[0136] A2x is the absorbance of the film after heat treatment at wavelength λ.

[0137] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin used.

[0138] The resin composition of the present invention can be preferably used as a resin composition for optical filters. As optical filters, color filters, near infrared transmission filters, near infrared cut-off filters, etc. can be cited, preferably color filters. In addition, the resin composition of the present invention can be preferably used as a resin composition for solid-state imaging elements, and can be preferably used as a resin composition for forming pixels of the optical filter used in the solid-state imaging element.

[0139] As a color filter, a filter having colored pixels that transmit light of a specific wavelength can be cited, preferably a filter having at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. The color filter can be formed using a resin composition containing a color material.

[0140] As a near infrared cut filter, a filter having a maximum absorption wavelength in the range of 700 to 1800 nm can be cited. The maximum absorption wavelength of the near infrared cut filter is preferably in the range of 700 to 1300 nm, and more preferably in the range of 700 to 1100 nm. In addition, the transmittance of the near infrared cut filter in the entire range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. In addition, the transmittance at at least one point in the range of 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the near infrared cut filter to the absorbance A550 at a wavelength of 550 nm, i.e., absorbance Amax / absorbance A550, is preferably 20 to 500, more preferably 50 to 500, further preferably 70 to 450, and particularly preferably 100 to 400. The near infrared cut filter can be formed using a resin composition containing a near infrared absorbing color material.

[0141] The near-infrared transmission filter is a filter that transmits at least a portion of the near-infrared rays. The near-infrared transmission filter is preferably a filter that blocks at least a portion of the visible light but transmits at least a portion of the near-infrared rays. As the near-infrared transmission filter, preferably, there is a filter that satisfies the spectral characteristics that the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). The near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).

[0142] (1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm.

[0143] (2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm.

[0144] (3): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 830 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1000 to 1500 nm.

[0145] (4): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 950 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1100 to 1500 nm.

[0146] (5): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 1050 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1200 to 1500 nm.

[0147] As a preferred mode of the spectral characteristics possessed by the resin composition of the present invention, the following mode can be cited: when a film with a thickness of 5 μm is formed using the resin composition, the spectral characteristics that the maximum value of the transmittance in the thickness direction of the above-mentioned film within the range of wavelengths of 360 to 700 nm is 50% or more are satisfied. The resin composition satisfying such spectral characteristics can be preferably used as a resin composition for forming pixels 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.

[0148] The resin composition possessed by the above-mentioned spectral characteristics preferably contains a colored color material. For example, a resin composition comprising a red color material and a yellow color material can be preferably used as a red pixel forming resin composition. In addition, a resin composition comprising a blue color material and a purple color material can be preferably used as a blue pixel forming resin composition. In addition, a resin composition comprising a green color material can be preferably used as a green or cyan pixel forming resin composition. When the resin composition is used as a green pixel forming resin composition, in addition to the green color material, it is preferably further comprised of a yellow color material.

[0149] As another preferred embodiment of the spectral characteristics of the resin composition of the present invention, a spectral characteristic that satisfies the ratio of the minimum value Amin of the absorbance in the range of wavelengths 400 to 640 nm to the absorbance B at a wavelength of 1500 nm, i.e., Amin / B, of 5 or more can be cited. A resin composition satisfying such spectral characteristics can be preferably used as a resin composition for forming a near-infrared transmission filter. The value of the above-mentioned absorbance ratio, i.e., Amin / B, is preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more.

[0150] Here, the absorbance Aλ at the wavelength λ is defined by the following formula (λ1).

[0151] Aλ=-log(Tλ / 100)······(λ1)

[0152] Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ.

[0153] 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 measuring the absorbance in a film state, it is preferably measured using a film obtained by applying the composition on a glass substrate by spin coating or the like and drying at 100° C. for 120 seconds using a hot plate or the like.

[0154] The resin composition of the present invention preferably satisfies any one of the following spectral characteristics (Ir1) to (Ir5).

[0155] (Ir1): The ratio of the minimum value A1 of the absorbance in the wavelength range of 400 to 640 nm to the maximum value B1 of the absorbance in the wavelength range of 800 to 1500 nm, i.e., the value A1 / B1, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that shields light in the wavelength range of 400 to 640 nm and transmits light with a wavelength greater than 750 nm can be formed.

[0156] (Ir2): The ratio of the minimum value A2 of the absorbance in the wavelength range of 400 to 750 nm to the maximum value B2 of the absorbance in the wavelength range of 900 to 1500 nm, i.e., the value A2 / B2 is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that shields light in the wavelength range of 400 to 750 nm and transmits light with a wavelength greater than 850 nm can be formed.

[0157] (Ir3): The ratio of the minimum value A3 of the absorbance in the wavelength range of 400 to 830 nm to the maximum value B3 of the absorbance in the wavelength range of 1000 to 1500 nm, i.e., the value A3 / B3 is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that shields light in the wavelength range of 400 to 830 nm and transmits light with a wavelength greater than 950 nm can be formed.

[0158] (Ir4): The ratio of the minimum absorbance value A4 in the wavelength range of 400 to 950 nm to the maximum absorbance value B4 in the wavelength range of 1100 to 1500 nm, i.e., the value A4 / B4 is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that shields light in the wavelength range of 400 to 950 nm and transmits light with a wavelength greater than 1050 nm can be formed.

[0159] (Ir5): The ratio of the minimum value A5 of the absorbance in the wavelength range of 400 to 1050 nm to the maximum value B5 of the absorbance in the wavelength range of 1200 to 1500 nm, i.e., the value A5 / B5 is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that shields light in the wavelength range of 400 to 1050 nm and transmits light with a wavelength greater than 1150 nm can be formed.

[0160] The resin composition of the present invention is preferably a resin composition for forming a pattern by photolithography. According to this mode, a pixel of fine size can be easily formed. Therefore, in particular, it can be preferably used as a pixel forming resin composition for the optical filter used in the solid-state imaging element. For example, a resin composition containing a component having a group containing an ethylenically unsaturated bond (for example, a resin having a group containing an ethylenically unsaturated bond, a monomer having a group containing an ethylenically unsaturated bond) and a photopolymerization initiator can be preferably used as a resin composition for forming a pattern by photolithography. The resin composition for forming a pattern by photolithography also preferably further includes an alkali-soluble resin.

[0161] The resin composition of the present invention can also be used as a black matrix-forming resin composition or a light-shielding film-forming resin composition.

[0162] Hereinafter, each component used for the resin composition of the present invention will be described.

[0163] <Color material A>

[0164] The resin composition of the present invention contains a color material A (hereinafter referred to as a color material). Examples of the color material include white color materials, black color materials, color color materials, and near-infrared absorption color materials. In addition, in the present invention, the white color material includes not only pure white but also light gray color materials close to white (for example, off-white, light gray, etc.).

[0165] The color material preferably includes at least one selected from chromatic color materials, black color materials and near-infrared absorption color materials, more preferably includes at least one selected from chromatic color materials and near-infrared absorption color materials, further preferably includes chromatic color materials, and further preferably includes at least one chromatic color material selected from red color materials, yellow color materials, blue color materials and purple color materials.

[0166] Furthermore, the color material preferably includes a chromatic color material and a near-infrared absorbing color material, and also preferably includes two or more chromatic color materials and a near-infrared absorbing color material. Furthermore, black can be formed by a combination of two or more chromatic color materials. Furthermore, the color material also preferably includes a black color material and a near-infrared absorbing color material. According to these aspects, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. Regarding the combination of color materials that form black with a combination of two or more chromatic color materials, reference can be made to Japanese Patent Publication No. 2013-077009, Japanese Patent Publication No. 2014-130338, International Publication No. 2015 / 166779, etc.

[0167] The color material contained in the coloring composition of the present invention can use a color material containing a pigment. The pigment can be any of an inorganic pigment and an organic pigment. From the perspectives of many color changes, ease of dispersion, safety, etc., an organic pigment is preferred. In addition, the pigment preferably includes at least one selected from a color pigment and a near-infrared absorbing pigment, and more preferably includes a color pigment.

[0168] Furthermore, the pigment preferably includes at least one selected from phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, and quinoline yellow pigments, more preferably includes at least one selected from phthalocyanine pigments, diketopyrrolopyrrole pigments, and pyrrolopyrrole pigments, and further preferably includes phthalocyanine pigments or diketopyrrolopyrrole pigments. Furthermore, the phthalocyanine pigment is preferably a phthalocyanine pigment without a central metal or a phthalocyanine pigment having copper or zinc as a central metal, because it is easy to form a film whose spectral characteristics are not easily changed after heating to a high temperature (for example, 300° C. or more).

[0169] The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. As long as 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 addition, in the present invention, the primary particle size of the pigment can be observed by a transmission electron microscope and obtained based on the photographs obtained. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding thereto is calculated as the primary particle size of the pigment. In addition, the average primary particle size in the present invention is set to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0170] (color material)

[0171] As the color material, there can be mentioned a color material having a maximum absorption wavelength in the range of 400 to 700 nm. For example, yellow color material, orange color material, red color material, green color material, purple color material, blue color material, etc. can be mentioned. From the viewpoint of heat resistance, the color material is preferably a pigment (color pigment), more preferably a red pigment, a yellow pigment and a blue pigment, and further preferably a red pigment and a blue pigment. As specific examples of color pigments, for example, the color pigments shown below can be mentioned.

[0172] CI 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 9, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine), 233 (quinoline), 234 (aminoketone), 235 (aminoketone), 236 (aminoketone), etc. (the above are yellow pigments),

[0173] CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, orange pigments),

[0174] CI 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 (xanthenes, Organo Ultramarine, Bluish Red), 295 (monoazo), 296 (diazo), 297 (aminoketone), etc. (the above are red pigments),

[0175] CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), 66 (phthalocyanine), etc. (above, green pigments),

[0176] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethanes), 61 (xanthenes), etc. (the above, purple pigments),

[0177] CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo type), 88 (methine type), etc. (the above are blue pigments).

[0178] Among these color pigments, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 272, CI Pigment Red 122, and CI Pigment Red 177 are preferred as red pigments because they can easily form a film whose spectral characteristics are unlikely to change even after heating to a high temperature (e.g., 300° C. or higher). CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16 are preferred as blue pigments.

[0179] Furthermore, as a green pigment, a zinc phthalocyanine halogenide 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. As a specific example, the compounds described in International Publication No. 2015 / 118720 can be cited. Furthermore, as a green pigment, the compounds described in the specification of Chinese Patent Application No. 106909027, the phthalocyanine compounds having a phosphate ester as a ligand described in International Publication No. 2012 / 102395, the phthalocyanine compounds described in Japanese Patent Application Publication No. 2019-008014, the phthalocyanine compounds described in Japanese Patent Application Publication No. 2018-180023, the compounds described in Japanese Patent Application Publication No. 2019-038958, etc. can also be used.

[0180] Furthermore, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment, and specific examples thereof include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0181] As yellow pigments, compounds described in Japanese Patent Application Laid-Open No. 2017-201003, compounds described in Japanese Patent Application Laid-Open No. 2017-197719, compounds described in paragraphs 0011 to 0062 and 0137 to 0276 of Japanese Patent Application Laid-Open No. 2017-171912, compounds described in paragraphs 0010 to 0062 and 0138 to 0295 of Japanese Patent Application Laid-Open No. 2017-171913, compounds described in paragraphs 0011 to 0062 and 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171914, compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of Japanese Patent Application Laid-Open No. 2017-171915 can also be used. A compound, a quinoline yellow compound described in paragraphs 0011 to 0034 of Japanese Patent Application Laid-Open No. 2013-054339, a quinoline yellow compound described in paragraphs 0013 to 0058 of Japanese Patent Application Laid-Open No. 2014-026228, an isoindoline compound described in Japanese Patent Application Laid-Open No. 2018-062644, a quinoline yellow compound described in Japanese Patent Application Laid-Open No. 2018-203798, a quinoline yellow compound described in Japanese Patent Application Laid-Open No. 2018-062578, a quinoline yellow compound described in Japanese Patent No. 6432076, a quinoline yellow compound described in Japanese Patent Application Laid-Open No. 2018-155881, a quinoline yellow compound described in Japanese Patent Application Laid-Open No. 2018-111757 Quinoline yellow compounds, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2018-040835, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2017-197640, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2016-145282, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2014-085565, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2014-021139, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2013-209614, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2013-209435, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2013-181015, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2013-06 Quinoline yellow compounds described in Japanese Patent Publication No. 1622, quinoline yellow compounds described in Japanese Patent Publication No. 2013-032486, quinoline yellow compounds described in Japanese Patent Publication No. 2012-226110, quinoline yellow compounds described in Japanese Patent Publication No. 2008-074987, quinoline yellow compounds described in Japanese Patent Publication No. 2008-081565, quinoline yellow compounds described in Japanese Patent Publication No. 2008-074986, quinoline yellow compounds described in Japanese Patent Publication No. 2008-074985, quinoline yellow compounds described in Japanese Patent Publication No. 2008-050420, quinoline yellow compounds described in Japanese Patent Publication No. 2008-031281,Quinoline yellow compounds described in Japanese Patent Publication No. 48-032765, quinoline yellow compounds described in Japanese Patent Publication No. 2019-008014, quinoline yellow compounds described in Japanese Patent Publication No. 6607427, compounds described in Korean Patent Publication No. 10-2014-0034963, compounds described in Japanese Patent Publication No. 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Japanese Patent No. 6607427, quinoline yellow dimers described in Japanese Patent Publication No. 2020-033521, compounds represented by the following formula (QP1), compounds represented by the following formula (QP2). In addition, from the perspective of improving the color value, it is also preferable to use polymers of these compounds. 、

[0182] [Chemical formula 8]

[0183]

[0184] In formula (QP1), X 1 ~X 16 Each independently represents a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include compounds described in paragraph 0016 of Japanese Patent No. 6443711.

[0185] [Chemical formula 9]

[0186]

[0187] In formula (QP2), Y 1 ~Y 3 Each independently represents a halogen atom. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or more. Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

[0188] As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure as described in Japanese Patent Publication No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, naphthol azo compounds described in Japanese Patent Publication No. 2012-229344, compounds described in Japanese Patent No. 6516119, compounds described in Japanese Patent No. 6525101, etc. can also be used. As red colorants, compounds having a structure in which an aromatic hydrocarbon ring group having a group bonded to an oxygen atom, a sulfur atom, or a nitrogen atom is introduced into an aromatic hydrocarbon ring bonded to a diketopyrrolopyrrole skeleton can also be used. As such a compound, a compound represented by the formula (DPP1) is preferred, and a compound represented by the formula (DPP2) is more preferred.

[0189] [Chemical formula 10]

[0190]

[0191] In the above formula, R 11 and R 13 Each independently represents a substituent, R 12 and R 14 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n11 and n13 each independently represent an integer of 0 to 4, and X 12 and X 14 Each independently represents an oxygen atom, a sulfur atom or a nitrogen atom, and X 12 When it is an oxygen atom or a sulfur atom, m12 represents 1, X 12 When it is a nitrogen atom, m12 represents 2, X 14 When it is an oxygen atom or a sulfur atom, m14 represents 1, X 14 When it is a nitrogen atom, m14 represents 2. 11 and R 13 Preferred specific examples of the substituents 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, a trifluoromethyl group, a sulfoxide group, and a sulfone group.

[0192] Regarding the preferred diffraction angles of various pigments, reference may be made to Japanese Patent No. 6561862, Japanese Patent No. 6413872, and Japanese Patent No. 6281345, the contents of which are incorporated into this specification.

[0193] As color dyes, pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridine compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azo methine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, pyrrole methylene compounds can be cited. In addition, methine dyes recorded in Japanese Patent Publication No. 2019-073695, methine dyes recorded in Japanese Patent Publication No. 2019-073696, methine dyes recorded in Japanese Patent Publication No. 2019-073697, and methine dyes recorded in Japanese Patent Publication No. 2019-073698 can also be used.

[0194] Two or more chromatic color materials may also be used in combination. Furthermore, when two or more chromatic color materials are used in combination, black can be formed by the combination of two or more chromatic color materials. As such a combination, for example, the following (1) to (7) can be cited. When two or more chromatic color materials are included in the resin composition and black is presented by the combination of two or more chromatic color materials, the resin composition of the present invention can be preferably used as a resin composition for forming a near infrared transmission filter.

[0195] (1) A method containing red colorant and blue colorant.

[0196] (2) A method containing red, blue and yellow colorants.

[0197] (3) A method containing red color material, blue color material, yellow color material and purple color material.

[0198] (4) A method containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material.

[0199] (5) A method containing a red color material, a blue color material, a yellow color material, and a green color material.

[0200] (6) A method containing a red colorant, a blue colorant, and a green colorant.

[0201] (7) A method containing a yellow colorant and a purple colorant.

[0202] (White color material)

[0203] As white color materials, inorganic pigments (white pigments) such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide can be cited. The white pigment is preferably a particle having a titanium atom, more preferably titanium oxide. In addition, the white pigment is preferably a particle having a refractive index of 2.10 or more for light of a wavelength of 589 nm. The refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

[0204] Furthermore, as the white pigment, titanium oxide described in "Titanium Oxide Physical Properties and Application Technology, Manabu Seino, pp. 13-45, published on June 25, 1991, published by Gihodo Publishing" can also be used.

[0205] White pigments can be made of not only a single inorganic substance, but also particles composed of other materials. For example, it is preferred to use particles with pores or other materials inside, particles with multiple inorganic particles attached to core particles, and core and shell composite particles composed of core particles composed of polymer particles and shells composed of inorganic nanoparticles. As core and shell composite particles composed of core particles composed of the above-mentioned polymer particles and shells composed of inorganic nanoparticles, for example, it can be recorded in paragraphs 0012 to 0042 of Japanese Patent Publication No. 2015-047520, which is incorporated into this specification.

[0206] White pigment can also use hollow inorganic particles.Hollow inorganic particles refer to the inorganic particles with hollow structure inside, and represent the hollow inorganic particles surrounded by shell.As hollow inorganic particles, the hollow inorganic particles recorded in Japanese Unexamined Patent Publication No. 2011-075786, International Publication No. 2013 / 061621, Japanese Unexamined Patent Publication No. 2015-164881 etc. can be enumerated, and these contents are incorporated in this specification.

[0207] (Black color material)

[0208] As black color material, there is no particular limitation, and known black color materials can be used. For example, as inorganic black color material, inorganic pigments (black pigments) such as carbon black, titanium black, and graphite can be cited, preferably carbon black, titanium black, and more preferably titanium black. Titanium black refers to black particles containing titanium atoms, preferably low-order titanium oxide, titanium oxynitride. Titanium black can be surface-modified as needed for the purpose of improving dispersibility, inhibiting cohesion, etc. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. In addition, it is also possible to use a treatment with a water-repellent substance as shown in Japanese Patent Publication No. 2007-302836. As black pigments, color index (CI) pigment black 1, 7, etc. can be cited. Regarding titanium black, it is preferred that the primary particle size and average primary particle size of each particle are small. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersed material. For example, the following dispersion can be cited: a dispersion containing titanium black particles and silicon dioxide particles, wherein the ratio of Si atoms to Ti atoms in the dispersion is adjusted to be within the range of 0.20 to 0.50. For the above-mentioned dispersion, reference can be made to the records of paragraphs 0020 to 0105 of Japanese Patent Publication No. 2012-169556, which are incorporated into this specification. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (product name: manufactured by Mitsubishi Materials Corporation), Tilack D (product name: manufactured by Ako Kasei Co., Ltd.), etc.

[0209] In addition, as organic black color materials, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. can be cited. As bisbenzofuranone compounds, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc. can be cited, for example, "Irgaphor Black" manufactured by BASF can be obtained. As perylene compounds, compounds described in paragraphs 0016 to 0020 of Japanese Patent Publication No. 2017-226821, CI Pigment Black 31, 32, etc. can be cited. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available, for example, as "CHROMO FINE BLACK A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

[0210] The color material used for the resin composition of the present invention may be only the above-mentioned black color material, or may further include a color color material. According to this mode, it is easy to obtain a film that can form an excellent light-shielding property in the visible region. When a black color material and a color color material are used as a color material, the mass ratio of the two is preferably black color material: color color material = 100: 10 to 300, and more preferably 100: 20 to 200. In addition, as the above-mentioned black color material, a black pigment is preferably used, and as the above-mentioned color color material, a color pigment is preferably used.

[0211] Preferred combinations of black color materials and chromatic color materials include the following, for example.

[0212] (A-1) A form containing an organic black color material and a blue color material.

[0213] (A-2) An embodiment containing an organic black color material, a blue color material, and a yellow color material.

[0214] (A-3) An embodiment in which an organic black color material, a blue color material, a yellow color material, and a red color material are contained.

[0215] (A-4) An embodiment in which an organic black color material, a blue color material, a yellow color material, and a violet color material are contained.

[0216] In the embodiment (A-1) above, the mass ratio of the organic black color material to the blue color material is preferably organic black color material:blue color material=100:1-70, more preferably 100:5-60, and even more preferably 100:10-50.

[0217] In the above embodiment (A-2), the mass ratio of the organic black color material, the blue color material and the yellow color material is preferably organic black color material: blue color material: yellow color material = 100:10-90:10-90, more preferably 100:15-85:15-80, and even more preferably 100:20-80:20-70.

[0218] In the above-mentioned method (A-3), the mass ratio of organic black colorant, blue colorant, yellow colorant and red colorant is preferably organic black colorant: blue colorant: yellow colorant: red colorant = 100:20~150:1~60:10~100, more preferably 100:30~130:5~50:20~90, and further preferably 100:40~120:10~40:30~80.

[0219] In the above-mentioned method (A-4), the mass ratio of organic black colorant, blue colorant, yellow colorant and purple colorant is preferably organic black colorant: blue colorant: yellow colorant: purple colorant = 100:20~150:1~60:10~100, more preferably 100:30~130:5~50:20~90, and further preferably 100:40~120:10~40:30~80.

[0220] (Near infrared absorbing color material)

[0221] The near infrared absorbing color material is preferably a pigment, more preferably an organic pigment. Furthermore, the near infrared absorbing color material preferably has a maximum absorption wavelength in the range of a wavelength greater than 700 nm and less than 1400 nm. Furthermore, the maximum absorption wavelength of the near infrared absorbing color material is preferably less than 1200 nm, more preferably less than 1000 nm, and further preferably less than 950 nm. Furthermore, in the near infrared absorbing color material, the absorbance A at a wavelength of 550 nm is preferably less than 1000 nm. 550 and the absorbance A at the maximum absorption wavelength max The ratio is A 550 / A max It is preferably less than 0.1, more preferably less than 0.05, further preferably less than 0.03, and particularly preferably less than 0.02. The lower limit is not particularly limited, for example, it can be set to more than 0.0001, and can also be set to more than 0.0005. As long as the ratio of the above absorbance is within the above range, it can be used as a near-infrared absorbing color material with excellent visible light transparency and near-infrared shielding properties. In addition, in the present invention, the values ​​of the absorbance of the near-infrared absorbing color material at the maximum absorption wavelength and each wavelength are values ​​obtained based on the absorption spectrum of a film formed using a resin composition containing the near-infrared absorbing color material.

[0222] As the near infrared absorbing color material, there is no particular limitation, and examples thereof include pyrrolopyrrole compounds, cyanine compounds, squaryl compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, crotonium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethyl compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiol metal complexes, etc. As the pyrrolopyrrole compound, examples thereof include compounds described in paragraphs 0016 to 0058 of Japanese Unexamined Patent Publication No. 2009-263614, compounds described in paragraphs 0037 to 0052 of Japanese Unexamined Patent Publication No. 2011-068731, and compounds described in paragraphs 0010 to 0033 of International Publication No. 2015 / 166873. Examples of the squaric acid compound include compounds described in paragraphs 0044 to 0049 of Japanese Patent Application Publication No. 2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application No. 6065169, compounds described in paragraph 0040 of International Publication No. 2016 / 181987, compounds described in Japanese Patent Application Publication No. 2015-176046, and compounds described in paragraph 0072 of International Publication No. 2016 / 190162. , compounds described in paragraphs 0196 to 0228 of Japanese Patent Application Publication No. 2016-074649, compounds described in paragraph 0124 of Japanese Patent Application Publication No. 2017-067963, compounds described in International Publication No. 2017 / 135359, compounds described in Japanese Patent Application Publication No. 2017-114956, compounds described in Japanese Patent No. 6197940, compounds described in International Publication No. 2016 / 120166, etc. Examples of cyanine compounds include compounds described in paragraphs 0044 to 0045 of Japanese Patent Application Laid-Open No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese Patent Application Laid-Open No. 2002-194040, compounds described in Japanese Patent Application Laid-Open No. 2015-172004, compounds described in Japanese Patent Application Laid-Open No. 2015-172102, compounds described in Japanese Patent Application Laid-Open No. 2008-088426, compounds described in paragraph 0090 of International Publication No. 2016 / 190162, compounds described in Japanese Patent Application Laid-Open No. 2017-031394, etc. Examples of crotonium compounds include compounds described in Japanese Patent Application Laid-Open No. 2017-082029.Examples of the iminium compound include compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, and compounds described in paragraphs 0048 to 0063 of International Publication No. 2018 / 043564. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153, titanyl phthalocyanine described in JP-A-2006-343631, compounds described in paragraphs 0013 to 0029 of JP-A-2013-195480, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, and compounds described in International Publication No. 2020 / 071470. Examples of the naphthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153. Examples of the disulfide metal complex include compounds described in JP-A-5733804.

[0223] Furthermore, as the near-infrared absorbing color material, the squaric acid compounds described in Japanese Patent Publication No. 2017-197437, the squaric acid compounds described in Japanese Patent Publication No. 2017-025311, the squaric acid compounds described in International Publication No. 2016 / 154782, the squaric acid compounds described in Japanese Patent No. 5884953, the squaric acid compounds described in Japanese Patent No. 6036689, the squaric acid compounds described in Japanese Patent No. 5810604, and the squaric acid compounds described in Japanese Patent No. 6036689 can also be used. The squaric acid compound described in paragraphs 0090 to 0107 of International Publication No. 2017 / 213047, the pyrrole ring-containing compound described in paragraphs 0019 to 0075 of Japanese Patent Publication No. 2018-054760, the pyrrole ring-containing compound described in paragraphs 0078 to 0082 of Japanese Patent Publication No. 2018-040955, the pyrrole ring-containing compound described in paragraphs 0043 to 0069 of Japanese Patent Publication No. 2018-002773, The squaryl acid compound having an aromatic ring at the amide α position described in paragraphs 0024 to 0086 of Japanese Patent Application Laid-Open No. 2018-041047, the amide-linked squaryl acid compound described in Japanese Patent Application Laid-Open No. 2017-179131, the compound having a pyrrole bis-type squaryl acid skeleton or a crotonium skeleton described in Japanese Patent Application Laid-Open No. 2017-141215, the dihydrocarbazole bis-type squaryl acid compound described in Japanese Patent Application Laid-Open No. 2017-082029, the The asymmetric compounds described in paragraphs 0027 to 0114 of Gazette No. 068120, the pyrrole ring-containing compounds (carbazole type) described in Japanese Patent Gazette No. 2017-067963, the phthalocyanine compounds described in Japanese Patent Gazette No. 6251530, the color materials described in Japanese Patent Gazette No. 2013-077009, Japanese Patent Gazette No. 2014-130338, and International Publication No. 2015 / 166779, or a combination of the color materials described in these documents, etc.

[0224] The content of the color material in the total solid content of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.

[0225] Furthermore, the content of the pigment in the total solid content of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.

[0226] Furthermore, the content of the dye in the color material is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0227] And, from the reason that it is easy to more effectively suppress the film thickness change when the obtained film is heated to a high temperature, the resin composition of the present invention is also preferably substantially free of dye. When the resin composition of the present invention substantially does not include a dye, the content of the dye in the total solid content of the resin composition of the present invention is preferably below 0.1% by mass, more preferably below 0.05% by mass, and particularly preferably does not contain.

[0228] <Resin B>

[0229] (Specific resin (resin b-1))

[0230] The resin composition of the present invention includes a resin B (hereinafter also referred to as a resin). The resin included in the resin composition includes a resin b-1 (hereinafter also referred to as a specific resin) having a structure represented by formula (1). The specific resin is also a resin of the present invention.

[0231] [Chemical formula 11]

[0232]

[0233] In formula (1), X 1 represents a 4-valent linking group,

[0234] X 2 represents a divalent linking group,

[0235] R 11 , R 12 , R 21 , R 22 and R 23 each independently represents a hydrogen atom or a substituent,

[0236] Lp 1 represents an n+1 valent connecting group,

[0237] Lp 2 represents a divalent linking group,

[0238] P 1 represents the polymer chain,

[0239] n represents an integer of 1 or greater.

[0240] [n]

[0241] In formula (1), n ​​represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1.

[0242] [X 1 ]

[0243] In formula (1), as X 1The tetravalent linking group represented is preferably a group containing a hydrocarbon group. As the hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be mentioned. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group can be any of a straight chain, a branched chain, and a cyclic group. In addition, the cyclic aliphatic hydrocarbon group can be a monocyclic ring or a condensed ring. In addition, the cyclic aliphatic hydrocarbon group can have a cross-linked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group can have a substituent. As a substituent, the substituent T described later can be mentioned.

[0244] Examples of the group containing a hydrocarbon group include a hydrocarbon group and a group in which two or more hydrocarbon groups are bonded via a single bond or a linking group.

[0245] Examples of the linking group for linking two or more hydrocarbon groups include -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.

[0246] X 1 The tetravalent linking group represented by is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and more preferably a group containing an aromatic hydrocarbon ring. 1 The tetravalent linking group represented by is preferably a fluorine atom or a sulfonyl group (-SO 2 Among them, from the reason that a specific resin can form a film with excellent solubility in a solvent and excellent heat resistance, X 1 The tetravalent linking group represented is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring. As the group containing a fluorine atom and an aromatic hydrocarbon ring, it is preferably a group in which two or more aromatic hydrocarbon groups are bonded by a linking group and the above-mentioned linking group is a linking group containing a fluorine atom, or a group in which two or more aromatic hydrocarbon groups are bonded by a single bond or a linking group and the above-mentioned aromatic hydrocarbon group is substituted by a group containing a fluorine atom. As the above-mentioned linking group containing a fluorine atom, -C(CF 3 ) 2 -, etc. The fluorine atom-containing group is preferably a fluorinated alkyl group, and more preferably a trifluoromethyl group.

[0247] And, X 1The tetravalent linking group represented is also preferably a group represented by any of the formulas (D-1) to (D-3).

[0248] [Chemical formula 12]

[0249]

[0250] In formula (D-1) to formula (D-3), Cy each independently represents an aliphatic hydrocarbon ring, and R d1 represents a straight-chain or branched aliphatic hydrocarbon group, X d1 Indicates a single bond or a divalent connecting group, * 1 ~* 4 They represent connecting keys respectively.

[0251] The aliphatic hydrocarbon ring represented by Cy in formula (D-1) to formula (D-3) may be a monocyclic aliphatic hydrocarbon ring or a condensed ring. Furthermore, the aliphatic hydrocarbon ring may have a cross-linked 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.

[0252] In formula (D-1), * 1 and* 2 ,* 3 and* 4 Preferably, they are present at adjacent positions on the aliphatic hydrocarbon ring Cy.

[0253] R of formula (D-2) d1 represents a straight-chain or branched aliphatic hydrocarbon group, preferably a straight-chain or branched aliphatic saturated hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2. In formula (D-2), * 3 and* 4 Preferably, the aliphatic hydrocarbon group R d1 There is one on each of the adjacent carbon atoms. In formula (D-2), * 3 and* 4 Preferably, they are present at adjacent positions on the aliphatic hydrocarbon ring Cy.

[0254] In formula (D-3), X d1 represents a single bond or a divalent linking group, preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a single bond or a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NHC(=O)-, or a group formed by combining two or more of these, more preferably an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S- or -S(=O) 2 - is more preferably -CH 2 -、-O-、-S-、-S(=O)2 -、-C(CF 3 ) 2 -or-C(CH 3 ) 2 -.

[0255] And, X 1 The tetravalent linking group represented is also preferably a group represented by formula (E-1).

[0256] [Chemical formula 13]

[0257]

[0258] In formula (E-1), Ar each independently represents an aromatic hydrocarbon ring, and X e1 represents a divalent linking group containing a fluorine atom, * 1 ~* 4 They represent connecting keys respectively.

[0259] The number of carbon atoms in the aromatic hydrocarbon ring represented by Ar in formula (E-1) is preferably 6 to 30, and more preferably 6 to 20. The aromatic hydrocarbon ring represented by Ar is preferably a benzene ring.

[0260] X in formula (E-1) e1 It is preferably an alkylene group having 1 to 10 carbon atoms substituted by a fluorine atom, more preferably an alkylene group having 1 to 5 carbon atoms substituted by a fluorine atom, and further preferably -C(CF 3 ) 2 -、-C(CF 3 )(C 2 F 5 )-or-C(C 2 F 5 ) 2 -, especially preferably -C(CF 3 ) 2 -. In formula (D-1), * 1 and* 2 ,* 3 and* 4 Preferably, they are present at adjacent positions on the aromatic ring structure Ar.

[0261] As X 1 Specific examples of the tetravalent linking group represented by include groups having structures represented by any of formulae (I-1) to (I-28).

[0262] [Chemical formula 14]

[0263]

[0264] In formulas (I-1) to (I-28), X 1 ~X3 represents 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 They may be bonded to form a ring, and * represents a bond with other structures in formula (1).

[0265] As X 1 ~X 3 The divalent linking group represented by may be -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 -, phenylene 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. N represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

[0266] X 1 ~X 3 Preferably, each independently is a single bond, -SO 2 -or-C(Rx) 2 -, more preferably -SO 2 -or-C(Rx) 2 -, more preferably -C(Rx) 2 -. And, -C(Rx) 2 - preferably -C(CH 3 ) 2 -or-C(CF 3 ) 2 -, more preferably -C(CF 3 ) 2 -.

[0267] L is preferably -CH=CH-.

[0268] R 1 and R 2 Preferably, each independently is a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom.

[0269] [X 2 ]

[0270] In formula (1), X 2 represents a divalent linking group. 2 Examples of the divalent linking group include a hydrocarbon group and a group in which two or more hydrocarbon groups are linked via a single bond or a linking group.

[0271] Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of a straight chain, a branched chain, and a cyclic group. Furthermore, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Furthermore, the cyclic aliphatic hydrocarbon group may have a cross-linked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T described below.

[0272] Examples of the linking group for linking 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, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer greater than 1, preferably 1 to 10).

[0273] X 2 The divalent linking group represented by is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and more preferably a group containing an aromatic hydrocarbon ring. 2 The divalent linking group represented by is preferably a fluorine atom or a sulfonyl group (-SO 2 Among them, from the reason that a specific resin can form a film with excellent solubility in a solvent and excellent heat resistance, X 2 The divalent linking group represented is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring. As the group containing a fluorine atom and an aromatic hydrocarbon ring, it is preferably a group in which two or more aromatic hydrocarbon groups are bonded by a linking group and the above-mentioned linking group is a linking group containing a fluorine atom, or a group in which two or more aromatic hydrocarbon groups are bonded by a single bond or a linking group and the above-mentioned aromatic hydrocarbon group is substituted by a group containing a fluorine atom. As the above-mentioned linking group containing a fluorine atom, -C(CF 3 ) 2 - etc. As the above-mentioned group containing fluorine atoms, a fluorinated alkyl group is preferred, and a trifluoromethyl group is more preferred. 2 When the divalent linking group represented is a group containing a fluorine atom and an aromatic hydrocarbon ring, for example, a group having the following structure is preferred.

[0274] [Chemical formula 15]

[0275]

[0276] In the above structures, * indicates a bonding site with other structures.

[0277] X 2 The divalent connecting group represented is preferably a group derived from the structure of a diamine compound. As the diamine compound, for example, the following compounds can be mentioned.

[0278] [Chemical formula 16]

[0279]

[0280] [Chemical formula 17]

[0281]

[0282] [Chemical formula 18]

[0283]

[0284] [Chemical formula 19]

[0285]

[0286] [R 11 , R 12 , R 21 , R 22 and R 23 ]

[0287] In formula (1), R 11 , R 12 , R 21 , R 22 and R 23 Each independently represents a hydrogen atom or a substituent.

[0288] As the substituent, an alkyl group, an aryl group, a heterocyclic group, etc. can be mentioned. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group can be any of a straight chain, a branched chain, and a cyclic group, preferably a straight chain or a branched chain, and more preferably a straight chain. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The heterocyclic group can be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The types of heteroatoms constituting the heterocyclic group can include nitrogen atoms, oxygen atoms, sulfur atoms, etc. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group can be a monocyclic ring or a 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 the substituent T described below, a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a blocked isocyanate group.

[0289] In formula (1), R 11 and R 12 Preferably, it is a hydrogen atom. 21 , R 22 and R 23 , and preferably a hydrogen atom. In addition, a part of them may form a carboxylate or an amine salt.

[0290] [Lp 1 ]

[0291] In formula (1), Lp 1 represents an n+1 valent linking group. Examples of the n+1 valent linking group include a hydrocarbon group, -NRp-, -N<, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRpCO-, -CONRp-, and a group formed by combining two or more of these. Rp represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom.

[0292] Examples of the n+1-valent linking group include a group represented by the formula (Lp-1) and a group represented by the formula (Lp-2).

[0293] [Chemical formula 20]

[0294]

[0295] In formula (Lp-1), Rp 1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Lp la It represents a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a single bond or a linking group.

[0296] In formula (Lp-2), Lp 1bIt represents a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a single bond or a linking group.

[0297] In formula (Lp-1) and formula (Lp-2), n represents an integer greater than 1, and *1 represents the same as -NR 23 The bond between the carbonyl carbon in CO- and Lp in formula (1) 2 The connection key.

[0298] About Rp 1 Specific examples of the alkyl, aryl and heterocyclic groups represented by include 11 , R 12 , R 21 , R 22 and R 23 The group described in item.

[0299] As Lp 1a and Lp 1b The hydrocarbon group represented by the present invention includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of a straight chain, a branched chain, and a cyclic group. Furthermore, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Furthermore, the cyclic aliphatic hydrocarbon group may have a cross-linked structure. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. As a substituent, the substituent T described below may be mentioned.

[0300] Examples of the linking group for linking two or more hydrocarbon groups include -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.

[0301] Lp 1 The n+1-valent linking group represented is preferably a group represented by the formula (Lp-10), and more preferably a group represented by the formula (Lp-11).

[0302] [Chemical formula 21]

[0303]

[0304] In formula (Lp-10), Lp 11 Represents a single bond or n+1 valent connecting group, Rp 11represents a substituent, n represents an integer greater than 1, m represents an integer from 0 to 4, and *1 represents the same as -NR 23 The bond between the carbonyl carbon in CO- and Lp in formula (1) 2 The connecting key of m Rp 11 It can be the same or different.

[0305] In formula (Lp-11), Lp 12 Represents a single bond or n+1 valent connecting group, Rp 11 represents a substituent, n represents an integer greater than 1, m represents an integer from 0 to 4, and *1 represents the same as -NR 23 The bond between the carbonyl carbon in CO- and Lp in formula (1) 2 The connecting key of m Rp 11 It can be the same or different.

[0306] As Lp of formula (Lp-10) 11 The n+1-valent linking group represented by may be 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. Examples of the hydrocarbon group include the above groups. Rp 12 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0307] Lp of formula (Lp-11) 12 The n+1-valent linking group represented by is preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a single bond or a linking group. Examples of the linking group that links 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.

[0308] As Rp of formula (Lp-10) and formula (Lp-11): 11 The substituent represented by includes the substituent T described later, and is preferably a carboxyl group, a halogen atom or a hydroxyl group, and more preferably a carboxyl group.

[0309] In Formula (Lp-10) and Formula (Lp-11), n ​​represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0310] In formula (Lp-10) and formula (Lp-11), m represents an integer of 0 to 4, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2. 11 At least one of them is preferably a carboxyl group.

[0311] [Lp 2 ]

[0312] In formula (1), Lp 2 The divalent linking group includes a hydrocarbon group, -NRp 21 -、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp 21 CO-、-CONRp 21 - and groups formed by combining two or more of these. 21 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of a straight chain, a branched chain, and a cyclic group. Furthermore, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Furthermore, the cyclic aliphatic hydrocarbon group may have a cross-linked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group and the like. 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 further preferably a group containing -S-.

[0313] Lp 2 The divalent linking group represented is preferably -S- or -O-, and more preferably -S-.

[0314] [P 1 ]

[0315] In formula (1), P 1 Represents a polymer chain. 1The weight average molecular weight is preferably 500 to 50,000. The lower limit is preferably 800 or more, more preferably 1,000 or more. The upper limit is preferably 20,000 or less, more preferably 10,000 or less. If the weight average molecular weight of the above-mentioned polymer chain is within the above-mentioned range, it is easy to obtain better pigment dispersibility. The weight average molecular weight of the polymer chain can be measured by GPC (gel permeation chromatography). More specifically, it can be calculated based on the weight average molecular weight of the raw material monomer used to introduce the polymer chain.

[0316] P 1 The polymer chain represented preferably contains repeating units of at least one structure selected from the group consisting of a poly(meth)acrylic acid structure, a polystyrene structure, a polyether structure, and a polyester structure, more preferably contains repeating units of at least one structure selected from the group consisting of a poly(meth)acrylic acid structure and a polystyrene structure, and further preferably contains repeating units of a poly(meth)acrylic acid structure from the viewpoint of the dispersibility and heat resistance of the pigment. 1 The polymer chain represented also preferably contains repeating units of a polyether structure or repeating units of a polyester structure. 1 When the polymer chain represented by EMI1.1 contains repeating units of a polyether structure, the number of repeating units of the polyether structure is preferably 9 or more. 1 When the polymer chain represented includes repeating units of a polyester structure, the number of repeating units of the polyester structure is preferably 5 or more.

[0317] P 1 The represented polymer chain may have a crosslinking group. As a crosslinking group, groups containing ethylenically unsaturated bonds such as vinyl, (meth) allyl, (meth) acryloyl, epoxy, cyclohexane and other cyclic ether groups, blocked isocyanate groups, etc. can be cited. In addition, in this specification, a blocked isocyanate group refers to a group that can generate an isocyanate group by heat, for example, a group that allows a blocking agent to react with an isocyanate group to protect the isocyanate group can be preferably exemplified. As a blocking agent, oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds, imide compounds, etc. can be cited. Regarding the blocking agent, the compounds described in paragraphs 0115 to 0117 of Japanese Patent Publication No. 2017-067930 can be cited, and the content is incorporated into this specification. In addition, the blocked isocyanate group is preferably a group that can generate an isocyanate group by heat at 90 to 260°C.

[0318] P 1 The polymer chain represented also preferably has a tertiary alkyl group. Examples of the tertiary alkyl group include a tert-butyl group and the like.

[0319] P 1The polymer chain represented preferably includes a repeating unit represented by any of formulas (P1-1) to (P1-6), more preferably includes a repeating unit represented by formula (P1-5) or (P1-6), and further preferably includes a repeating unit represented by formula (P1-5). 1 The polymer chain represented by also preferably includes a repeating unit represented by any of the formulas (P1-1) to (P1-4). 1 When the polymer chain represented by includes repeating units of formula (P1-4), the number of repeating units of formula (P1-4) is preferably 9 or more. 1 When the represented polymer chain includes repeating units of formula (P1-1) to formula (P1-3), the number of repeating units of these structures is preferably 5 or more.

[0320] [Chemical formula 22]

[0321]

[0322] In the above formula, R G1 and R G2 Each represents an alkylene group. G1 and R G2 The alkylene group represented 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 further preferably a linear or branched alkylene group having 3 to 12 carbon atoms.

[0323] In the above formula, R G3 It 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.

[0324] In the above formula, Q G1 Indicates -O- or -NR q -, R q represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. G1 Preferred is -O-.

[0325] R q The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched, and more preferably linear.

[0326] R q The number of carbon atoms of the aryl group represented is preferably 6-30, more preferably 6-20, and even more preferably 6-12.

[0327] R qThe heterocyclic group represented may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The types of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, sulfur atoms, etc. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring.

[0328] The above-mentioned alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. As the substituent, the substituent T described below can be mentioned.

[0329] In the above formula, L G1 represents a single bond or an arylene group, and is preferably a single bond.

[0330] In the above formula, L G2 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, preferably a group containing an alkylene group or an arylene group. LG1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom. The above-mentioned alkylene group and arylene group may have a substituent or may be unsubstituted. As the substituent, the substituent T described below can be mentioned.

[0331] In the above formula, R G4 R represents a hydrogen atom or a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl thioether group, an aryl thioether group, a heterocyclic thioether group, a group containing an ethylenically unsaturated bond, an epoxy group, an oxetane group, and a blocked isocyanate group. G4 It is preferably at least one selected from an alkyl group, an aryl group, a group containing an ethylenically unsaturated bond, an epoxy group, and an oxetanyl group, and more preferably at least one selected from a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a tert-butyl group.

[0332] In the above formula, R G5 represents a hydrogen atom or a methyl group, R G6 R represents an aryl group. G6 The number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. G6The aryl group represented may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl thioether group, an aryl thioether group, a heterocyclic thioether group, a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a blocked isocyanate group.

[0333] P 1 The polymer chains shown may contain two or more repeating units.

[0334] (Substituent T)

[0335] Alkyl (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl (preferably an alkynyl group having 2 to 30 carbon atoms), aryl (preferably an aryl group having 6 to 30 carbon atoms), amino (preferably an amino group having 0 to 30 carbon atoms), alkoxy (preferably an alkoxy group having 1 to 30 carbon atoms), aryloxy (preferably an aryloxy group having 6 to 30 carbon atoms), heteroaryloxy (preferably a heteroaryloxy group having 1 to 30 carbon atoms), acyl (preferably an acyl group having 2 to 30 carbon atoms) ), alkoxycarbonyl (preferably an alkoxycarbonyl having 2 to 30 carbon atoms), aryloxycarbonyl (preferably an aryloxycarbonyl having 7 to 30 carbon atoms), acyloxy (preferably an acyloxy having 2 to 30 carbon atoms), acylamino (preferably an acylamino having 2 to 30 carbon atoms), alkoxycarbonylamino (preferably an alkoxycarbonylamino having 2 to 30 carbon atoms), aryloxycarbonylamino (preferably an aryloxycarbonylamino having 7 to 30 carbon atoms), sulfonamide (preferably a sulfonamide having 0 to 30 carbon atoms), carbamoyl thio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably a heteroarylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), The alkylsulfinyl group may be an alkylsulfinyl group having 1 to 30 carbon atoms), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably a heteroarylsulfinyl group having 1 to 30 carbon atoms), a urea group (preferably a urea group having 1 to 30 carbon atoms), a phosphoramide group (preferably a phosphoramide 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.), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfinic acid group, a hydrazine group, an imino group, and a heterocyclic group. When these groups are further substituted groups, they may further have a substituent. As further substituents, the groups described in the substituent T above can be mentioned.

[0336] In the specific resin, the structure represented by the above formula (1) is preferably a structure represented by formula (1-1).

[0337] [Chemical formula 23]

[0338]

[0339] In formula (1-1), X 1 represents a 4-valent linking group,

[0340] X 2 represents a divalent linking group,

[0341] R 11 , R 12 , R 21 , R 22 and R 23 each independently represents a hydrogen atom or a substituent,

[0342] R 11 Represents a substituent, m Rp 11 Can be the same or different.

[0343] Lp 11 represents an n+1 valent connecting group,

[0344] Lp 2 represents a divalent linking group,

[0345] P 1 represents the polymer chain,

[0346] n represents an integer greater than 1,

[0347] m represents an integer of 0-4.

[0348] X in formula (1-1) 1 , X 2 , R 11 , R 12 , R 21 , R 22 , R 23 , Lp 2 , P 1 and n and X in formula (1) 1 , X 2 , R 11 , R 12 , R 21 , R 22 , R 23 , Lp 2 , P 1 and n have the same meaning.

[0349] Lp of formula (1-1) 11 , Rp11 and m and Lp of formula (Lp-10) 11 , Rp 11 and m have the same meaning.

[0350] The specific resin may contain an imide cyclization structure of the structure represented by the above formula (1).

[0351] The specific example resin may further include a structure represented by formula (100). According to this embodiment, more excellent dispersibility can be obtained.

[0352] [Chemical formula 24]

[0353]

[0354] In formula (100), X 101 represents a 4+q valent connecting group,

[0355] X 102 represents a divalent linking group,

[0356] R 111 , R 112 , R 121 and R 122 each independently represents a hydrogen atom or a substituent,

[0357] Lp 101 represents a divalent linking group,

[0358] P 101 represents the polymer chain,

[0359] q represents an integer of 1 or more.

[0360] R of formula (100) 111 , R 112 , R 121 , R 122 and P 101 R 11 , R 12 , R 21 , R 22 and P 1 have the same meaning.

[0361] In formula (100), q represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0362] As X in formula (100) 102 The divalent linking group represented by may be X in formula (1): 2 The preferred range of the divalent linking group described in is also the same.

[0363] In formula (100), as X101 The 4+q-valent linking group represented is preferably a group containing a hydrocarbon group. As the hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be mentioned. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group can be any of a straight chain, a branched chain, and a cyclic group. In addition, the cyclic aliphatic hydrocarbon group can be a monocyclic ring or a condensed ring. In addition, the cyclic aliphatic hydrocarbon group can have a cross-linked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group can have a substituent. As a substituent, the above-mentioned substituent T can be mentioned.

[0364] Examples of the group containing a hydrocarbon group include a hydrocarbon group and a group in which two or more hydrocarbon groups are bonded via a single bond or a linking group.

[0365] Examples of the linking group for linking two or more hydrocarbon groups include -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, preferably a hydrogen atom. 101 The carbon atom of Lp 101 Furthermore, X is also preferably 101 The nitrogen atom and Lp 101 Bonding.

[0366] As X 101 The 4+q-valent linking group represented is preferably a group containing an aromatic hydrocarbon ring because it has a strong affinity for the pigment and is less likely to generate foreign matter. Examples of the group containing an aromatic hydrocarbon ring include a group represented by formula (X-1).

[0367] [Chemical formula 25]

[0368]

[0369] In formula (X-1), *1 represents the P of formula (100). 101 The connecting bond of *2 represents the X of formula (100) 101 Bonded -CO- link, Rx 1 and Rx 2 Each independently represents a substituent, m1 represents an integer of 0 to 3, m2 represents an integer of 0 to 3, n represents an integer greater than 1, and X 100 It represents a 2+n-valent linking group.

[0370] As X 100 The 2+n-valent linking group represented by may be 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. Examples of the hydrocarbon group include the above groups. Rx 101 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0371] As Rx 1 and Rx 2 The substituent represented by includes the above-mentioned substituent T. Specific examples include a halogen atom, an alkyl group, and a carboxyl group.

[0372] m1 and m2 are preferably each independently an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0373] In formula (100), Lp 101 The divalent linking group includes a hydrocarbon group, -NR L1 -、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NR L1 CO-、-CONR L1 - and a group consisting of two or more of these. L1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of a straight chain, a branched chain, and a cyclic group. Furthermore, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Furthermore, the cyclic aliphatic hydrocarbon group may have a cross-linked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. 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 further preferably a group containing -S-.

[0374] Lp 101 The divalent linking group represented is preferably a group represented by formula (Lp-101) or formula (Lp-201), and more preferably a group represented by formula (Lp-101).

[0375] [Chemical formula 26]

[0376]

[0377] In formula (Lp-101) and formula (Lp-102), Lp 111 represents a single bond or a divalent linking group, and *1 represents the X in formula (100) 101 The connecting bond of *2 represents the P of formula (100). 101 The connection key.

[0378] As Lp 111 The divalent linking group represented by may be a hydrocarbon group, or a group having a structure in which two or more hydrocarbon groups are bonded via a single bond or a linking group. L1 -、-SO-、-SO 2 -, -CO-, -0-, -COO-, -OCO-, -S-, -NR L1 CO- and -CONR L1 -. R L1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0379] The specific resin may contain an imide cyclization structure of the structure represented by the above formula (100).

[0380] The acid value of the specific resin is preferably 10 to 150 mgKOH / g. The upper limit is preferably 100 mgKOH / g or less, more preferably 80 mgKOH / g or less. The lower limit is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more.

[0381] The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 200,000, more preferably 2,500 to 100,000, and further preferably 3,000 to 50,000.

[0382] The 5% mass reduction temperature of the specific resin by TG / DTA (thermal mass measurement / thermal differential measurement) under a nitrogen atmosphere is preferably 280° C. or higher, more preferably 300° C. or higher, and further 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 lower. The 5% mass reduction temperature can be determined by a known TG / DTA measurement method as a temperature at which the mass reduction rate becomes 5% when the resin is left to stand at a specific temperature for 5 hours under a nitrogen atmosphere.

[0383] The specific resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and even more preferably 2% or less when left to stand at 300°C for 5 hours in a nitrogen atmosphere. The lower limit of the mass reduction rate is not particularly limited, and may be 0% or more.

[0384] The mass reduction rate is a value calculated as a ratio of mass reduction in the specific resin before and after being left to stand at 300° C. for 5 hours in a nitrogen atmosphere.

[0385] For example, specific resin can be synthesized by reacting acid dianhydride with diamine compound to synthesize polyamic acid, and then reacting with end-capping agent (end-capping agent macromonomer) having groups and polymer chains reacting with terminal amine sites of polyamic acid respectively to synthesize. End-capping agents (other end-capping agents) other than end-capping agent macromonomer can be further used as needed. As other end-capping agents, monoamine, acid anhydride, monocarboxylic acid, monocarboxylic acid chloride, monocarboxylic acid halide compound or monocarboxylic acid active ester etc. can be cited.

[0386] The molar ratio of the acid dianhydride to the diamine compound is preferably 0.5 to 1.5 mol, more preferably 0.7 to 1.3 mol, and even more preferably 0.9 to 1.1 mol, relative to 1 mol of the diamine compound. Also, the molar ratio of the diamine compound to the end-capping agent macromonomer is preferably 0.1 to 2 mol, more preferably 0.2 to 1.5 mol, and even more preferably 0.5 to 1.2 mol, relative to 1 mol of the diamine compound.

[0387] Examples of the terminal blocking agent macromonomer include compounds represented by the formula (EDM).

[0388] [Chemical formula 27]

[0389]

[0390] In the formula (EDM), R ED represents an anhydride group, a halogenated acyl group or an isocyanate group,

[0391] Lp ED1 represents an n+1 valent group,

[0392] The above n+1 valent group is a hydrocarbon group or a hydrocarbon group selected from -NRp ED1 -、-N<、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO- and -CONRp ED1 -a group of a structure composed of at least one group in combination,

[0393] R ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

[0394] Lp ED2 Indicates -O- or -S-,

[0395] P ED1 represents the polymer chain,

[0396] n represents an integer of 1 to 4.

[0397] R of formula (EDM) ED The acid anhydride group represented by is preferably a cyclic acid anhydride group. ED The anhydride group represented by is preferably a group represented by the formula (R ED1 -11)~Formula (R ED1 -13), more preferably a group represented by the formula (R ED1 -13). Furthermore, the halogenated acyl group is preferably a group represented by the formula (R ED1 -21) represented by a group.

[0398] [Chemical formula 28]

[0399]

[0400] 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 the same ED1 The connection key.

[0401] As R ED11 and R ED12 The substituent represented by includes the above-mentioned substituent T, and is preferably a halogen atom, a carboxyl group, an alkyl group or a hydroxyl group, and more preferably a carboxyl group.

[0402] As R ED21 The halogen atom represented by is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

[0403] r is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0404] Lp as formula (EDM) ED1 The hydrocarbon group in may include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of a straight chain, a branched chain, and a cyclic group. Furthermore, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Furthermore, the cyclic aliphatic hydrocarbon group may have a cross-linked structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. As the substituent, the above-mentioned substituent T may be mentioned.

[0405] Formula (EDM) Lp ED2 It represents -O- or -S-, preferably -S-.

[0406] Formula (EDM) P ED1 The polymer chain represented by 1 The polymer chains indicated have the same meaning.

[0407] In the formula (EDM), n is preferably 1 or 2.

[0408] The end-capping agent macromonomer is preferably a compound having an acid anhydride group, more preferably a compound represented by formula (EDM1), and further preferably a compound represented by formula (EDM2). The compound represented by formula (EDM1) and the compound represented by formula (EDM2) are compounds of the present invention.

[0409] [Chemical formula 29]

[0410]

[0411] In formula (EDM1), R ED1 represents anhydride group,

[0412] Lp ED1 represents an n+1 valent group,

[0413] The above n+1 valent group is a hydrocarbon group or a hydrocarbon group selected from -NRp ED1 -、-N<、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO- and -CONRp ED1 -a group of a structure composed of at least one group in combination,

[0414] R ES1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

[0415] Lp ED2 Indicates -O- or -S-,

[0416] P ED1 represents a polymer chain including a repeating unit represented by any of formula (P1-1) to formula (P1-4),

[0417] n represents an integer of 1 to 4.

[0418] [Chemical formula 30]

[0419]

[0420] In formula (EDM2), R ED12 represents a halogen atom, an alkyl group, a carboxyl group or a hydroxyl group,

[0421] Lp ED1a represents an n+1 valent group,

[0422] The above n+1 valent group is a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a single bond or a linking group.

[0423] The above-mentioned concubinage group is -NRp ED1 -、-SO-、-SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO-or-CONRp ED1 ,

[0424] R ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,

[0425] Lp ED2 Indicates -O- or -S-,

[0426] P ED1 represents a polymer chain including a repeating unit represented by any of formula (P1-1) to formula (P1-4),

[0427] r represents an integer from 0 to 3,

[0428] n represents an integer of 1 to 4.

[0429] [Chemical formula 31]

[0430]

[0431] In formula (P1-1) to formula (P1-4), R G1 and R G2 respectively represent an alkylene group.

[0432] R of formula (EDM1) ED1 The anhydride group represented by the formula (EDM) is ED The anhydride group described in has the same meaning as that in .

[0433] Regarding P of formula (EDM1) ED1 The details of the polymer chain represented by 1 The contents described in the represented polymer chain are the same.

[0434] Formula (EDM1) Lp ED1 , Lp ED2 and n and Lp of formula (EDM) ED1 , Lp ED2 and n have the same meaning.

[0435] In the formula (EDM2), r is an integer of 0 to 3, and r is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0436] As Lp of formula (EDM2) ED1a The hydrocarbon group in the formula (EDM2) has the same meaning as the hydrocarbon group described in the formula (EDM). ED1a The n+1-valent group represented is preferably a hydrocarbon group.

[0437] Regarding P of formula (EDM2) ED1 The details of the polymer chain represented by 1 The contents described in the represented polymer chain are the same.

[0438] Formula (EDM2) Lp ED2 and n and Lp of formula (EDM) ED2 and n have the same meaning.

[0439] Specific examples of the terminal-capping agent macromonomer include terminal-capping agent macromonomers EDM-1 to EDM-40 described in the examples below.

[0440] For example, the capping agent macromonomer can be synthesized by the following method.

[0441] (1) A method of synthesizing by subjecting a macromonomer obtained by radically polymerizing a radically polymerizable compound using a chain transfer agent having one hydroxyl group and one or two mercapto groups to an esterification reaction with an acid anhydride or an acid anhydride chloride.

[0442] (2) A method of synthesizing by subjecting a compound having two mercapto groups to an acid anhydride having a group containing an ethylenically unsaturated bond, followed by ring-opening polymerization of a lactone.

[0443] (3) A method of synthesizing by coupling a macromonomer obtained by radically polymerizing 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.

[0444] (4) A method of synthesizing by reacting a compound having one anhydride group, carboxyl group or acyl halide with a polymer having a hydroxyl group or an amino group at the terminal. The compound having one anhydride group and carboxyl group or acyl halide used in the synthesis is preferably trimellitic anhydride and trimellitic anhydride chloride because the macromonomer can be synthesized with high purity and high yield.

[0445] (5) A method of synthesizing by chlorinating a macromonomer obtained by radically polymerizing a radical polymerizable compound using a chain transfer agent having one carboxyl group and one mercapto group (for example, mercaptopropionic acid).

[0446] (6) A method of synthesizing a macromonomer obtained by ring-opening polymerization of lactone using a compound having one or two hydroxyl groups and one mercapto group (for example, mercaptoethanol, mercaptopropanol, mercaptohexanol, mercaptoglycerol, etc.) and reacting it with an ene-thiol reaction of a compound having an isocyanate group and a group containing an unsaturated bond.

[0447] If hydrochloric acid remains, the end-capping agent macromonomer may become the cause of deterioration and corrosion, so it is preferably removed. When anhydride chloride is used in the raw material, it is preferably synthesized by separating the produced hydrochloride after mixing the raw materials in the presence of a base. As a base, it can be an organic base or an inorganic base. In the case of an organic base, tertiary alkylamines, aromatic tertiary amines, heterocyclic aromatic amines, etc. are used. For example, triethylamine, diisopropylethylamine, tributylamine, diethylaniline, pyridine, 4,4-dimethylaminopyridine, 2-picoline, 2,6-dipicoline, imidazole, 1-methylimidazole, 1-ethylimidazole, triazole, tetrazole, etc. can be cited. As a separation method, a method of filtering (natural filtration, pressure filtration, reduced pressure filtration, centrifugal filtration) using a filter, a method of separating a liquid into an organic layer and an aqueous layer, a method of centrifugal separation, a method of adsorption (silica gel column, activated carbon, etc.), etc. can be cited.

[0448] (Other resins)

[0449] The resin composition of the present invention may contain other resins other than the above-mentioned specific resin as resins. As other resins, for example, resins having alkali developability or resins as dispersants may be cited. In addition, by-products when synthesizing specific resins such as decomposition products of end-capping agent macromonomers and reaction products of diamines and end-capping agent macromonomers may be contained.

[0450] [Alkali-developable resin]

[0451] The weight average molecular weight (Mw) of the alkali-developable resin is preferably 3000 to 2000000. The upper limit is more preferably 1000000 or less, and further preferably 500000 or less. The lower limit is more preferably 4000 or more, and further preferably 5000 or more.

[0452] As the resin with alkali developability, (meth) acrylic resin, polyimide resin, polyether resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyimide resin, etc. can be cited, preferably (meth) acrylic resin and polyimide resin, more preferably (meth) acrylic resin. And, as other resins, the resins recorded in paragraphs 0041 to 0060 of Japanese Patent Publication No. 2017-206689, the resins recorded in paragraphs 0022 to 0071 of Japanese Patent Publication No. 2018-010856, the resins recorded in Japanese Patent Publication No. 2017-057265, the resins recorded in Japanese Patent Publication No. 2017-032685, the resins recorded in Japanese Patent Publication No. 2017-075248, and the resins recorded in Japanese Patent Publication No. 2017-066240 can also be used.

[0453] Furthermore, as the resin with alkali developability, it is preferred to use a resin with an acid group. According to this method, the developability of the resin composition can be further improved. As the acid group, phenolic hydroxyl, carboxyl, sulfonic, phosphoric, phosphonic acid, active imide, sulfonamide, etc. can be cited, preferably carboxyl. Furthermore, as the resin with an acid group, it is also possible to use a resin in which an acid anhydride is reacted with a hydroxyl group generated in epoxy ring opening to introduce an acid group. As such resin, the resins described in Japanese Patent Gazette No. 6349629 can be cited. For example, a resin with an acid group can be used as an alkali-soluble resin.

[0454] The alkali-developable resin preferably contains repeating units having an acid group in the side chain, and more preferably contains 1 to 70 mol% of repeating units having an acid group in the side chain among all repeating units of the resin. The upper limit of the content of repeating units having an acid group in the side chain is preferably 50 mol% or less, and more preferably 40 mol% or less. The lower limit of the content of repeating units having an acid group in the side chain is preferably 2 mol% or more, and more preferably 5 mol% or more.

[0455] The acid value of the alkali-developable resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. In addition, the acid value of the resin having an acid group is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.

[0456] The alkali-developable resin also preferably has a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, and a (meth)acryloyl group. An allyl group and a (meth)acryloyl group are preferred, and a (meth)acryloyl group is more preferred.

[0457] The resin having a group containing an ethylenically unsaturated bond preferably contains a repeating unit having a group containing an ethylenically unsaturated bond in the side chain, and more preferably contains 5 to 80 mol% of repeating units having a group containing an ethylenically unsaturated bond in the side chain among all repeating units of the resin. The upper limit of the content of the repeating unit having a group containing an ethylenically unsaturated bond in the side chain is preferably 60 mol% or less, more preferably 40 mol% or less. The lower limit of the content of the repeating unit having a group containing an ethylenically unsaturated bond in the side chain is preferably 10 mol% or more, more preferably 15 mol% or more.

[0458] The alkali-developable resin preferably includes repeating units derived from a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds are also referred to as “ether dimers”).

[0459] [Chemical formula 32]

[0460]

[0461] In formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

[0462] [Chemical formula 33]

[0463]

[0464] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), reference can be made to the description of Japanese Unexamined Patent Publication No. 2010-168539, the contents of which are incorporated herein.

[0465] As specific examples of the ether dimer, reference can be made to paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-029760, for example, the contents of which are incorporated herein.

[0466] The alkali-developable resin also preferably contains a repeating unit derived from a compound represented by the following formula (X).

[0467] [Chemical formula 34]

[0468]

[0469] 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, R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

[0470] As the resin having alkali developability, for example, resins having the following structures are mentioned. In the following structural formula, Me represents a methyl group.

[0471] [Chemical formula 35]

[0472]

[0473] 〔Dispersant〕

[0474] The resin composition of the present invention can also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of base groups. Regarding the acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, it is preferably a resin in which the amount of acid groups accounts for 70 mol% or more, and more preferably a resin consisting essentially of only acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and further preferably 60 to 105 mgKOH / g. In addition, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of base groups is greater than the amount of acid groups. The basic dispersant (basic resin) preferably has a base content exceeding 50 mol % when the total of the acid group content and the base content is 100 mol %. The base group of the basic dispersant is preferably an amino group.

[0475] The resin used as the dispersant preferably contains a repeating unit having an acid group.

[0476] The resin used as the dispersant is also preferably a graft polymer. Examples of the graft polymer include the resins described in paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

[0477] The resin used as a dispersant is also preferably a polyimine dispersant (polyimine resin) containing a nitrogen atom on at least one of the main chain and the side chain. As a polyimine dispersant, a resin having a main chain and a side chain and having a basic nitrogen atom on at least one of the main chain and the side chain is preferred, wherein the main chain contains a partial structure having a functional group with a pKa of less than 14, and the number of atoms in the side chain is 40 to 10,000. There is no particular limitation on the basic nitrogen atom as long as it is a basic nitrogen atom. As polyimine dispersants, resins described in paragraphs 0102 to 0166 of Japanese Patent Gazette No. 2012-255128 can be cited, and the content is incorporated into this specification.

[0478] The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0479] Dispersants can also be obtained as commercial products, and specific examples thereof include DISPERBYK series (e.g., DISPERBYK-111, 161, etc.) manufactured by BYK-Chemie GmbH, Solsperse series (e.g., Solsperse 36000, etc.) manufactured by Lubrizol, etc. In addition, pigment dispersants described in paragraphs 0041 to 0130 of Japanese Unexamined Patent Publication No. 2014-130338 can also be used, and the contents are incorporated into this specification. Furthermore, as the dispersant, compounds described in JP-A-2018-150498, JP-A-2017-100116, JP-A-2017-100115, JP-A-2016-108520, JP-A-2016-108519, and JP-A-2015-232105 can be used.

[0480] Furthermore, the resin described as the dispersant can also be used for purposes other than the dispersant, for example, it can also be used as a binder.

[0481] The content of the resin in the total solid content of the resin composition is preferably 5 to 60% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.

[0482] The content of the specific resin in the total solid content of the resin composition is preferably 5 to 60% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.

[0483] The content of the specific resin is preferably 10 to 80 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and the upper limit is preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

[0484] Furthermore, the resin composition of the present invention preferably comprises more than 20% by mass of a specific resin in the composition removing the color material from the total solid content of the resin composition, more preferably comprises more than 30% by mass, and further preferably comprises more than 40% by mass. The upper limit can be set to 100% by mass, can also be set to less than 90% by mass, and can also be set to less than 85% by mass. As long as the content of the specific resin is within the above range, it is easy to form a film with excellent heat resistance, and it is easier to suppress the shrinkage of the film after heating. Furthermore, when an inorganic film is formed on the surface of the film obtained using the resin composition of the present invention, even if the laminate is exposed to high temperature, it is also possible to suppress the generation of cracks on the inorganic film.

[0485] Furthermore, the total content of the color material and the above-mentioned specific resin in the total solid content of the resin composition is preferably 25 to 100% by mass. The lower limit is more preferably 30% by mass or more, and further preferably 40% by mass or more. The upper limit is more preferably 90% by mass or less, and further preferably 80% by mass or less.

[0486] In the resin composition, relative to 100 parts by mass of the above-mentioned specific resin, the content of the above-mentioned other resins is preferably less than 230 parts by mass, more preferably less than 200 parts by mass, and further preferably less than 150 parts by mass. The lower limit can be 0 parts by mass, can also be set to more than 5 parts by mass, and can also be set to more than 10 parts by mass. In addition, it is also preferred that the resin composition does not substantially include the above-mentioned other resins. According to this mode, it is easy to form a film with excellent heat resistance. The situation that substantially does not include other resins refers to that the content of other resins in the total solid content of the resin composition is less than 0.1% by mass, preferably less than 0.05% by mass, and more preferably does not contain.

[0487] <Solvent C>

[0488] The resin composition of the present invention contains solvent C (hereinafter referred to as solvent). As a solvent, there is basically no particular restriction as long as the solubility of each component and the coating property of the resin composition are satisfied. The solvent is preferably an organic solvent. As an organic solvent, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. can be cited, preferably at least one selected from ester solvents, ether solvents, alcohol solvents and ketone solvents. For details of these, reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated into this specification. In addition, cyclic alkyl substituted ester solvents and cyclic alkyl substituted ketone solvents can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, sulfolane, anisole, and the like. However, sometimes, for environmental reasons, it is preferred to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents (for example, it can be set to less than 50 mass ppm (parts per million), can be set to less than 10 mass ppm, or can be set to less than 1 mass ppm relative to the total amount of the organic solvent).

[0489] In the present invention, it is preferred to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion: parts per billion) or less. Organic solvents of the mass ppt (parts pertrillion: parts per trillion) level can be used as needed, and such organic solvents are provided, for example, by Toyo Gosei Co., Ltd (Chemical Industry Daily, November 13, 2015). As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter can be cited. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

[0490] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may contain only one type or multiple types.

[0491] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0492] The content of the organic solvent in the resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

[0493] <Pigment derivatives>

[0494] The resin composition of the present invention preferably contains a pigment derivative. As a pigment derivative, a compound having a structure in which a part of the chromophore is substituted with an acid group, a base or a phthalimide methyl group can be cited. As the chromophore constituting the pigment derivative, a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindoline skeleton, a quinoline yellow skeleton, a reduction skeleton, a metal complex skeleton, etc. can be cited, preferably a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a quinoline yellow skeleton, an isoindoline skeleton and a phthalocyanine skeleton, more preferably an azo skeleton and a benzimidazolone skeleton. As the acid group possessed by the pigment derivative, a sulfo group and a carboxyl group are preferred, and a sulfo group is more preferred. As the base group possessed by the pigment derivative, an amino group is preferred, and a tertiary amino group is more preferred.

[0495] As the pigment derivative, a pigment derivative having excellent visible light transparency (hereinafter also referred to as a transparent pigment derivative) can also be used. The maximum value (εmax) of the molar absorption coefficient of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L·mol -1 cm -1 Below, more preferably 1000 L·mol -1 cm -1 Below, more preferably 100 L·mol -1 cm -1 For example, the lower limit of εmax is 1L·mol -1 cm -1 Above, it can also be 10L·mol -1 cm -1 above.

[0496] Specific examples of the pigment derivatives include Japanese Patent Application Laid-Open Nos. 56-118462, 63-264674, 01-217077, 03-009961, 03-026767, 03-153780, 03-0456 62, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, Japanese Patent Application Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, International Publication No. 2011 / 024896, No. 0086 to 0098, paragraphs 0063 to 0094 of International Publication No. 2012 / 102399, paragraph 0082 of International Publication No. 2017 / 038252, paragraph 0171 of Japanese Patent Application Publication No. 2015-151530, paragraphs 0162 to 0183 of Japanese Patent Application Publication No. 2011-252065, Japanese Patent Application Publication No. 2003-081972, Japanese Patent Application Publication No. 2014-031973, paragraph 0171 of Japanese Patent Application Publication No. 2014-031974, paragraph 0171 of Japanese Patent Application Publication No. 2014-031973 ... Compounds described in this patent No. 5299151, Japanese Patent Application Publication No. 2015-172732, Japanese Patent Application Publication No. 2014-199308, Japanese Patent Application Publication No. 2014-085562, Japanese Patent Application Publication No. 2014-035351, Japanese Patent Application Publication No. 2008-081565, and Japanese Patent Application Publication No. 2019-109512.

[0497] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

[0498] <Polymerizable Monomer>

[0499] The resin composition of the present invention preferably contains a polymerizable monomer. As a polymerizable monomer, for example, a known compound that can be crosslinked by free radicals, acid or heat can be used. As a polymerizable monomer, a compound having a group containing an ethylenically unsaturated bond, a compound having a cyclic ether group, etc. can be cited, preferably a compound having a group containing an ethylenically unsaturated bond. As a group containing an ethylenically unsaturated bond, vinyl, (methyl) allyl, (methyl) acryloyl, etc. can be cited. As a cyclic ether group, epoxy, cyclohexane, etc. can be cited. A compound having a group containing an ethylenically unsaturated bond can be preferably used as a free radical polymerizable monomer. And, a compound having a cyclic ether group can be preferably used as a cationic polymerizable monomer. The polymerizable monomer is preferably a multifunctional polymerizable monomer. That is, the polymerizable monomer is preferably a monomer having more than two polymerizable groups such as a group containing an ethylenically unsaturated bond or a cyclic ether group.

[0500] The molecular weight of the polymerizable monomer is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and further preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.

[0501] (Compound having a group containing an ethylenically unsaturated bond)

[0502] As the compound having a group containing an ethylenically unsaturated bond used as a polymerizable monomer, a polyfunctional compound is preferred. That is, a compound containing two or more groups containing an ethylenically unsaturated bond is preferred, a compound containing three or more groups containing an ethylenically unsaturated bond is more preferred, a compound containing 3 to 15 groups containing an ethylenically unsaturated bond is further preferred, and a compound containing 3 to 6 groups containing an ethylenically unsaturated bond is further preferred. Furthermore, the compound having a group containing an ethylenically unsaturated bond is preferably a 3-15-functional (meth)acrylate compound, and more preferably a 3-6-functional (meth)acrylate compound. Specific examples of the compound having a group containing an ethylenically unsaturated bond include compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraphs 0254 to 0257 of JP-A-2008-292970, paragraphs 0034 to 0038 of JP-A-2013-253224, paragraph 0477 of JP-A-2012-208494, JP-A-2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent No. 2017-194662, and the contents thereof are incorporated into the present specification.

[0503] Preferred examples of the compound having a group containing an ethylenically unsaturated bond include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, SARTOMER Company, Inc. (SR454, SR499). As the compound having a group containing an ethylenically unsaturated bond, diglycerol EO (ethylene oxide) modified (meth) acrylate (commercially available product, M-460; manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-AO (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc.

[0504] Furthermore, as the compound having a group containing an ethylenically unsaturated bond, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferably used. Examples of commercially available trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and 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, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARADGPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0505] Compounds having groups containing ethylenically unsaturated bonds can also use compounds having acid groups. By using compounds having acid groups, the generation of developer residues can be suppressed. Examples of acid groups include carboxyl groups, sulfonic groups, phosphoric acid groups, and the like, preferably carboxyl groups. Commercially available products of polymerizable monomers having acid groups include ARONIX M-305, M-510, M-520, ARONIXTO-2349 (manufactured by TOAGOSEI CO., LTD.), and the like. The preferred acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in terms of manufacturing and handling.

[0506] It is also preferred that the compound having a group containing an ethylenically unsaturated bond is a compound having a caprolactone structure. Compounds having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

[0507] Compounds having a group containing an ethylenically unsaturated bond can also use compounds having an alkylene oxide group. Compounds having an alkylene oxide group are preferably compounds having an ethylene oxide group and / or a propylene oxide group, more preferably compounds having an ethylene oxide group, and further preferably tri- to hexa-functional (meth)acrylate compounds having 4 to 20 ethylene oxide groups. Commercially available polymerizable compounds having an alkylene oxide group include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethylene oxide groups, manufactured by SARTOMER Company, Inc., and KAYARAD TPA-330, a trifunctional (meth)acrylate having three isobutylene oxide groups.

[0508] Compounds having a fluorene skeleton may also be used as compounds having a group containing an ethylenically unsaturated bond. Commercially available compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0509] As the compound having a group containing an ethylenically unsaturated bond, it is also preferable to use a compound substantially free of environmentally regulated substances such as toluene. Examples of commercially available products of such a compound include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0510] As the compound having a group containing an ethylenically unsaturated bond, urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also preferred. In addition, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 are also preferably used. In addition, commercial products such as UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (manufactured by KYOEISHA CHEMICAL Co., LTD.) can also be used as polymerizable compounds.

[0511] (Compound having a cyclic ether group)

[0512] As a compound having a cyclic ether group used as a polymerizable monomer, a compound having an epoxy group (hereinafter, also referred to as an epoxy compound) and a compound having an oxycyclobutane group (hereinafter, also referred to as an oxycyclobutane compound) can be cited. The epoxy compound is preferably a multifunctional epoxy compound. That is, the epoxy compound is preferably a compound having two or more epoxy groups. The upper limit of the number of epoxy groups is preferably 20 or less, more preferably 10 or less. And, the oxycyclobutane compound is preferably a multifunctional oxycyclobutane compound. That is, the oxycyclobutane compound is preferably a compound having two or more oxycyclobutane groups. The upper limit of the number of oxycyclobutane groups is preferably 20 or less, more preferably 10 or less.

[0513] Commercially available products of epoxy compounds include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and commercial products described in paragraph 0189 of Japanese Patent Application Publication No. 2011-221494. Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA CORPORATION), 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, DL C-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (above Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (all manufactured by NIPPON STEEL & SUMIKIN MATERIALS CO., LTD.), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, Serviners B0134, B0177 (manufactured by Daicel Corporation), TETRAD-X (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.), etc.

[0514] As commercially available products of the oxetane compound, OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ TX-100 (all manufactured by TOAGOSEI CO., LTD.), etc. can be used.

[0515] The content of the polymerizable monomer in the total solid content of the resin composition is preferably 0.1 to 40% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.

[0516] When a compound having a group containing an ethylenically unsaturated bond is used as a polymerizable monomer, the content of the compound having a group containing an ethylenically unsaturated bond as a polymerizable monomer is preferably 1 to 50 parts by mass relative to 100 parts by mass of the above-mentioned specific resin. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

[0517] When a compound having a cyclic ether group is used as a polymerizable monomer, the content of the compound having a cyclic ether group as a polymerizable monomer is preferably 1 to 50 parts by mass relative to 100 parts by mass of the specific resin. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

[0518] When a compound having a group containing an ethylenically unsaturated bond and a compound having a cyclic ether group are used as a polymerizable monomer, the resin composition preferably contains 10 to 500 parts by mass of a compound having a cyclic ether group relative to 100 parts by mass of a compound having a group containing an ethylenically unsaturated bond. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is preferably 400 parts by mass or less, more preferably 300 parts by mass or less. As long as the ratio of the two is within the above range, a film having better heat resistance (crack suppression and film shrinkage suppression) can be formed.

[0519] <Photopolymerization Initiator>

[0520] The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitized to light in the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photo-radical polymerization initiator.

[0521] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, an imidazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a biimidazole compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from the group consisting of a biimidazole compound, an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, peroxide-based photopolymerization initiators described in MATERIALSTAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313 can be cited, and these contents are incorporated into this specification.

[0522] Examples of the biimidazole compound include 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. Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF), etc. Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF), etc. Examples of commercially available products of the acylphosphine compound include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0523] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. As commercial products, Irgacure-OXE01, Irgacure-OXE02, Irgacure-OXE03, Irgacure-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). In addition, as oxime compounds, non-coloring compounds or compounds with high transparency and low color change are also preferably used. As commercial products, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (manufactured by ADEKA CORPORATION) and the like can be cited.

[0524] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466.

[0525] Furthermore, as the photopolymerization initiator, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505.

[0526] As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and compound (C-3) described in JP-A-2013-164471.

[0527] As a photopolymerization initiator, an oxime compound having a substituent having a hydroxyl group bonded to a carbazole skeleton can also be used. As such a photopolymerization initiator, compounds described in International Publication No. 2019 / 088055 can be cited.

[0528] As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. As specific examples of the oxime compound having a nitro group, there can be cited the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071, and ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION).

[0529] As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0530] As a photopolymerization initiator, an oxime compound having a substituent having a hydroxyl group bonded to a carbazole skeleton can also be used. As such a photopolymerization initiator, compounds described in International Publication No. 2019 / 088055 can be cited.

[0531] Specific examples of the oxime compound are shown below, but the present invention is not limited to these.

[0532] [Chemical formula 36]

[0533]

[0534] [Chemical formula 37]

[0535]

[0536] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured by a spectrophotometer (Varian Cary-5 spectrophotometer), using ethyl acetate, at a concentration of 0.01 g / L.

[0537] As the photopolymerization initiator, a photoradical polymerization initiator having difunctional or trifunctional functions or more can be used. By using such photoradical polymerization initiators, more than two free radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound of an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent etc. becomes high, and becomes difficult to separate out over time, thereby being able to improve the stability over time of the resin combination. Specific examples of the bifunctional or trifunctional or higher photoradical polymerization initiator include dimers of oxime compounds described in JP-T 2010-527339, JP-T 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-T 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds described in JP-T 2013-522445. (E) and compound (G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Unexamined Patent Application Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Unexamined Patent Application Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, the oxime ester compound described in Japanese Patent No. 6469669, etc.

[0538] The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. Only one photopolymerization initiator may be used, or two or more may be used.

[0539] <<Silane coupling agent>>

[0540] The resin composition of the present invention can contain a silane coupling agent. In this specification, a silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. In addition, a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can produce a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, etc. can be cited, preferably an alkoxy group. 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, for example, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, etc. can be cited, preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604, and the contents thereof are incorporated into the present specification.

[0541] The content of the silane coupling agent in the total solid content of the resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one kind or two or more kinds.

[0542] <Curing Accelerator>

[0543] The resin composition of the present invention may further contain a curing accelerator for the purpose of promoting the reaction of the resin and the polymerizable compound or lowering the curing temperature. The curing accelerator may also be a hydroxymethyl compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of Japanese Patent Publication No. 2015-034963), an amine, a phosphonium salt, an amidine salt, an amide compound (for example, a curing agent described in paragraph 0186 of Japanese Patent Publication No. 2013-041165), an alkali generator (for example, an ionic compound described in Japanese Patent Publication No. 2014-055114), a cyanate compound (for example, , compounds described in paragraph 0071 of Japanese Patent Publication No. 2012-150180), alkoxysilane compounds (for example, alkoxysilane compounds having an epoxy group described in Japanese Patent Publication No. 2011-253054), onium salt compounds (for example, compounds exemplified as acid generators in paragraph 0216 of Japanese Patent Publication No. 2015-034963, compounds described in Japanese Patent Publication No. 2009-180949), etc.

[0544] 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, more preferably 0.8 to 6.4% by mass, based on the total solid content of the resin composition.

[0545] <Polymerization Inhibitor>

[0546] The resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, first cerium salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.

[0547] <Surfactant>

[0548] The resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used. As for the surfactant, the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779 may be cited, and the contents are incorporated into this specification.

[0549] The surfactant is preferably a fluorine-based surfactant. By including a fluorine-based surfactant in the resin composition, the liquid properties (especially fluidity) are further improved, and the liquid saving property can be further improved. In addition, a film with less uneven thickness can be formed.

[0550] 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. Fluorine-based surfactants having a fluorine content within this range are effective in terms of thickness uniformity and liquid saving of the coating film, and also have good solubility in the resin composition.

[0551] As fluorine-based surfactants, surfactants described in paragraphs 0060 to 0064 of Japanese Patent Publication No. 2014-041318 (corresponding paragraphs 0060 to 0064 of International Publication No. 2014 / 017669), surfactants described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, and surfactants described in Japanese Patent Publication No. 2020-008634 are included in this specification. As commercially available products of fluorine-based surfactants, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all DIC CORPORATION), FLUORAD FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC INC.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA SOLUTIONS INC.), Futurgent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (all manufactured by NEOS COMPANY LIMITED), etc.

[0552] In addition, as for fluorine-based surfactants, polymers of fluorine-containing vinyl ether compounds having fluorinated alkyl or fluorinated alkylene ether groups and hydrophilic vinyl ether compounds are also preferably used. As such fluorine-based surfactants, reference can be made to the records of Japanese Patent Publication No. 2016-216602, which is incorporated into this specification.

[0553] The fluorine-based surfactant can also use block polymers. For example, the compounds described in Japanese Patent Publication No. 2011-089090 can be cited. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains: a repeating unit from a (meth)acrylate compound having a fluorine atom; and a repeating unit from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy, propyleneoxy). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[0554] [Chemical formula 38]

[0555]

[0556] The weight average molecular weight of the above compound is preferably 3000 to 50000, for example, 14000. In the above compound, % indicating the ratio of the repeating unit is mol %.

[0557] In addition, the fluorine-containing surfactant can also use a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in the side chain. As a specific example, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, for example, MEGAFACE RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation, etc. Fluorine-containing surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327.

[0558] The content of the surfactant in the total solid content of the resin composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be only one or two or more. In the case of two or more, the total amount is preferably within the above range.

[0559] <Ultraviolet light absorber>

[0560] The resin composition of the present invention can contain an ultraviolet light absorber. The ultraviolet light absorber can use a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl triazine compound, an indole compound, a triazine compound, etc. For details of these, reference can be made to paragraphs 0052 to 0072 of Japanese Patent Publication No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Publication No. 2013-068814, and paragraphs 0061 to 0080 of Japanese Patent Publication No. 2016-162946, which are incorporated into this specification. As a commercially available product of an ultraviolet light absorber, for example, UV-503 (made by DAITO CHEMICAL CO., LTD.) can be cited. In addition, as benzotriazole compounds, MYUA series made by MIYOSHI OIL & FAT CO., LTD. can be cited (Chemical Industry Daily, February 1, 2016). In addition, the ultraviolet absorber can also use the compounds described in paragraphs 0049 to 0059 of Japanese Patent Gazette No. 6268967. The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. The ultraviolet absorber can be used in only one kind or in two or more kinds. When two or more kinds are used, the total amount is preferably within the above range.

[0561] <Antioxidants>

[0562] The photosensitive composition of the present invention can contain an antioxidant. As an antioxidant, phenolic compounds, sub-phosphate compounds, thioether compounds, etc. can be mentioned. As a phenolic compound, any phenolic compound of a known phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. Preferably, a compound having a substituent at a position adjacent to a phenolic hydroxyl group (ortho position). As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenolic group and a sub-phosphate group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus antioxidant. In addition, the antioxidant can also use compounds described in the Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one antioxidant can be used, or two or more can be used. When two or more are used, the total amount is preferably within the above range.

[0563] <Other ingredients>

[0564] The resin composition of the present invention may contain sensitizers, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, levelers, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.) as needed. By appropriately containing these ingredients, properties such as film physical properties can be adjusted. Regarding these ingredients, for example, the records of paragraphs 0183 and later of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, etc., can be referenced, and these contents are incorporated into this specification. In addition, the resin composition may contain potential antioxidants as needed. As a potential antioxidant, the following compounds can be mentioned: compounds in which the site acting as an antioxidant is protected by a protecting group, and the protecting group is detached by heating at 100 to 250 ° C or heating at 80 to 200 ° C in the presence of an acid / base catalyst and acts as an antioxidant. As a potential antioxidant, compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219 can be mentioned. As a commercially available product, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) can be mentioned.

[0565] 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 、SiO 2 The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and further preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0566] The resin composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include compounds described in paragraphs 0036 to 0037 of Japanese Patent Application Laid-Open No. 2017-198787, compounds described in paragraphs 0029 to 0034 of Japanese Patent Application Laid-Open No. 2017-146350, compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of Japanese Patent Application Laid-Open No. 2017-129774, and compounds described in paragraphs 0049 to 0052 of Japanese Patent Application Laid-Open No. 201 The compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of Japanese Patent Application No. 7-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of Japanese Patent Application No. 2017-122803, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017 / 164127, and Japanese Patent Application No. 2017-186546 The compounds described in paragraphs 0034 to 0047 of Japanese Patent Application Laid-Open No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese Patent Application Laid-Open No. 2012-145604, the compounds described in paragraphs 0018 to 0021 of Japanese Patent Application Laid-Open No. 2012-103475, the compounds described in paragraphs 0011 to 0022 of Japanese Patent Application Laid-Open No. 2011- The compounds described in paragraphs 0015 to 0018 of Japanese Patent Application No. 257591, the compounds described in paragraphs 0017 to 0021 of Japanese Patent Application No. 2011-191483, the compounds described in paragraphs 0108 to 0116 of Japanese Patent Application No. 2011-145668, the compounds described in paragraphs 0103 to 0153 of Japanese Patent Application No. 2011-253174, and the like.

[0567] In the resin composition of the present invention, the content of the free metal that is not bonded or coordinated with the pigment is preferably less than 100ppm, more preferably less than 50ppm, further preferably less than 10ppm, and particularly preferably substantially free of. According to this mode, it is possible to expect the effects of stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics with improvement of dispersibility, stabilization of curable components, suppression of conductivity variation accompanying dissolution of metal atoms / metal ions, improvement of display characteristics, etc. Furthermore, the effects described in Japanese Patent Publication No. 2012-153796, Japanese Patent Publication No. 2000-345085, Japanese Patent Publication No. 2005-200560, Japanese Patent Publication No. 08-043620, Japanese Patent Publication No. 2004-145078, Japanese Patent Publication No. 2014-119487, Japanese Patent Publication No. 2010-083997, Japanese Patent Publication No. 2017-090930, Japanese Patent Publication No. 2018-025612, Japanese Patent Publication No. 2018-025797, Japanese Patent Publication No. 2017-155228, Japanese Patent Publication No. 2018-036521, etc. can also be obtained. As the kind of the above-mentioned free metal, 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 etc. can be enumerated. And, in the resin composition of the present invention, the content of the free halogen that is not bonded or coordinated with the pigment etc. is preferably below 100ppm, more preferably below 50ppm, further preferably below 10ppm, and particularly preferably substantially not containing. As halogen, F, Cl, Br, I and these anions can be enumerated. As the method for reducing the free metal and halogen in the resin composition, methods such as cleaning, filtration, ultrafiltration based on ion exchange water, and purification based on ion exchange resin can be enumerated.

[0568] From the perspective of environmental regulation, the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts is sometimes regulated. In the resin composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (especially perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts and perfluoroalkyl carboxylic acid (especially perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01ppb to 1,000ppb, more preferably in the range of 0.05ppb to 500ppb, and further preferably in the range of 0.1ppb to 300ppb. The resin composition of the present invention may also be substantially free of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts. For example, by using a compound that can be a substitute for perfluoroalkyl sulfonic acid and its salts and a compound that can be a substitute for perfluoroalkyl carboxylic acid and its salts, a resin composition that substantially does not contain perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts can also be selected. As a compound that can be a substitute for a regulated compound, for example, a compound that is excluded from the regulated object due to the difference in the number of carbon atoms of the perfluoroalkyl group can be cited. However, the above content does not prevent the use of perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt. The resin composition of the present invention may also contain perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt within the maximum allowable range.

[0569] The resin composition of the present invention also preferably contains substantially no terephthalate. Here, “substantially contains” means that the content of terephthalate in the total amount of the resin composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0570] <Storage Container>

[0571] There is no particular limitation on the storage container of the resin composition, and a known storage container can be used. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials and the resin composition, it is also preferred to use a multilayer bottle having a container inner wall composed of 6 kinds of 6 layers of resins, or a bottle having a 7-layer structure in which 6 kinds of resins are set. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited. In addition, the inner wall of the container is also preferably made of glass, stainless steel, etc., for the purpose of preventing metal from dissolving from the inner wall of the container, improving the storage stability of the resin composition, or suppressing the deterioration of components.

[0572] <Method for preparing resin composition>

[0573] The resin composition of the present invention can be prepared by mixing the components. When preparing the resin composition, all the components can be dissolved and / or dispersed in a solvent at the same time to prepare the resin composition, or each component can be appropriately divided into more than 2 parts of solution or dispersion as needed, and these are mixed during use (during coating) to prepare the resin composition.

[0574] And, when preparing resin composition, preferably include pigment dispersion process. In pigment dispersion process, as mechanical force for dispersing pigment, compression, extrusion, impact, shearing, pitting etc. can be mentioned. As the specific example of these processes, bead milling, sand milling, roller milling, ball milling, coating stirring, micro jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion etc. can be mentioned. And, in the pulverization of pigment in sand mill (bead mill), preferably by using micro beads with small diameter, increase the filling rate of micro beads etc. and improve the pulverization efficiency under the condition of processing. And, preferably after pulverization treatment, remove coarse particles by filtering, centrifugation etc. In addition, regarding the pigment dispersion process and the disperser, it is preferred to use the process and the disperser described in paragraph 0022 of "Dispersion Technology Collection, JOHOKIKO CO., LTD., July 15, 2005" or "Dispersion Technology and Industrial Practical Application Comprehensive Data Collection Centering on Suspension (Solid / Liquid Dispersion System), Business Development Center Publishing Department, October 10, 1978", and Japanese Patent Publication No. 2015-157893. In addition, in the pigment dispersion process, the particles can be finely processed by a salt milling process. For example, the raw materials, devices, processing conditions, etc. used in the salt milling process can refer to the records of Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629.

[0575] When preparing resin combination, for the purpose of removing impurities, reducing defects, etc., it is preferred to filter the resin combination with a filter. As a filter, as long as it is a filter used for filtering purposes, it can be used without particular limitation. For example, filters using raw materials such as polyolefin resins (including high density, ultra-high molecular weight polyolefin resins) such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and the like fluororesins, nylon (such as nylon-6, nylon-6,6) and polyamide resins, polyethylene, polypropylene (PP) and the like can be enumerated. Among these raw materials, preferably polypropylene (including high-density polypropylene) and nylon.

[0576] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and further preferably 0.05 to 0.5 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. Regarding the filter, various filters provided by NIHON PALL Corporation (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (Formerly Nippon Mykrolis Corporation) and KITZMICROFILTER Corporation can be used.

[0577] Furthermore, it is also preferred to use a fibrous filter material as the filter. Examples of the fibrous filter material include polypropylene fiber, nylon fiber, glass fiber, etc. 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 ROKI TECHNO CO., LTD.

[0578] When using a filter, different filters (e.g., a first filter and a second filter, etc.) can be combined. At this time, filtering using each filter can be performed only once or twice or more. In addition, filters with different pore sizes can be combined within the above range. In addition, filtering using the first filter is performed only on the dispersion, and filtering can be performed with the second filter after mixing other components. In addition, the filter can be appropriately selected according to the hydrophilicity and hydrophobicity of the resin composition.

[0579] (membrane)

[0580] The film of the present invention is a film obtained from the resin composition of the present invention. The film of the present invention can be used for filters such as color filters, near infrared transmission filters, and near infrared cut filters. In addition, the film of the present invention can also be used for black matrices, light shielding films, etc.

[0581] The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0582] When the film of the present invention is used as a color filter, the film of the present invention preferably has a hue of green, red, blue, cyan, magenta or yellow. In addition, the film of the present invention can be preferably used as a colored pixel of a color filter. As colored pixels, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be cited.

[0583] 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 present in the range of wavelengths of 700 to 1800 nm, more preferably in the range of wavelengths of 700 to 1300 nm, and further preferably in the range of wavelengths of 700 to 1100 nm. In addition, the transmittance of the film in all ranges of wavelengths of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. In addition, the transmittance of the film at least one point in the range of wavelengths of 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm, i.e., absorbance Amax / absorbance A550, is preferably 20 to 500, more preferably 50 to 500, further preferably 70 to 450, and particularly preferably 100 to 400.

[0584] When the film of the present invention is used as a near-infrared transmission filter, the film of the present invention preferably has any one of the following spectral characteristics (i1) to (i5), for example.

[0585] (i1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm. A film having such spectral characteristics will shield light in the wavelength range of 400 to 640 nm and allow light with a wavelength greater than 750 nm to pass through.

[0586] (i2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. A film having such spectral characteristics will shield light in the wavelength range of 400 to 750 nm and allow light with a wavelength greater than 850 nm to pass through.

[0587] (i3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. A film having such spectral characteristics will shield light in the wavelength range of 400 to 830 nm and allow light with a wavelength greater than 950 nm to pass through.

[0588] (i4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. A film having such spectral characteristics will shield light in the wavelength range of 400 to 950 nm and allow light with a wavelength greater than 1050 nm to pass through.

[0589] (i5): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm. A film having such spectral characteristics will shield light in the wavelength range of 400 to 1050 nm and allow light with a wavelength greater than 1150 nm to pass through.

[0590] Furthermore, the thickness of the film of the present invention after heat treatment at 300°C for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, and particularly preferably 99% or more.

[0591] Furthermore, the thickness of the film after heat treatment at 350°C for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, and particularly preferably 99% or more.

[0592] Furthermore, the thickness of the film after heat treatment at 400°C for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, and particularly preferably 99% or more.

[0593] <Method for producing film>

[0594] The film of the present invention can be manufactured by applying the resin composition of the present invention to a support. The method for manufacturing the film of the present invention preferably further comprises a step of forming a pattern (pixel). As a method for forming the pattern (pixel), photolithography and dry etching can be cited, preferably photolithography.

[0595] (Photolithography)

[0596] First, the situation of manufacturing film by patterning by photolithography is described. The patterning based on photolithography preferably includes the process of forming a resin composition layer on a support using the resin composition of the present invention, the process of exposing the resin composition layer in a pattern, and the process of developing and removing the unexposed part of the resin composition layer to form a pattern (pixel). It is also possible to set the process (pre-baking process) of baking the resin composition layer and the process (post-baking process) of baking the developed pattern (pixel) as needed.

[0597] In the process of forming a resin composition layer, a resin composition layer is formed on a support using the resin composition of the present invention. As a support, there is no particular limitation and it can be appropriately selected according to the purpose. For example, a glass substrate, a silicon substrate, etc. can be cited, preferably a silicon substrate. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the silicon substrate. In addition, a black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. In addition, in order to improve the adhesion with the upper layer, prevent the diffusion of substances or the flattening of the substrate surface, a base layer can be provided on the silicon substrate. When measured with diiodomethane, the surface contact angle of the base layer is preferably 20 to 70°. And, when measured with water, it is preferably 30 to 80°. As long as the surface contact angle of the base layer is within the above range, the wettability of the resin composition is good. For example, the surface contact angle of the base layer can be adjusted by adding a surfactant or the like.

[0598] As a coating method of the resin composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit spin coating method; a pre-wetting method (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle jetting, etc., flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.; a transfer method using a mold, etc.; a nanoimprint method, etc. There is no particular limitation on the applicable method in inkjet, and examples thereof include the method described in "Expansion and Use of Inkjet - Infinite Possibilities in Patents -, published in February 2005, SumitbeTechon Research Co., Ltd." (particularly pages 115 to 133), or Japanese Patent Publication No. 2003-262716, Japanese Patent Publication No. 2003-185831, Japanese Patent Publication No. 2003-261827, Japanese Patent Publication No. 2012-126830, Japanese Patent Publication No. 2006-169325, etc. In addition, the coating method of the resin composition can also utilize the method described in International Publication No. 2017 / 030174 and International Publication No. 2017 / 018419, and these contents are incorporated into this specification.

[0599] The resin composition layer formed on the support may be dried (prebaked). When the film is manufactured by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit can be set to above 50°C, for example, and can also be set to above 80°C. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0600] Next, the resin composition layer is exposed in a pattern (exposure step). For example, a stepper, a scanner, etc. are used to expose the photosensitive composition layer through a mask having a predetermined mask pattern, thereby exposing in a pattern. Thus, the exposed portion can be cured.

[0601] As radiation (light) that can be used for exposure, g-rays, i-rays, etc. can be cited. In addition, light with a wavelength of 300nm or less (preferably light with a wavelength of 180 to 300nm) can also be used. As light with a wavelength of 300nm or less, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm), etc. can be cited, preferably KrF rays (wavelength 248nm). In addition, a light source with a long wavelength of 300nm or more can also be used.

[0602] Furthermore, during exposure, exposure can be performed by continuous irradiation of light, or exposure can be performed by pulsed irradiation (pulse exposure). In addition, pulse exposure refers to an exposure method in which light irradiation and pause are repeated in a short cycle (for example, less than milliseconds) to perform exposure. In the case of pulse exposure, the pulse width is preferably less than 100 nanoseconds (ns), more preferably less than 50 nanoseconds, and further preferably less than 30 nanoseconds. The lower limit of the pulse width is not particularly limited, and can be set to more than 1 femtosecond (fs), and can also be set to more than 10 femtoseconds. The frequency is preferably more than 1kHz, more preferably more than 2kHz, and further preferably more than 4kHz. The upper limit of the frequency is preferably less than 50kHz, more preferably less than 20kHz, and further preferably less than 10kHz. The maximum instantaneous illumination is preferably 50000000W / m 2 More preferably 100000000 W / m 2 More preferably, 200000000 W / m 2 Furthermore, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m 2 Below, more preferably 800000000 W / m 2 Below, more preferably 500000000 W / m 2 Below. In addition, pulse width refers to the time of light irradiation in the pulse cycle. And, frequency refers to the number of pulse cycles per 1 second. And, maximum instantaneous illuminance refers to the average illuminance of light in the pulse cycle during the irradiation time. And, pulse cycle refers to the cycle in which the irradiation and pause of light in pulse exposure are regarded as one cycle.

[0603] For example, the irradiation amount (exposure amount) is preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2 The oxygen concentration during exposure can be appropriately selected. In addition to exposure under the atmosphere, exposure can also be performed in a low oxygen environment with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen environment with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be appropriately set, and can usually be selected from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 、15000W / m 2 or 35000W / m 2 The oxygen concentration and exposure illuminance conditions can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2, oxygen concentration is 35 volume % and illumination is 20000 W / m 2 wait.

[0604] Next, the unexposed portion of the resin composition layer is removed by development to form a pattern (pixel). The unexposed portion of the resin composition layer can be removed by development using a developer. As a result, the resin composition of the unexposed portion in the exposure process is dissolved into the developer, and only the photocured portion remains. For example, the temperature of the developer is preferably 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the following process can be repeated multiple times: the developer is shaken off every 60 seconds, and a new developer is supplied.

[0605] The developer can include organic solvents, alkali developers, etc., and alkali developers can be preferably used. As an alkali developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkali agent with pure water is preferably used. As an alkali agent, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic alkaline compounds or inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. can be mentioned. From the perspective of environment and safety, the alkali agent is preferably a compound with a large molecular weight. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Furthermore, the developer may further contain a surfactant. As the surfactant, the above-mentioned surfactants can be cited, preferably a nonionic surfactant. From the viewpoint of facilitating transportation and storage, the developer may be first prepared as a concentrated solution and diluted to a desired concentration when used. The dilution ratio is not particularly limited, for example, it can be set in the range of 1.5 to 100 times. Furthermore, it is also preferred to wash (rinse) with pure water after development. Furthermore, it is preferred to rinse as follows: while rotating the support body on which the developed resin composition layer is formed, a rinsing liquid is supplied to the developed resin composition layer. Furthermore, it is also preferred to move the nozzle that sprays the rinsing liquid from the center of the support body to the peripheral portion of the support body. At this time, when the nozzle is moved from the center of the support body to the peripheral portion, the nozzle can be moved while gradually reducing the moving speed. By rinsing in this way, the unevenness in the surface of the rinse can be suppressed. Furthermore, the same effect can be obtained by gradually reducing the rotation speed of the support body while moving the nozzle from the center of the support body to the peripheral portion.

[0606] After development, it is preferred to perform additional exposure treatment and heating treatment (post-baking) after drying. Additional exposure treatment and post-baking are curing treatments after development for making a fully cured film. For example, the heating temperature in the post-baking is preferably 100 to 240°C, more preferably 200 to 240°C. The developed film can be post-baked in a continuous or intermittent manner using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in a manner that achieves the above conditions. When performing additional exposure treatment, the light used for exposure is preferably light with a wavelength of less than 400nm. In addition, the additional exposure treatment can be performed by the method described in Korean Patent Gazette No. 10-2017-0122130.

[0607] (Dry Etching Method)

[0608] The pattern formation by dry etching preferably includes the following steps: using the resin composition of the present invention to form a resin composition layer on a support, curing the resin composition layer as a whole to form a cured layer, forming a photoresist layer on the cured layer, exposing the photoresist layer in a pattern and then developing it to form a photoresist pattern, using the photoresist pattern as a mask and dry etching the cured layer using an etching gas. When forming the photoresist layer, it is preferred to further perform a pre-baking treatment. In particular, as a process for forming the photoresist layer, it is preferred to perform a heating treatment after exposure and a heating treatment after development (post-baking treatment). For the content of forming a pattern by dry etching, reference can be made to the records of paragraphs 0010 to 0067 of Japanese Patent Gazette No. 2013-064993, which are incorporated into this specification.

[0609] <Optical filter>

[0610] The optical filter of the present invention has the above-mentioned film of the present invention. As the type of the optical filter, as the optical filter, a color filter, a near-infrared transmission filter, a near-infrared cutoff filter, etc. can be cited, and a color filter is preferred. As the color filter, it is preferred 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 solid-state imaging elements such as CCD (charge coupled device) and CMOS (complementary metal oxide film semiconductor), image display devices, etc.

[0611] In the optical filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 5 μm or less, more preferably 1 μm or less, and further 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 further preferably 0.3 μm or more.

[0612] The width of the pixel included in the color filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and further preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, further preferably 1.0 μm or less, and further preferably 0.8 μm or less. In addition, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0613] It is preferred that each pixel included in the filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably less than 100 nm, more preferably less than 40 nm, and further preferably less than 15 nm. There is no specified lower limit, for example, it is preferably greater than 0.1 nm. Regarding the surface roughness of the pixel, for example, it can be measured using AFM (atomic force microscope) Dimension3100 manufactured by Veeco. In addition, the water contact angle on the pixel can be set to an appropriately preferred value, usually in the range of 50 to 110°. For example, the contact angle can be measured using a contact angle meter CV-DT·A type (manufactured by Kyowa Interface Science Co., LTD.). In addition, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. The upper limit is not specified, but is preferably 10 14 For example, the volume resistance value of the pixel can be measured using an ultra high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

[0614] In the optical filter, a protective layer may also be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxidation resistance, low reflection, hydrophilicity and hydrophobicity, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. As a method for forming the protective layer, a method of coating a protective layer-forming resin composition dissolved in an organic solvent, a chemical vapor deposition method, a method of attaching a molded resin with an adhesive material, etc. can be cited. Examples of the component constituting the protective layer include (meth) acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, polyurethane resins, aromatic polyamide resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluororesins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al 2 O 3 、Mo、SiO 2 、Si 2 N 4 For example, in the case of a protective layer for the purpose of preventing oxidation, the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 Furthermore, in the case of a protective layer for the purpose of reducing reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

[0615] When the protective layer is formed by coating the protective layer forming resin composition, as the coating method of the protective layer forming resin composition, known methods such as spin coating, casting, screen printing, inkjet method can be used. The organic solvent contained in the protective layer forming resin composition can use a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When the protective layer is formed by chemical vapor deposition, as chemical vapor deposition, known chemical vapor deposition (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0616] The protective layer may contain organic / inorganic microparticles, absorbents of light of a specific wavelength (e.g., ultraviolet rays, near infrared rays, etc.), refractive index modifiers, antioxidants, adhesives, surfactants and other additives as needed. As examples of organic / inorganic microparticles, for example, polymer microparticles (e.g., silicone microparticles, polystyrene microparticles, melamine resin microparticles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silicon dioxide, calcium carbonate, barium sulfate, etc. can be cited. The absorbent of light of a specific wavelength can use a known absorbent. The content of these additives can be appropriately adjusted, preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, relative to the total mass of the protective layer. In addition, as a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Publication No. 2017-151176 can also be used.

[0617] The filter may also have a structure in which each pixel is embedded in a space divided into a grid shape by a partition wall. In addition, the resin composition of the present invention can also be preferably used for the pixel structure described in International Publication No. 2019 / 102887.

[0618] <Solid-state imaging device>

[0619] The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging device of the present invention is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following structures.

[0620] That is, there are a plurality of photodiodes and a transfer electrode composed of polysilicon etc. constituting a light-receiving area of ​​a solid-state imaging element (CCI) (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on the substrate, a light-shielding film having only an opening for the light-receiving portion of the photodiode on the photodiode and the transfer electrode, a device protection film composed of silicon nitride etc. formed in a manner covering the entire surface of the light-shielding film and the light-receiving portion of the photodiode on the light-shielding film, and a color filter on the device protection film. Furthermore, it may be a structure having a focusing mechanism (e.g., a microlens, etc., the same below) on the device protection film and on the lower side of the color filter (the side close to the substrate) or a structure having a focusing mechanism on the color filter. Furthermore, the color filter may also have a structure in which, for example, each colored pixel is embedded in a space divided into a grid shape by a partition wall. Preferably, the refractive index of the partition wall at this time is lower than that of each colored pixel. As an example of an imaging device with such a structure, there can be cited Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, International Publication No. 2018 / 043654, and the device described in the specification of U.S. Patent Application Publication No. 2018 / 0040656. In addition, as described in Japanese Patent Publication No. 2019-211559, an ultraviolet absorption layer can be provided in the structure of the solid-state imaging element to improve light resistance. In addition to being able to be used as a digital camera and an electronic device (mobile phone, etc.) with a camera function, the imaging device having the solid-state imaging element of the present invention can also be used as a vehicle-mounted camera or a surveillance camera. In addition, the solid-state imaging element assembled with the color filter of the present invention can be further assembled with other color filters, near-infrared cutoff filters, organic photoelectric conversion films, etc. in addition to the color filter of the present invention.

[0621] <Image Display Device>

[0622] The image display device of the present invention has the above-mentioned film of the present invention. As the image display device, a liquid crystal display device, an organic electroluminescent display device, etc. can be cited. The definition of the image display device and the details of each image display device are recorded in, for example, "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Device (written by Junzhang Ibuki, Sangyo Tosho Publishing Co., Ltd., published in 1989)", etc. In addition, regarding the liquid crystal display device, it is recorded in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, KogyoChosakai Publishing Co., Ltd., published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

[0623] Example

[0624] Below, give embodiment and the present invention is further described in detail.The material, usage amount, ratio, processing content, processing sequence etc. shown in the following embodiment can be appropriately changed as long as it does not depart from the gist of the present invention.Therefore, the scope of the present invention is not limited to the specific example shown below.

[0625] <Measurement of Weight Average Molecular Weight (Mw) of Sample>

[0626] The weight average molecular weight of the sample was measured by gel permeation chromatography (GPC) under the following conditions.

[0627] Column type: A column combining TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000

[0628] Developing solvent: tetrahydrofuran

[0629] Column temperature: 40℃

[0630] Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1 mass %)

[0631] Device name: HLC-8220GPC manufactured by Tosoh Corporation

[0632] Detector: RI (refractive index) detector

[0633] Calibration curve matrix resin: polystyrene resin

[0634] <Measurement of Acid Value of Sample>

[0635] The acid value of a sample indicates the mass of potassium hydroxide required to neutralize the acidic components per 1 g of solid content in the sample. The acid value of a sample was measured as follows. That is, the sample to be measured was dissolved in a mixed solvent of tetrahydrofuran / water = 9 / 1 (mass ratio), and the obtained solution was subjected to neutralization titration at 25°C using a potentiometric titrator (product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.) with a 0.1 mol / L potassium hydroxide aqueous solution. The inflection point of the titration pH curve was taken as the titration endpoint, and the acid value was calculated by the following formula.

[0636] A=56.11×Vs×0.5×f / w

[0637] A: Acid value (mgKOH / g)

[0638] Vs: Amount of 0.1 mol / L potassium hydroxide aqueous solution required for titration (mL)

[0639] f: titration of 0.1 mol / L potassium hydroxide aqueous solution

[0640] w: mass of sample (g) (converted into solid content)

[0641] <Synthesis of Capping Agent Macromonomer>

[0642] (Synthesis Example 1-1) Synthesis Example of End-Capping Agent Macromonomer EDM-1

[0643] 2.3 g of 2-mercaptoethanol, 35 g of ε-caprolactone and 0.5 g of monobutyltin oxide were added to a three-necked flask replaced with nitrogen, and heated and stirred at 90°C for 2 hours and at 120°C for 6 hours to obtain a polymer having an SH group and an OH group at both ends of the polyester. After cooling to 5°C, 0.5 g of acetyl chloride was added, and further stirred for 2 hours, thereby sealing the OH group terminal and obtaining a polymer having a single terminal SH group. Next, 4.1 g of 2-acryloyloxyethyl isocyanate (Karenz AOI, manufactured by SHOWA DENKO KK) and 0.3 g of a polymerization initiator (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added, and heated and stirred at 80°C for 2 hours to perform an ene-thiol reaction, thereby obtaining an end-capping agent macromonomer EDM-1.

[0644] (Synthesis Examples 1-2, 1-3) Synthesis Examples of End-Capping Macromonomers EDM-2 and EDM-3

[0645] The end-capping agent macromonomers EDM-2 and EDM-3 were synthesized in the same manner as in Synthesis Example 1-1.

[0646] (Synthesis Example 1-4) Synthesis Example of End-Capping Agent Macromonomer EDM-4

[0647] In a three-necked flask purged with nitrogen, 181.3 g of methyl methacrylate and 200.2 g of butyl acrylate were added, and diluted with 590 g of propylene glycol monomethyl ether acetate. The mixture was heated to 75°C under a nitrogen atmosphere. Next, 9.2 g of 3-mercaptopropionic acid and 2.2 g of a polymerization initiator (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added, and the mixture was heated and stirred at 75°C under a nitrogen atmosphere for 8 hours. 7.3 g of thionyl chloride was added to the obtained polymer solution, and the mixture was further heated and stirred at 75°C for 2 hours. The weight average molecular weight of the obtained end-capping agent macromonomer EDM-4 was 7400.

[0648] (Synthesis Example 1-5) Synthesis Example of End-Capping Agent Macromonomer EDM-5

[0649] The end-capping agent macromonomer EDM-5 was synthesized in the same manner as in Synthesis Example 1-4.

[0650] (Synthesis Example 1-6) Synthesis Example of End-Capping Agent Macromonomer EDM-6

[0651] In a three-necked flask substituted with nitrogen, 181.3 g of methyl methacrylate and 200.2 g of butyl acrylate were added, and diluted with 590 g of propylene glycol monomethyl ether acetate. It was heated to 75°C under a nitrogen environment. Next, 19.9 g of 6-mercaptohexanol and 2.2 g of a polymerization initiator (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added, and heated and stirred at 75°C under a nitrogen environment for 8 hours. 37.3 g of pyromellitic anhydride was added to the obtained polymer solution, and heated and stirred at 75°C for further 2 hours. The unreacted pyromellitic anhydride was filtered out as an insoluble matter. The weight average molecular weight of the obtained end-capping agent macromonomer EDM-6 was 2400.

[0652] (Synthesis Example 1-7) Synthesis Example of End-Capping Agent Macromonomer EDM-7

[0653] The end-capping agent macromonomer EDM-7 was synthesized in the same manner as in Synthesis Example 1-6.

[0654] (Synthesis Example 1-8) Synthesis Example of End-Capping Agent Macromonomer EDM-8

[0655] In a three-necked flask purged with nitrogen, 6.1 g of 6-mercaptohexanol, 35 g of ε-caprolactone and 0.5 g of monobutyltin oxide were added, and the mixture was heated and stirred at 90°C for 2 hours and at 120°C for 6 hours, thereby obtaining a polymer having an SH group and an OH group at both ends of the polyester. After cooling to 5°C, 0.5 g of acetyl chloride was added, and the mixture was further stirred for 2 hours, thereby sealing the OH end and obtaining a polymer having a single terminal SH. Next, 5.5 g of itaconic anhydride and 0.3 g of a polymerization initiator (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added, and the mixture was heated and stirred at 80°C for 2 hours to perform an ene-thiol reaction, thereby obtaining an end-capping agent macromonomer EDM-8.

[0656] (Synthesis Examples 1-9 to 1-15) Synthesis Examples of End-Capping Macromonomers EDM-9 to EDM-15

[0657] The end-capping agent macromonomers EDM-9 to EDM-15 were synthesized in the same manner as in Synthesis Examples 1-8.

[0658] (Synthesis Example 1-16) Synthesis Example of End-Capping Agent Macromonomer EDM-16

[0659] In a three-necked flask purged with nitrogen, 281.3 g of methyl methacrylate and 100.2 g of butyl acrylate were added, and diluted with 590 g of propylene glycol monomethyl ether acetate. The mixture was heated to 75° C. under a nitrogen atmosphere. Next, 13.9 g of a chain transfer agent (AAA-1) and 2.5 g of a polymerization initiator (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added, and the mixture was heated and stirred at 75° C. under a nitrogen atmosphere for 8 hours. The weight average molecular weight of the end-capping agent macromonomer EDM-16 obtained was 7400.

[0660] [Chemical formula 39]

[0661]

[0662] (Synthesis Examples 1-17 to 1-20) Synthesis Examples of End-Capping Macromonomers EDM-17 to EDM-20

[0663] The end-capping agent macromonomers EDM-17 to EDM-20 were synthesized in the same manner as in Synthesis Examples 1-16.

[0664] (Synthesis Example 1-21) Synthesis Example of End-Capping Agent Macromonomer EDM-21

[0665] In a three-necked flask substituted with nitrogen, 151.3 g of methyl methacrylate and 230.2 g of butyl acrylate were added, and diluted with 590 g of propylene glycol monomethyl ether acetate. It was heated to 75°C under a nitrogen environment. Next, 20.9 g of 6-mercaptohexanol and 2.0 g of a polymerization initiator (V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added, and heated and stirred at 75°C under a nitrogen environment for 8 hours. The obtained polymer solution of terminal hydroxyl groups was cooled to 5°C, 32.1 g of trimellitic anhydride chloride was added, and 15.3 g of pyridine was added dropwise over 6 hours. It was further stirred at room temperature for 24 hours, and the insoluble matter was removed by filtration. The weight average molecular weight of the obtained end-capping agent macromonomer EDM-21 was 7800.

[0666] (Synthesis Examples 1-22 to 1-40) Synthesis Examples of End-Capping Agent Macromonomers EDM-22 to EDM-40

[0667] The end-capping agent macromonomers EDM-22 to EDM-40 were synthesized in the same manner as in Synthesis Examples 1-21.

[0668] The structures and weight average molecular weights (Mw) of the end-capping macromonomers EDM-1 to EDM-40 are shown below. In addition, in Poly, the numerical values ​​of the repeating units marked with EDM-1 to EDM-3, EDM-8 to EDM-15, EDM-27 to EDM-29 represent the number of repeating units, and the numerical values ​​of the repeating units marked with EDM-4, ​​EDM-6, EDM-16, EDM-19 to EDM-21, EDM-24 to EDM-26, EDM-30, EDM-33 to EDM-36, EDM-39, and EDM-40 represent the molar ratio of the repeating units. In addition, the structure described in Poly is P of formula (1) 1 .

[0669] [Table 1]

[0670]

[0671] [Table 2]

[0672]

[0673] [Table 3]

[0674]

[0675] <Resin Synthesis Example>

[0676] (Synthesis Example 2-1) Synthesis of Resin B-1

[0677] 3.3 g of 1,3-phenylenediamine (diamine DA-1: manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of propylene glycol monomethyl ether acetate were added to a three-necked flask purged with nitrogen, and the mixture was heated to 40°C. 2.2 g of pyromellitic anhydride (dianhydride AA-1: manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was heated and stirred at 40°C for 6 hours to obtain an amic acid prepolymer having amino groups at both ends. 19 g (in terms of solid content) of the end-capping macromonomer EDM-1 was added to the prepolymer solution, and the mixture was heated and stirred at 40°C for 2 hours to obtain a 30% propylene glycol monomethyl ether acetate solution of resin B-1. The weight average molecular weight of the obtained resin B-1 was 20,600, and the acid value was 55 mgKOH / g.

[0678] (Synthesis Examples 2-2 to 2-93) Synthesis of Resins B-2 to B-93

[0679] 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 addition amounts described in the following table. The weight average molecular weight (Mw) and acid value of each resin are summarized in the following table.

[0680] [Table 4]

[0681]

[0682] [Table 5]

[0683]

[0684] [Table 6]

[0685]

[0686] The end-capping agent macromonomers EDM-1 to EDM-40 are compounds of the above structures, respectively. Furthermore, the acid dianhydrides AA-1 to AA-8, the diamines DA-1 to DA-7, and the end-capping agents ED-1 to ED-3 are compounds of the structures shown below, respectively.

[0687] [Chemical formula 40]

[0688]

[0689] [Chemical formula 41]

[0690]

[0691] [Chemical formula 42]

[0692]

[0693] <Production of Dispersion Liquid>

[0694] The mixed solution of the raw materials listed in the following table was mixed and dispersed for 3 hours using a bead mill (using zirconia beads with a diameter of 0.3 mm), and then dispersed at a pressure of 2000 MPa and a flow rate of 500 g / min using a high-pressure disperser NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain each dispersion.

[0695] [Table 7]

[0696]

[0697] [Table 8]

[0698]

[0699] [Table 9]

[0700]

[0701] [Table 10]

[0702]

[0703] [Table 11]

[0704]

[0705] [Table 12]

[0706]

[0707] [Table 13]

[0708]

[0709] [Table 14]

[0710]

[0711] The unit of the numerical values ​​described in the above table is part by mass. Among the raw materials shown in the above table, the details of the raw materials represented by abbreviations are as follows.

[0712] 〔Color material〕

[0713] PR264: CI Pigment Red 264 (red pigment, diketopyrrolopyrrole pigment)

[0714] PR254: CI Pigment Red 254 (red pigment, diketopyrrolopyrrole pigment)

[0715] PR179: CI Pigment Red 179

[0716] PB15:6:CI Pigment Blue 15:6 (blue pigment, phthalocyanine pigment)

[0717] PB16: CI Pigment Blue 16 (blue pigment, phthalocyanine pigment)

[0718] PG7: CI Pigment Green 7

[0719] PG36: CI Pigment Green 36

[0720] PG58: CI Pigment Green 58

[0721] PY129: CI Pigment Yellow 129

[0722] PY185: CI Pigment Yellow 185

[0723] PY215: CI Pigment Yellow 215

[0724] PV23: CI Pigment Violet 23

[0725] IRGAPHORE: Irgaphor Black S 0100 CF (manufactured by BASF, a compound having the following structure, a lactam pigment)

[0726] [Chemical formula 43]

[0727]

[0728] PBk32: CI Pigment Black 32 (compound of the following structure, perylene pigment)

[0729] [Chemical formula 44]

[0730]

[0731] 〔Pigment derivatives〕

[0732] Derivative 1: Compound with the following structure

[0733] [Chemical formula 45]

[0734]

[0735] Derivative 2: Compound with the following structure

[0736] [Chemical formula 46]

[0737]

[0738] 〔Resin (dispersant)〕

[0739] (Specific resin)

[0740] 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 resins

[0741] (Comparative resin)

[0742] cB-1: Resin having the following structure (weight average molecular weight: 10885, acid value: 74 mgKOH / g. "Polym" means that a polymer chain having a structure in which repeating units of the structure represented by "Polym" are bonded to the number of the attached numerical value is bonded to a sulfur atom (S).

[0743] [Chemical formula 47]

[0744]

[0745] 〔Solvent〕

[0746] C-1: Propylene glycol monomethyl ether acetate

[0747] C-2: Propylene glycol monomethyl ether

[0748] C-3: Cyclohexanone

[0749] <Manufacturing of resin composition>

[0750] The raw materials described in the following table were mixed to prepare resin compositions of Examples and Comparative Examples.

[0751] [Table 15]

[0752]

[0753] [Table 16]

[0754]

[0755] [Table 17]

[0756]

[0757] Among the raw materials described in the above tables, the details of the raw materials represented by abbreviations are as follows.

[0758] 〔Dispersion liquid〕

[0759] Dispersions R1 to R26, B1 to B25, G1 to G27, Bk1 to Bk20, CR1, CB1, CG1, CBk1 to 3: the above dispersions

[0760] 〔Resin〕

[0761] Ba-1: Resin having the following structure (the values ​​indicated in the main chain are molar ratios. The weight average molecular weight is 11,000)

[0762] [Chemical formula 48]

[0763]

[0764] Ba-2: Resin having the following structure (the values ​​indicated in the main chain are molar ratios. The weight average molecular weight is 15,000)

[0765] [Chemical formula 49]

[0766]

[0767] Ba-3: Resin having the following structure (the numerical values ​​indicated in the main chain are molar ratios. The total value of x, y and z is 50. Mw = 15000)

[0768] [Chemical formula 50]

[0769]

[0770] Bb-1: Resin having the following structure (the values ​​indicated in the main chain are molar ratios. The weight average molecular weight is 13,000)

[0771] [Chemical formula 51]

[0772]

[0773] 〔Polymerizable monomer〕

[0774] D-1: Acrylate compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

[0775] D-2: Epoxy compound (TETRAD-X, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., N,N,N',N'-tetraepoxypropyl-m-xylene diamine)

[0776] D-3: Cyclohexane compound (OXT-221, manufactured by TOAGOSEI CO., LTD., 3-ethyl-3{[(3-ethylcyclohexane-3-yl)methoxy]methyl}cyclohexane)

[0777] D-4: Oxycyclobutane compound (OX-SQ TX-100, manufactured by TOAGOSEI CO., LTD.)

[0778] 〔Photopolymerization initiator〕

[0779] E-1: Omnirad 379EG (manufactured by IGM Resins BV, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one)

[0780] E-2: Irgacure OXE01 (manufactured by BASF, oxime compound)

[0781] E-3: Compound with the following structure

[0782] [Chemical formula 52]

[0783]

[0784] 〔Solvent〕

[0785] C-1: Propylene glycol monomethyl ether acetate

[0786] C-2: Propylene glycol monomethyl ether

[0787] C-3: Cyclohexanone

[0788] <Evaluation>

[0789] [Evaluation of dispersibility]

[0790] (Storage stability)

[0791] In each embodiment and comparative example, the viscosity (mpa·s) of the resin composition was measured using "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the resin composition was left to stand at 45°C, shaded, and for 3 days, and the viscosity (mpa·s) was measured again. Based on the viscosity difference (ΔVis) before and after the above standing, the storage stability was evaluated according to the following evaluation criteria. It can be said that the smaller the value of the viscosity difference (ΔVis), the better the storage stability of the resin composition and the better the dispersibility of the pigment. The above viscosity measurements were all carried out in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, and the temperature of the resin composition was adjusted to 25°C.

[0792] -Evaluation Criteria-

[0793] A: ΔVis is 0.5 mPa·s or less.

[0794] B: ΔVis is greater than 0.5 mPa·s and less than or equal to 1.0 mPa·s.

[0795] C: ΔVis is greater than 1.0 mPa·s and less than 2.0 mPa·s.

[0796] D: ΔVis is greater than 2.0 mPa·s and less than 2.5 mPa·s.

[0797] E: ΔVis is greater than 2.5 mPa·s.

[0798] (Particle size)

[0799] The resin composition obtained above was divided into 20 ml sample bottles using a dynamic light scattering particle size distribution measuring device (HORIBA, Ltd., LB-500) in accordance with JIS8826:2005, and diluted and adjusted with propylene glycol monomethyl ether acetate so that the solid content concentration was 0.2 mass%. At a temperature of 25°C, a 2 ml quartz cell for measurement was used, and the data of the above dilution was read 50 times, thereby obtaining the arithmetic mean of the number-based pigment particle size (number average particle size). It can be said that the smaller the value of the number average particle size of the pigment, the better the dispersibility of the pigment.

[0800] -Evaluation Criteria-

[0801] A: The number average particle size of the pigment is 0.05 μm or less.

[0802] B: The number average particle size of the pigment is greater than 0.05 μm and less than 0.10 μm.

[0803] C: The number average particle size of the pigment is greater than 0.10 μm and less than 0.20 μm.

[0804] D: The number average particle size of the pigment is greater than 0.20 μm and less than 0.50 μm.

[0805] E: The number average particle size of the pigment is larger than 0.50 μm.

[0806] [Evaluation of film shrinkage]

[0807] In each embodiment and comparative example, the resin composition was applied to a glass substrate by spin coating, dried at 100°C for 120 seconds (pre-baking) using a hot plate, and then heated at 200°C for 30 minutes (post-baking) using an oven, thereby producing a film with a thickness of 0.60 μm. Regarding the film thickness, a portion of the film was removed to expose the surface of the glass substrate, and the height difference between the surface of the glass substrate and the coating film (the thickness of the coating film) was measured using a stylus height difference meter (DektakXT, manufactured by Bruker Corporation). Then, the obtained film was heat-treated at 300°C for 5 hours in a nitrogen environment. The film thickness of the film after heat treatment was measured in the same way, and the film shrinkage was calculated according to the following formula, and the film shrinkage was evaluated according to the following evaluation criteria. The following T 0 and T 1 The measurements were performed in a laboratory controlled at 22±5° C. and 60±20% in temperature and humidity, with the substrate temperature adjusted to 25° C. It can be said that the smaller the film shrinkage rate, the more the film shrinkage is suppressed, which is a preferable result.

[0808] Film shrinkage (%) = (1-(T 1 / T 0 ))×100

[0809] T 0 : Film thickness of the film immediately after production (=0.60 μm)

[0810] T 1 : Film thickness after heating at 300°C for 5 hours in a nitrogen atmosphere

[0811] -Evaluation Criteria-

[0812] A: The film shrinkage rate is 1% or less.

[0813] B: The film shrinkage ratio is more than 1% and 5% or less.

[0814] C: The film shrinkage ratio is greater than 5% and less than 10%.

[0815] D: The film shrinkage ratio is more than 10% and less than 30%.

[0816] E: The film shrinkage is greater than 30%.

[0817] [Evaluation of cracks]

[0818] In each of the examples and comparative examples, the resin composition was applied onto a glass substrate by spin coating, dried at 100°C for 120 seconds (pre-baking) using a hot plate, and then heated at 200°C for 30 minutes (post-baking) using an oven to produce a film having a thickness of 0.60 μm. Next, a 200 nm layer of SiO was deposited on the surface of the obtained film by sputtering. 2 The inorganic film was formed on the surface of the film and heated at 300°C for 5 hours in a nitrogen atmosphere. The surface of the inorganic film after the heat treatment was observed with an optical microscope and the number of 2 The number of cracks was counted and the presence or absence of cracks was evaluated according to the following evaluation criteria.

[0819] -Evaluation Criteria-

[0820] A: Every 1cm 2 The number of cracks is 0.

[0821] B: Every 1cm 2 The number of cracks is 1 to 10.

[0822] C: Every 1cm 2 The number of cracks is 11 to 50.

[0823] D: Every 1cm 2 The number of cracks ranges from 51 to 100.

[0824] E: Every 1cm 2 The number of cracks is more than 101.

[0825] [Table 18]

[0826]

[0827] [Table 19]

[0828]

[0829] [Table 20]

[0830]

[0831] When the resin composition of the embodiment is used, the evaluation of storage stability and particle size is excellent compared with the case where the resin composition of the comparative example is used, and the dispersibility of the pigment is excellent. In addition, when the resin composition of the embodiment is used, the film shrinkage is small compared with the case where the resin composition of the comparative example is used, and the generation of cracks is suppressed. Therefore, it can be said that compared with the resin composition of the comparative example, the process window in the process after the film manufacturing can be expanded.

[0832] (Example 1000: Patterning by Photolithography)

[0833] The resin composition of Example 1 was spin-coated on a silicon wafer, dried at 100°C for 120 seconds (pre-baking) using a hot plate, and then heated at 200°C for 30 minutes (post-baking) using an oven to produce a resin composition layer with a thickness of 0.60 μm. Next, a mask pattern arranged in a 4 mm × 3 mm area with a square non-mask portion of 1.1 μm on each side was exposed using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) at 500 mJ / cm 2 The resin composition layer was exposed by irradiating light of a wavelength of 365 nm with an exposure amount of . Next, the silicon wafer formed with the exposed resin composition was placed on a horizontal turntable of a spin / spray developer (DW-30 model, manufactured by CHEMITRONICS CO., Ltd.), and a developer (CD-2000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform puddle development at 23°C for 60 seconds. Next, the silicon wafer was rotated at a rotation speed of 50 rpm, and pure water was supplied from a spray nozzle from above the rotation center to perform a rinsing treatment, and then spray drying was performed to form a pattern (pixel).

[0834] The produced silicon wafer with pixels was divided into two, and one of them was heat-treated at 300°C for 5 hours in a nitrogen environment (hereinafter, one is referred to as the substrate before the 300°C heat treatment and the other is referred to as the substrate after the 300°C heat treatment). The cross-section of the pixels formed on the substrate before the 300°C heat treatment and the substrate after the 300°C heat treatment was evaluated using a scanning electron microscope (SEM). The height (thickness) of the pixels formed on the substrate after the 300°C heat treatment was 97% of the height (thickness) of the pixels formed on the substrate before the 300°C heat treatment.

Claims

1. A compound represented by formula (EDM1), In formula (EDM1), R ED1 represents anhydride group, Lp ED1 represents an n+1 valent group, wherein the n+1 valent group is a hydrocarbon group or a hydrocarbon group and a group selected from -NRp Ed1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO- and -CONRp ED1 -a group of a structure composed of at least one group in combination, R ED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Lp ED2 Indicates -O- or -S-, p ED1 represents a polymer chain including a repeating unit represented by any of formula (P1-1) to formula (P1-4), n represents an integer from 1 to 4, In formula (P1-1) to formula (P1-4), R G1 and R G2 respectively represent an alkylene group.

2. The compound according to claim 1, wherein The compound represented by the formula (EDM1) is a compound represented by the formula (EDM2), In formula (EDM2), R ED12 represents a halogen atom, an alkyl group, a carboxyl group or a hydroxyl 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 via a single bond or a linking group, wherein the linking group is -NRp ED1 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO-or-CONRp ED1 , R EO1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Lp ED2 Indicates -O- or -S-, P ED1 represents a polymer chain including a repeating unit represented by any of the formulas (P1-1) to (P1-4), r represents an integer from 0 to 3, n represents an integer of 1 to 4.

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