WO2019049635A1

WO2019049635A1 - Near infrared ray-absorbable organic pigment, resin composition, method for producing near infrared ray-absorbable organic pigment, method for adjusting spectrum of near infrared ray-absorbable organic pigment, film, laminate, near infrared ray cut filter, near infrared ray transmission filter, solid-state imaging element, image display device, and infrared ray sensor

Info

Publication number: WO2019049635A1
Application number: PCT/JP2018/030562
Authority: WO
Inventors: 和敬高橋; 峻輔北島; 季彦松村
Original assignee: 富士フイルム株式会社
Priority date: 2017-09-11
Filing date: 2018-08-17
Publication date: 2019-03-14
Also published as: JPWO2019049635A1; JP6976341B2; TW201912757A

Abstract

Provided is a near infrared ray-absorbable organic pigment having excellent near infrared ray-shielding performance. Also provided are: a resin composition; a method for producing a near infrared ray-absorbable organic pigment; a method for adjusting a spectrum of a near infrared ray-absorbable organic pigment; a film; a laminate; a near infrared ray cut filter; a near infrared ray transmission filter; a solid-state imaging element; an image display device; and an infrared ray sensor. The near infrared ray-absorbable organic pigment has: a maximum absorption wavelength falling within the wavelength range from 650 to 1400 nm; an A550/Amax value, which is a ratio of an absorbance A550 at a wavelength of 550 nm to an absorbance Amax at a maximum absorption wavelength, of less than 0.1; an average primary particle diameter of 1 to 200 nm; and a degree of crystallinity of 0.70 to 0.98 as measured from a powder X-ray diffraction spectrum.

Description

Near infrared absorbing organic pigment, resin composition, method of producing near infrared absorbing organic pigment, spectral adjustment method of near infrared absorbing organic pigment, film, laminate, near infrared cut filter, near infrared transmission filter, solid-state imaging device, image display Device and infrared sensor

The present invention relates to near infrared absorbing organic pigments. Further, a resin composition, a method of producing a near infrared absorbing organic pigment, a method of adjusting the spectral of the near infrared absorbing organic pigment, a film, a laminate, a near infrared cut filter, a near infrared transmission filter, a solid imaging element, an image display device, and an infrared sensor About.

CCDs (charge coupled devices) and CMOS (complementary metal oxide semiconductors), which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since these solid-state imaging devices use silicon photodiodes having sensitivity to infrared light in their light receiving portions, there are cases where near-infrared cut filters are used to perform visibility correction.

The near-infrared cut filter is known to be manufactured using a resin composition containing a near-infrared absorber such as a near-infrared absorbing organic pigment in order to enhance near-infrared shielding properties (for example, Patent Documents 1 to 3) .

International Publication WO2016 / 035695 JP, 2014-191190, A JP 2014-224921 A

In recent years, near infrared absorbers, such as near infrared absorbing organic pigments, are required to achieve both high visible transparency and near infrared shielding properties.

Therefore, an object of the present invention is to provide a near infrared absorbing organic pigment excellent in visible transparency and near infrared shielding properties. Further, a resin composition, a method of producing a near infrared absorbing organic pigment, a method of adjusting the spectral of the near infrared absorbing organic pigment, a film, a laminate, a near infrared cut filter, a near infrared transmission filter, a solid imaging element, an image display device, and an infrared sensor To provide.

Under these circumstances, as a result of intensive investigations conducted by the present inventor, the present inventors have found that a specific near infrared absorbing organic pigment is excellent in visible transparency and near infrared shielding properties, and have completed the present invention. The present invention provides the following.
<1> A near infrared absorbing organic pigment having a maximum absorption wavelength in a wavelength range of 650 to 1400 nm,
The near infrared absorbing organic pigment has an A ₅₅₀ / A _max of less than 0.1, which is the ratio of the absorbance A _{550 at} a wavelength of 550 nm to the absorbance A _max at a maximum absorption wavelength,
The average primary particle diameter of the near infrared absorbing organic pigment is 1 to 200 nm,
A near-infrared-absorbing organic pigment having a crystallinity of 0.70 to 0.98 represented by the following formula in a powder X-ray diffraction spectrum of the near-infrared-absorbing organic pigment;
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
<2> and absorbance A ₁ at 50nm shorter wavelength than the maximum absorption wavelength of the near infrared absorbing organic pigments, A ₁ / A _max is 0.57 which is the ratio between the absorbance A _max at the maximum absorption wavelength of the near infrared absorbing organic pigment The near-infrared absorbing organic pigment according to <1>, which is ̃0.9.
<3> A ₁ / A _max which is the ratio of the absorbance A _{1 at a} wavelength 50 nm shorter than the maximum absorption wavelength of the near-infrared absorption organic pigment and the absorbance A _{max at} the maximum absorption wavelength of the near-infrared absorption organic pigment is near The near-infrared absorption organic pigment as described in <1> or <2> higher 5% or more than the value in case the average primary particle diameter of an infrared-absorption organic pigment is 1500 nm.
<4> The near-infrared-absorbing organic pigment according to any one of <1> to <3>, wherein the near-infrared-absorbing organic pigment has a maximum absorption wavelength in a wavelength range of 650 to 780 nm.
<5> The near-infrared-absorbing organic pigment according to any one of <1> to <4>, wherein the average long / short side ratio of primary particles of the near-infrared-absorbing organic pigment is 0.3 to 0.99.
<6> The near-infrared-absorbing organic pigment according to any one of <1> to <5>, wherein the near-infrared-absorbing organic pigment is at least one selected from a pyrrolopyrrole compound and a squalilium compound.
<7> A resin composition comprising the near-infrared-absorbing organic pigment according to any one of <1> to <6>, and a resin.
<8> The resin composition according to <7>, further including a coloring material which transmits infrared light and shields visible light.
<9> has a maximum absorption wavelength in the wavelength range of 650 ~ 1400 nm, near infrared, which is the ratio between the absorbance A _max in the absorbance A ₅₅₀ and the maximum absorption wavelength in the wavelength 550 nm A ₅₅₀ / A _max is less than 0.1 An absorbing pigment is milled to give an average primary particle size of 1 to 200 nm, and a near infrared absorbing organic compound having a crystallinity of 0.70 to 0.98 represented by the following formula in a powder X-ray diffraction spectrum. A method of producing a pigment;
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
<10> has a maximum absorption wavelength in the wavelength range of 650 ~ 1400 nm, near infrared, which is the ratio between the absorbance A _max in the absorbance A ₅₅₀ and the maximum absorption wavelength in the wavelength 550 nm A ₅₅₀ / A _max is less than 0.1 An absorbing pigment is milled to give an average primary particle size of 1 to 200 nm, and a near infrared absorbing organic compound having a crystallinity of 0.70 to 0.98 represented by the following formula in a powder X-ray diffraction spectrum. Method of spectral adjustment of pigment;
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
<11> absorbance A ₁ at 50nm shorter wavelength than the maximum absorption wavelength of the near infrared absorbing organic pigment after milling, A ₁ / A _max is the ratio between the absorbance A _max at the maximum absorption wavelength of the near infrared absorbing organic pigment The spectral adjustment method of the near-infrared absorption organic pigment as described in <10> which is 5% or more higher than the value of the near-infrared absorption organic pigment before a milling process.
The film | membrane obtained using the resin composition as described in <12><7> or <8>.
The laminated body which has a film as described in <12> on a <13> support body.
<14> The laminate according to <13>, wherein the support is a glass base containing copper.
The near-infrared cut off filter which has a film | membrane as described in <15><12>.
The near-infrared penetration filter which has a film as described in <16><12>.
The solid-state image sensor which has a film | membrane as described in <17><12>.
The image display apparatus which has a film | membrane as described in <18><12>.
The infrared sensor which has a film | membrane as described in <19><12>.

ADVANTAGE OF THE INVENTION According to this invention, the near-infrared absorption organic pigment excellent in visible transparency and near-infrared shielding can be provided. Further, a resin composition, a method of producing a near infrared absorbing organic pigment, a method of adjusting the spectral of the near infrared absorbing organic pigment, a film, a laminate, a near infrared cut filter, a near infrared transmission filter, a solid imaging element, an image display device, and an infrared sensor Can be provided.

It is a schematic diagram showing one embodiment of an infrared sensor.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
In the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Moreover, as light used for exposure, active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like can be mentioned.
In the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acryl” represents both or either of acrylic and methacryl, “(meth) acrylate” ) Acryloyl represents either or both of acryloyl and methacryloyl.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, near-infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
As used herein, total solids refers to the total mass of all components of the composition excluding the solvent.
In the present specification, the term "process" is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
The term "pigment" as used herein means a compound that is difficult to dissolve in a specific solvent. For example, the pigment preferably has a solubility of 0.1 g or less, more preferably 0.01 g or less, in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C.

<Near-infrared absorbing organic pigment>
The near-infrared-absorbing organic pigment of the present invention is a near-infrared-absorbing organic pigment having a maximum absorption wavelength in the wavelength range of 650 to 1400 nm,
The above-mentioned near infrared absorbing organic pigment has an A ₅₅₀ / A _max of less than 0.1, which is the ratio of the absorbance A _{550 at} a wavelength of 550 nm to the absorbance A _max at a maximum absorption wavelength,
The average primary particle diameter of the near infrared absorbing organic pigment is 1 to 200 nm,
In the powder X-ray diffraction spectrum of the near-infrared ray absorbing organic pigment, the value of the crystallinity represented by the following formula is characterized to be 0.70 to 0.98.
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.

As a result of intensive investigations by the inventor of the present invention on near infrared absorbing organic pigments, the average primary particle diameter is 1 to 200 nm, and the value of crystallinity represented by the above formula is 0.70 to 0.98. It has been found that the near infrared absorbing organic pigment has excellent visible transparency, is excellent in absorption in a wide range near the maximum absorption wavelength, and can shield near infrared rays of a wide range of wavelengths. Although the detailed reason is unknown, by adjusting the primary particle diameter and the degree of crystallinity of the near-infrared absorbing organic pigment in the above range, the association of the near-infrared absorbing organic pigment is appropriately broken and the crystallinity is appropriate. It is assumed that as a result, the absorption in a wide range near the maximum absorption wavelength is improved without impairing the spectral characteristics in the visible region. In addition, since the primary particle diameter is in the above range, the influence of scattering and the like is reduced, and the visible transparency can also be improved while improving the near infrared ray shielding property.

The near-infrared-absorbing organic pigment of the present invention can block a wider range of near-infrared light while being excellent in visible transparency, and therefore, when the near-infrared-absorbing organic pigment is used for a near-infrared cut filter, A near infrared cut filter capable of blocking a wide range of near infrared rays can be provided. Moreover, when this near-infrared absorption organic pigment is used for a near-infrared transmission filter, it can be set as the near-infrared transmission filter which can permeate | transmit near-infrared light with little noise. In the near infrared ray transmission filter, the near infrared ray absorbing organic pigment has a role of limiting the light in the near infrared region to be transmitted to a longer wavelength side.

Further, by using the near-infrared-absorbing organic pigment of the present invention, the viewing-angle dependency of the near-infrared cut filter or near-infrared transmission filter can be further improved, and the occurrence of defects can be suppressed more effectively.

The near-infrared-absorbing organic pigment of the present invention has a crystallinity of 0.70 to 0.98. The upper limit is more preferably 0.96 or less, and still more preferably 0.94 or less. The lower limit is more preferably 0.80 or more, and still more preferably 0.85 or more. If the value of crystallinity degree is the said range, near-infrared shielding can be improved, without impairing the spectral characteristics of the visible region of a near-infrared absorption organic pigment. More specifically, the visible transparency is good, and the absorption in a wide range near the maximum absorption wavelength of the near infrared absorbing organic pigment can be enhanced to shield a wider range of near infrared rays. The crystallinity of the near infrared absorbing organic pigment can be adjusted by a method such as adjusting the milling conditions of the near infrared absorbing organic pigment. For example, if it is desired to increase the degree of crystallinity, the milling temperature may be increased, or the ratio of grinding agent / pigment (mass ratio) may be increased. If the degree of crystallization is desired to be decreased, the milling temperature may be decreased. The ratio (mass ratio) may be lowered.

The peak derived from crystals in the present invention means a sharp peak having a full width at half maximum of 1 ° or less at the peak of the diffraction intensity. Moreover, the peak derived from the amorphous means a peak whose full width at half maximum in the peak of the diffraction intensity exceeds 3 °. In the present invention, the values of Ic and Ia are the lowest at the diffraction intensity 2θ of the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment in the region of 5 to 15 ° and 25 to 35 °. It is a value calculated using a spectrum correction value obtained by subtracting a baseline value from an actual measured value of a powder X-ray diffraction spectrum, using a straight line connecting a point with the lowest diffraction intensity in a region as a baseline. The powder X-ray diffraction spectrum of the near infrared absorbing organic pigment can be measured by the method described in the examples described later.

The average primary particle diameter of the near-infrared-absorbing organic pigment of the present invention is 1 to 200 nm. The lower limit is more preferably 5 nm or more, and further preferably 10 nm or more. The upper limit is more preferably 100 nm or less, and still more preferably 50 nm or less. If the average primary particle diameter of the near-infrared absorbing organic pigment is in the above range, the near-infrared shielding property can be enhanced without impairing the spectral characteristics of the near-infrared absorbing organic pigment in the visible region. More specifically, the visible transparency is good, and the absorptivity of the near-infrared absorbing organic pigment in the vicinity of the maximum absorption wavelength can be increased to shield a wider range of near-infrared light.

The variation coefficient of the primary particle diameter of the near-infrared-absorbing organic pigment of the present invention is preferably 20 to 35%. The lower limit is more preferably 21% or more, and still more preferably 22% or more. The upper limit is more preferably 33% or less, further preferably 30% or less, still more preferably 29% or less, and still more preferably 28% or less. If the variation coefficient of the primary particle diameter of the near infrared absorbing organic pigment is in the above range, the visible transparency of the near infrared absorbing organic pigment can be improved. The variation coefficient of the primary particle diameter of the near-infrared-absorbing organic pigment is defined by the following equation.
Coefficient of variation of primary particle diameter of near infrared absorbing organic pigment = (standard deviation of primary particle diameter of near infrared absorbing organic pigment / arithmetic average value of primary particle diameter of near infrared absorbing organic pigment) × 100

The average long and short side ratio of primary particles of the near-infrared-absorbing organic pigment of the present invention is preferably 0.30 to 0.99. The lower limit is more preferably 0.35 or more, and still more preferably 0.40 or more. The upper limit is more preferably 0.90 or less, still more preferably 0.80 or less. If the average long and short side ratio of the primary particles of the near infrared absorbing organic pigment is in the above range, near infrared shielding properties can be enhanced while maintaining excellent visible transparency.

The variation coefficient of the long-short ratio of the near-infrared-absorbing organic pigment of the present invention is preferably 10 to 30%. The lower limit is more preferably 12% or more, and still more preferably 14% or more. The upper limit is more preferably 29% or less, still more preferably 28% or less. If the variation coefficient of the long and short side ratio of the near infrared absorbing organic pigment is in the above range, the visible transparency of the near infrared absorbing organic pigment can be improved. The variation coefficient of the ratio of the long and short sides of the near infrared absorbing organic pigment is defined by the following equation.
Coefficient of variation of long / short side ratio of near infrared absorbing organic pigment = (standard deviation of long / short side ratio of near infrared absorbing organic pigment / arithmetic mean value of long / short side ratio of near infrared absorbing organic pigment) × 100

In the present invention, the primary particle diameter and the long side ratio of the near infrared absorbing organic pigment can be determined from the obtained photograph by observing the primary particles of the near infrared absorbing organic pigment by a transmission electron microscope. Specifically, the projection area of the primary particles of the near infrared absorbing organic pigment is determined, and the equivalent circle diameter corresponding thereto is calculated as the primary particle diameter of the near infrared absorbing organic pigment. In addition, the ratio of the short side to the long side of the primary particle (short side / long side) is determined from the projected picture to calculate the long / short side ratio. In the present invention, the average primary particle diameter and the average long and short side ratio are taken as the arithmetic mean value of the primary particle diameter and the long and short side ratio of primary particles of 400 near infrared absorbing organic pigments. Also, the longest diameter of the primary particles is called the long side, and the shortest diameter is called the short side. That is, in the case of an ellipse, the major axis is the long side and the minor axis is the short side. In addition, primary particles of the near infrared absorbing organic pigment refer to independent particles without aggregation.

The near infrared absorbing organic pigment of the present invention has a maximum absorption wavelength in the wavelength range of 650 to 1400 nm. The maximum absorption wavelength of the near infrared absorbing organic pigment is preferably 1200 nm or less, more preferably 1000 nm or less, and still more preferably 780 nm or less. The maximum absorption wavelength of the near infrared absorbing organic pigment is preferably 700 nm or more, and more preferably 720 nm or more. It is particularly preferable that the near infrared absorbing organic pigment have a maximum absorption wavelength in the wavelength range of 650 to 780 nm, because the effect of the present invention is more easily exhibited.

In the near-infrared absorbing organic pigment of the present invention, A ₅₅₀ / A _max, which is the ratio of the absorbance A _{550 at} a wavelength of 550 nm to the absorbance A _max at a maximum absorption wavelength, is less than 0.1 and 0.05 or less Preferably, it is 0.03 or less, more preferably 0.02 or less. The lower limit is preferably low, for example, preferably 0.001 or more. If the above-mentioned ratio is the above-mentioned range, it can be considered as a near-infrared absorption organic pigment excellent in visible transparency and near-infrared shielding.

The near infrared absorbing organic pigment of the present invention has an A ₁ / A _max of 0.5 to 0.9 which is a ratio of the absorbance A _{1 at a} wavelength 50 nm shorter than the maximum absorption wavelength and the absorbance A _max at the maximum absorption wavelength. Is preferred. The above-mentioned ratio is more preferably 0.8 or less, still more preferably 0.7 or less. The above-mentioned ratio is more preferably 0.56 or more, further preferably 0.57 or more. If the above-mentioned ratio is the above-mentioned range, it can be considered as a near-infrared absorption organic pigment which can shield a wider range of near-infrared light.

Near infrared absorbing organic pigment of the present invention, the value of the A ₁ / A _max is higher than 5% than the value of A ₁ / A _max if the average primary particle diameter of the near-infrared-absorbing organic pigment is 1500nm Is preferably 7% or more, more preferably 10% or more.

In the present invention, the maximum absorption wavelength of the near infrared absorbing organic pigment and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of a film formed using a resin composition containing the near infrared absorbing organic pigment.

In the present invention, the compound type of the near infrared light absorbing organic pigment is not particularly limited, but pyrrolopyrrole compounds, rylene compounds, oxonol compounds, squarylium compounds, cyanine compounds, croconium compounds, phthalocyanine compounds, naphthalocyanine compounds, pyrilium compounds, It is preferably at least one selected from azurenium compounds, indigo compounds and pyrromethene compounds, more preferably at least one selected from pyrrolopyrrole compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds and naphthalocyanine compounds, It is further preferable that it is a pyrrole compound or a squarylium compound, and it is particularly preferable that it is a pyrrolopyrrole compound. Particularly in the case of pyrrolopyrrole compounds, near infrared shielding properties can be more effectively improved while having excellent visible transparency.

The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ represent R ⁴ may be combined with each other to form a ring, and each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, and R ⁴ is an R R ^4A and R ^4B may each independently represent a substituent, which may be covalently bonded or coordinated with at least one selected from ¹ a ¹ , R ¹ ^b and R ³ . R ^4A and R ^4B may be bonded to each other to form a ring. About the detail of Formula (PP), Paragraph No. 0017 of the Unexamined-Japanese-Patent No. 2009-263614, Paragraph No. 0011 of the Unexamined-Japanese-Patent No. 2011-68731, Paragraph No. 0010 of the international publication WO2015 / 166873 The contents of which are incorporated herein by reference.

In formula (PP), R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. In addition, the alkyl group, the aryl group and the heteroaryl group represented by R ^1a and R ^1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in Paragraph Nos. 0020 to 0022 of JP 2009-263614 A, and the following substituent T.

(Substituent T)
An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably An aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably 6 to carbon atoms 30) aryloxy group), heteroaryloxy group, acyl group (preferably having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably having 2 to 30 carbon atoms) Is an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acylo group having 2 to 30 carbon atoms). A), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably 7 to carbon atoms) 30) aryloxycarbonylamino group), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably having 1 to 30 carbon atoms) Alkylthio group), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 1 to 30 carbon atoms) Preferably having 6 to 30 carbon atoms, heteroarylsul Group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms) Ureido group (preferably having a carbon number of 1 to 30), hydroxyl group, carboxyl group, sulfo group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imidic acid group, mercapto group, halogen atom, cyano group, alkyl And a sulfino group, an arylsulfino group, a hydrazino group, an imino group and a heteroaryl group (preferably having a carbon number of 1 to 30). When these groups further have a substitutable site, they may further have a substituent. As the further substituent, the groups described for the above-mentioned substituent T can be mentioned.

In formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T. At least one of R ² and R ³ is preferably an electron-withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-withdrawing group. Here, the substituent constants determined by the Hammett rule include σp values and σm values. These values can be found in many general books. In the present invention, a substituent having a Hammett's substituent constant σ value of 0.2 or more can be exemplified as the electron-withdrawing group. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (σ p value = 0.66), a carboxyl group (—COOH: σ p value = 0.45), and an alkoxycarbonyl group (eg, —COOMe: σ p value = 0. 45), an aryloxycarbonyl group (for example, -COOPh: σp value = 0.44), a carbamoyl group (for example, -CONH ₂ : σp value = 0.36), an alkylcarbonyl group (for example, -COMe: σp value = 0.50), an arylcarbonyl group (for example, -COPh: σp value = 0.43), an alkylsulfonyl group (for example, -SO ₂ Me: σp value = 0.72), an arylsulfonyl group (for example, -SO ₂ Ph: σp value = 0.68) and the like, and a cyano group is preferable. Here, Me represents a methyl group, and Ph represents a phenyl group. The Hammett's substituent constant σ value can be referred to, for example, paragraph Nos. 0017 to 0018 of JP-A-2011-68731, the contents of which are incorporated herein.

In formula (PP), R ² preferably represents an electron-withdrawing group (preferably a cyano group), and R ³ preferably represents a heteroaryl group. The heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a fused ring, preferably a single ring or a fused ring having 2 to 8 condensations, and more preferably a single ring or a fused ring having 2 to 4 condensations. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. The heteroaryl group is preferably a group represented by the following formula (A-1) or a group represented by (A-2), and a group represented by preferable.

In formula (A-1), X ¹ represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R ^a1 and R ^a2 are Each independently represents a hydrogen atom or a substituent, and R ^a1 and R ^a2 may be bonded to each other to form a ring. * Represents a connecting hand.
Examples of the substituent represented by R ^a1 , R ^a2 and R ^X1 to R ^X3 include a substituent T, and an alkyl group, an aryl group and a halogen atom are preferable.

The ring formed by combining R ^a1 and R ^a2 is preferably an aromatic ring. When R ^a1 and R ^a2 form a ring, as (A-1), a group represented by (A-1-1) below, a group represented by (A-1-2), etc. It can be mentioned.

In the formula, X ¹ represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R ^101a to R ^109a each independently represent hydrogen Represents an atom or a substituent. * Represents a connecting hand. The substituent represented by R ^101a to R ^109a includes a substituent T. X ¹ is preferably O or S, more preferably O.

In formula (A-2), Y ¹ to Y ⁴ each independently represent N or CR ^Y1 , at least two of Y ¹ to Y ⁴ are CR ^Y1 , and R ^Y1 is a hydrogen atom or a substituent And adjacent R ^Y1 may be bonded to each other to form a ring. * Represents a connecting hand. The substituent represented by R ^Y1 includes a substituent T, and an alkyl group, an aryl group and a halogen atom are preferable.

At least two of Y ¹ to Y ⁴ may be CR ^{Y 1} , and adjacent R ^{Y 1} may be bonded to each other to form a ring. The ring formed by bonding adjacent R ^Y1 is preferably an aromatic ring. When adjacent R ^Y1s form a ring, examples of (A-2) include groups represented by (A-2-1) to (A-2-5) below.

In the formula, each of R ^201a to R ^227a independently represents a hydrogen atom or a substituent, and * represents a linking hand. The substituent represented by R ^201a to R ^227a includes a substituent T.

In formula (PP), R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by —BR ^4A R ^4B , and a hydrogen atom, an alkyl group, an aryl group or —BR ^The group represented by ^4A R ^4B is more preferably a group represented by -BR ^4A R ^4B . The substituent represented by R ^4A and R ^4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and an aryl group Particularly preferred. These groups may further have a substituent. Two R ⁴ 's in the formula (PP) may be the same or different. R ^4A and R ^4B may be bonded to each other to form a ring.

As the squarylium compound, a compound represented by the following formula (SQ) is preferable.

In formula (SQ), each of A ¹ and A ² independently represents an aryl group, a heteroaryl group or a group represented by formula (A-1);

In formula (A-1), Z ¹ represents a nonmetal atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, and d represents 0 or 1. The wavy line represents a connecting hand. The details of the formula (SQ) are described in paragraph Nos. 0020 to 0049 of JP2011-208101A, paragraph Nos. 0043 to 0062 of Patent No. 6065169, and paragraph Nos. 0024 to 0040 of International Publication WO2016 / 181987. The contents of these are incorporated herein by reference.

In the formula (SQ), the cation is present in a delocalized manner as follows.

The squarylium compound is preferably a compound represented by the following formula (SQ-1).

Ring A and ring B each independently represent an aromatic ring,
X ^A and X ^B each independently represent a substituent,
G ^A and G ^B each independently represent a substituent,
kA represents an integer of 0 to n _A , k _B represents an integer of 0 to n _B ,
n _A and n _B each represent the maximum number of groups that can be substituted on ring A or ring B,
X ^A and G ^A , X ^B and G ^B , and X ^A and X ^B may bond to each other to form a ring, and when there are a plurality of G ^A and G ^B respectively, they may be bonded to each other to form a ring structure May be formed.

The substituent represented by G ^A and G ^B, include the substituent T described by the formula (PP) as described above.

Examples of the substituent represented by X ^A and X ^B, preferably a group having an active hydrogen, -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2, -NHCOR X1, -CONR X1 R X2, -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -NHSO ₂ R ^X1 , -B (OH) ₂ and -PO (OH) ₂ are more preferable, and -OH, -SH and -NR ^X1 R ^X2 are more preferable. Each of R ^X1 and R ^X1 independently represents a hydrogen atom or a substituent. As a substituent which X ^A and X ^B represent, an alkyl group, an aryl group, or heteroaryl group is mentioned, An alkyl group is preferable.

Ring A and ring B each independently represent an aromatic ring. The aromatic ring may be a single ring or a fused ring. Specific examples of the aromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thia Train ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring or a naphthalene ring is preferable. The aromatic ring may be unsubstituted or may have a substituent. As a substituent, the substituent T demonstrated by the formula (PP) mentioned above is mentioned.

X ^A and G ^A , X ^B and G ^B , and X ^A and X ^B may bond to each other to form a ring, and when there are a plurality of G ^A and G ^B respectively, they may be bonded to each other to form a ring You may form. The ring is preferably a 5- or 6-membered ring. The ring may be a single ring or may be a fused ring. When X ^A and G ^A , X ^B and G ^B , X ^A and X ^B , G ^A or ^{B B} bond together to form a ring, these may be directly bonded to form a ring; The ring may be formed through a divalent linking group consisting of the groups -CO-, -O-, -NH-, -BR- and combinations thereof. R represents a hydrogen atom or a substituent. As a substituent, the substituent T demonstrated by Formula (PP) mentioned above is mentioned, An alkyl group or an aryl group is preferable.

kA represents an integer of 0 to n _A , k _B represents an integer of 0 to n _B , n _A represents the number of the largest groups that can be substituted on ring A, n _B can be substituted on ring B Represents the largest number of groups. Each of kA and kB is preferably independently 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

The squarylium compound is also preferably a compound represented by the following formula (SQ-10), formula (SQ-11) or formula (SQ-12).
Formula (SQ-10)

Formula (SQ-11)

Formula (SQ-12)

In formulas (SQ-10) to (SQ-12), each X is a group of one or more hydrogen atoms optionally substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group. (1) or a divalent organic group represented by the formula (2).
-(CH ₂ ) _n1-... (1)
In formula (1), n1 is 2 or 3.
_{_{- (CH 2) n2 -O- (}} CH 2) n3 - ··· (2)
In the formula (2), n2 and n3 are each independently an integer of 0 to 2, and n2 + n3 is 1 or 2.
Each of R ¹ and R ² independently represents an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent or may be unsubstituted. As a substituent, the substituent T demonstrated by the formula (PP) mentioned above is mentioned.
R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
n is 2 or 3.

The cyanine compound is preferably a compound represented by the formula (C).
Formula (C)

In the formula, each of Z ¹ and Z ² independently represents a nonmetallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed.
R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ¹ represents a methine chain having an odd number of methine groups,
a and b are each independently 0 or 1;
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary to balance the charge, and the site represented by Cy in the formula is an anion moiety Where X ¹ represents a cation, c represents the number necessary to balance the charge, and c is a molecule in which the charge at the site represented by Cy in the formula is neutralized within the molecule It is 0.

As a specific example of the near infrared absorbing organic pigment, a compound having the following structure and the like can be mentioned. In the following structural formulae, Me is a methyl group and Ph is a phenyl group. Among the following compounds, (A-1), (A-7) to (A-22), (A-53) to (A-57) are pyrrolopyrrole compounds, and (A-2) is a lylene group. (A-3) is a naphthalocyanine compound, (A-4) is an oxonol compound, and (A-5), (A-23) to (A-42) are squarylium compounds. And (A-6) are zinc phthalocyanine compounds, (A-43) and (A-44) are croconium compounds, and (A-45) to (A-47) are pyrromethene compounds, and (A-) 48) and (A-49) are indigo compounds, (A-50) and (A-51) are pyrylium compounds, and (A-52) are azulenium compounds.

<Method of producing near infrared absorbing organic pigment>
Next, the method for producing the near-infrared-absorbing organic pigment of the present invention will be described.
The method for producing the near-infrared-absorbing organic pigment of the present invention has a maximum absorption wavelength in the wavelength range of 650 to 1400 nm, and the ratio of the absorbance A _{550 at} a wavelength 550 nm to the absorbance A _max at the maximum absorption wavelength A ₅₅₀ / A _The near-infrared absorbing pigment having a _max of less than 0.1 is milled to an average primary particle diameter of 1 to 200 nm, and the value of crystallinity represented by the above formula in the powder X-ray diffraction spectrum is 0.70 to It is characterized in that it is set to 0.98.

The milling process of the near-infrared absorbing organic pigment may be carried out by kneading and polishing the near-infrared-absorbing organic pigment in the presence of a water-soluble organic solvent and a water-soluble inorganic salt.

The water-soluble inorganic salt acts as a grinding agent and promotes the refinement of the near-infrared-absorbing organic pigment by being kneaded with the near-infrared-absorbing organic pigment. Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, sodium sulfate, aluminum sulfate, sodium hydrogen carbonate and the like, with preference given to sodium chloride and sodium sulfate. These water-soluble inorganic salts can be used as ground products. These water-soluble inorganic salts can be used alone or in combination of two or more.

The average particle diameter (volume based 50% diameter (D50)) of the water-soluble inorganic salt is preferably 15 μm or more, and more preferably 18 μm or more. The upper limit is preferably 50 μm or less, and more preferably 30 μm or less. The near-infrared-absorbing organic pigment has a hardness lower than that of a chromatic color organic pigment or an inorganic pigment, and when kneading and polishing is performed using a water-soluble inorganic salt having a small particle diameter, the near-infrared-absorbing organic pigment is Or the crystal structure of the near-infrared-absorbing organic pigment may change to lower the visible transparency, etc., but the water-soluble inorganic salt having a suitably large particle size (preferably having an average particle size of By using a water-soluble inorganic salt of 15 μm or more, the crystallinity (the degree of crystallinity) can be appropriately adjusted while suppressing the distortion of the crystal structure of the near-infrared-absorbing organic pigment and the like. Furthermore, the near infrared absorbing organic pigment can be miniaturized.

The amount of the water-soluble inorganic salt is preferably 2.5 to 20 times, more preferably 4 to 18 times, and still more preferably 7 to 18 times the mass of the near infrared absorbing organic pigment. The lower limit is particularly preferably 8 times or more, and most preferably 10 times or more. The upper limit is particularly preferably 17 times or less, and most preferably 16 times or less. If the amount of the water-soluble inorganic salt is in the above-mentioned range, the crystallinity (degree of crystallinity) can be appropriately adjusted while suppressing the distortion of the crystal structure of the near-infrared-absorbing organic pigment and the like. Furthermore, the near infrared absorbing organic pigment can be miniaturized.

The water-soluble organic solvent acts as a binder for the near-infrared absorbing organic pigment and the water-soluble inorganic salt, and the hardness and viscosity of the mixture containing the near-infrared absorbing organic pigment, the water-soluble inorganic salt and the water-soluble organic solvent While giving, it can suppress the crystal growth and crystal transition of the near infrared absorption organic pigment. The solubility of the water-soluble organic solvent in 100 g of water at 23 ° C. is preferably 20 g or more, more preferably 50 g or more, and still more preferably 100 g or more. According to this aspect, the water-soluble inorganic salt can be efficiently washed with water. Specific examples of the water-soluble organic solvent include alkylene glycols such as ethylene glycol and propylene glycol, condensation products of alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polyethylene-propylene glycol, etc., methoxyethanol, polyethylene glycol Alkyl ethers of (poly) alkylene glycols such as monomethyl ether, glycerin and the like can be mentioned, and the reason is that the mixture containing the near infrared ray absorbing organic pigment, the water soluble inorganic salt and the water soluble organic solvent gives appropriate hardness and viscosity. A highly viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol, polyethylene glycol is preferred. The water-soluble organic solvent can be used singly or in combination of two or more. The optimum amount of the water-soluble organic solvent varies depending on the amount of the near-infrared-absorbing organic pigment, the amount of the water-soluble inorganic salt, the kneading conditions (temperature, kneading speed etc.), the characteristics of the kneader used, etc. 0.10 to 0.35 times is preferable, 0.12 to 0.30 times is more preferable, and 0.15 to 0.25 times is more preferable with respect to the total mass of the water-soluble inorganic salt. If the amount of the water-soluble organic solvent is in the above-mentioned range, it is possible to impart appropriate hardness and viscosity to a mixture containing the near-infrared-absorbing organic pigment, the water-soluble inorganic salt and the water-soluble organic solvent.

As a kneader, a double-arm kneader, a flasher, a planetary mixer or the like may be used as long as it has the ability to knead the above mixture. For refinement, a double-arm kneader with high shear force is more preferable.

The temperature (milling temperature) at the time of kneading is set in accordance with the temperature dependency of the crystal growth rate of the near infrared absorbing organic pigment and the crystal transition property. Generally, the lower the temperature, the smaller the crystal growth rate. On the other hand, the wettability of the water-soluble organic solvent to the pigment surface and the penetration speed of the water-soluble organic solvent into the pigment mass are as fast as high temperature. The sizing of the near infrared absorbing organic pigment is developed by the balance of both miniaturization and crystal growth. For example, 0 to 120 ° C. is preferable. The lower limit is more preferably 5 ° C. or more, further preferably 10 ° C. or more, still more preferably 15 ° C. or more, and particularly preferably 20 ° C. or more. The upper limit is more preferably 100 ° C. or less, still more preferably 80 ° C. or less, still more preferably 60 ° C. or less, and particularly preferably 50 ° C. or less. If the milling temperature is in the above range, it is easy to adjust the values of the average primary particle diameter and the degree of crystallinity of the near infrared absorbing organic pigment to the above range. Furthermore, it is easy to produce a near-infrared absorbing organic pigment excellent in visible transparency, near-infrared shielding property and heat resistance.

At the time of kneading and polishing of the near-infrared-absorbing organic pigment, a water-soluble inorganic salt or a water-soluble organic solvent can be added according to the progress of refinement and sizing of the near-infrared-absorbing organic pigment. Further, the discharge and re-kneading of the pigment kneaded material is not limited to one time, and may be performed a plurality of times.

At the time of kneading and polishing of the near infrared absorbing organic pigment, it is also possible to carry out crystal transition together with the refining of the near infrared absorbing organic pigment. Moreover, a pigment derivative and a surface treatment agent can also be added for refinement | miniaturization and crystal-type control of a near-infrared absorption organic pigment.
The kneaded material after the kneading and polishing is purified by a known purification method such as washing with water, an acid, an alkali or the like to isolate a finely divided near-infrared-absorbing organic pigment. It is preferable to carry out the washing process and to isolate for the reason of environmental load reduction. After washing with water, the near-infrared-absorbing organic pigment in a water-containing state may be used as it is, or it may be dried and used to reduce water content. The drying treatment method is not particularly limited, but it is preferable to carry out by hot air drying from the viewpoint of productivity improvement. When the drying treatment is carried out, the water content of the near infrared absorbing organic pigment is preferably 5% or less, more preferably 2% or less.

The ratio of the absorbance A _{1 at a} wavelength 50 nm shorter than the maximum absorption wavelength of the near infrared absorption organic pigment produced by the present invention to the absorbance A _{max at} the maximum absorption wavelength of the near infrared absorption organic pigment is A ₁ / A _max It has characteristics higher than the value of the near infrared absorbing organic pigment before the milling treatment. Although the detailed reason is unclear, while the average primary particle diameter is adjusted to 1 to 200 nm by milling and the value of the crystallinity is set to 0.70 to 0.98, the association of the near infrared absorbing organic pigment is appropriate. It is assumed that the crystallinity can be moderately disturbed, and as a result, the absorptivity in the vicinity of the maximum absorption wavelength is improved as compared with the state before the milling treatment. The value of the above A ₁ / A _max of the near-infrared-absorbing organic pigment produced according to the present invention is preferably 5% or more higher than the value of the near-infrared-absorbing organic pigment before the milling treatment, and is preferably 7% or more higher Preferably, it is more preferably 10% or more.

<Spectroscopic adjustment method>
Next, the spectral adjustment method of the near-infrared-absorbing organic pigment of the present invention will be described. The spectral adjustment method of the near-infrared absorbing organic pigment of the present invention has a maximum absorption wavelength in the wavelength range of 650 to 1400 nm, and the ratio of the absorbance A _{550 at} a wavelength 550 nm to the absorbance A _max at the maximum absorption wavelength A ₅₅₀ / The near-infrared absorbing pigment having an A _max of less than 0.1 is milled to an average primary particle diameter of 1 to 200 nm, and the value of crystallinity represented by the above formula in the powder X-ray diffraction spectrum is 0.70. It is characterized in that it is made to be ~ 0.98.
According to the present invention, the above-mentioned near-infrared absorbing pigment is milled to give an average primary particle diameter of 1 to 200 nm, and the value of crystallinity represented by the following formula in the powder X-ray diffraction spectrum is 0.70 to By setting it as 0.98, the absorptivity in the vicinity of the maximum absorption wavelength is improved as compared with the state before the milling treatment, and a wider range of near infrared rays can be absorbed.

The spectral adjustment method of the near-infrared absorbing organic pigment of the present invention comprises the absorbance A _{1 at a} wavelength 50 nm shorter than the maximum absorption wavelength of the near-infrared absorbing organic pigment after milling and the absorbance A at the maximum absorption wavelength of the near-infrared absorbing organic pigment the ratio of the _{_max} a ₁ / a _max is preferably higher than 5% than the value of the near-infrared-absorbing organic pigment prior to milling, it is more preferably at least 7% higher, still it is higher than 10% preferable.

<Resin composition>
Next, the resin composition of the present invention will be described. The resin composition of the present invention comprises the above-described near-infrared-absorbing organic pigment of the present invention and a resin.

<< Near-infrared absorbing organic pigment >>
The resin composition of the present invention contains the above-mentioned near-infrared-absorbing organic pigment of the present invention. The content of the near-infrared-absorbing organic pigment of the present invention is preferably 0.1 to 60% by mass with respect to the total solid content of the resin composition. As for a minimum, 1 mass% or more is more preferable, and 5 mass% or more is still more preferable. The upper limit is more preferably 50% by mass or less and still more preferably 40% by mass or less.

<< Resin >>
The resin composition of the present invention contains a resin. The resin is blended, for example, in applications of dispersing particles such as pigments in a composition and applications of a binder. In addition, resin used mainly for disperse | distributing particle | grains, such as a pigment, is also called a dispersing agent. However, such application of the resin is an example, and the resin can also be used for purposes other than such application.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. 3,000 or more are preferable and, as for a minimum, 5,000 or more are more preferable.

As the resin, (meth) acrylic resin, epoxy resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, urethane resin etc. are mentioned. As cyclic olefin resin, norbornene resin can be preferably used from a viewpoint of heat resistance improvement. Examples of commercially available products of norbornene resin include ARTON series (for example, ARTON F 4520) manufactured by JSR Corporation. As a commercial item of polyimide resin, Neoprim (registered trademark) series (for example, C3450) manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like can be mentioned. Examples of the epoxy resin include epoxy resins which are glycidyl ethers of phenol compounds, epoxy resins which are glycidyl ethers of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins Epoxy resin, glycidyl amine epoxy resin, epoxy resin obtained by glycidylating halogenated phenols, condensate of silicon compound having an epoxy group and silicon compound other than the above, polymerizable unsaturated compound having an epoxy group, and others Copolymers with other polymerizable unsaturated compounds may, for example, be mentioned. Moreover, as an epoxy resin, mer proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (day Oil Co., Ltd. product, epoxy group-containing polymer, etc. can also be used. As the urethane resin, 8UH-1006 and 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.) can also be used.

Further, as the resin, a resin described in an example of International Publication WO 2016/088645, a resin described in JP-A-2017-57265, a resin described in JP-A-2017-32685, JP-A-2017 It is also possible to use the resin described in Japanese Patent Application Laid-Open No. 0-75248 and the resin described in JP-A-2017-066240, the contents of which are incorporated herein. Further, a resin having a fluorene skeleton can also be preferably used. As resin which has fluorene frame, resin of the following structure is mentioned. In the following structural formulae, A represents the residue of a carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride and diphenyl ether tetracarboxylic acid dianhydride And M is a phenyl or benzyl group. The resin having a fluorene skeleton can be referred to the description of US Patent Application Publication No. 2017/0102610, the contents of which are incorporated herein.

The resin used in the present invention preferably contains a resin having an acid group and / or a hydroxyl group, and more preferably contains a resin having an acid group. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable. These acid groups may be of only one type, or of two or more types. The resin having an acid group can also be used as an alkali-soluble resin.

As a resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples thereof include alkali-soluble polymers such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, novolac resin, etc. A phenol resin, an acidic cellulose derivative having a carboxyl group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxyl group are mentioned. In particular, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenyl maleimide, N-cyclohexyl maleimide and the like can also be used. These other monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types.

The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include (meth) allyl group and (meth) acryloyl group. Commercially available products include Dianal NR series (Mitsubishi Rayon Co., Ltd.), Photomer 6173 (Carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all are Osaka organic) Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all from Daicel Co., Ltd.), Ebecryl 3800 (Daicel UBC Co., Ltd.), Acrycure RD-F8 (Co., Ltd.) Nippon Catalyst Co., Ltd. and the like.

Resin having an acid group is benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) A multicomponent copolymer consisting of acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, those obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No. 7-1420654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene Macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used.

The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that it is a polymer containing a repeating unit derived from a component.

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

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.

As a specific example of the ether dimer, paragraph [0317] of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein. The ether dimer may be only one type, or two or more types.

The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).

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

The resin having an acid group is described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding US patent application publication No. 2012/0235099, paragraphs 0685 to 0700), JP-A-2012-198408. No. 0076-0099 can be referred to, and the contents thereof are incorporated herein. Moreover, the resin which has an acidic radical can also use a commercial item. For example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) and the like can be mentioned.

The acid value of the resin having an acid group is preferably 30 to 200 mg KOH / g. The lower limit is more preferably 50 mg KOH / g or more, and still more preferably 70 mg KOH / g or more. The upper limit is more preferably 150 mg KOH / g or less, and still more preferably 120 mg KOH / g or less.

As resin which has an acidic radical, resin of the following structure etc. are mentioned, for example. In the following structural formulae, Me represents a methyl group.

In the resin composition of the present invention, it is also preferable to use a resin having repeating units represented by formulas (A3-1) to (A3-7) as the resin.

In the formula, R ⁵ represents a hydrogen atom or an alkyl group, L ⁴ to L ⁷ each independently represent a single bond or a divalent linking group, and R ¹⁰ to R ¹³ each independently represent an alkyl group or an aryl group . Each of R ¹⁴ and R ¹⁵ independently represents a hydrogen atom or a substituent.

The carbon number of the alkyl group represented by R ⁵ is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R ⁵ is preferably a hydrogen atom or a methyl group.

Examples of the divalent linking group represented by L ⁴ to L ⁷ include an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , -NR ^10- (R ¹⁰ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. The cyclic alkylene group may be either monocyclic or polycyclic. The carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.

The alkyl group represented by R ¹⁰ to R ¹³ may be linear, branched or cyclic, preferably cyclic. The alkyl group may have a substituent or may be unsubstituted. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The carbon number of the aryl group represented by R ¹⁰ to R ¹³ is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. R ¹⁰ is preferably a cyclic alkyl group or an aryl group. R ¹¹ and R ¹² are preferably linear or branched alkyl groups. R ¹³ is preferably a linear alkyl group, a branched alkyl group or an aryl group.

The substituent represented by R ¹⁴ and R ¹⁵ is a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, aryloxy group, heteroaryloxy group, Alkylthio group, arylthio group, heteroarylthio group, -NR ^a1 R ^a2 , -COR ^a3 , -COOR ^a4 , -OCOR ^a5 , -NHCOR ^a6 , -CONR ^a7 R ^a8 , -NHCONR ^a9 R ^a10 , -NHCOOR ^a11 ,- _{^{_{SO 2 R a12, -SO 2 oR}}} a13, include -NHSO ₂ R ^a14 or -SO ₂ NR ^a15 R ^a16. Each of R ^a1 to R ^a16 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Among them, at least one of R ¹⁴ and R ¹⁵ preferably represents a cyano group or -COOR ^a4 . R ^a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.

Examples of commercially available resins having a repeating unit represented by the formula (A3-7) include ARTON F 4520 (manufactured by JSR Corporation). In addition, for details of the resin having a repeating unit represented by the formula (A3-7), the descriptions in paragraphs “0053” to “0075” and “0127 to 0130” of JP 2011-100084 A can be referred to, and the contents thereof are described in this specification. Incorporated into the book.

The resin composition of the present invention can also contain a resin as a dispersant. The dispersant includes an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. Resins consisting only of groups are more preferred. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mg KOH / g, more preferably 50 to 105 mg KOH / g, and still more preferably 60 to 105 mg KOH / g. Moreover, a basic dispersing agent (basic resin) represents resin whose quantity of a basic group is larger than the quantity of an acidic radical. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50% by mole, where the total amount of the amount of acid groups and the amount of basic groups is 100% by mole. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersing agent contains a repeating unit having an acid group, it is possible to further reduce the residue generated on the base of the pixel when forming a pattern by photolithography.

It is also preferable that the resin used as the dispersant is a graft copolymer. The graft copolymer is excellent in the dispersibility of the pigment and the dispersion stability after aging since the graft copolymer has affinity with the solvent by the graft chain. The details of the graft copolymer can be referred to the description of Paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

In the present invention, it is also preferable to use, as the resin, an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine dispersant comprises a structural unit having a partial structure X having a functional group having a pKa of 14 or less and a side chain containing a side chain Y having an atom number of 40 to 10,000, and having a main chain and a side chain The resin which has a basic nitrogen atom in at least one side is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. With regard to the oligoimine dispersant, the description in paragraphs [0102] to [0166] of JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein. Specific examples of the oligoimine dispersant include the following. The following resin is also a resin having an acid group (alkali soluble resin). Further, as the oligoimine dispersant, the resins described in paragraph Nos. 0168 to 0174 of JP 2012-255128 A can be used.

The dispersant is also available as a commercial product, and as such specific examples, Disperbyk-111 (manufactured by BYK Chemie), Solsparse 76500 (manufactured by Nippon Lubrizol Co., Ltd.) and the like can be mentioned. In addition, pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein. Moreover, the resin etc. which have an acidic radical mentioned above can also be used as a dispersing agent.

The content of the resin is preferably 1 to 80% by mass with respect to the total solid content of the resin composition. As for a minimum, 5 mass% or more is more preferable, and 7 mass% or more is still more preferable. The upper limit is more preferably 50% by mass or less, still more preferably 40% by mass or less, and still more preferably 30% by mass or less.
The content of the resin having an acid group is preferably 0.1 to 80% by mass with respect to the total solid content of the resin composition. The upper limit is more preferably 50% by mass or less, still more preferably 40% by mass or less, and still more preferably 30% by mass or less. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is still more preferable.
The content of the resin as the dispersant is preferably 0.1 to 40% by mass with respect to the total solid content of the resin composition. 20 mass% or less is more preferable, and, as for an upper limit, 10 mass% or less is more preferable. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is further more preferable. The content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. The upper limit is more preferably 80 parts by mass or less, and still more preferably 75 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

<< Other Near Infrared Absorbing Compounds >>
The resin composition of the present invention may further contain a near infrared absorber (also referred to as another near infrared absorber) other than the above-described near infrared absorbing organic pigment. Other near infrared absorbing compounds include dyes. Examples of the compound species include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, rylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimmonium compounds, dithiol compounds, triarylmethane compounds, piromethene compounds, Azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, copper compounds and the like can be mentioned. As a commercial item of other near-infrared absorbers, for example, SDO-C33 (made by Arimoto Chemical Industry Co., Ltd.), EEX COLOR IR-14, EEX Color IR-10A, EEX Color TX-EX-801B EEX COLOR TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820 Shigenox NIA-839 (Hakoko Chemical Co., Ltd.), Epolite V-63, Epolight 3801, Epolight 3036 EPOLIN Co., Ltd., PRO-JET 825 LDI (Fujifilm Co., Ltd.), NK-3027, NK-5060 (Hayashibara Co., Ltd.), YKR-3070 (Mitsui Chemical Co., Ltd.), etc. It is.

In addition, inorganic particles can also be used as another near infrared absorber. The inorganic particles are preferably metal oxide particles or metal particles. Examples of metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, fluorine-doped tin dioxide (F-doped) SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, etc. may be mentioned. Examples of metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles, and the like. Moreover, a tungsten oxide type compound can be used as an inorganic particle. The tungsten oxide based compound is preferably cesium tungsten oxide. For details of the tungsten oxide based compound, paragraph 0080 of JP-A-2016-006476 can be referred to, and the contents thereof are incorporated in the present specification. The shape of the inorganic particles is not particularly limited, and may be spherical, non-spherical, sheet-like, wire-like or tube-like.

800 nm or less is preferable, as for the average particle diameter of inorganic particle, 400 nm or less is more preferable, and 200 nm or less is still more preferable. When the average particle size of the inorganic particles is in such a range, the visible transparency is good. From the viewpoint of avoiding light scattering, the smaller the average particle diameter, the better, but from the viewpoint of ease of handling at the time of production, etc., the average particle diameter of the inorganic particles is usually 1 nm or more.

When the resin composition of the present invention contains another near infrared absorber, the content of the other near infrared absorber is 0.1 to 80 parts by mass with respect to 100 parts by mass of the near infrared absorbing organic pigment of the present invention Is preferable, 5 to 60 parts by mass is more preferable, and 10 to 40 parts by mass is more preferable.

<< Achromatic coloring agent >>
The resin composition of the present invention can contain a chromatic coloring agent. In the present invention, a chromatic coloring agent means a coloring agent other than a white coloring agent and a black coloring agent. The chromatic coloring agent is preferably a coloring agent having a maximum absorption wavelength in the range of 400 nm to less than 650 nm. The chromatic coloring agent may be a pigment or a dye. Preferably it is a pigment.

The pigment is preferably an organic pigment, and the following can be mentioned. However, the present invention is not limited to these.
Color Index (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, 35, 53, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 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, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59 (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42 etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 60, 64, 66, 79, 80 (the above, blue pigment),
These organic pigments can be used alone or in combination of two or more.

The dye is not particularly limited, and known dyes can be used. The chemical structure includes pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes can be used. In addition, multimers of these dyes may be used. Further, dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

When the resin composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the resin composition. 0.5 mass% or more is preferable, and, as for a lower limit, 1.0 mass% or more is more preferable. 60 mass% or less is preferable, and, as for the upper limit, 50 mass% or less is more preferable.
The content of the chromatic coloring agent is preferably 10 to 1000 parts by mass, and more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the near infrared absorbing organic pigment.
Further, the total amount of the chromatic coloring agent, the near infrared absorbing organic pigment and the other near infrared absorbing agent described above is preferably 1 to 80% by mass with respect to the total solid content of the resin composition. 5 mass% or more is preferable, and, as for a lower limit, 10 mass% or more is more preferable. 70 mass% or less is preferable, and, as for the upper limit, 60 mass% or less is more preferable. When the resin composition of the present invention contains two or more types of chromatic coloring agents, the total amount of them is preferably within the above range.

Moreover, it is also preferable that the resin composition of this invention does not contain a chromatic coloring agent substantially. Having substantially no chromatic coloring agent means that the content of the chromatic coloring agent is preferably 0.05% by mass or less with respect to the total solid content of the resin composition, and is 0.01% by mass or less Is more preferable, and it is further preferable not to contain a chromatic coloring agent.

<< Colorant that transmits infrared rays and blocks visible light >>
The resin composition of the present invention can also contain a coloring material that transmits infrared rays and blocks visible light (hereinafter, also referred to as a coloring material that blocks visible light).
In the present invention, the color material that blocks visible light is preferably a color material that absorbs light in the violet to red wavelength range. Further, in the present invention, the coloring material for blocking visible light is preferably a coloring material for blocking light having a wavelength of 450 to 650 nm. Further, it is preferable that the coloring material that blocks visible light is a coloring material that transmits light in the wavelength range of 900 to 1300 nm.
In the present invention, it is preferable that the coloring material that blocks visible light satisfy at least one of the following requirements (A) and (B).
(A): A black color is formed by a combination of two or more chromatic colorants, including two or more chromatic colorants.
(B): Contains an organic black colorant.

As the chromatic coloring agent, those mentioned above can be mentioned. Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds and the like, with bisbenzofuranone compounds and perylene compounds being preferred. As the bisbenzofuranone compounds, those described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication WO 2014/208348, JP-A-2015-525260, etc. Compounds are mentioned. Examples of commercially available products of bisbenzofuranone compounds include "Irgaphor Black" manufactured by BASF. As perylene compounds, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-1-170601, JP-A-2-32664 and the like, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika.

Examples of combinations of chromatic colorants in the case of forming a black color by the combination of two or more chromatic colorants include the following.
(1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant and a red colorant.
(2) An embodiment containing a yellow colorant, a blue colorant and a red colorant.
(3) An embodiment containing a yellow colorant, a purple colorant and a red colorant.
(4) An embodiment containing a yellow colorant and a purple colorant.
(5) An embodiment containing a green coloring agent, a blue coloring agent, a purple coloring agent and a red coloring agent.
(6) An embodiment containing a purple colorant and an orange colorant.
(7) An embodiment containing a green colorant, a purple colorant and a red colorant.
(8) An embodiment containing a green colorant and a red colorant.

When the resin composition of the present invention contains a coloring material that blocks visible light, the content of the coloring material that blocks visible light is preferably 60% by mass or less based on the total solid content of the resin composition, and 50 % By mass or less is more preferable, 30% by mass or less is more preferable, 20% by mass or less is even more preferable, and 15% by mass or less is particularly preferable. The lower limit may be, for example, 0.1% by mass or more and may be 0.5% by mass or more.
Moreover, it is also preferable that the resin composition of this invention does not contain the coloring material which shades visible light substantially. The content of the coloring material for blocking visible light is preferably 0.05% by mass or less with respect to the total solid content of the resin composition that substantially no coloring material for blocking visible light is contained, It is more preferable that it is 0.01 mass% or less, and it is still more preferable not to contain the coloring material which shields visible light.

<< pigment derivative >>
The resin composition of the present invention can contain a pigment derivative. The pigment derivative includes a compound in which at least one group selected from an acid group and a basic group is bonded to a dye skeleton. As a pigment derivative, the compound represented by Formula (B1) is preferable.

In formula (B1), P represents a dye skeleton, L represents a single bond or a linking group, X represents an acid group or a basic group, m represents an integer of 1 or more, n represents an integer of 1 or more In the case where m is 2 or more, the plurality of L and X may be different from each other, and when n is 2 or more, the plurality of X may be different from each other.

The dye skeleton represented by P includes pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, thiazine indigo dye skeleton, azo dye skeleton, quinophthalone Dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzoimidazole dye skeleton, and at least one selected from benzoimidazole dye skeleton And at least one selected from pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton and benzimidazolone dye skeleton is more preferable, and pyrrolopyrrole dye skeleton is more preferable. Element skeleton is particularly preferred.

The linking group represented by L is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms The group is preferable, may be unsubstituted, and may further have a substituent. As a substituent, the substituent T demonstrated by the formula (PP) mentioned above is mentioned.

Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imidic acid group. As the carboxamide group, a group represented by -NHCOR ^X1 is preferable. The sulfonic acid amide group is preferably a group represented by —NHSO ₂ R ^X2 . The imide group is preferably a group represented by —SO ₂ NHSO ₂ R ^X3 , —CONHSO ₂ R ^X4 , —CONHCOR ^X5 or —SO ₂ NHCOR ^X6 . Each of R ^X1 to R ^X6 independently represents a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group which R ^X1 to R ^X6 represent may further have a substituent. As the further substituent, the substituent T described in the above-mentioned formula (PP) can be mentioned, and a halogen atom is preferable, and a fluorine atom is more preferable.
An amino group is mentioned as a basic group which X represents.

As a pigment derivative, the compound of the following structure is mentioned. Further, JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, JP-A-3-153780. Patent Publication Nos. Hei 3-45662, Hei 4-285669, Hei 6-145546, Hei 6-212088, Hei 6-240158, Hei 10-30063, Compounds described in JP-A-10-195326, paragraph Nos. 0086 to 0098 of International Publication WO 2011/024896, paragraph 0063 to 0094 etc. of International Publication WO 2012/102399, a paragraph of International Publication WO 2016/035695 Compound described in No. 0053, a compound described in Patent No. 5299151 Can also have, the contents of which are incorporated herein.

When the resin composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. 3 mass parts or more are more preferable, and 5 mass parts or more are still more preferable. The upper limit value is more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less. When the content of the pigment derivative is in the above range, the dispersibility of the pigment can be enhanced, and the aggregation of the pigment can be efficiently suppressed. A pigment derivative may use only 1 type and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes said range.

<< solvent >>
The resin composition of the present invention can contain a solvent. Examples of the solvent include water and organic solvents. The solvent is basically not particularly limited as long as the solubility of each component and the coatability of the resin composition are satisfied, but the solvent is preferably selected in consideration of the coatability and safety of the resin composition.

Examples of the organic solvent include, for example, esters, ethers, ketones, aromatic hydrocarbons and the like. For details of these, reference can be made to paragraph No. 0223 of International Publication WO 2015/166779, the content of which is incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. In the present invention, the organic solvent may be used singly or in combination of two or more. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of solubility improvement. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene etc.) as a solvent due to environmental reasons etc. (For example, 50 mass ppm (parts per part of the total amount of organic solvent) or less, or 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 parts per billion or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

As a method of removing impurities such as metal from the solvent, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter can be mentioned. As a filter hole diameter of a filter used for filtration, 10 micrometers or less are preferred, 5 micrometers or less are more preferred, and 3 micrometers or less are still more preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or two or more types may be contained.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass, with respect to the total amount of the resin composition.

<< Curable compound >>
The resin composition of the present invention preferably contains a curable compound. As the curable compound, known compounds which can be crosslinked by a radical, an acid or heat can be used. As a hardenable compound, a polymeric compound, a compound which has an epoxy group, etc. are mentioned, for example. Examples of the polymerizable compound include compounds having a group having an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound is preferably a radical polymerizable compound.

(Polymerizable compound)
The polymerizable compound is preferably a compound having two or more groups having an ethylenically unsaturated bond, and more preferably a compound having three or more groups having an ethylenically unsaturated bond. The upper limit of the number of groups having an ethylenically unsaturated bond in the polymerizable compound is, for example, preferably 15 or less, more preferably 6 or less. The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound. The polymerizable compound may be in any of chemical forms such as monomers, prepolymers and oligomers, but monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3,000. The upper limit is more preferably 2000 or less, still more preferably 1500 or less. The lower limit is more preferably 150 or more, and still more preferably 250 or more. Moreover, it is also preferable that a polymeric compound is a compound which does not have molecular weight distribution substantially. Here, as the compound substantially having no molecular weight distribution, a compound having a degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.0 to 1.5 is preferable, 1.0 to 1.3 is more preferable. With regard to the polymerizable compounds, refer to the descriptions in paragraphs “0095 to 0108” of JP 2009-288705, paragraphs 0225 to 0258 in JP 2013-29760, and paragraphs 0254 to 0257 in JP 2008-292970. And their contents are incorporated herein.

Examples of the polymerizable compound include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku (manufactured by Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku) (A-DPH-12E; Shin-Nakamura Chemical Co., Ltd. product), and compounds having a structure in which these (meth) acryloyl groups are linked via ethylene glycol and / or propylene glycol residues ( For example, S commercially available from Sartmar 454, SR499) is preferable. These oligomer types can also be used. Moreover, as a polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available products of trifunctional (meth) acrylate compounds include Alonics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.

A polymerizable compound having an acid group can also be used as the polymerizable compound. By using the polymerizable compound having an acid group, the polymerizable compound in the unexposed area is easily removed at the time of development, and the generation of development residues can be suppressed. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, A carboxyl group is preferable. Commercially available products of the polymerizable compound having an acid group include Alonics M-510 and M-520 (manufactured by Toagosei Co., Ltd.).

The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mg KOH / g, more preferably 5 to 30 mg KOH / g. If the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the solubility in a developer is good, and if 40 mg KOH / g or less, it is advantageous in terms of production and handling. Furthermore, the curability is excellent.

A polymerizable compound having a caprolactone structure can also be used as the polymerizable compound. Moreover, the polymeric compound which has an alkylene oxy group can also be used as a polymeric compound. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. Hexafunctional (meth) acrylate compounds are more preferred. As a commercial item of a polymerizable compound having an alkyleneoxy group, for example, SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) having three isobutylene oxy groups Examples thereof include KAYARAD TPA-330 which is an acrylate.

As polymerizable compounds, urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and JP-B-58 The urethane compounds having an ethylene oxide-based skeleton described in JP-49,860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Also, use of addition polymerizable compounds having an amino structure or a sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Is also preferred. As a commercial item, UA-7200 (Shin-Nakamura Chemical Co., Ltd. product), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, Examples include AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).
Further, as the polymerizable compound, compounds described in JP-A-2017-48367, JP-A-5605891 and JP-A-6031807 can also be used.
In addition, as the polymerizable compound, 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. can also be used.

(Compound having an epoxy group)
The resin composition of the present invention can contain a compound having an epoxy group as a curable compound. The compound having an epoxy group is preferably a compound having two or more epoxy groups in one molecule. The compound having an epoxy group is preferably a compound having 2 to 100 epoxy groups. The upper limit of the epoxy group may be, for example, 10 or less, or 5 or less.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. It is more preferable that it is / equivalent.

The compound having an epoxy group may be a low molecular weight compound (for example, having a molecular weight of less than 1000) or a macromolecular compound (for example, having a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). . The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

Compounds having an epoxy group are described in paragraph Nos. 0034 to 0036 of JP2013-011869A, paragraph Nos. 0147 to 0156 of JP2014-043556A, and paragraph Nos. 0085 to 0092 of JP2014-089408A. The compounds can also be used. The contents of these are incorporated herein. Commercial products of compounds having an epoxy group include EHPE 3150 (manufactured by Daicel Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), Adekaglycylol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer) Etc.

In the resin composition of the present invention, the content of the curable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the resin composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less and still more preferably 40% by mass or less. The curable compounds may be used alone or in combination of two or more. When 2 or more types are used together, it is preferable that the total amount of them becomes the said range.

When the resin composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the resin composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The polymerizable compounds may be used alone or in combination of two or more. When using 2 or more types of polymeric compounds together, it is preferable that the total amount of them becomes said range.

When the resin composition of the present invention contains a compound having an epoxy group as a curable compound, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass with respect to the total solid content of the resin composition. . The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more. When 2 or more types are used together, it is preferable that the total amount of them becomes the said range.
When the resin composition of the present invention contains a polymerizable compound as a curable compound and a compound having an epoxy group, the mass ratio of the polymerizable compound to the compound having an epoxy group is the mass of the polymerizable compound: epoxy group The weight of the compound having the compound is preferably 100: 1 to 100: 400, more preferably 100: 1 to 100: 100, and still more preferably 100: 1 to 100: 50.

<< photoinitiator >>
The resin composition of the present invention can contain a photopolymerization initiator. In particular, when the resin composition of the present invention contains a polymerizable compound, it is preferable to contain a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.
As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound, a hexaarylbiimidazole, an oxime compound, an organic peroxide, Thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds and the like can be mentioned. The photopolymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole from the viewpoint of exposure sensitivity. Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, and oxime compounds, α-hydroxy ketone compounds, α-hydroxy ketone compounds More preferred are compounds selected from amino ketone compounds and acyl phosphine compounds, and more preferred are oxime compounds. As the photopolymerization initiator, the description in paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of commercially available α-hydroxy ketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (manufactured by BASF Corporation) and the like. Examples of commercially available α-amino ketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Corporation). Examples of commercially available products of acyl phosphine compounds include IRGACURE-819, DAROCUR-TPO (all manufactured by BASF Corp.) and the like.

As oxime compounds, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, compounds described in JP-A-2006-342166, J. C. S. Perkin II (1979, pp. 1653-1660), a compound described in J. Am. C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), a compound described in JP-A-2000-66385, Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-19766, Patent No. Examples thereof include compounds described in 6065596, compounds described in International Publication WO2015 / 152153, and compounds described International Publication WO2017 / 051680. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one and the like. As a commercial item, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, made by BASF Corporation), TR-PBG-304 (made by Changzhou strong electronic new material Co., Ltd.), Adeka Optomer N-1919 (Photopolymerization initiator 2 described in JP-A-2012-14052, manufactured by ADEKA Co., Ltd.). Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and being hard to discolor. Examples of commercially available products include Adeka ARKules NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. As specific examples of the oxime compound having a fluorene ring, compounds described in JP-A-2014-137466 can be mentioned. This content is incorporated herein.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3) and the like. The contents of these are incorporated herein.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. As specific examples of the oxime compound having a nitro group, compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, The compounds described in Paragraph Nos. 0007 to 0025 of Patent No. 4223071, Adeka ARKLS NCI-831 (manufactured by ADEKA Co., Ltd.) can be mentioned.

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication WO 2015/036910.

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

The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. Further, from the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or at a wavelength of 405 nm is preferably high, more preferably 1,000 to 300,000, and 2,000 to 300,000. Is more preferable, and 5,000 to 200,000 is particularly preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

In the present invention, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator. As specific examples of such a photopolymerization initiator, paragraph Nos. 0417 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015 / 004565, JP-A-2016-532675. , A dimer of the oxime compound described in paragraph Nos. 0039 to 0055 of International Publication WO 2017/033680, a compound (E) and a compound (G) described in JP-A-2013-522445, an international Examples thereof include Cmpd 1 to 7 described in published WO 2016/034963.

It is also preferable that the photopolymerization initiator contains an oxime compound and an α-amino ketone compound. By using the both in combination, developability is improved and a pattern having excellent rectangularity can be easily formed. When the oxime compound and the α-amino ketone compound are used in combination, the amount of the α-amino ketone compound is preferably 50 to 600 parts by mass, and more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass, with respect to the total solid content of the resin composition. The resin composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<< polymerization inhibitor >>
The resin composition of the present invention can contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts and the like). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the resin composition. The content of the polymerization inhibitor is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polymerizable compound. The upper limit is more preferably 0.5 parts by mass or less, still more preferably 0.2 parts by mass or less. The lower limit is more preferably 0.01 parts by mass or more, and still more preferably 0.03 parts by mass or more. The resin composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.

<< UV Absorbent >>
The resin composition of the present invention can contain an ultraviolet absorber. As the ultraviolet light absorber, conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds and the like can be used. The details of these can be referred to the descriptions of paragraphs 0052 to 0072 of JP 2012-208374 A and paragraphs 0317 to 0334 of JP 2013-68814 A, the contents of which are incorporated herein. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.). In addition, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) made by Miyoshi Yushi may be used. As a ultraviolet absorber, the compound represented by Formula (UV-1)-Formula (UV-3) is preferable, and the compound represented by Formula (UV-1) or Formula (UV-3) is more preferable, and a formula The compound represented by (UV-1) is more preferable.

In formula (UV-1), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0 to 4.
In formula (UV-2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or an alkyl group, and R ²⁰³ and R ²⁰⁴ each independently represent a substituent.
In formula (UV-3), each of R ³⁰¹ to R ³⁰³ independently represents a hydrogen atom or an alkyl group, and R ³⁰⁴ and R ³⁰⁵ each independently represent a substituent.

Specific examples of the compounds represented by Formula (UV-1) to Formula (UV-3) include the following compounds.

The content of the ultraviolet light absorber is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass, with respect to the total solid content of the resin composition. In the present invention, the ultraviolet absorber may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<< Silane coupling agent >>
The resin composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, functional groups other than hydrolyzable groups are preferably groups that form an interaction or bond with the resin to exhibit affinity. For example, a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group etc. are mentioned, and a (meth) acryloyl group and an epoxy group are preferable. Examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604, the contents of which are It is incorporated in the specification.

The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, and more preferably 0.05 to 10.0% by mass, with respect to the total solid content of the resin composition. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount of them is in the above range.

<< Surfactant >>
The resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The surfactant can be referred to in paragraphs [0238 to 0245] of International Publication WO 2015/166779, the content of which is incorporated herein.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the resin composition of the present invention, the liquid properties (in particular, the fluidity) can be further improved, and the liquid saving property can be further improved. In addition, a film with small thickness unevenness can also be manufactured.

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. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the composition is also good.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraph Nos. 0060 to 0064 of JP-A-2014-41318 (paragraph Nos. 0060 to 0064 of corresponding international publication 2014/17669) and the like, and the like. Examples thereof include the surfactants described in paragraphs 0117 to 0132 of JP2011-132503A, the contents of which are incorporated herein. As commercially available products of fluorine-based surfactants, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, R304, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Corporation), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, made by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, made by OMNOVA Corporation), etc. may be mentioned. .

Further, the fluorine-based surfactant is a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved when heat is applied to volatilize the fluorine atom is also preferable. It can be used. As such a fluorochemical surfactant, Megafuck DS series (Chemical Chemical Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS -21 can be mentioned.

In addition, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant. Such fluorine-based surfactants can be referred to the description of JP-A-2016-216602, the contents of which are incorporated herein.

As the fluorine-based surfactant, a block polymer can also be used. For example, compounds described in JP-A-2011-89090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) (meth) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorinated surfactant used in the present invention.

The weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of repeating units is mol%.

In addition, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. As specific examples, compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megaface RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. As the fluorine-based surfactant, compounds described in Paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company company), Tetronics 304, 701, 704, 901, 904, 150R1 (BAS). Manufactured by Nippon Steel Co., Ltd., Solsparse 20000 (manufactured by Nippon Lubrisol Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.) and the like.

As the cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 1 is used. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).

As silicone type surfactant, for example, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (more than Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) , BYK 307, BYK 323, BYK 330 (above, manufactured by Big Chemie Co., Ltd.), and the like.

The content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% to 1.0% by mass, with respect to the total solid content of the resin composition. The surfactant may be only one type, or two or more types. In the case of two or more types, it is preferable that the total amount of them is in the above range.

<< Antioxidant >>
The resin composition of the present invention can contain an antioxidant. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. The compound which has a substituent in the site | part (ortho position) adjacent to phenolic hydroxyl group is preferable. The aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, a phosphorus antioxidant can also be used conveniently for antioxidant. As a phosphorus antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl And the like]) oxy] ethyl] amine, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. And Adekastab AO-330 (above, ADEKA Co., Ltd.) and the like. Moreover, the polyfunctional hindered amine antioxidant described in International Publication WO17 / 006600 can also be used as an antioxidant.

The content of the antioxidant is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass, with respect to the total solid content of the resin composition of the present invention. One type of antioxidant may be used or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes said range.

<< Other ingredients >>
The resin composition of the present invention may, if necessary, be a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (eg, conductive particles, a filler, an antifoamer, Flame retardants, leveling agents, release accelerators, perfumes, surface tension modifiers, chain transfer agents, etc.) may be contained. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, in JP-A-2012-003225, paragraph No. 0183 or later (corresponding to US Patent Application Publication No. 2013/0034812, paragraph No. 0237), JP-A-2008-250074, paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein.
Moreover, the resin composition of the present invention may contain a latent antioxidant, if necessary. A latent antioxidant is a compound in which the site that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C., or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. In some cases, compounds in which the protective group is eliminated to function as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication WO 2014/021023, International Publication WO 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219. Examples of commercially available products include Adeka ARKRUZ GPA-5001 (manufactured by ADEKA Co., Ltd.) and the like.

The viscosity (23 ° C.) of the resin composition of the present invention is preferably in the range of 1 to 3000 mPa · s, for example, when a film is formed by coating. The lower limit is more preferably 3 mPa · s or more, and still more preferably 5 mPa · s or more. The upper limit is more preferably 2000 mPa · s or less, and still more preferably 1000 mPa · s or less.

The thixotropic property of the resin composition of the present invention is preferably low. The thixotropic property can be represented by an index of Ti value. For example, in the viscosity measured using an E-type viscometer (RE 85L manufactured by Toki Sangyo Co., Ltd.), η (20 rpm) / η when the viscosities of rotation are 20 rpm and 50 rpm are η (20 rpm) and η (50 rpm), respectively. The value of (50 rpm) is taken as the Ti value. The closer the Ti value is to 1, the lower the thixotropic property. Regarding the Ti value obtained by such a measurement method, the Ti value at 23 ° C. is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, and 0.9 More preferably, it is -1.1.

There is no particular limitation on the container for containing the resin composition of the present invention, and a known container can be used. In addition, as a storage container, a multi-layered bottle in which the inner wall of the container is made of a resin of six types and six layers, and a bottle having a seven-layer structure of six types of resin for the purpose of suppressing contamination with impurities in raw materials and resin compositions. It is also preferred to use As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.

The application of the resin composition of the present invention is not particularly limited. For example, it can be preferably used for forming a near infrared cut filter or the like. Moreover, the resin composition of this invention can also form the near-infrared penetration filter which can permeate | transmit only the near-infrared light more than a specific wavelength by containing the color material which shields visible light. Therefore, the resin composition of the present invention can also be preferably used for formation of a near infrared ray transmission filter and the like.

<Method of Preparing Resin Composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing a resin composition, all components may be simultaneously dissolved or dispersed in a solvent to prepare a resin composition, and if necessary, two or more solutions or dispersions in which each component is appropriately blended. May be prepared in advance and mixed at the time of use (at the time of application) to prepare a resin composition.

Further, since the resin composition of the present invention contains a pigment, it is preferable to include a process of dispersing the pigment. In the process of dispersing the pigment, mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. In addition, the process and the dispersing machine for dispersing the pigment are the dispersion technology and industrial application centering on “Dispersion Technology Complete, Information Technology Co., Ltd. issued July 15, 2005” and “suspension (solid / liquid dispersion system)” The process and the dispersing machine described in Paragraph No. 0022 of JP-A-2015-157893, published on October 10, 1978, can be suitably used.

In preparation of the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign substances and reducing defects. As a filter, if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular. For example, a fluorocarbon resin such as polytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon (for example, nylon-6, nylon-6, 6), or a polyolefin resin such as polyethylene or polypropylene (PP) Filters made of materials such as polyolefin resins of Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore diameter of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the pore diameter of the filter is in the above range, fine foreign particles can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specifically, filter cartridges of SBP type series (SBP 008 and the like), TPR type series (TPR 002, TPR 005 and the like), and SHPX type series (SHPX 003 and the like) manufactured by Loki Techno, Inc. can be mentioned.

When using filters, different filters (eg, a first filter, a second filter, etc.) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
Moreover, you may combine the filter of a different hole diameter within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is selected from various filters provided by Nippon Pall Co., Ltd. (DFA4201 NXEY etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (old Japan Microlith Co., Ltd.) or Kitz Micro Filter Co., Ltd. can do.
The second filter can be made of the same material as the first filter.
In addition, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed with the second filter.

<Membrane>
Next, the film of the present invention will be described. The film of the present invention is formed using the above-described resin composition of the present invention. The film of the present invention can be preferably used for near infrared cut filters, near infrared transmission filters, and the like. The film of the present invention may have a pattern or may be a film having no pattern (flat film).

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

When the film of the present invention is used as a near infrared cut filter, the film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 650 to 1400 nm. The maximum absorption wavelength is preferably 1200 nm or less, more preferably 1000 nm or less, and still more preferably 780 nm or less. 700 nm or more is preferable and, as for a maximum absorption wavelength, 720 nm or more is more preferable. It is particularly preferred that the film of the present invention has a maximum absorption wavelength in the range of 650 to 780 nm.

When the film of the present invention is used as a near infrared cut filter, the film of the present invention preferably has an average transmittance of 70% or more, more preferably 80% or more, and still more preferably 85% or more. , 90% or more is particularly preferable. In addition, the transmittance is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more in the whole range of wavelengths of 400 to 550 nm. In addition, the transmittance at at least one point in the wavelength range of 650 to 1400 nm is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less.

The films of the present invention can also be used in combination with color filters containing chromatic colorants. A color filter can be manufactured using a coloring composition containing a chromatic coloring agent. The chromatic coloring agents include the above-mentioned chromatic coloring agents. The coloring composition can further contain a resin, a curable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet light absorber, and the like. The details of these include the materials mentioned above, which can be used.

When the film of the present invention is used as a near infrared cut filter and is used in combination with the film of the present invention and a color filter, it is preferable that a color filter be disposed on the optical path of the film of the present invention. For example, the film of the present invention and a color filter can be laminated and used as a laminate. In the laminate, the film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention may be formed on a support other than the support on which the color filter is formed. Between the film and the color filter, another member (for example, a microlens, a flattening layer, etc.) constituting the solid-state imaging device may be interposed.

The film of the present invention can also be used by laminating on a support. As a support body, semiconductor base materials, such as a silicon | silicone, and a transparent base material are mentioned. The transparent substrate is not particularly limited as long as it is made of a material that can transmit at least visible light. For example, the base material comprised with materials, such as glass, a crystal | crystallization, resin, is mentioned. Glass is preferred as the material of the transparent substrate. That is, the transparent substrate is preferably a glass substrate. Examples of the glass include soda lime glass, borosilicate glass, non-alkali glass, quartz glass, copper-containing glass and the like. Examples of the copper-containing glass include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercially available products of copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.) and the like. Examples of crystals include quartz, lithium niobate, sapphire and the like. Examples of the resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene and ethylene vinyl acetate copolymer, acrylic resins such as norbornene resin, polyacrylate and polymethyl methacrylate, urethane resin and vinyl chloride resin And fluorine resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl alcohol resins and the like. Moreover, in order to improve the adhesiveness of a support body and the film | membrane of this invention, the base layer etc. may be provided in the surface of a support body.

In the present invention, the near-infrared cut filter means a filter that transmits light in the visible region (visible light) and blocks at least part of light in the near-infrared region (near infrared). . The near infrared cut filter may transmit all light of wavelengths in the visible region, and among light of wavelengths in the visible region, transmits light of a specific wavelength region and blocks light of a specific wavelength region It may be Further, in the present invention, the color filter means a filter that transmits light in a specific wavelength range and blocks light in a specific wavelength range, out of light of wavelengths in the visible range. Further, in the present invention, the near-infrared transmission filter means a filter that shields visible light and transmits at least a part of near-infrared light.

The film of the present invention can be used in various devices such as solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices.

<Laminate>
The laminate of the present invention has the film of the present invention on a support. As a support body, a transparent base material is mentioned, It is preferable that it is a glass base material, and it is more preferable that it is a glass base material containing copper. In particular, when the film of the present invention is used as a near infrared cut filter, a wide range of near infrared light can be blocked by laminating the film of the present invention on a copper-containing glass substrate.

<Near infrared cut filter>
Next, the near infrared cut filter of the present invention will be described. The near infrared cut filter of the present invention has the above-described film of the present invention. In the near infrared cut filter of the present invention, the above-mentioned film of the present invention may be laminated on a support. This near infrared cut filter can be preferably used for the application of a solid-state imaging device. The support includes a transparent substrate. Moreover, in order to improve the adhesiveness of a support body and the film | membrane of this invention, the base layer etc. may be provided in the surface of a support body. When the film of the present invention is used by being laminated on a glass substrate, the film of the present invention is a film formed by using a composition containing a silane coupling agent and / or a compound having an epoxy group. Is preferred. According to this aspect, the adhesion between the glass substrate and the film of the present invention can be further strengthened.

In the near-infrared cut filter of the present invention, when the above-mentioned film of the present invention is laminated on a support, the near-infrared cut filter may further have a dielectric multilayer film in addition to the film of the present invention. preferable. According to this aspect, it is possible to provide a near-infrared cut filter having a wide viewing angle and excellent near-infrared shielding properties. The dielectric multilayer film may be provided on one side or both sides of the support. When the dielectric multilayer film is provided on one side of the support, the manufacturing cost can be reduced. In the case where the dielectric multilayer film is provided on both sides of the support, it is possible to obtain a near infrared cut filter which has high strength and is less likely to be warped. In addition, the dielectric multilayer film may or may not be in contact with the support. The near infrared cut filter of the present invention preferably has the film of the present invention between the transparent substrate and the dielectric multilayer film, and the film of the present invention is in contact with the dielectric multilayer film. With such a configuration, the film of the present invention is shielded from oxygen and humidity by the dielectric multilayer film, and the light resistance and the moisture resistance of the near infrared cut filter are improved. Furthermore, a near-infrared cut filter having a wide viewing angle and excellent near-infrared shielding properties can be easily obtained.

In the present invention, the dielectric multilayer film is a film that shields infrared rays by utilizing the effect of light interference. Specifically, it is a film formed by alternately laminating two or more dielectric layers (high refractive index material layers and low refractive index material layers) having different refractive indexes. As a material forming the high refractive index material layer, it is preferable to use a material having a refractive index of 1.7 or more (preferably 1.7 to 2.5). For example, a small amount of titanium oxide, tin oxide and / or cerium oxide, etc., containing titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide as a main component The thing is mentioned. As a material forming the low refractive index material layer, it is preferable to use a material having a refractive index of 1.6 or less (preferably 1.2 to 1.6). For example, silica, alumina, lanthanum fluoride, magnesium fluoride and sodium aluminum hexafluoride can be mentioned. The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably a thickness of 0.1 λ to 0.5 λ of the wavelength λ (nm) of infrared light to be blocked. The total number of laminations of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 2 to 100, more preferably 2 to 60, and still more preferably 2 to 40. The details of the dielectric multilayer film can be referred to the description in paragraph Nos. 0255 to 0259 of JP-A-2014-41318, the contents of which are incorporated herein.

In the case where the near infrared cut filter of the present invention has the film of the present invention, a support, and a dielectric multilayer film, the order of lamination of the layers is not particularly limited. For example, the following (1) to The layer structure of 10) is mentioned. Hereinafter, the support is referred to as layer A, the film of the present invention as layer B, and the dielectric multilayer film as layer C.
(1) Layer A / layer B / layer C
(2) Layer A / layer C / layer B
(3) Layer C / layer A / layer B
(4) Layer B / layer A / layer B / layer C
(5) Layer C / layer A / layer B / layer C
(6) Layer B / layer A / layer C / layer B
(7) Layer C / layer A / layer C / layer B
(8) Layer C / layer B / layer A / layer B / layer C
(9) layer C / layer B / layer A / layer C / layer B
(10) Layer B / layer C / layer A / layer C / layer B

The near-infrared cut filter of the present invention may further have a copper-containing layer, an ultraviolet absorbing layer, and the like in addition to the film of the present invention. When the near infrared cut filter further includes a copper-containing layer, a near infrared cut filter having a wide viewing angle and excellent near infrared shielding properties can be easily obtained. Further, the near infrared cut filter further has an ultraviolet absorbing layer, whereby the near infrared cut filter having excellent ultraviolet shielding properties can be obtained. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO 2015/099060 can be referred to, the contents of which are incorporated herein. Examples of the layer containing copper include a layer formed using a composition containing a copper complex.

<Near infrared ray transmission filter>
Next, the near infrared ray transmission filter of the present invention will be described. The near infrared ray transmission filter of the present invention has the above-described film of the present invention. As a near-infrared permeation | transmission filter, the filter which light-shields visible light and permeate | transmits the light of wavelength 900 nm or more is mentioned, for example. As a specific example, the spectral characteristic in which the maximum value of the transmittance of light in the wavelength range of 400 to 830 nm is 20% or less and the minimum value of the transmittance of light in the wavelength range of 1000 to 1300 nm is 80% or more The filter which it has is mentioned. In the near infrared cut filter of the present invention, the above-mentioned film of the present invention may be laminated on a support. As a support body, semiconductor base materials, such as a silicon | silicone mentioned above, and a transparent base material are mentioned. It is also preferable that the near infrared ray transmission filter of the present invention has a pixel using the film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black and colorless. In the near-infrared transmitting filter of the present invention, the above-mentioned film of the present invention may have a pattern or may be a film having no pattern (flat film).

<Method of producing membrane>
Next, the method for producing the membrane of the present invention will be described. The film of the present invention can be produced through the step of applying the resin composition of the present invention.

In the method for producing a film of the present invention, the resin composition of the present invention is preferably coated on a support. Examples of the support include semiconductor substrates such as silicon and the above-mentioned transparent substrates. An organic film, an inorganic film, etc. may be formed in these base materials. Examples of the material of the organic film include the above-mentioned resins. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In addition, a black matrix may be formed on the support to separate each pixel. In addition, the support may be provided with a subbing layer, if necessary, for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate. Moreover, when using a glass base material as a support body, it is preferable to form an inorganic membrane on a glass base material, or to carry out the de-alkali treatment of the glass base material, and to use.

A known method can be used as a method of applying the resin composition. For example, dropping method (drop casting); slit coating method; spraying method; roll coating method; spin coating method (spin coating); cast coating method; slit and spin method; pre-wet method (for example, JP 2009-145395A) Methods described in the publication); Ink jet (for example, on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer methods using a mold or the like; nanoimprint methods and the like. The application method in the inkjet is not particularly limited, and for example, the method (in particular, page 115-) disclosed in "Spread and usable inkjet-unlimited possibilities in patents-published in February 2005, resident Betechno Research" Methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. It can be mentioned. Moreover, regarding the coating method of the resin composition, the descriptions of International Publication WO 2017/030174 and International Publication WO 2017/018419 can be referred to, and the contents thereof are incorporated in the present specification.

The composition layer formed by applying the resin composition may be dried (prebaked). In the case of forming a pattern by a low temperature process, the prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less. The lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more. By performing the prebake temperature at 150 ° C. or less, for example, when the photoelectric conversion film of the image sensor is made of an organic material, the characteristics of the organic material can be more effectively maintained. The pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Prebaking can be performed with a hot plate, an oven, or the like.

After prebaking, heat treatment (postbaking) may be further performed. When post-baking, the post-baking temperature is preferably, for example, 100 to 240.degree. From the viewpoint of film curing, 180 to 240 ° C. is more preferable. The post-baking time is preferably 2 to 10 minutes, more preferably 4 to 8 minutes. Post baking can be performed with a hot plate, an oven or the like.

The method for producing a film of the present invention may further include the step of forming a pattern. Examples of the pattern formation method include a pattern formation method using a photolithography method and a pattern formation method using a dry etching method. When the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the process of forming a pattern will be described in detail.

(When forming a pattern by photolithography)
In the pattern formation method by the photolithography method, a step of exposing the composition layer formed by applying the resin composition of the present invention in a pattern (exposure step) and developing and removing the composition layer of the unexposed area And the step of forming a pattern (developing step).

<< exposure step >>
In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured. As radiation (light) which can be used at the time of exposure, ultraviolet rays such as g-line and i-line are preferable, and i-line is more preferable. Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2, most preferably 0.08 ~ 0.5J / cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed under the atmosphere, for example, under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (eg, 15% by volume, 5% by volume, substantially oxygen free , And may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) in which the oxygen concentration exceeds 21% by volume. Also, the exposure illuminance can be set appropriately, and can usually be selected from the range of 1000 W / m ² to 100000 W / m ² (for example, 5000 W / m ² , 15000 W / m ² , 35000 W / m ² ) . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.

<< Development Process >>
Next, the composition layer in the unexposed area of the composition layer after exposure is developed and removed to form a pattern. The development removal of the composition layer in the unexposed area can be carried out using a developer. As a result, the composition layer in the unexposed area in the exposure step is eluted into the developer, and only the photocured area remains on the support. As a developing solution, an alkaline developing solution which does not damage the solid-state imaging device or circuit of the base is desirable. The temperature of the developing solution is preferably, for example, 20 to 30.degree. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying the developer anew may be repeated several times.

As an alkaline agent used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7 -Organic alkaline compounds such as undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate Um, sodium silicate, and inorganic alkaline compound such as sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight in terms of the environment and safety. As the developer, an alkaline aqueous solution obtained by diluting such an alkaline agent with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Also, a surfactant may be used in the developer. As an example of surfactant, the surfactant mentioned above is mentioned and nonionic surfactant is preferable. The developer may be prepared once as a concentrate and diluted to a concentration required for use, from the viewpoint of transportation and storage convenience. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) by a pure water after image development.

It is also possible to carry out heat treatment (post bake) after drying after development. Post-baking is a post-development heat treatment to complete film curing. When post-baking, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 180 to 230 ° C. is more preferable.

(When patterning by dry etching)
Patterning by the dry etching method cures the composition layer on the support to form a cured layer, and then forms a patterned photoresist layer on the cured layer, and then is patterned. It can carry out by methods, such as dry-etching using etching gas with respect to a hardened | cured material layer, using a photoresist layer as a mask. In formation of a photoresist layer, it is preferable to perform a prebaking process further. In particular, as the formation process of the photoresist layer, a mode in which heat treatment after exposure and heat treatment (post-bake treatment) after development are preferably performed. For the pattern formation by the dry etching method, the description in paragraphs “0010” to “0067” of JP 2013-064993 can be referred to, and the contents thereof are incorporated in the present specification.

<Solid-state imaging device>
The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device of the present invention is the configuration having the film of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. For example, the following configuration may be mentioned.

A light shield comprising a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon and the like on the support, light shielding made of tungsten or the like in which only the light receiving portion of the photodiode and the transfer electrodes are opened. A device protection film made of silicon nitride or the like which has a film formed on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode, and has the film of the present invention on the device protection film is there. Furthermore, a configuration having a condensing means (for example, a micro lens etc. hereinafter the same) on the device protective film and under the film of the present invention (closer to the support), or on the film of the present invention It may be a configuration having means. In addition, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a grid shape by partition walls. The partition walls in this case preferably have a lower refractive index than each pixel. As an example of an imaging device having such a structure, devices described in JP 2012-227478 A and JP 2014-179577 A can be mentioned.

<Image display device>
The image display apparatus of the present invention includes the film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For the definition and details of the image display device, for example, "Electronic display device (authored by Akio Sasaki, published by Industry Research Association, 1990)", "Display device (authored by Ibuki Jun, industrial book, Ltd.) Etc.). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”. There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology." The image display device may have a white organic EL element. It is preferable that it is a tandem structure as a white organic EL element. JP-A-2003-45676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development-High luminance, high accuracy, long life, know-how collection", about the tandem structure of organic EL elements, Technical Information Association, It is described on pages 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element is preferably one having strong maximum emission peaks in the blue region (430 to 485 nm), the green region (530 to 580 nm) and the yellow region (580 to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferable.

<Infrared sensor>
The infrared sensor of the present invention has the above-described film of the present invention. The configuration of the infrared sensor of the present invention is the configuration having the film of the present invention, and there is no particular limitation as long as the configuration functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described using the drawings.
In FIG. 1, reference numeral 110 denotes a solid-state imaging device. A near-infrared cut filter 111 and a near-infrared transmission filter 114 are disposed on the imaging region of the solid-state imaging device 110. Further, on the near infrared cut filter 111, a color filter 112 is laminated. A microlens 115 is disposed on the incident light hν side of the color filter 112 and the near infrared ray transmission filter 114. A planarization layer 116 is formed to cover the microlenses 115.

The near infrared cut filter 111 can be formed using the resin composition of the present invention. The spectral characteristics of the near infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) to be used.

The color filter 112 is a color filter in which a pixel for transmitting and absorbing light of a specific wavelength in the visible region is formed, and is not particularly limited, and a conventionally known color filter for forming a pixel can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraph Nos. 0214 to 0263 of JP-A-2014-043556 can be referred to, the contents of which are incorporated herein.

The characteristic of the near infrared ray transmission filter 114 is selected in accordance with the emission wavelength of the infrared LED to be used. For example, when the emission wavelength of the infrared LED is 850 nm, the near-infrared transmission filter 114 has a maximum light transmittance of 20% or less (preferably 15% or less) in the wavelength range of 400 to 750 nm. More preferably, it is 10% or less, and the minimum value of light transmittance in the thickness direction in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more) preferable. Also, for example, when the emission wavelength of the infrared LED is 940 nm, the near-infrared transmission filter 114 has a maximum value of 20% or less (preferably 15%) in the wavelength range of 400 to 830 nm of the light transmittance in the thickness direction. Or less, more preferably 10% or less), and the minimum value of light transmittance in the thickness direction in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more) Is preferred.

In the infrared sensor shown in FIG. 1, a near infrared cut filter (another near infrared cut filter) different from the near infrared cut filter 111 may be further disposed on the planarization layer 116. Other near infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. The details of these may be mentioned above. In addition, as another near infrared cut filter, a dual band pass filter may be used. Further, in the infrared sensor shown in FIG. 1, the positions of the near infrared cut filter 111 and the color filter 112 may be interchanged. In addition, another layer may be disposed between the solid-state imaging device 110 and the near-infrared cut filter 111 and / or between the solid-state imaging device 110 and the near-infrared transmission filter 114. As another layer, the organic substance layer etc. which were formed using the composition containing a polymeric compound, resin, and a photoinitiator are mentioned. In addition, a planarization layer may be formed on the color filter 112.

Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

[Test Example 1]
<Production of near infrared absorbing organic pigment>
The pigment, grinding agent and caking agent described in the following table are charged into Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the temperature of the kneaded material in the apparatus is the temperature (milling temperature) described in the following table The temperature was controlled so as to become k and the kneading time was as described in the following table.
The kneaded product after the kneading and polishing is washed with 10 L of water at 24 ° C. to remove the grinding agent and the caking agent, and dried at 80 ° C. for 24 hours in a heating oven to obtain a near infrared absorbing organic pigment as a milling pigment. Pigments (Examples 1 to 5) were obtained.
Comparative Example 1 is a near-infrared-absorbing organic pigment not subjected to milling treatment.

The materials described in the above table are as follows.
(Pigment)
Pigment 1: Compound of the following structure (it is a near infrared absorbing organic pigment)

Pigment 2: Compound of the following structure (it is a near infrared absorbing organic pigment)

(Milling agent)
Grinding agent 1: Neutral anhydrous mirabilite E (average particle size (50% diameter based on volume (D 50)) = 20 μm, manufactured by Mitajiri Chemical Co., Ltd.)
Grinding agent 2: Nakuru UM (average particle size (50% diameter based on volume (D 50)) = 50 μm, manufactured by Nikai Salt Co., Ltd.)
(Caking agent)
DEG: Diethylene glycol

<Evaluation>
(Measurement of average primary particle size of near infrared absorbing organic pigment)
The primary particles of the near-infrared-absorbing organic pigment of Examples 1 to 5 and Comparative Example 1 were observed by a transmission electron microscope, and the average primary particle size was determined from the obtained photograph. Specifically, the projection area of the primary particles of the near infrared absorbing organic pigment is determined, and the circle equivalent diameter corresponding thereto is taken as the primary particle diameter of the near infrared absorbing organic pigment. The arithmetic mean value of the primary particle diameter of primary particles of 400 near infrared absorbing organic pigments was taken as the average primary particle diameter.

(Average long and short side ratio of primary particles of near infrared absorbing organic pigment)
The primary particles of the near-infrared-absorbing organic pigment of Examples 1 to 5 and Comparative Example 1 were observed by a transmission electron microscope, and the average long / short side ratio was determined from the obtained photograph. Specifically, the ratio (short side / long side) of the short side to the long side of the primary particle of the near-infrared-absorbing organic pigment was determined from the projected photograph to calculate the long side ratio.

(Measurement of powder X-ray diffraction spectrum of near infrared absorbing organic pigment)
As a measuring apparatus, using a sample horizontal type X-ray diffraction apparatus RINT-TTR III manufactured by Rigaku, diffraction angle 2θ = 5 ° to 55 °, voltage 50 kV, current 300 mA, scan speed 4 ° / min, step interval 0.1 Powder X-ray diffraction spectra of the near-infrared-absorbing organic pigments of Examples 1 to 5 and Comparative Example 1 were measured under the conditions of slits (scattering 0.05 mm, divergence 10 mm, light reception 0.15 mm).

(Measurement of crystallinity)
In the powder X-ray diffraction spectrum, a baseline connecting the lowest point in the region of diffraction angles 2θ of 5 to 15 ° and the lowest point in the region of 25 to 35 ° is a baseline. The crystallinity degree was measured using the following formula using the spectrum correction value which subtracted the value of the baseline from.
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from crystals in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more, and Ia is derived from amorphous in the powder X-ray diffraction spectrum It is the maximum value of the peak diffraction intensity.
Note that a peak having a full width at half maximum of 1 ° or less is defined as a peak derived from a crystal. Further, a peak whose full width at half maximum exceeds 3 ° is taken as a peak derived from amorphous.

(Spectroscopic characteristics)
3.13 parts by mass of the near-infrared-absorbing organic pigment of Examples and Comparative Examples, 0.63 parts by mass of Pigment Derivative 1, 2.25 parts by mass of Dispersant 1, and propylene glycol monomethyl ether acetate (PGMEA) 44 parts by mass and 66 parts by mass of zirconia beads having a diameter of 0.5 mm were mixed and subjected to dispersion treatment for 120 minutes with a paint shaker, and then the zirconia beads were separated by decantation to prepare a dispersion.

Pigment derivative 1: The following compound

Dispersant 1: Resin of the following structure (weight average molecular weight = 21000). The numerical value attached to the main chain represents the molar ratio of repeating units, and the numerical value attached to the side chain represents the number of repeating units.

10 parts by mass of the dispersion using the near-infrared-absorbing organic pigment of the examples and comparative examples obtained above and 10 parts by mass of resin A (Cyclomer P (ACA) 230AA manufactured by Daicel Co., Ltd.) are mixed. The sample solution was prepared.
The sample solution was applied on a glass substrate by spin coating so that the film thickness after application was 0.3 μm, and then heated at 100 ° C. for 2 minutes using a hot plate. Next, exposure was performed at 1000 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.). Furthermore, it heated at 220 degreeC for 5 minutes using the hotplate, and formed the film. With respect to the substrate on which the film is formed, maximum absorption wavelength, absorbance A _{max at} maximum absorption wavelength, absorbance A _{550 at} wavelength 550 nm, maximum absorption using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corp.) absorbance a ₁ in 50nm shorter wavelength were respectively measured than the wavelength, which is the ratio between the absorbance a ₅₅₀ and the absorbance a _{_max} a ₅₅₀ / a _max, which is the ratio between the absorbance a ₁ and absorbance a _max a ₁ / a _max Were calculated respectively. The smaller the value of A ₅₅₀ / A _max, the better the visible transparency. Further, as the value of A ₁ / A _max is closer to 1, it means that the absorptivity in a wide range near the maximum absorption wavelength is excellent, and the near infrared ray shielding properties are excellent.

As shown in the above table, the near-infrared-absorbing organic pigment of the example has characteristics that the absorbance ratio A ₅₅₀ / A _max is smaller than that of Comparative Example 1, and the absorbance ratio A ₁ / A _max is high, The near infrared absorbing organic pigment of the example was also excellent in near infrared shielding while having excellent visible transparency.

[Test Example 2]
<Preparation of pigment dispersion>
(Pigment dispersion liquid A-1)
The following raw materials are mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.)) using zirconia beads of 0.3 mm in diameter for 3 hours to obtain a pigment Dispersion A-1 was prepared.
Near-infrared absorbing organic pigment of Example 1 5.35 parts by mass Pigment derivative 1 2.15 parts by mass Dispersing agent 1 6.0 parts by mass Propylene glycol methyl ether acetate (PGMEA)・ 86.5 parts by mass

(Pigment dispersion liquid A-2)
A pigment dispersion A-2 was prepared in the same manner as the pigment dispersion A-1, except that the near infrared absorbing organic pigment of Example 2 was used instead of the near infrared absorbing organic pigment of Example 1.

(Pigment dispersion liquid A-3)
A pigment dispersion A-3 was prepared in the same manner as the pigment dispersion A-1, except that the near infrared absorbing organic pigment of Example 3 was used instead of the near infrared absorbing organic pigment of Example 1.

(Pigment dispersion A-4)
A pigment dispersion A-4 was prepared in the same manner as the pigment dispersion A-1, except that the near infrared absorbing organic pigment of Example 4 was used instead of the near infrared absorbing organic pigment of Example 1.

(Pigment Dispersion A-5)
A pigment dispersion A-5 was prepared in the same manner as the pigment dispersion A-1, except that the near infrared absorbing organic pigment of Example 5 was used instead of the near infrared absorbing organic pigment of Example 1.

(Pigment dispersion liquid A-6)
A pigment dispersion A-6 was prepared in the same manner as the pigment dispersion A-1, except that the near infrared absorbing organic pigment of Comparative Example 1 was used instead of the near infrared absorbing organic pigment of Example 1.

<Preparation of Resin Composition>
The resin composition was prepared by mixing the raw materials described in the following table.

The raw materials described in the above table are as follows.
Pigment Dispersion Solutions A-1 to A-6: Pigment Dispersion Solutions A-1 to A-6 Described Above
Color materials B-1 and B-2: compounds of the following structures

Alkali-soluble resin 1: Resin of the following structure (Mw = 41000, the numerical value attached to the main chain is a molar ratio)

Resin 1: Resin synthesized by the following method (a propylene glycol monomethyl ether acetate solution having a solid concentration of 35% by mass)
14 g of benzyl methacrylate, 12 g of N-phenylmaleimide, 15 g of 2-hydroxyethyl methacrylate, 10 g of styrene and 20 g of methacrylic acid are dissolved in 200 g of propylene glycol monomethyl ether acetate, and further 3 g of 2,2'-azoisobutyronitrile and α-methyl 5 g of styrene dimer was charged. After purging the inside of the reaction vessel with nitrogen, it was heated at 80 ° C. for 5 hours while stirring and bubbling nitrogen to synthesize resin 1.
Additive 1: Bis- (4-tert-butylphenyl) iodonium nonafluorobutane sulfonate Epoxy compound 1: EPICLON N-695 (manufactured by DIC Corporation)
Polymerizable compound 4: Reitotop C-357 (a propylene glycol monomethyl ether acetate solution having a solid concentration of 20% by mass) manufactured by Gunei Chemical Industry Co., Ltd.
Surfactant 1: The following compound (Mw = 14000). In the following formulas,% indicating the proportion of repeating units is mol%.

Surfactant 2: FTX-218D (manufactured by Neos Co., Ltd.)
Organic solvent 1: Propylene glycol methyl ether acetate Organic solvent 2: Cyclohexanone

<Fabrication of membrane>
The resin composition was applied on a glass substrate by spin coating so that the film thickness after application was 0.3 μm, and then heated at 100 ° C. for 2 minutes using a hot plate. Next, exposure was performed at 1000 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.). Furthermore, it heated at 220 degreeC for 5 minutes using the hotplate, and formed the film.

<Evaluation of spectral characteristics>
With respect to the substrate on which the film is formed, maximum absorption wavelength, absorbance A _{max at} maximum absorption wavelength, absorbance A _{550 at} wavelength 550 nm, maximum absorption using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corp.) absorbance a ₁ in 50nm shorter wavelength were respectively measured than the wavelength, which is the ratio between the absorbance a ₅₅₀ and the absorbance a _{_max} a ₅₅₀ / a _max, which is the ratio between the absorbance a ₁ and absorbance a _max a ₁ / a _max Were calculated respectively. The smaller the value of A ₅₅₀ / A _max, the better the visible transparency. Further, as the value of A ₁ / A _max is closer to 1, it means that the absorptivity in a wide range near the maximum absorption wavelength is excellent, and the near infrared ray shielding properties are excellent. Each of Examples 101 to 105 and Comparative Example 101 had the maximum absorption wavelength in the range of 650 to 780 nm.

<Evaluation of viewing angle dependency>
The incident angle is changed to be vertical (angle 0 degree) and 40 degrees with respect to the film surface, and in the visible region to the near infrared region of wavelengths of 600 nm or more, The shift amount was evaluated according to the following criteria.
A: shift amount of wavelength less than 5 nm B: shift amount of wavelength not less than 5 nm and less than 20 nm C: shift amount of wavelength not less than 20 nm

As shown in the above table, the example had a value of A ₅₅₀ / A _max smaller than that of the comparative example, and A ₁ / A _max had a value closer to one. For this reason, the example was higher in visible transparency than the comparative example, and was excellent in near-infrared shielding properties. Furthermore, the viewing angle dependency was also good.

[Test Example 3]
<Preparation of pigment dispersion>
The following raw materials are mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.)) using zirconia beads of 0.3 mm in diameter, and Pigment dispersions B-1 to B-7 were prepared.

(Pigment dispersion liquid B-1)
18. Mixed pigment of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139 (red pigment: yellow pigment = 12.5: 5.5 (mass ratio)) ... 18. 0 parts by mass Dispersant 1 ... 8.1 parts by mass Propylene glycol methyl ether acetate (PGMEA) ... 73.1 parts by mass

(Pigment Dispersion B-2)
Mixed pigment of blue pigment (CI Pigment Blue 15: 6) and purple pigment (CI Pigment Violet 23) (blue pigment: violet pigment = 14.3: 3.7 (mass ratio)) -18.0 parts by mass Dispersant 1-3.1 parts by mass Alkali-soluble resin 2-5.0 parts by mass Cyclohexanone-31.2 parts by mass PGMEA-42.7 parts by mass

(Pigment Dispersion B-3)
Blue pigment (CI Pigment Blue 15: 6) ... 12.5 parts by mass Dispersant 2 ... 4.4 parts by mass PGMEA ... 83.01 parts by mass

(Pigment dispersion liquid B-4)
Yellow pigment (CI Pigment Yellow 139) ... 11.0 parts by mass Dispersant 2 ... 4.4 parts Pigment derivative 2 ... 1.59 parts by mass PGMEA ... 83.01 Parts by mass

(Pigment Dispersion B-5)
Blue pigment (CI Pigment Blue 15: 6) ... 10.0 parts by mass Purple pigment (CI Pigment Violet 23) ... 2.5 parts by mass Dispersant 2 ... 4.4 mass Part PGMEA · · 83.01 parts by mass

(Pigment dispersion liquid B-6)
Black pigment (Irgaphor Black) ... 12.59 parts by mass Dispersant 3 ... 4.4 parts by mass PGMEA ... 83.01 parts by mass

(Pigment dispersion liquid B-7)
Black pigment (CI Pigment Black 32) ... 12.59 parts by mass Dispersant 2 ... 4.4 parts by mass PGMEA ... 83.01 parts by mass

The raw materials used for pigment dispersions B-1 to B-7 are as follows.
Dispersant 1: Dispersant 1 described above
Dispersant 2: Resin of the following structure (Mw = 24000, the numerical value attached to the main chain is a molar ratio, the numerical value attached to the side chain is the number of repeating units)

Dispersant 3: Resin of the following structure (Mw = 20000, the numerical value attached to the main chain is the molar ratio, the numerical value attached to the side chain is the number of repeating units)

Alkali-soluble resin 2: Alkali-soluble resin 2 described later
Pigment derivative 2: compound of the following structure

The raw materials described in the above table are as follows.
Pigment dispersions A-1, A-6, B-1 to B-7: the above-mentioned pigment dispersions A-1, A-6, B-1 to B-7
Alkali-soluble resin 2: resin of the following structure (acid value: 70 mg KOH / g, Mw = 11000, the numerical value attached to the main chain is a molar ratio. Me in the structural formula is a methyl group)

Polymerizable compound 1: A mixture of compounds of the following structure (a mixture of a left compound and a right compound in a molar ratio of 7: 3)

Polymerizable compound 2: Compound of the following structure

Polymerizable compound 3: Compound of the following structure (a + b + c = 3)

Silane coupling agent 1: Compound of the following structure (Et in the following structural formula is an ethyl group)

Polymerization inhibitor: p-methoxyphenol UV absorber: UV-503 (made by Daito Chemical Co., Ltd.)
Photoinitiator 1: Compound of the following structure

Photopolymerization initiator 2: IRGACURE-OXE04 (manufactured by BASF)
Photopolymerization initiator 3: IRGACURE-OXE02 (manufactured by BASF)
Photopolymerization initiator 4: Compound of the following structure

Surfactant 1: Surfactant 1 described above
Organic solvent 1: Propylene glycol methyl ether acetate

<Evaluation of spectral characteristics>
The resin composition was applied on a glass substrate by spin coating so that the film thickness after application was 0.3 μm, and then heated at 100 ° C. for 2 minutes using a hot plate. Next, exposure was performed at 1000 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.). Furthermore, it heated at 220 degreeC for 5 minutes using the hotplate, and formed the film. For the substrate on which the film is formed, the transmittance of light in the wavelength range of 400 to 1400 nm and the light transmittance of wavelength 700 nm, using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) Was measured.

<Evaluation of defects>
A resist CT-2000L solution (Fuji Film Electronics Materials Co., Ltd. product) is coated on a silicon wafer using a spin coater to a film thickness of 2 μm, dried by heating at 220 ° C for 1 hour, and transparent cured. A film (subbed layer) was formed.
The resin composition is applied on the undercoating layer of the obtained silicon wafer with undercoating layer using a spin coater so that the dry film thickness is 1.0 μm, prebaked at 100 ° C. for 120 seconds, and then on the silicon wafer. A film was formed. Foreign matter contained in this film is detected using foreign matter evaluation apparatus COMPLAS III (Applied Materials Co., Ltd.), and from all detected foreign matter, foreign matter having a maximum width of 1.0 μm or more, which causes yield reduction ( Coarse particles were classified visually. The number of foreign substances classified into the maximum width of 1.0 μm or more (the number per 1 cm ² ) was counted, and the defect performance was evaluated using the obtained value as an index.

In the examples, the maximum value of the transmittance of light in the wavelength range of 400 to 830 nm was 20% or less, and the minimum value of the transmittance of light in the wavelength range of 1000 to 1300 nm was 80% or more. In addition, as shown in the above table, the example was superior to the comparative example in the light shielding property at a wavelength of 700 nm. For this reason, the example was able to transmit near infrared rays with less noise than the comparative example. Further, in the example, the number of foreign matter was smaller than in the comparative example, and the defect performance was good.

[Test Example 4]
The resin compositions of Examples 101 to 108 were applied by spin coating on a silicon wafer such that the film thickness after film formation was 1.0 μm. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.), exposure was performed at a dose of 1000 mJ / cm ² through a mask having a 2 μm square Bayer pattern.
Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed by spin shower and was further rinsed with pure water. Next, a 2 μm square Bayer pattern (near infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.
Next, on the Bayer pattern of the near infrared cut filter, the red composition was applied by spin coating so that the film thickness after film formation was 1.0 μm. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.), exposure was performed at a dose of 1000 mJ / cm ² through a mask having a 2 μm square Bayer pattern. Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed by spin shower and was further rinsed with pure water. Next, the red composition was patterned on the Bayer pattern of the near infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form colored patterns of red, green and blue.
Next, a composition for forming a near infrared ray transmission filter was applied on the film on which the color pattern was formed by a spin coating method so that the film thickness after film formation was 2.0 μm. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.), exposure was performed at a dose of 1000 mJ / cm ² through a mask having a 2 μm square Bayer pattern. Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed by spin shower and was further rinsed with pure water. Next, the near-infrared transmission filter was patterned on the missing part of the near-infrared cut filter pattern by heating at 200 ° C. for 5 minutes using a hot plate. This was incorporated into a solid-state imaging device according to a known method.
The obtained solid-state imaging device was irradiated with light from an infrared light emitting diode (infrared LED) light source under a low illuminance environment (0.001 Lux), an image was captured, and the image performance was evaluated. The subject was clearly recognized on the image. In addition, the incident angle dependency was good.

The Red composition, the Green composition, the Blue composition and the composition for forming a near infrared ray transmission filter used in Test Example 4 are as follows.

(Red composition)
The following components were mixed and stirred, and then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a red composition.
Red pigment dispersion liquid: 51.7 parts by mass Resin 11: 0.6 parts by mass Polymerizable compound 2: 0.6 parts by mass Photopolymerization initiator 11: 0.4 parts by mass Surfactant 11 ... 4.2 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Chemical Industries, Ltd.) ... 0.3 parts by mass Propylene glycol monomethyl ether acetate (PGMEA) ... 42.6 parts by mass

(Green composition)
The following components were mixed and stirred, followed by filtration using a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Green composition.
Green pigment dispersion ··· 73.7 parts by mass Resin 11 · · · 0.3 parts by mass Polymerizable compound 11 · · · 1.2 parts by mass Photopolymerization initiator 11 · · · 0.6 parts by mass Surfactant 11 ... 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Chemical Industries, Ltd.) ... 0.5 parts by mass PGMEA ... 19.5 parts by mass

(Blue composition)
The following components were mixed and stirred, and then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Blue composition.
Blue pigment dispersion 44.9 parts by mass Resin 11 ··· 2.1 parts by mass Polymerizable compound 11 · · · 1.5 parts by mass Polymerizable compound 2 · · · 0.7 parts by mass Photopolymerization initiator 11 · · · -0.8 parts by mass Surfactant 11 · · · 4.2 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Chemical Industries, Ltd.) · · · 0.3 parts by mass PGMEA · · 45.8 parts by mass

(Composition for near infrared ray transmission filter formation)
The following components were mixed and stirred, followed by filtration using a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a composition for forming a near infrared ray transmission filter.
Pigment dispersion 1-1 ... 46.5 parts by mass Pigment dispersion 1-2 ... 37.1 parts by mass Polymerizable compound 1 ... 1.8 parts by mass Resin 11 ... 1.1 parts by mass Photopolymerization initiator 12 ··· 0.9 parts by weight Surfactant 11 ··· 4.2 parts by weight Polymerization inhibitor (p-methoxyphenol) ··· 0.001 parts by weight Silane coupling agent 1 ··· 0.6 parts by mass PGMEA ... 7.8 parts by mass

The raw materials used for the Red composition, the Green composition, the Blue composition, and the composition for forming a near infrared ray transmission filter are as follows.

Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. A mixed solution of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was used as a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a red pigment dispersion.

Green pigment dispersion C. I. Pigment Green 36, 6.4 parts by mass, C.I. I. A mixed solution of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA was added to a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a green pigment dispersion.

Blue pigment dispersion C.I. I. Pigment Blue 15: 6, 9.7 parts by mass, C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA is a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a blue pigment dispersion.

・ Pigment dispersion liquid 1-1
A mixed solution of the following composition is mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.)) using zirconia beads of 0.3 mm diameter. Pigment dispersion liquid 1-1 was prepared.
Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139) 11.8 parts by mass Resin (Disperbyk-111, manufactured by BYK Chemie): 9.1 parts by mass PGMEA ... 79.1 parts by mass

・ Pigment dispersion liquid 1-2
A mixed solution of the following composition is mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.)) using zirconia beads of 0.3 mm diameter. Pigment dispersion liquid 1-2 was prepared.
Mixed pigment composed of blue pigment (CI Pigment Blue 15: 6) and purple pigment (CI Pigment Violet 23) 12.6 parts by mass Resin (Disperbyk-111, manufactured by BYK Chemie) 2.0 parts by weight Resin A 3.3 parts by weight Cyclohexanone 31.2 parts by weight PGMEA 50.9 parts by weight Resin A: Resin of the following structure (Mw = 14, 000, the ratio in structural units is the molar ratio)

Polymerizable compound 1: The above-mentioned polymerizable compound 1
Polymerizable compound 2: The above-mentioned polymerizable compound 2
Polymerizable compound 11: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Resin 11: Alkali-soluble resin 2 described above
Photopolymerization initiator 11: IRGACURE-OXE01 (manufactured by BASF)
Photopolymerization initiator 12: compound of the following structure

Surfactant 11: 1 mass% PGMEA solution of the following mixture (Mw = 14000). In the following formulas,% indicating the proportion of repeating units is mass%.

-Silane coupling agent 1: The above-mentioned silane coupling agent 1.

110: solid-state imaging device, 111: near infrared cut filter, 112: color filter, 114: near infrared transmission filter, 115: microlens, 116: flattening layer

Claims

A near infrared absorbing organic pigment having a maximum absorption wavelength in the range of 650 to 1400 nm,
The near infrared absorbing organic pigment has an A 550 / A max which is a ratio of an absorbance A 550 at a wavelength of 550 nm to an absorbance A max at the maximum absorption wavelength is less than 0.1.
The average primary particle diameter of the near infrared absorbing organic pigment is 1 to 200 nm,
A near-infrared-absorbing organic pigment having a crystallinity of 0.70 to 0.98 represented by the following formula in a powder X-ray diffraction spectrum of the near-infrared-absorbing organic pigment:
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
The absorbance A 1 at 50nm shorter wavelength than the maximum absorption wavelength of the near infrared absorbing organic pigment, wherein A 1 / A max is 0.57 which is the ratio between the absorbance A max at the maximum absorption wavelength of the near infrared absorbing organic pigment ~ The near-infrared absorbing organic pigment according to claim 1, which is 0.9.
The ratio A 1 / A max , which is the ratio of the absorbance A 1 at a wavelength 50 nm shorter than the maximum absorption wavelength of the near infrared absorption organic pigment and the absorbance A max at the maximum absorption wavelength of the near infrared absorption organic pigment, is the near infrared radiation The near-infrared absorption organic pigment according to claim 1 or 2, which is 5% or more higher than the value when the average primary particle diameter of the absorption organic pigment is 1,500 nm.
The near-infrared-absorbing organic pigment according to any one of claims 1 to 3, wherein the near-infrared-absorbing organic pigment has a maximum absorption wavelength in a wavelength range of 650 to 780 nm.
The near-infrared-absorbing organic pigment according to any one of claims 1 to 4, wherein an average long / short side ratio of primary particles of the near-infrared-absorbing organic pigment is 0.3 to 0.99.
The near-infrared-absorbing organic pigment according to any one of claims 1 to 5, wherein the near-infrared-absorbing organic pigment is at least one selected from a pyrrolopyrrole compound and a squalilium compound.
A resin composition comprising the near-infrared-absorbing organic pigment according to any one of claims 1 to 6 and a resin.
The resin composition according to claim 7, further comprising a coloring material that transmits infrared light and shields visible light.
A near infrared absorbing pigment having a maximum absorption wavelength in a wavelength range of 650 to 1400 nm and having an A 550 / A max which is a ratio of an absorbance A 550 at a wavelength 550 nm to an absorbance A max at the maximum absorption wavelength is less than 0.1. Of the near-infrared-absorbing organic pigment having an average primary particle diameter of 1 to 200 nm and a crystallinity of 0.70 to 0.98 represented by the following formula in a powder X-ray diffraction spectrum: Production method;
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
A near infrared absorbing pigment having a maximum absorption wavelength in a wavelength range of 650 to 1400 nm and having an A 550 / A max which is a ratio of an absorbance A 550 at a wavelength 550 nm to an absorbance A max at the maximum absorption wavelength is less than 0.1. Of the near-infrared-absorbing organic pigment having an average primary particle diameter of 1 to 200 nm and a crystallinity of 0.70 to 0.98 represented by the following formula in a powder X-ray diffraction spectrum: Spectral adjustment method;
Crystallinity = [Ic / (Ia + Ic)]
In the formula, Ic is the maximum value of the diffraction intensity of the peak derived from the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more,
Ia is the maximum value of the diffraction intensity of the peak derived from amorphous in the powder X-ray diffraction spectrum.
The ratio A 1 / A max, which is the ratio of the absorbance A 1 at a wavelength 50 nm shorter than the maximum absorption wavelength of the near infrared absorption organic pigment after the milling treatment, and the absorbance A max at the maximum absorption wavelength of the near infrared absorption organic pigment is The method for spectral adjustment of a near-infrared-absorbing organic pigment according to claim 10, wherein the value is 5% or more higher than the value of the near-infrared-absorbing organic pigment before the milling treatment.
A film obtained by using the resin composition according to claim 7 or 8.
A laminate comprising the membrane according to claim 12 on a support.
The laminate according to claim 13, wherein the support is a copper-containing glass substrate.
A near infrared cut filter comprising the film according to claim 12.
A near infrared ray transmission filter comprising the membrane according to claim 12.
A solid-state imaging device comprising the film according to claim 12.
An image display apparatus comprising the film according to claim 12.
An infrared sensor comprising the film according to claim 12.