TW201815985A - Near-infrared absorbing organic pigment, pigment dispersion, curable composition, film, near-infrared cut filter, laminate, solid state imaging element, image display device, and infrared sensor - Google Patents

Abstract

Provided is a near-infrared ray absorbing organic pigment having exceptional transparency in the visible ray region and exceptional heat resistance. In addition, provided are a pigment dispersion, a curable composition, a film, a near-infrared cut filter, a laminate, a solid state imaging element, an image display device, and an infrared sensor. In a powder X-ray diffraction spectrum, this near-infrared ray absorbing organic pigment has a peak of diffraction intensity in a region in which the diffraction angle 2[Theta] is 5 to 12 DEG, and the full width at half maximum of a peak at which the diffraction intensity in said region is highest is 0.3 to 0.6 DEG.

Description

Near-infrared absorbing organic pigment, pigment dispersion, hardenable composition, film, near-infrared cut filter, multilayer body, solid-state imaging element, image display device, and infrared sensor

The present invention relates to a near-infrared absorbing organic pigment, a pigment dispersion, a hardenable composition, a film, a near-infrared cut filter, a multilayer body, a solid-state imaging device, an image display device, and an infrared sensor.

CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor) are solid-state imaging devices that use color images in video cameras, digital cameras, and mobile phones with camera functions. Since these solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light-receiving sections, near-infrared cut-off filters are sometimes used to correct visual acuity.

In order to improve infrared shielding properties, a method for producing a near-infrared cut filter using a hardening composition containing a near-infrared absorbing agent such as a near-infrared absorbing organic pigment is known (for example, Patent Documents 1 and 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2014-191190 [Patent Document 2] International Publication No. WO2014 / 185518

A near-infrared absorbing agent such as a near-infrared absorbing organic pigment is required to have excellent infrared shielding properties and excellent visibility and transparency. When a near-infrared cut filter or the like is produced using a curable composition containing a near-infrared absorbing organic pigment or the like, heating may be performed for drying or curing. However, when the heat resistance of the near-infrared absorbing organic pigment is low, coloration may occur due to heating, resulting in a decrease in visible transparency.

An object of the present invention is to provide a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance. In addition, a pigment dispersion liquid, a curable composition, a film, a near-infrared cut filter, a multilayer body, a solid-state imaging device, an image display device, and an infrared sensor are provided.

Under these circumstances, the present inventors conducted intensive studies, and as a result, found that the near-infrared-absorbing organic pigment described later is excellent in visible transparency and heat resistance, and completed the present invention. The present invention provides the following. <1> A near-infrared absorbing organic pigment having a peak of diffraction intensity in a powder X-ray diffraction spectrum in a region with a diffraction angle of 2θ of 5 to 12 °, and a peak having the largest diffraction intensity in the aforementioned region. The full width at half maximum is 0.3 to 0.6 °. <2> The near-infrared absorbing organic pigment according to <1>, wherein the full width at half maximum is 0.3 to 0.45 °. <3> The near-infrared-absorbing organic pigment according to <1> or <2>, wherein the average primary particle diameter of the near-infrared-absorbing organic pigment is 10 to 100 nm. <4> The near-infrared-absorbing organic pigment according to <1> or <2>, wherein the average primary particle diameter of the near-infrared-absorbing organic pigment is 20 to 45 nm. <5> The near-infrared absorbing organic pigment according to any one of <1> to <4>, wherein the coefficient of variation of the primary particle diameter of the near-infrared absorbing organic pigment is 20 to 35%. <6> The near-infrared-absorbing organic pigment according to any one of <1> to <5>, wherein the average length-to-short-side ratio of the near-infrared-absorbing organic pigment is 0.5 to 0.9. <7> The near-infrared absorbing organic pigment according to any one of <1> to <6>, wherein the coefficient of variation of the aspect ratio of the near-infrared absorbing organic pigment is 10 to 30%. <8> The near-infrared absorbing organic pigment according to any one of <1> to <7>, wherein the value of the crystallinity represented by the following formula of the near-infrared absorbing organic pigment is 0.9 to 0.99; crystallinity = [ Ic / (Ia + Ic)] where Ic is the maximum diffraction intensity from the peak of the crystal in the powder X-ray diffraction spectrum in the region where the diffraction angle 2θ is 15 ° or more, and Ia is the powder X-ray The maximum value of the diffraction intensity derived from the amorphous peak in the diffraction spectrum. <9> The near-infrared absorbing organic pigment according to any one of <1> to <8>, wherein the near-infrared absorbing organic pigment is at least one selected from the group consisting of a pyrrolopyrrole compound and a squaraine compound. <10> A pigment dispersion liquid comprising the near-infrared absorbing organic pigment according to any one of <1> to <9>, a resin, and a solvent. <11> The pigment dispersion liquid according to <10>, further comprising a pigment derivative. <12> A curable composition containing the near-infrared absorbing organic pigment according to any one of <1> to <9>, a resin, a curable compound, and a solvent. <13> A film using the curable composition according to <12>. <14> A near-infrared cut-off filter having the film according to <13>. <15> A laminated body comprising the film according to <13> and a color filter containing a colorant. <16> A solid-state imaging device having the film according to <13>. <17> An image display device including the film according to <13>. <18> An infrared sensor having the film according to <13>. [Inventive effect]

According to the present invention, a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance can be provided. In addition, a pigment dispersion liquid, a curable composition, a film, a near-infrared cut filter, a multilayer body, a solid-state imaging device, an image display device, and an infrared sensor can be provided.

Hereinafter, the content of this invention is demonstrated in detail. In this specification, "~" is used as a meaning which includes the numerical value described before and after that as a lower limit value and an upper limit value. In the description of the group (atomic group) in this specification, the unsubstituted and unsubstituted tags include a group (atomic group) having no substituent, and also include a group (atomic group) having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) without substituents, but also alkyl groups (substituted alkyl groups) with substituents. In this specification, as long as "exposure" is not specified, not only exposure using light but also drawing using particle beams such as electron beams and ion beams is also included in the exposure. Examples of the light used in the exposure include bright line spectrum of a mercury lamp, actinic radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams, such as an excimer laser, and radiation. In this specification, "(meth) acrylate" means both or any one of acrylate and methacrylate, "(meth) acrylic" means both or any one of acrylic and methacrylic, and "(formaldehyde "Meth) acrylfluorenyl" means both or both acrylmethyl and methacrylmethyl. In this specification, weight average molecular weight and number average molecular weight are defined by the polystyrene conversion value measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mm ID (inner diameter) × 15.0). cm) was used as a column, and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution was used as an eluent. In this specification, near-infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In this specification, the term "process" includes not only an independent process, but in the case where it cannot be clearly distinguished from other processes, as long as the desired effect of the process can be achieved, it is also included in this term. In the present specification, a pigment refers to a compound that is not easily soluble in a specific solvent. For example, the solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.

<Near-infrared-absorbing organic pigment> The near-infrared-absorbing organic pigment of the present invention is characterized in that the powder X-ray diffraction spectrum has a peak of diffraction intensity in a region with a diffraction angle 2θ of 5 to 12 °. The full width at half maximum of the peak with the highest diffraction intensity is 0.3 to 0.6 °.

The present inventors conducted intensive research, and as a result, found that in the powder X-ray diffraction spectrum of near-infrared absorbing organic pigments, there is a peak of diffraction intensity in a region with a diffraction angle 2θ of 5 to 12 °. The near-infrared-absorbing organic pigment having a peak full-width at half maximum having a diffraction intensity of 0.3 to 0.6 ° is excellent in visible transparency and heat resistance. Although the detailed reason is unknown, it is speculated that with the full-width at half maximum of the peak with the largest diffraction intensity being 0.3 to 0.6 °, the crystallites of the near-infrared absorbing organic pigment have a moderate size and less scattering. The proportion of the combined pigment molecules becomes higher, and as a result, the visible transparency and heat resistance can be improved. The powder X-ray diffraction spectrum of the near-infrared-absorbing organic pigment can be measured by a method described in Examples described later.

It is preferable to have the peak having the largest diffraction intensity among the near-infrared-absorbing organic pigments of the present invention in a region where the diffraction angle 2θ is 6 to 10 °, and it is more preferable to have a peak in a region of 6 to 9 °, which is 6.5 to 8.5 A region of ° is more preferable. According to this aspect, visible transparency and heat resistance can be further improved. The full width at half maximum of the peak having the highest diffraction intensity is preferably 0.3 to 0.45 °. According to this aspect, it can be seen that transparency and heat resistance are particularly good. In addition, in the present invention, with respect to the full width at half maximum of the peak having the highest diffraction intensity in the powder X-ray diffraction spectrum, the diffraction intensity having the maximum diffraction angle 2θ in a region of 5 to 12 ° can be used. The peak fitting is obtained by the Lorentz function [y = A / (1 + ((x-x0) / w) ² ) + h]. Among them, y is the intensity, A is the peak height, x is 2θ, x0 is the peak position, w is the peak width (half-peak half-width), and h is the base line.

The average primary particle diameter of the near-infrared absorbing organic pigment of the present invention is preferably 10 to 100 nm. The lower limit is preferably 15 nm or more, more preferably 20 nm or more, even more preferably 25 nm or more, and particularly preferably 30 nm or more. The upper limit is preferably below 90 nm, more preferably below 80 nm, even more preferably below 60 nm, and particularly preferably below 45 nm. The average primary particle diameter of the near-infrared-absorbing organic pigment is preferably 20 to 45 nm, and particularly preferably 30 to 45 nm. By setting the average primary particle diameter of the near-infrared-absorbing organic pigment to 100 nm or less, it is possible to further improve visible transparency. In addition, by setting the average primary particle diameter of the near-infrared-absorbing organic pigment to 10 nm or more, the effect of improving dispersion stability can be obtained. In addition, as the average primary particle diameter of the near-infrared-absorbing organic pigment becomes smaller, the heat resistance tends to decrease, but the near-infrared-absorbing organic pigment having the above-mentioned diffraction characteristics has excellent heat resistance even if the average primary particle diameter is small. Sex.

The coefficient of variation 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 preferably 21% or more, and more preferably 22% or more. The upper limit is preferably 33% or less, more preferably 30% or less, more preferably 29% or less, and 28% or less. When the coefficient of variation of the primary particle diameter of the near-infrared absorbing organic pigment is within the above range, it is possible to further improve visible transparency. The coefficient of variation of the primary particle diameter of the near-infrared-absorbing organic pigment is defined by the following formula. Coefficient of variation of the primary particle size of the near-infrared absorbing organic pigment = (standard deviation of the primary particle size of the near-infrared absorbing organic pigment / the arithmetic mean of the primary particle size of the near-infrared absorbing organic pigment) × 100

The average long-to-short side ratio of the near-infrared absorbing organic pigment of the present invention is preferably 0.5 to 0.9. The lower limit is preferably 0.53 or more, and more preferably 0.56 or more. The upper limit is preferably 0.8 or less, and more preferably 0.7 or less. When the average aspect ratio of the near-infrared-absorbing organic pigment is within the above range, the effect of improving heat resistance can be expected.

The variation coefficient of the aspect ratio of the near-infrared absorbing organic pigment of the present invention is preferably 10 to 30%. The lower limit is preferably 13% or more, and more preferably 16% or more. The upper limit is preferably 28% or less, and more preferably 26% or less. When the coefficient of variation of the aspect ratio of the near-infrared absorbing organic pigment is within the above range, the effect of improving the visibility and transparency can be expected. The coefficient of variation of the aspect ratio of the near-infrared-absorbing organic pigment is defined by the following formula. Coefficient of variation of the aspect ratio of the near-infrared-absorbing organic pigment = (standard deviation of the aspect ratio of the near-infrared-absorbing organic pigment / the arithmetic mean of the aspect ratio of the near-infrared-absorbing organic pigment) × 100

In the present invention, the primary particles of the near-infrared-absorbing organic pigment can be observed with a transmission electron microscope, and the primary particle diameter and the length-to-edge ratio of the near-infrared-absorbing organic pigment can be obtained from the obtained photos. Specifically, the projected area of the primary particles of the near-infrared-absorbing organic pigment is obtained, and an equivalent circular 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 (short side / long side) of the primary particle was obtained from the projected photo to calculate the length to short side ratio. The average primary particle diameter and the average length-to-edge ratio in the present invention are the arithmetic average values of the primary particle diameter and the length-to-edge ratio of 400 primary particles of near-infrared-absorbing organic pigment. In addition, the longest diameter of a primary particle is called a long side, and the shortest diameter is called a short side. That is, in the case of an ellipse, the long axis is the long side and the short axis is the short side. The primary particles of the near-infrared-absorbing organic pigment are independent particles that are not aggregated.

In the present invention, the value of the crystallinity represented by the following formula of the near-infrared absorbing organic pigment is preferably 0.9 to 0.99, more preferably 0.91 to 0.98, and still more preferably 0.93 to 0.96. When the value of crystallinity is within the above range, heat resistance can be further improved. Crystallinity = [Ic / (Ia + Ic)] In the formula, Ic is in the region where the diffraction angle 2θ is 15 ° or more. The maximum diffraction intensity from the peak of the crystal in the powder X-ray diffraction spectrum, Ia It is the maximum value of the diffraction intensity derived from the amorphous peak in the powder X-ray diffraction spectrum.

In addition, in the present invention, the crystal-derived peak refers to a sharper peak having a full width at half maximum at a peak of diffraction intensity of 1 ° or less. In addition, the peak derived from amorphous refers to a peak whose full width at half maximum at a peak of diffraction intensity exceeds 3 °. Further, in the present invention, the values of Ic and Ia are the points at which the diffraction angle 2θ of the diffraction angle of the powder X-ray diffraction spectrum of the near-infrared-absorbing organic pigment is 2θ, and the diffraction intensity is the lowest in the region of 5 to 15 °. The straight line of the point with the lowest diffraction intensity in the region of ~ 35 ° is used as the baseline, and the value is calculated by subtracting the baseline correction value from the measured value of the powder X-ray diffraction spectrum.

The type of the near-infrared-absorbing organic pigment of the present invention is not particularly limited as long as it is an organic pigment having a maximum absorption wavelength in the near-infrared region (preferably in the range of 700 to 1000 nm). The organic pigment refers to a pigment composed of an organic compound. The near-infrared-absorbing organic pigment of the present invention is preferably at least one selected from the group consisting of pyrrolopyrrole compounds, squalylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, and diimine compounds. At least one selected from the group consisting of a pyrrolopyrrole compound, a squaraine compound, and a cyanine compound is more preferable, a pyrrolopyrrole compound or a squaraine compound is more preferred, and a pyrrolopyrrole compound is particularly preferred. In particular, in the case of a pyrrolopyrrole compound, it is possible to more effectively improve visible transparency and heat resistance.

As the pyrrolopyrrole compound, a compound represented by the formula (PP) is preferable. [Chemical Formula 1] 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 may be bonded to each other to form a ring. R ⁴ each 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 may be covalently bonded to at least one selected from R ^1a , R ^1b, and R ³ R ^4A and R ^4B each independently represent a substituent.

R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, an aryl group or a heteroaryl group is preferred, and an aryl group is more preferred. The carbon number of the alkyl group represented by R ^1a and R ^1b is preferably 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 10. The carbon number of the aryl group represented by R ^1a and R ^1b is preferably 6-30, more preferably 6-20, and particularly preferably 6-12. The number of carbon atoms constituting the heteroaryl group represented by R ^1a and R ^1b is preferably 1 to 30, and more preferably 1 to 12. Examples of the type of the hetero atom constituting the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 is preferable, and 1 to 2 is more preferable. Heteroaryl based monocyclic or fused rings are preferred, monocyclic or fused rings with a condensation number of 2 to 8 are preferred, and monocyclic or fused rings with a condensation number of 2 to 4 are more preferred. The alkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted. It is preferable to have a substituent. Examples of the substituent include those described in the substituent T described later. Among them, alkoxy and hydroxyl are preferred. The alkoxy group is preferably an alkoxy group having a branched alkyl group. As the group represented by R ^1a and R ^1b , an aryl group having an alkoxy group having a branched alkyl group as a substituent or an aryl group having a hydroxyl group as a substituent is preferred. The carbon number of the branched alkyl group is preferably 3 to 30, and more preferably 3 to 20.

R ² and R ³ each independently represent a hydrogen atom or a substituent. R ² and R ³ may be bonded to form a ring. It is preferable that at least one of R ² and R ³ is an electron withdrawing group. It is preferable that R ² and R ³ each independently represent a cyano group or a heteroaryl group. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of Japanese Patent Application Laid-Open No. 2009-263614. The above is incorporated into this specification. Examples of the substituent include the following substituents T. (Substituent T) Alkyl (preferably carbon number 1-30), alkenyl (preferably carbon number 2-30), alkynyl (preferably carbon number 2-30), aryl (preferably 6-30 carbons), amine (preferably 0-30 carbons), alkoxy (preferably 1-30 carbons), aryloxy (preferably 6-30 carbons), heteroaryl Oxy (preferably 1-30 carbons), fluorenyl (preferably 1-30 carbons), alkoxycarbonyl (preferably 2-30 carbons), aryloxycarbonyl (preferably carbons) 7-30), fluorenyloxy (preferably 2-30 carbons), fluorenylamino (preferably 2-30 carbons), alkoxycarbonylamino (preferably 2-30 carbons) Aryloxycarbonylamino (preferably 7 to 30 carbons), sulfamoyl (preferably 0 to 30 carbons), carbamoyl (preferably 1 to 30 carbons), alkylthio (Preferably 1-30 carbons), arylthio (preferably 6-30 carbons), heteroarylthio (preferably 1-30 carbons), alkylsulfonyl (preferably Carbon number 1-30), arylsulfonyl (preferably 6-30), heteroarylsulfonyl (preferably 1-30), alkylsulfinyl (preferably carbon 1-30), arylsulfinylene (preferably 6-30 carbons), heteroarylsulfinylene (preferably 1-30 carbons), ureido (preferably 1 to 30 carbons) 30), amido phosphate (preferably carbon number 1-30), hydroxyl, mercapto, halogen atom, cyano, sulfo, carboxyl, nitro, hydroxamic acid, sulfinyl, hydrazine, Amine group and heteroaryl group (preferably having 1 to 30 carbon atoms). When these groups are groups which can be further substituted, they may further have a substituent. As a further substituent, the group demonstrated by the said substituent T is mentioned.

It is preferable that at least one of R ² and R ³ is an electron withdrawing group. A substituent with a positive sigma value (sigma value) of the Hammett substituent group functions as an electron withdrawing group. Here, the substituent constants obtained by the Hammett's equation include σp and σm values. These values can be viewed in a large number of general publications. In the present invention, a substituent having a Hammett substituent constant σ value of 0.2 or more can be exemplified as an electron withdrawing group. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and 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 (σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), an alkoxycarbonyl group (-COOMe: σp value = 0.45), and an aryloxycarbonyl group ( For example, -COOPh: σp value = 0.44), carbamate (for example -CONH ₂ : σp value = 0.36), alkylcarbonyl (for example -COMe: σp value = 0.50), arylcarbonyl (for example -COPh: σp Value = 0.43), alkylsulfonyl (for example, -SO ₂ Me: σp value = 0.72), arylsulfonyl (for example, -SO ₂ Ph: σp value = 0.68), and the like. Here, Me represents a methyl group and Ph represents a phenyl group. In addition, regarding the value of the Hammett substituent constant σ, refer to, for example, paragraph numbers 0017 to 0018 of Japanese Patent Application Laid-Open No. 2011-68731, which is incorporated into the present specification.

When R ² and R ³ are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered ring (preferably a 5- or 6-membered ring). As the formed ring, it is generally preferred to use it as an acidic core in the merocyanine pigment. As a specific example, refer to paragraphs 0019 to 0021 of Japanese Patent Application Laid-Open No. 2011-68731, which is incorporated herein. In the manual.

R ² represents an electron withdrawing group (preferably a cyano group), and R ³ represents a heteroaryl group. Heteroaryl is more preferably a 5-membered ring or a 6-membered ring. In addition, a heteroaryl monocyclic or fused ring is preferred, a monocyclic or fused ring with a condensation number of 2 to 8 is more preferred, and a monocyclic or fused ring with a condensation number of 2 to 4 is more preferred. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms.

When R ⁴ represents an alkyl group, an aryl group, or a heteroaryl group, the alkyl group, the aryl group, and the heteroaryl group are the same as those described in R ^1a and R ^1b , and the preferred ranges are also the same.

When R ⁴ represents -BR ^4A R ^4B , R ^4A and R ^4B each independently represent a substituent. Examples of the substituents represented by R ^4A and R ^4B include the above-mentioned substituent T. A halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferred, and the alkyl group, aryl group, or heteroaryl group is More preferably, aryl is particularly preferred. Specific examples of the group represented by -BR ^4A R ^4B include a difluoroboryl group, a diphenylboryl group, a dibutylboryl group, a dinaphthylboryl group, and a catecholboryl group. Among them, diphenylboryl is particularly preferred.

When R ⁴ represents a metal atom, examples of the metal atom include magnesium, aluminum, calcium, barium, zinc, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, platinum, aluminum, zinc, vanadium, and iron , Copper, palladium, iridium and platinum are particularly preferred.

R ⁴ may be covalently bonded or coordinated to at least one of R ^1a , R ^1b, and R ^3. In particular, R ⁴ and R ³ are preferably coordinated and bonded. R ⁴ is a hydrogen atom or a group represented by -BR ^4A R ^4B (especially a diphenylboryl group).

Specific examples of the compound represented by the formula (PP) include the following compounds. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. [Chemical Formula 2]

The near-infrared absorbing organic pigment having the above-mentioned characteristics can be produced by, for example, adjusting the pulverization conditions of the near-infrared absorbing organic pigment. For example, a method of kneading and grinding a near-infrared-absorbing organic pigment in the presence of a water-soluble organic solvent and a water-soluble inorganic salt to produce it can be mentioned. The average primary particle diameter of the kneaded and grounded near-infrared absorbing organic pigment is preferably in the range of 10 to 100 nm, and the average primary particle diameter of the kneaded and grounded into the near-infrared absorbing organic pigment is preferably in the range of 20 to 45 nm.

The water-soluble inorganic salt functions as a grinding agent, and is kneaded with the near-infrared-absorbing organic pigment to promote the miniaturization of the near-infrared-absorbing organic pigment. Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, sodium sulfate, aluminum sulfate, and sodium bicarbonate, and sodium chloride and sodium sulfate are preferred. As these water-soluble inorganic salts, pulverized products can be used. Moreover, these water-soluble inorganic salts can be used individually by 1 type, and the mixture of 2 or more types can also be used.

The average particle 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. Compared with colored organic pigments or inorganic pigments, the hardness of near-infrared absorbing organic pigments is lower. If a water-soluble inorganic salt with a small particle size is used for kneading and grinding, the near-infrared absorbing organic pigments may be used during kneading and grinding. The structure is deformed, or the crystal structure of the near-infrared absorbing organic pigment is changed, and the transparency is reduced. However, by using a water-soluble inorganic salt having a moderately large particle size (preferably a water-solubility having an average particle size of 15 μm or more) (Inorganic salt), while suppressing deformation of the crystal structure of the near-infrared absorbing organic pigment, etc., and can appropriately adjust the crystallinity (crystallinity). Furthermore, the near-infrared-absorbing organic pigment can be made finer (for example, the average primary particle diameter is 10 to 100 nm). Therefore, it is easy to produce a near-infrared absorbing organic pigment having the above-mentioned characteristics in the powder X-ray diffraction spectrum and having an average primary particle diameter in a range of 10 to 100 nm. Furthermore, it is possible to further improve the visible transparency and heat resistance of the near-infrared-absorbing organic pigment.

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 relative to the mass of the near-infrared absorbing organic pigment. The lower limit is particularly preferably 8 times or more, and 10 times or more is the best. The upper limit is particularly preferably 17 times or less, and the most preferable is 16 times or less. When the amount of the water-soluble inorganic salt is within the above range, it is possible to suppress the deformation of the crystal structure of the near-infrared-absorbing organic pigment and to appropriately adjust the crystallinity (crystallinity). Furthermore, the near-infrared-absorbing organic pigment can be made finer (for example, the average primary particle diameter is 10 to 100 nm). Therefore, it is easy to produce a near-infrared absorbing organic pigment having the above-mentioned characteristics in the powder X-ray diffraction spectrum and having an average primary particle diameter in a range of 10 to 100 nm. Furthermore, it is possible to further improve the visible transparency and heat resistance of the near-infrared-absorbing organic pigment.

The water-soluble organic solvent acts as a binder for near-infrared-absorbing organic pigments and water-soluble inorganic salts, and imparts hardness and stickiness to a mixture containing near-infrared-absorbing organic pigments, water-soluble inorganic salts, and water-soluble organic solvents, and can suppress the The near-infrared absorbs the crystal growth or crystal transfer of organic pigments. 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 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, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, and polyethylene-propylene glycol. Condensates of diols, alkyl ethers of (poly) alkanediols such as methoxyethanol, polyethylene glycol monomethyl ether, glycerol, etc., are derived from organic pigments containing near infrared absorption, water-soluble inorganic salts, and water-soluble organic compounds. The reason that the mixture of the solvents imparts a moderate hardness and stickiness is preferably a highly viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol, and polyethylene glycol. The water-soluble organic solvent may be used singly or in a mixture of two or more kinds. The amount of water-soluble organic solvents varies depending on the amount of near-infrared-absorbing organic pigments, the amount of water-soluble inorganic salts, the mixing conditions (temperature, mixing speed, etc.), the characteristics of the kneader used, etc. However, relative to the total mass of the near-infrared-absorbing organic pigment and the water-soluble inorganic salt, it is preferably 0.10 to 0.35 times, more preferably 0.12 to 0.30 times, and still more preferably 0.15 to 0.25 times. When the amount of the water-soluble organic solvent is within the above range, it is possible to impart a moderate hardness and a sticky feeling to a mixture containing a near-infrared-absorbing organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent.

The kneader may be any one capable of kneading the above-mentioned mixture, and a two-arm kneader, a flasher, a planetary mixer, or the like can be used. A dual-arm kneader with a strong shearing force for miniaturization is more preferred.

The temperature (milling temperature) during kneading is set in accordance with the temperature dependency or crystal transferability of the crystal growth rate of the near-infrared-absorbing organic pigment. Generally, the lower the temperature, the lower the crystal growth rate. On the other hand, the higher the temperature, the faster the wettability of the water-soluble organic solvent to the pigment surface and the penetration rate of the water-soluble organic solvent of the pigment block. The particle size classification of near-infrared absorbing organic pigments progresses with the balance between miniaturization and crystal growth. For example, 0 ° C or higher is preferred, 10 ° C or higher is more preferred, 20 ° C or higher is further preferred, 30 ° C or higher is further preferred, and 40 ° C or higher is further preferred. Among them, the reason is that it is easy to produce a near-infrared absorbing organic pigment excellent in visible transparency and heat resistance while adjusting the average primary particle diameter in the range of 10 to 100 nm, and it is particularly preferable that it is 50 ° C or higher. The upper limit is preferably 120 ° C or lower, and more preferably 100 ° C or lower.

When the kneading and grinding of the near-infrared-absorbing organic pigment is performed, the water-soluble inorganic salt or the water-soluble organic solvent can be added according to the progress of miniaturization and particle size classification of the near-infrared-absorbing organic pigment. The discharge and re-kneading of the pigment kneaded product is not limited to one time, and may be performed a plurality of times.

When the kneading and grinding of the near-infrared-absorbing organic pigment is performed, crystal transfer can be performed simultaneously with the miniaturization of the near-infrared-absorbing organic pigment. In addition, in order to control the miniaturization and crystal form of the near-infrared-absorbing organic pigment, a pigment derivative or a surface treatment agent may be added. The kneaded and ground kneaded product is purified by a known purification method such as washing with water, acid, alkali, or the like, and is separated into a refined near-infrared absorbing organic pigment. For reasons of reducing the environmental load, it is better to perform separation by water washing treatment. After the water-washing treatment, the water-containing near-infrared absorbing organic pigment can be used directly, or the water can be reduced by drying treatment. The drying method is not particularly limited, but it is preferably performed by hot air drying for reasons of improving productivity. When the drying process is performed, the moisture content of the near-infrared-absorbing organic pigment is preferably 5% or less, and more preferably 2% or less.

<Pigment dispersion liquid> Next, the pigment dispersion liquid of this invention is demonstrated. The pigment dispersion liquid of this invention contains the said near-infrared absorbing organic pigment, resin, and solvent.

The viscosity (23 ° C) of the pigment dispersion liquid of the present invention is preferably 2 to 30 mPa · s. The lower limit is preferably 3 mPa · s or more, and more preferably 4 mPa · s or more. The upper limit is preferably 20 mPa · s or less, and more preferably 15 mPa · s or less.

The thixotropy of the pigment dispersion of the present invention is preferably low. Shake can be expressed by an index of Ti value. For example, in the viscosity measured using an E-type viscometer (RE85L manufactured by TOKI SANGYO CO., LTD.), The viscosity at a rotation speed of 20 rpm and 50 rpm is set to η (20 rpm) and η (20 rpm) at η (50 rpm), respectively. The value of / η (50 rpm) was set to the Ti value. The closer the Ti value is to 1, the lower the shake resistance. Regarding the Ti value obtained by this measurement method, the Ti value at 23 ° C is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, and even more preferably 0.9 to 1.1.

The pigment dispersion liquid of the present invention preferably has a maximum absorption wavelength in a range of 700 to 1000 nm. The ratio of the absorbance A550 at a wavelength of 550 nm to the absorbance Amax at a maximum absorption wavelength, that is, the absorbance A550 / absorbance Amax is preferably 0.002 to 0.040, more preferably 0.003 to 0.030, and still more preferably 0.004 to 0.020. The ratio of the absorbance A400 at a wavelength of 400 nm to the absorbance Amax at a maximum absorption wavelength, that is, the absorbance A400 / absorbance Amax is preferably 0.005 to 0.150, more preferably 0.020 to 0.100, and still more preferably 0.050 to 0.070. It is more preferable to have the maximum absorption wavelength in the pigment dispersion of the present invention in the range of 720 to 980 nm, and it is more preferable to have the maximum absorption wavelength in the pigment dispersion of the present invention in the range of 740 to 960 nm.

<<< Near-infrared-absorbing organic pigment> The pigment dispersion liquid of this invention contains the said near-infrared-absorbing organic pigment. The content of the near-infrared-absorbing organic pigment is more preferably 30 to 99% by mass, more preferably 50 to 99% by mass, and still more preferably 60 to 99% by mass relative to the total solid content of the pigment dispersion.

<<< solvent >> The dispersion liquid of this invention contains a solvent. Examples of the solvent include organic solvents. Examples of the organic solvent include the following organic solvents. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate Ester, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropanoates (e.g., Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Methyl ester, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, Propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl ester, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkane Ethyl-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acid esters, propylene glycol monopropyl ether acetate, and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene. However, for environmental reasons, it may be preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent (for example, it can be 50 ppm by mass relative to the total amount of organic solvents ( parts per million (parts per million) or less, or 10 mass ppm or less, or 1 mass ppm or less).

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more organic solvents are used in combination, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and A mixed solution of two or more kinds of propylene glycol methyl ether acetate is preferable.

In the present invention, it is preferable to use a solvent with a small metal content, and the metal content of the solvent is, for example, 10 mass ppb (parts per billion) or less. A solvent in the quality ppt (parts per trillion) grade can be used as needed, and this high-purity solvent is provided by, for example, TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, thin film distillation, and the like) or filtration using a filter. The filter pore diameter of the filter used in the filtration is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds of the same number of atoms and different structures). The isomers may include only one kind or plural kinds.

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

The content of the solvent relative to the total amount of the pigment dispersion is preferably 60 to 92% by mass, more preferably 70 to 90% by mass, and still more preferably 75 to 89% by mass. The solvent may be one kind, or two or more kinds. When two or more solvents are included, the total amount is preferably within the above range.

<< Resin> The pigment dispersion liquid of the present invention contains a resin. The resin is blended for the purpose of dispersing pigments and the like. A resin mainly used for dispersing pigments and the like is also referred to as a dispersant. However, this use of the resin is an example, and the resin can also be used for purposes other than this use.

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, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

As the resin used as the dispersant, one or more members selected from the group consisting of acid resins, basic resins, and amphoteric resins are preferable, and one or more members selected from the group of acid resins and amphoteric resins are more preferable. In the present invention, an acidic resin means a resin having an acid group, and means a resin having an acid value of 5 mgKOH / g or more and an amine value of less than 5 mgKOH / g. It is preferable that the acidic resin does not have a basic group. As an acid group which an acid resin has, a carboxyl group, a phosphate group, a sulfo group, a phenolic hydroxyl group, etc. are mentioned, for example, A carboxyl group is preferable. The acid value of the acid resin is preferably 5 to 200 mgKOH / g. The lower limit is more preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is more preferably 100 mgKOH / g or less, and more preferably 60 mgKOH / g or less. The amine value of the acidic resin is preferably 2 mgKOH / g or less, and more preferably 1 mgKOH / g or less. In the present invention, the basic resin means a resin having a basic group, and means a resin having an amine value of 5 mgKOH / g or more and an acid value of less than 5 mgKOH / g. It is preferable that the basic resin does not have an acid group. As the basic group possessed by the basic resin, an amine group is preferred. The amine value of the basic resin is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and still more preferably 5 to 100 mgKOH / g. In the present invention, an amphoteric resin means a resin having an acid group and a basic group, and means a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more. Examples of the acid group include the foregoing, and a carboxyl group is preferred. As the basic group, an amine group is preferred. The amphoteric resin preferably has an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more. The acid value is more preferably 5 to 200 mgKOH / g. The lower limit is more preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less. The amine value is preferably 5 to 200 mgKOH / g. The lower limit is more preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less. The ratio of the acid value to the amine value of the amphoteric resin is the acid value: amine value = 1: 4 to 4: 1 is more preferable, and 1: 3 to 3: 1 is more preferable.

The resin preferably contains a repeating unit having an acid group. By using a resin containing a repeating unit having an acid group, it is possible to further reduce residues generated on the substrate of a pixel when a pattern is formed by photolithography.

Resins can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers according to their structure. Examples of the terminally modified polymer include a polymer having a phosphate group at a terminal described in Japanese Patent Application Laid-Open No. 3-112992, Japanese Patent Application No. 2003-533455, and Japanese Patent Application Laid-Open No. 2002-273191. Polymers having a sulfo group at the ends described in the gazette and the like, polymers having a partial skeleton or a heterocyclic ring having an organic pigment described in JP 9-77994 and the like. In addition, as described in Japanese Patent Application Laid-Open No. 2007-277514, two or more adhesion sites (acid groups, basic groups, partial skeletons or heterocycles of organic pigments, etc.) to the pigment surface are introduced into the polymer terminal. Polymers are also preferred because of their excellent dispersion stability. Examples of the graft polymer include poly (lower alkylene) described in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application No. 8-507960, and Japanese Patent Application Laid-Open No. 2009-258668. Imine) and polyester reaction product, polyallylamine and polyester reaction product described in Japanese Patent Application Laid-Open No. 9-169821, etc., Japanese Patent Application Laid-Open No. 10-339949, Japanese Patent Application Laid-Open No. 2004 Copolymer of a macromonomer and a monomer having a nitrogen atom described in Japanese Patent Publication No. -37986, etc., Japanese Patent Application Publication No. 2003-238837, Japanese Patent Application Publication No. 2008-9426, Japanese Patent Application Publication No. 2008-81732 A graft polymer having a partial skeleton or a heterocyclic ring having an organic pigment as described in Japanese Patent Application Publication No. 2010-106268 and the like, and a copolymer of a macromonomer and an acid group-containing monomer described in Japanese Patent Application Laid-Open No. 2010-106268 and the like. As the block type polymer, the block type polymers described in Japanese Patent Application Laid-Open No. 2003-49110, Japanese Patent Application Laid-Open No. 2009-52010, and the like are preferable.

In the present invention, a graft copolymer containing a repeating unit represented by any one of the following formulae (11) to (14) can also be used as the resin.

[Chemical Formula 3]

In the formulae (11) to (14), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ^4, and X ⁵ each independently represent hydrogen. An atom or a monovalent group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent group, R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a monovalent group, n, m, p, and q each independently represent an integer of 1 to 500, and j and k each independently represent an integer of 2 to 8. In formula (13), when p is 2 to 500, a plurality of R ³ may be the same as or different from each other. In formula (14), when q is 2 to 500, a plurality of X ⁵ and R ^{4 are present.} They may be the same as or different from each other.

About the said graft copolymer, the description of the paragraph number 0025-0094 of Unexamined-Japanese-Patent No. 2012-255128 can be referred, and the said content is integrated into this specification. Specific examples of the graft copolymer include the following resins. In addition, the resins described in paragraphs 0072 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128 can be cited, and the contents are incorporated into this specification.

Further, as the resin, an oligoimide-based dispersant containing a nitrogen atom in at least one of a main chain and a side chain can be used. As the oligoimide-based dispersant, a resin having a repeating unit including a partial structure X and a side chain including a side chain Y having 40 to 10,000 atoms and having a basic nitrogen atom in at least one of a main chain and a side chain is: Preferably, the partial structure X has a functional group of pKa14 or less. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Examples of the oligoimide-based dispersant include a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeat represented by the formula (I-2a) Unit of resin, etc.

[Chemical Formula 4] R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). a each independently represents an integer of 1 to 5. * Indicates a connection between repeating units. R ⁸ and R ⁹ are groups having the same meaning as R ¹ . L-based single bond, alkylene (carbon number 1 to 6 is preferred), alkylene (carbon number 2 to 6 is preferred), alkylene (carbon number 6 to 24 is preferred), hetero-arylene Group (carbon number 1 to 6 is preferred), imine group (carbon number 0 to 6 is preferred), ether group, thioether group, carbonyl group or a combination of these. Among them, a single bond or -CR ⁵ R ⁶ -NR ^7- (imide group becomes X or Y) is preferred. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, and an alkyl group (carbon numbers of 1 to 6 are preferred). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. La is ^a structural site that forms a ring structure with CR ⁸ CR ⁹ and N, and a structural site that forms a non-aromatic heterocyclic ring with 3 to 7 carbon atoms together with the carbon atoms of CR ⁸ CR ⁹ is preferred. It is more preferably a 5- to 7-membered non-aromatic heterocyclic structure site together with a carbon atom and N (nitrogen atom) of CR ⁸ CR ⁹ , more preferably a 5-membered non-aromatic heterocyclic structure site. The structural site where pyrrolidine is formed is particularly preferred. The structural site may further have a substituent such as an alkyl group. X represents a group having a functional group of pKa14 or less. Y represents a side chain having 40 to 10,000 atoms. The oligoimide-based dispersant may further contain, as a copolymerization component, one or more kinds selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5). When the oligoimide-based dispersant contains such a repeating unit, the dispersibility can be further improved.

[Chemical Formula 5]

R ¹ , R ² , R ⁸ , R ⁹ , L, La, a, and * have the same meanings as those in the formulae (I-1), (I-2), and (I-2a). Ya represents a side chain having 40 to 10,000 atoms having an anionic group. The repeating unit represented by the formula (I-3) can be added to a resin having a primary or secondary amine group in the main chain portion by adding an oligomer or polymer having a group that reacts with an amine to form a salt and make Formed by reaction.

Regarding the oligoimide-based dispersant, reference can be made to the descriptions in paragraphs 0102 to 0166 of Japanese Patent Application Laid-Open No. 2012-255128, and the above contents are incorporated into this specification. Specific examples of the oligoimide-based dispersant include the following. In addition, the resin described in paragraphs 0168 to 0174 of Japanese Patent Application Laid-Open No. 2012-255128 can be used. [Chemical Formula 6]

Resins can also be obtained as commercially available products, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie GmbH). In addition, the pigment dispersant described in Japanese Patent Application Laid-Open No. 2014-130338, paragraph numbers 0041 to 0130, can also be used, and this content is incorporated into this specification. As the resin, an alkali-soluble resin and the like described in a curable composition described later can also be used.

The content of the resin in the pigment dispersion liquid of the present invention is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the pigment. The upper limit is more preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less. The lower limit is more preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. When the content of the resin is within the above range, the dispersibility of the pigment is good.

<< Pigment derivative >> The pigment dispersion liquid of the present invention preferably further contains a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a group having a salt structure, or a phthalimide methyl group, and is represented by formula (B1) Pigment derivatives are preferred.

[Chemical Formula 7] In formula (B1), P represents a pigment structure, L represents a single bond or a linking group, X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide methyl group, and m represents 1 or more Integer, n represents an integer of 1 or more, when m is 2 or more, the plural L and X may be different from each other, and when n is 2 or more, the plural X may be different from each other.

In formula (B1), P represents a pigment structure, and is selected from the group consisting of pyrrolopyrrole pigment structures, diketopyrrolopyrrole pigment structures, quinacridone pigment structures, anthraquinone pigment structures, bisanthraquinone pigment structures, and benzoisoindole Indole pigment structure, thiazine indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, pyrene pigment structure, perionone pigment structure, benzo At least one of the imidazolone pigment structure, the benzothiazole pigment structure, the benzimidazole pigment structure, and the benzoxazole pigment structure is preferably selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacrid At least one of a pyridone pigment structure and a benzimidazolone pigment structure is further preferred, and a pyrrolopyrrole pigment structure is particularly preferred.

In formula (B1), L represents a single bond or a linking group. As the linking group, a group consisting 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 is preferable, and Substitution may further have a substituent. Specific examples include an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, -O-, -S-, -NR'-, -CO-, -SO ₂ -or a group including a combination thereof group. R 'represents a hydrogen atom, an alkyl group or an aryl group.

In the formula (B1), X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide methyl group. Examples of the acidic group include a carboxyl group and a sulfo group. As the basic group, an amine group is preferred, and a tertiary amine group is particularly preferred. Examples of the group having a salt structure include a salt of an acidic group and a salt of a basic group. Examples of the atom or atomic group constituting the salt include a metal atom and tetrabutylammonium. The metal atom is preferably an alkali metal atom or an alkaline earth metal atom. Examples of the alkali metal atom include lithium, sodium, and potassium. Examples of the alkaline earth metal atom include calcium and magnesium.

Specific examples of the pigment derivative include the following compounds. Also, Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 1-217077, Japanese Patent Application Laid-Open No. 3-9961, and Japanese Patent Application Laid-Open No. 3-26767 can also be used. Gazette, Japanese Patent Laid-Open No. 3-153780, Japanese Patent Laid-Open No. 3-45662, Japanese Patent Laid-Open No. 4-285669, Japanese Patent Laid-Open No. 6-145546, Japanese Patent Laid-Open No. 6-212088, Japanese Patent Laid-Open Japanese Patent Application Publication No. 6-240158, Japanese Patent Application Publication No. 10-30063, Japanese Patent Application Publication No. 10-195326, International Publication No. WO2011 / 024896, paragraph numbers 0086 to 0098, International Publication No. WO2012 / 102399, paragraph number 0063 to Compounds described in 0094 and the like, and compounds described in paragraph No. 0053 of International Publication No. WO2016 / 035695 are incorporated herein by reference. As pigment derivatives, the following compounds (B-1), (B-2), (B-3), (B-6), (B-15), (B-16), (B-18), (B-30), (B-61) and (B-62) are particularly good.

[Chemical Formula 8] [Chemical Formula 9]

When the pigment dispersion liquid of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit value is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved, and aggregation of the pigment can be effectively suppressed. The pigment derivative may be only one kind, or may be two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

<Preparation of Pigment Dispersion Liquid> The pigment dispersion liquid of the present invention can be prepared by mixing the aforementioned components. When preparing the pigment dispersion liquid, the components may be blended at one time, or the components may be blended one by one after being dissolved or dispersed in a solvent. In addition, the order of input and working conditions during blending are not particularly restricted. For example, a pigment dispersion can be prepared by simultaneously dissolving or dispersing all the components in a solvent.

In preparing the pigment dispersion liquid, a process including dispersing the pigment is preferable. In the process of dispersing a pigment, examples of the mechanical force used in dispersing the pigment include compression, pressing, impact, shear, and cavitation. Specific examples of such processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, and a sand mixer. , Jetjet mixer (flowjet mixer), high-pressure wet-type micronization, ultrasonic dispersion, etc. In addition, the process for dispersing pigments and the dispersing machine can make better use of "Encyclopedia of Dispersion Technology, issued by JOHOKIKO CO., LTD., July 15, 2005" or "centered on suspension (solid / liquid dispersion system) The actual comprehensive data collection of dispersive technology and industrial applications, issued by the Publishing Department of the Operation and Development Center, October 10, 1978, and the processes and dispersers described in paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893.

When preparing a pigment dispersion liquid, it is preferable to filter the pigment dispersion liquid with a filter for the purpose of removing foreign matter or reducing defects. The filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtering purposes and the like. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), polyolefin resins such as polyethylene, and polypropylene (PP) ( Filters containing materials such as high density, ultra high molecular weight polyolefin resins). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably 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. When the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fibers, nylon fibers, and glass fibers. Specific examples include filter cartridges of SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), SHPX series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

When using filters, you can combine different filters (for example, the first filter and the second filter, etc.). At this time, the filtration using each filter may be performed only once, or may be performed twice or more. Filters with different pore sizes can be combined within the above range. The pore size at this time can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by NIHON PALL LTD. (DFA4201NXEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon Mykrolis Corporation), or KITZ MICROFILTER CORPORATION can be selected. The second filter can be formed from the same material as the first filter.

<Curable composition> Next, the curable composition of this invention is demonstrated. The curable composition of the present invention includes the near-infrared-absorbing organic pigment, a resin, a curable compound, and a solvent. The curable composition of the present invention is also preferably a composition containing the pigment dispersion liquid and a curable compound. The curable composition of the present invention may be a photo-curable composition or a thermo-curable composition. In the case of the photocurable composition, a composition containing a polymerizable compound (preferably a radical polymerizable compound) and a photopolymerization initiator (preferably a photoradical polymerization initiator) is preferable.

<<< Near-infrared-absorbing organic pigment> The curable composition of this invention contains the said near-infrared-absorbing organic pigment. The content of the near-infrared-absorbing organic pigment is preferably 0.1 to 60% by mass based on the total solid content of the curable composition. The lower limit is preferably 1% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

<< Other Near-Infrared Absorbing Compounds >> The composition of the present invention may further include near-infrared absorbing compounds (also referred to as other near-infrared absorbing compounds) other than the above-mentioned near-infrared absorbing organic pigments. Examples of other near-infrared absorbing compounds include dyes. Examples of the compound type include a phthalocyanine compound, a naphthalocyanine compound, a ruthenium compound, a merocyanine compound, a ketonium compound, an oxacyanine compound, a diimine compound, a dithiol compound, and a triaryl group. Methane compounds, pyrrole methylene compounds, methine azo compounds, anthraquinone compounds, and dibenzofuranone compounds. As the phthalocyanine compound, naphthalocyanine compound, diimine compound, and ketonium compound, the compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 can be used, and the contents are incorporated into this specification . Moreover, IRA868 (made by Exiton Inc.), IRG-068 (made by Nippon Kayaku Co., Ltd.), etc. can also be used.

In addition, as other near-infrared absorbing compounds, inorganic particles can also be used. From the viewpoint of more excellent infrared shielding properties, inorganic particle-based metal oxide particles or metal particles are preferred. Examples of the 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, and fluorine-doped Tin oxide (F-doped SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. As the inorganic fine particles, a tungsten oxide-based compound can be used. The tungsten oxide-based compound is preferably a cesium tungsten oxide. For details of the tungsten oxide-based compound, refer to paragraph number 0080 of Japanese Patent Application Laid-Open No. 2016-006476, which is incorporated into this specification. The shape of the inorganic particles is not particularly limited, and is not related to the spherical shape or the non-spherical shape, and may be a sheet shape, a wire shape, or a tube shape.

The average particle diameter of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average particle diameter of the inorganic particles is within this range, it can be seen that the transparency is good. From the standpoint of avoiding light scattering, the smaller the average particle diameter, the better, but for reasons such as ease of handling at the time of manufacture, the average particle diameter of the inorganic particles is usually 1 nm or more.

When the curable composition of the present invention contains other near-infrared absorbing compounds, the content of other near-infrared absorbing compounds is preferably 0.1 to 80 parts by mass, and 5 to 60 parts by mass relative to 100 parts by mass of the near-infrared absorbing organic pigment. More preferably, 10 to 40 parts by mass is more preferable.

<<< Coloring agent> The curable composition of this invention can contain a coloring agent. In the present invention, a coloring agent refers to a coloring agent other than a white coloring agent and a black coloring agent. The coloring agent is preferably a coloring agent having absorption in a wavelength range of 400 nm or more and less than 650 nm.

In the present invention, the coloring agent may be a pigment or a dye. Pigment-based organic pigments are preferred. Examples of the organic pigment include the following. Color index (CI) Pigment Yellow (Pigment Yellow) 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (the above are yellow pigments); CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments) ; CI Pigment Red (Pigment Red) 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49 : 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105 , 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190 , 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (the above are red pigments); CI Pigment Green ( Pigment Green) 7, 10, 36, 37, 58, 59, etc. (the above are green pigments), CI Pigment Violet (Pigment Violet) 1, 19, 23, 27, 32, 37, 42, etc. (the above are purple pigments); CI Pigment Blue (Pigment Blue) 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (the above are Blue pigment), these organic pigments can be used alone or in combination with various organic pigments.

The dye is not particularly limited, and a known dye can be used. As the chemical structure, a pyrazole azo system, an aniline azo system, a triarylmethane system, an anthraquinone system, an anthrapyridone system, a benzylidene system, an oxacyanine system, and a pyrazolotria Azole azo, pyridone azo, cyanine, thiophenazine, pyrrolopyrazolyl azo, xanthene, phthalocyanine, benzopyran, indigo, pyrrole methylene Base and other dyes. A multimer of these dyes may also be used. The dyes described in Japanese Patent Application Laid-Open No. 2015-028144 and Japanese Patent Application Laid-Open No. 2015-34966 can also be used.

When the curable composition of the present invention contains a coloring agent, the content of the coloring agent is preferably 0.1 to 70% by mass based on the total solid content of the curable composition of the present invention. The lower limit is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The content of the colorant is preferably 10 to 1,000 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. The total amount of the coloring agent and the near-infrared absorbing organic pigment is preferably 1 to 80% by mass based on the total solid content of the curable composition of the present invention. The lower limit is preferably 5 mass% or more, and more preferably 10 mass% or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less. When the curable composition of the present invention contains two or more coloring agents, the total amount thereof is preferably within the above range.

<<< Color material that transmits infrared rays and blocks visible light >> The curable composition of the present invention may contain a color material that transmits infrared rays and block visible light (hereinafter, also referred to as a color material that blocks visible light). In the present invention, a color material that blocks visible light is preferably a color material that absorbs light in a wavelength range from purple to red. In the present invention, a color material that blocks visible light is preferably a color material that blocks light in a wavelength range of 450 to 650 nm. The color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm. In the present invention, it is preferable that the color material that blocks visible light satisfies at least one of the following requirements (1) and (2). (1): Two or more kinds of coloring agents are included, and black is formed by a combination of two or more kinds of coloring agents. (2): Contains organic black colorants. In the aspect (2), it is also preferable to further contain a coloring agent.

In the present invention, the organic black colorant, which is a color material that blocks visible light, is a material that absorbs visible light but transmits at least a part of infrared rays. Therefore, in the present invention, the organic black colorant, which is a color material that blocks visible light, does not include a black colorant that absorbs both visible light and infrared light, such as carbon black or titanium black.

Examples of the coloring agent include the above. Examples of the organic black colorant include a bisbenzofuranone compound, a methine azo compound, a fluorene compound, an azo compound, and the like. A bisbenzofuranone compound and a fluorene compound are preferable. Examples of the bisbenzofuranone compounds include those described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, and the like, which can be produced, for example, by BASF Corporation. "Irgaphor Black". Examples of the fluorene compound include C.I. Pigment Black 31, 32, and the like. Examples of the methine azo compound include those described in Japanese Patent Application Laid-Open No. 1-170601, Japanese Patent Application Laid-Open No. 2-34664, and the like, and can be produced, for example, by Daichiniseka Color & Chemicals Mfg. Co., Ltd. "CHROMO FINE BLACKA1103".

In the present invention, the ratio of the minimum value A of the absorbance of the color material that blocks visible light in the range of 450 to 650 nm to the minimum value B of the absorbance in the range of 900 to 1300 nm, that is, A / B is 4.5 or more. Better. The above-mentioned characteristics may be satisfied by one kind of material or a combination of plural kinds of materials. For example, in the case of the aspect (1), it is preferable that a plurality of color colorants are combined to satisfy the above-mentioned spectral characteristics. In the case of the aspect (2), the above-mentioned spectral characteristics can be satisfied by the organic black colorant. The above-mentioned spectral characteristics may be satisfied by a combination of an organic black colorant and a colorant.

Examples of the combination of color colorants when black is formed by a combination of two or more color colorants include the following. (1) A state containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant. (2) A state containing a yellow colorant, a blue colorant, and a red colorant. (3) A state containing a yellow colorant, a purple colorant, and a red colorant. (4) A state containing a yellow colorant and a purple colorant. (5) A state containing a green colorant, a blue colorant, a purple colorant, and a red colorant. (6) A state containing a purple colorant and an orange colorant. (7) A state containing a green colorant, a purple colorant, and a red colorant. (8) A state containing a green colorant and a red colorant.

Examples of the ratio (mass ratio) of each colorant include the following. [Table 1]

When the curable composition of the present invention contains a color material that blocks visible light, the content of the color material that blocks visible light is preferably 30% by mass or less, and more preferably 20% by mass or less relative to the total solid content of the curable composition. 15 mass% or less is more preferred. The lower limit may be, for example, 0.01% by mass or more, and may be 0.5% by mass or more. Moreover, the curable composition of this invention can also be set as the state which does not substantially contain the color material which blocks visible light. The color material that does not substantially block visible light means that the content of the color material that blocks visible light is preferably 0.005 mass% or less, and more preferably 0.001 mass% or less in the total solid content of the curable composition of the present invention. It is further preferred that no color material that blocks visible light is used.

<< Pigment derivative >> The curable composition of the present invention preferably contains a pigment derivative. As a pigment derivative, the pigment derivative demonstrated by the said pigment dispersion liquid is mentioned.

When the curable composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass based on 100 parts by mass of the pigment. The lower limit value is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. The pigment derivative may be only one kind, or may be two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

<< Resin> The curable composition of the present invention contains a resin. The resin is blended, for example, for use in dispersing a pigment or the like in a curable composition, or for use in an adhesive. A resin mainly used for dispersing pigments and the like is also referred to as a dispersant. However, this use of the resin is an example, and the resin can also be used for purposes other than this use.

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, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

Examples of the resin include the resins described in the pigment dispersion. In addition, (meth) acrylic resin, olefin-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polyfluorene resin, polyetherfluorene resin, polyphenylene sulfide resin, and polyarylene ether phosphine are used for oxidation. Also preferred are resins such as resins, polyimide resins, polyimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. These resins may be used singly or in combination of two or more kinds.

The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group. These acid groups may be only one kind, or two or more kinds. The resin having an acid group can also be used as an alkali-soluble resin. It can also be used as a dispersant.

The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 to 100,000. The number-average molecular weight (Mn) of the alkali-soluble resin is preferably 1,000 to 20,000. The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and more preferably 70 mg KOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

As the alkali-soluble resin, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferred from the viewpoint of heat resistance. Further, from the viewpoint of controlling the developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

As the alkali-soluble resin, a polymer having a carboxyl group in a side chain is preferable. Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolac resins. Equal alkali-soluble phenol resin, 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. In particular, copolymers of (meth) acrylic acid and other monomers capable of being copolymerized therewith are suitable as alkali-soluble resins. Examples of other monomers that can be copolymerized with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, vinyl compounds, and the like. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) Butyl acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid Benzyl ester, toluene methyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of the vinyl compound include styrene, α-methylstyrene, and vinyl toluene , Glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromer, polymethyl methacrylate macromer Wait. In addition, as the other monomers, it is possible to use an N-substituted cis-butylene diimide monomer described in Japanese Patent Application Laid-Open No. 10-300922, such as N-phenylcis-butene diimide, N-ring Hexyl cis butene difluorene imine and the like. The other monomers that can be copolymerized with the (meth) acrylic acid may be only one kind, or two or more kinds.

As the alkali-soluble resin, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid 2-hydroxyethyl can be preferably used. Ester copolymer, benzyl (meth) acrylate / (meth) acrylic acid / multiple copolymer of other monomers. Further, 2-hydroxypropyl (meth) acrylate / poly (meth) acrylate described in Japanese Patent Application Laid-Open No. 7-140654, which is obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, can also be preferably used. Styrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / formaldehyde Acrylic 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.

The alkali-soluble resin includes a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers"). A polymer obtained by polymerizing a monomer component is also preferable.

[Chemical Formula 10]

In the 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. [Chemical Formula 11] 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), reference can be made to the description in Japanese Patent Application Laid-Open No. 2010-168539.

In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, Linear or branched alkyl groups such as n-butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, Tertiary butyl cyclohexyl, dicyclopentadienyl, tricyclodecyl, isofluorenyl, adamantyl, 2-methyl-2-adamantyl and other alicyclic groups; 1-methoxyethyl Alkyl groups substituted with alkoxy groups such as alkyl, 1-ethoxyethyl; alkyl substituted with aryl groups such as benzyl; and the like. Among these, from the viewpoint of heat resistance, substituents of primary or secondary carbons such as methyl, ethyl, cyclohexyl, benzyl, etc., which are not easily removed by the action of acid or heat, are particularly preferred.

As a specific example of the ether dimer, for example, paragraph number 0317 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and this content is incorporated into this specification. The ether dimer may be only one kind, or two or more kinds.

The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X). [Chemical Formula 12] In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer from 1 to 15.

As the alkali-soluble resin, reference can be made to the description of paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraph numbers 0685 to 0700 of US Patent Application Publication No. 2012/0235099), and Japanese Patent Laid-Open No. 2012-198408 The descriptions of paragraph numbers 0076 to 0099 in the gazette are incorporated into this specification.

As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acrylfluorenyl group. The alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin having a polymerizable group in a side chain. Examples of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (polyurethane acrylic oligomer containing COOH), and Diamond Shamrock Co., Ltd. (Manufactured), Viscote R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (Daicel UCB Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

The content of the resin in the curable composition of the present invention is preferably 14 to 70% by mass based on the total solid content of the curable composition of the present invention. The lower limit is preferably 17% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less. The content of the resin having an acid group is preferably 14 to 70% by mass based on the total solid content of the curable composition of the present invention. The lower limit is preferably 17% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less. The content of the alkali-soluble resin is preferably 14 to 70% by mass based on the total solid content of the curable composition of the present invention. The lower limit is preferably 17% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.

<< Solvent> The curable composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the curable composition, but is preferably selected in consideration of the coatability and safety of the curable composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. For these details, the organic solvent described in the pigment dispersion liquid can be used. Examples of the organic solvent include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. Compared with methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. good.

The content of the solvent is more preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass based on the total amount of the curable composition. The curable composition of the present invention may contain only one kind of solvent, or may contain two or more kinds. When two or more solvents are contained, the total amount thereof is preferably within the above range.

<<< hardening compound> The hardening composition of this invention contains a hardening compound. As the curable compound, a known compound that can be crosslinked by radicals, acids, and heat can be used. Examples of the curable compound include a polymerizable compound and a compound having an epoxy group. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond group such as a vinyl group, a (meth) allyl group, and a (meth) acrylfluorenyl group. The polymerizable compound is preferably a radical polymerizable compound.

In the curable composition of the present invention, the content of the curable compound is preferably 0.1 to 50% by mass based on the total solid content of the curable composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 45% by mass or less, and more preferably 40% by mass or less. The curable compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

(Polymerizable Compound) The polymerizable compound may be 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 3000. The upper limit is more preferably 2000 or less, and further preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound. Specific examples of such compounds include paragraph numbers 0095 to 0108 of Japanese Patent Laid-Open No. 2009-288705, paragraph 0227 of Japanese Patent Laid-Open No. 2013-29760, and paragraph numbers 0254 to Japanese Patent Laid-Open No. 2008-292970 The compounds described in 0257 are incorporated into this specification.

The polymerizable compound is dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D- as a commercial product) 320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol Hexa (meth) acrylate (available commercially as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like (meth) A structure in which allyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, SR454, SR499 commercially available from Sartomer Company, Inc.) is preferred. These types of oligomers can also be used. In addition, as the polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane and propyloxy modified tri (meth) acrylate, and trimethylolpropane and ethyloxy were used. Trifunctional (meth) acrylic acid, such as modified tri (meth) acrylate, isocyanurate and ethyloxy modified tri (meth) acrylate, neopentyl tetraol tri (meth) acrylate Ester compounds are also preferred. Examples of commercially available trifunctional (meth) acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, and M- 306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A -TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 ( Nippon Kayaku Co., Ltd.).

As the polymerizable compound, a polymerizable compound having an acid group can also be used. By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion can be easily removed during development, and the development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group. A carboxyl group is preferred. Examples of commercially available polymerizable compounds having an acid group include ARONIX M-510 and M-520 (manufactured by TOAGOSEI CO., LTD.).

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

As the polymerizable compound, a polymerizable compound having a caprolactone structure can also be used. As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy gorup, and has a polymerizability of an ethyleneoxy group. Compounds are more preferred, and 3 to 6 functional (meth) acrylate compounds having 4 to 20 ethoxy groups are more preferred. As a commercially available product of a polymerizable compound having an alkyleneoxy group, for example, SR-494, which is a tetrafunctional (meth) acrylate having four ethyloxy groups, manufactured by Sartomer Company, Inc. KAYARAD TPA-330, which is a trifunctional (meth) acrylate with three isobutyloxy groups.

As the polymerizable compound, the urethanes described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Acrylates, or those having an ethylene oxide system described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Also preferred are skeleton urethane compounds. In addition, addition polymerization described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 is used. Sexual compounds are also preferred. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo. Kokusaku. Pulp. Co., Ltd.), and UA-7200 (Shin-Nakamura Chemical Co., Ltd.) .Manufactured), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by KYOEISHA CHEMICAL Co., Ltd. )Wait.

When the curable composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass based on the total solid content of the curable composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, and more preferably 20% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more polymerizable compounds are used in combination, the total amount is preferably within the above range.

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

The epoxy equivalent of the compound having an epoxy group (= the molecular weight of the compound having an epoxy group / the number of epoxy groups) is preferably 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g / equivalent Is even better.

The compound having an epoxy group may be any of a low molecular compound (for example, a molecular weight of less than 1,000) and a macromolecule (for example, a molecular weight of 1,000 or more, and in the case of a polymer, a weight average molecular weight of 1,000 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 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

Compounds having an epoxy group can also use paragraph numbers 0034 to 0036 of Japanese Patent Laid-Open No. 2013-011869, paragraph numbers 0147 to 0156 of Japanese Patent Laid-Open No. 2014-043556, and paragraph numbers of Japanese Patent Laid-Open No. 2014-089408. Compounds described in 0085 to 092. Such content is incorporated into this specification. In addition, for compounds (epoxy resins) having epoxy groups, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100 are used. G-01758 (made by NOF CORPORATION, epoxy-containing polymer) is also preferred.

When the curable composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass based on the total solid content of the curable composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, and more preferably 20% by mass or less. The compound having an epoxy group may be used singly or in combination of two or more kinds. When two or more types are used in combination, the total amount is preferably within the above range. The mass ratio of the polymerizable compound to the compound having an epoxy group is the mass of the polymerizable compound: the mass of the compound having an epoxy group = 100: 1 to 100: 400 is preferable, and 100: 1 to 100: 100 is More preferably, 100: 1 to 100: 50 is more preferable.

<< Photopolymerization initiator >> The curable composition of the present invention can contain a photopolymerization initiator. In particular, when the curable composition of the present invention contains a polymerizable compound, it is preferable to include a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a compound having sensitivity to light from the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), fluorenyl phosphine compounds such as fluorenylphosphine oxide, and hexaarylbiimidazole Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1384492, and Japan. Compounds described in Japanese Patent Application Laid-Open No. 53-133428, compounds described in German Patent No. 3370024, J. Org. Chem. Edited by FC Schaefer et al .; 29, 1527 (1964), Compounds described in Japanese Patent Laid-Open No. 62-58241, compounds described in Japanese Patent Laid-Open No. 5-281728, compounds described in Japanese Patent Laid-Open No. 5-34920, and US Patent No. 4212976 The compounds described.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalo methyl triazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, and α-aminoketones. Compounds, fluorenylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene Compounds in the group of iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-amino ketone compound, and a fluorenylphosphine compound can also be preferably used. For example, an α-amino ketone compound described in Japanese Patent Application Laid-Open No. 10-291969 and a phosphonium phosphine compound described in Japanese Patent No. 4225898 can also be used. As the α-hydroxy ketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (the above are manufactured by BASF) can be used. As the α-amino ketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (the above are manufactured by BASF) can be used. As the α-amino ketone compound, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used. As a fluorenylphosphine compound, IRGACURE-819 or DAROCUR-TPO (above manufactured by BASF) can be used as a commercially available product.

The photopolymerization initiator is preferably an oxime compound. Specific examples of the oxime compound include a compound described in Japanese Patent Laid-Open No. 2001-233842, a compound described in Japanese Patent Laid-Open No. 2000-80068, and a compound described in Japanese Patent Laid-Open No. 2006-342166. Compounds, compounds described in Japanese Patent Application Laid-Open No. 2016-21012, and the like. Examples of the oxime compound that can be preferably used in the present invention include 3-benzyloxyiminobutane-2-one and 3-ethoxyiminobutane-2-one 3-propanyloxyiminobutane-2-one, 2-ethoxyloxyiminopentane-3-one, 2-ethoxyloxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Carbooxyimino-1-phenylpropane-1-one and the like. In addition, JCSPerkin II (1979, p. 1653-p. 1660), JCSPerkin II (1979, p. 156-p. 162), Journal of Photopolymer Science and Technology (Journal of Photopolymer Science) and Technology) (1995, p. 202-p. 232), Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application No. 2004-534797, Japanese Patent Application Laid-Open No. 2006-342166 Compounds described in the bulletin. Among commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (the above are manufactured by BASF) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION), ADEKA ARKLS NCI-930 (made by ADEKA CORPORATION), and ADEKA OPTOMER N- 1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in JP 2012-14052).

In addition, as the oxime compound other than the above, a compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is connected to the N position of the carbazole ring can be used, and a hetero substitution is introduced into the benzophenone site. The compounds described in U.S. Patent No. 7626957, the compounds described in Japanese Patent Application Laid-Open No. 2010-15025 in which a nitro group is introduced into a pigment portion, and U.S. Patent Publication No. 2009-292039, and International Publication WO2009 / 131189 The ketoxime compound described in Japanese Patent Publication No. 7556910, which contains a triazine skeleton and an oxime skeleton in the same molecule, has Japan which has a maximum absorption at 405 nm and has good sensitivity to a g-ray light source. Compounds described in Japanese Patent Application Laid-Open No. 2009-221114.

As the oxime compound, a compound represented by the following formula (OX-1) can be preferably used. The oxime compound may be an oxime compound in which the N-O bond of the oxime is the (E) form, or an oxime compound in which the N-O bond of the oxime is the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 13]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. For details of the formula (OX-1), refer to the description of paragraph numbers 0276 to 0304 in Japanese Patent Application Laid-Open No. 2013-029760, which is incorporated into this specification.

As the photopolymerization initiator, the present invention can also use an oxime compound having a fluorene ring. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this specification.

As the photopolymerization initiator, the present invention can also use an oxime compound having a fluorine atom. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36-40 of Japanese Patent Application No. 2014-500852, and Japanese Patent Laid-Open Compound (C-3) and the like described in Gazette 2013-164471. This content is incorporated into this specification.

As the photopolymerization initiator, the present invention can use an oxime compound having a nitro group. It is also preferred that the oxime compound having a nitro group is a dimer. Specific examples of the nitro-containing oxime compound include those described in JP 2013-114249, paragraph numbers 0031 to 0047, and JP 2014-137466, paragraph numbers 0008 to 0012, 0070 to 079. Compound, the compound described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4222071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited to these.

[Chemical Formula 14] [Chemical Formula 15]

The oxime compound is more preferably a compound having a maximum absorption in a wavelength region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption in a wavelength region of 360 nm to 480 nm. The oxime compound is preferably a compound having a high absorbance at 365 nm and 405 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of a compound can be measured using a well-known method. For example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is preferably used for measurement at a concentration of 0.01 g / L using an ethyl acetate solvent.

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

The content of the photopolymerization initiator is more preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass based on the total solid content of the curable composition. When the content of the photopolymerization initiator is within the above range, more excellent sensitivity and patterning properties can be obtained. The curable composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more kinds. When two or more kinds of photopolymerization initiators are included, the total amount thereof is preferably within the above range.

<<< chain transfer agent> The curable composition of this invention can contain a chain transfer agent. According to this aspect, the film surface (pattern surface) can be hardened by exposure. Therefore, it is possible to suppress a reduction in film thickness and the like at the time of exposure, and it is easy to form a pattern having more excellent rectangularity.

Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters, thiol compounds, and the like, and thiol compounds are preferred. The thiol compound is preferably a compound having two or more (preferably 2 to 8 and more preferably 3 to 6) thiol groups in the molecule. Specific examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris ( 3-Mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and other heterocyclic thiol compounds, neopentaerythritol tetrakis (3 -Mercaptobutyrate), aliphatic thiol compounds such as 1,4-bis (3-mercaptobutyryloxy) butane, and the like. It is also preferable to use the following compounds. In addition, as commercially available products of the chain transfer agent, PEMP (thiol compound manufactured by NAGASE & CO., LTD.), Sanceler M (thiol compound manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD), and Karenz MT BD1 are mentioned. (Manufactured by SHOWA DENKO KK, thiol compounds), etc. [Chemical Formula 16]

The content of the chain transfer agent is preferably 0.2 to 5.0% by mass, and more preferably 0.4 to 3.0% by mass based on the total solid content of the curable composition. The content of the chain transfer agent is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass based on 100 parts by mass of the polymerizable compound.

<<< polymerization inhibitor> The curable composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, third-butylcatechol, benzoquinone, 4,4 '-Thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N-nitrosobenzene Hydroxylamine salts (ammonium salts, cerium salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the curable composition. The content of the polymerization inhibitor is preferably 0.001 to 1 part by mass based on 100 parts by mass of the polymerizable compound. The upper limit is preferably 0.5 parts by mass or less, and more preferably 0.2 parts by mass or less. The lower limit is preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more. The curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds of polymerization inhibitors are contained, the total amount thereof is preferably within the above range.

<<< ultraviolet absorbent> It is preferable that the curable composition of this invention contains an ultraviolet absorber. Examples of the ultraviolet absorber include a conjugated diene compound and a diketone compound. Examples of the conjugated diene-based compound include a compound represented by the formula (UV-1). [Chemical Formula 17]

In the formula (UV-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² may be the same as each other or may be Different, but do not mean hydrogen atoms at the same time.

The description of the substituent of the compound represented by Formula (UV-1) can refer to the description of paragraph number 0024-0033 of the international publication WO2009 / 123109, and this content is integrated in this specification. Specific examples of the compound represented by the formula (UV-1) include the exemplified compounds (1) to (14) of paragraph numbers 0034 to 0037 of International Publication No. WO2009 / 123109, which are incorporated into the present specification. . As a commercial item of the ultraviolet absorber represented by Formula (UV-1), UV503 (made by DAITO CHEMICAL CO., LTD.) Etc. are mentioned, for example.

Examples of the diketone compound include compounds represented by the following formula (UV-2). [Chemical Formula 18] In the formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0 to 4. Examples of the substituent include alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, Fluorenyloxy, amine, sulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, heteroaryloxycarbonylamino, sulfonamido, sulfamomidino, carbamoyl, alkylthio , Arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfinyl Group, urea group, phosphonium amino group, mercapto group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfinyl group, hydrazine group, imino group, silicon group, hydroxyl group, halogen atom, cyano group, etc And alkoxy are preferred. The carbon number of the alkyl group is preferably 1 to 20. Examples of the alkyl group include a straight chain, a branch, and a cyclic ring. A straight chain or a branch is preferable, and a branch is more preferable. The carbon number of the alkoxy group is preferably 1 to 20. Examples of the alkoxy group include a straight chain, a branch, and a cyclic ring. A straight chain or a branch is preferable, and a branch is more preferable. A combination in which one of R ¹⁰¹ and R ¹⁰² is an alkyl group and the other is an alkoxy group is preferable. m1 and m2 each independently represent 0 to 4. It is preferable that m1 and m2 are independently 0 to 2, 0 to 1 is more preferable, and 1 is particularly preferable.

Examples of the compound represented by the formula (UV-2) include the following compounds. [Chemical Formula 19]

As the ultraviolet absorber, Uvinul A (manufactured by BASF) can also be used. In addition, as the ultraviolet absorber, ultraviolet absorbers such as amine diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, and triazine compounds can be used. The compound described in Japanese Patent Application Laid-Open No. 2013-68814. As the benzotriazole compound, MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016) can be used.

Content of an ultraviolet absorber is 0.01-10 mass% with respect to the total solid content of the curable composition of this invention, More preferably, it is 0.01-5 mass%. The content of the ultraviolet absorber is preferably 5 to 100 parts by mass based on 100 parts by mass of the polymerizable compound. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.

<< Silane coupling agent> The curable composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the silane compound. The hydrolyzable group refers to a substituent directly connected to a silicon atom and capable of generating a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and a fluorenyl group. An alkoxy group is preferred. That is, a silane coupling agent is preferably a compound having an alkoxysilyl group. Moreover, a functional group other than a hydrolyzable group is preferably a group that exhibits affinity by interacting with or forming a bond with a resin. Examples include vinyl, styryl, (meth) acrylfluorenyl, mercapto, epoxy, oxetanyl, amino, urea, sulfide, isocyanate, and the like, (meth) propylene Amidino and epoxy are preferred. Examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, compounds described in paragraphs 0056 to 0066 of JP 2009-242604, and international publications. The compounds described in paragraphs 0229 to 0236 of WO2015 / 166779 are incorporated into this specification.

The content of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass based on the total solid content of the curable composition. The curable composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds. When two or more kinds of silane coupling agents are contained, the total amount thereof is preferably within the above range.

<<< Surfactant> The curable composition of the present invention may contain various surfactants from the viewpoint of further improving coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silica-based surfactant can be used. The surfactant can be referred to paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166779, which is incorporated into this specification.

By containing a fluorine-based surfactant in the curable composition of the present invention, the solution characteristics (especially the fluidity) when the coating liquid is prepared are further improved, and the uniformity of coating thickness and the liquid saving property can be further improved. . When a coating liquid using a hardening composition containing a fluorine-based surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid is reduced to improve the wettability to the coated surface, The coating property of the coated surface is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

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

Specific examples of the fluorine-based surfactant include those described in JP-A-2014-41318, paragraph numbers 0060 to 0064 (corresponding to International Publication No. 2014/17669, paragraph numbers 0060 to 0064), and the like. Surfactants and the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503 are incorporated herein. Examples of commercially available fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475 , MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780 (above manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-101 103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (The above are manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (the above are manufactured by OMNOVA Solutions Inc.), etc.

In addition, as the fluorine-based surfactant, an acrylic compound can be preferably used. The acrylic compound has a molecular structure having a functional group containing a fluorine atom, and a functional group containing a fluorine atom is cut off when a heat is applied, and the fluorine atom is cut. Volatile. Examples of such a fluorine-based surfactant include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Industry News, February 23, 2016), and examples include MEGAFACE DS-21, can use these.

As the fluorine-based surfactant, a block polymer can also be used. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2011-89090. A fluorine-based surfactant can also preferably use a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and derived from a compound having two or more (preferably) 5 or more) repeating units of a (meth) acrylate compound of an alkyleneoxy group (preferably an ethyloxy group or a propyloxy group). The following compounds can also be exemplified as fluorine-based surfactants used in the present invention. [Chemical Formula 20] The weight average molecular weight of the compound is preferably 3,000 to 50,000, and is, for example, 14,000. In the above-mentioned compounds, the percentage representing the proportion of the repeating unit is mass%.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation. , RS-72-K, etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of non-ionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, glycerol propane) Oxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass relative to the total solid content of the curable composition.

<< Other Components> The hardenable composition of the present invention may contain a sensitizer, a hardening accelerator, a filler, a thermal hardening accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, and other additives as necessary. Agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.). These components can be referred to the descriptions of paragraph numbers 0101 to 0104, 0107 to 0109, and the like of Japanese Patent Application Laid-Open No. 2008-250074, which are incorporated into this specification. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a sulfide compound having a molecular weight of 500 or more is more preferable. These can be used in combination of two or more. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. In particular, a compound having a substituent at a position (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred, and methyl, ethyl, propionyl, isopropylmethyl, butyl, isobutyl, and third butyl , Pentyl, isopentyl, tertiary pentyl, hexyl, octyl, isooctyl, 2-ethylhexyl are more preferred. In addition, an antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. As the antioxidant, a phosphorus-based antioxidant can be preferably used. Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetra (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] Dioxoheteroheptin-2-yl) oxy] ethyl] amine and bis (2,4-di-third-butyl-6-methylphenyl) At least one compound in the group of ethyl phosphate. These can be obtained as commercial products. Examples 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, Adekastab AO-330 ( ADEKA CORPORATION) and so on. The content of the antioxidant relative to the total solid content of the composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The antioxidant may be only one kind, or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.

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

The Ti value of the curable composition of the present invention at 23 ° C is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, and even more preferably 0.9 to 1.1. The Ti value of the curable composition can be measured by the method described in the above-mentioned pigment dispersion liquid column.

The curable composition of the present invention can be preferably used for forming a near-infrared cut filter, an infrared transmission filter, and the like.

<The manufacturing method of a curable composition> The curable composition of this invention can be prepared by mixing each said component. In addition, for the purpose of removing foreign matters or reducing defects, it is preferable to perform filtration with a filter. Regarding the type of the filter and the filtering method, those described in the preparation column of the pigment dispersion liquid can be cited, and the preferable ranges are also the same.

<Film, near-infrared cut filter> Next, the film of this invention is demonstrated. The film of the present invention is obtained by using the curable composition of the present invention. The film of the present invention can be preferably used as a filter such as a near-infrared cut filter or an infrared transmission filter. In addition, the optical filter has a preferable aspect including a pixel using the film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless. The film of the present invention can also be used as a hot-ray shielding filter. The film of the present invention may have a pattern, or may be a film (flat film) without a pattern. The film of the present invention may be used by being laminated on a support, or may be used by peeling the film of the present invention from the support. When the film of the present invention is used as an infrared transmission filter, the infrared transmission filter may be a filter that blocks visible light and transmits light having a wavelength of 900 nm or more. When the film of the present invention is used as an infrared transmission filter, a coloring material containing near-infrared absorbing organic pigments and blocking visible light is used (preferably a coloring material containing two or more coloring agents or at least an organic black) A filter of a hardening composition of a colorant) or a filter containing a layer of a color material that blocks visible light in addition to a layer containing a near-infrared absorbing organic pigment is preferable. When the film of the present invention is used as an infrared transmission filter, the near-infrared absorbing organic pigment has a function of restricting the transmitted light (near infrared) to a longer wavelength side.

The film 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 even 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 more preferably 0.3 μm or more.

The film of the present invention can also be used in combination with a color filter containing a colorant. A color filter can be manufactured using the coloring composition containing a coloring agent. As a coloring agent, the coloring agent demonstrated in the curable composition of this invention is mentioned. The coloring composition can further contain a resin, a curable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. The details of these include the materials described in the curable composition of the present invention, and these can be used. In addition, the film of the present invention may be a filter having a function as a near-infrared cut-off filter and a color filter by containing a coloring agent.

In the present invention, the near-infrared cut filter refers to a filter that transmits light (visible light) with a wavelength in the visible region and blocks at least a part of light (near infrared) with a wavelength in the near-infrared region. The near-infrared cut-off filter may be a person who transmits all light with a wavelength in the visible region, or may pass a light in a specific wavelength region among the light with a wavelength in the visible region and block the light in a specific wavelength region. In the present invention, the color filter refers to a filter that passes light in a specific wavelength region out of light in a visible region and blocks light in a specific wavelength region. The infrared transmission filter refers to a filter that blocks light with a wavelength in the visible region and transmits at least a part of light with a wavelength in the near-infrared region (near infrared).

When the film of the present invention is used as a near-infrared cut filter, it is preferable that the film of the present invention has a maximum absorption wavelength in the range of 700 to 1000 nm. The ratio of the absorbance A550 at a wavelength of 550 nm to the absorbance Amax at a maximum absorption wavelength, that is, the absorbance A550 / absorbance Amax is preferably 0.002 to 0.040, more preferably 0.003 to 0.030, and still more preferably 0.004 to 0.020. The ratio of the absorbance A400 at a wavelength of 400 nm to the absorbance Amax at a maximum absorption wavelength, that is, the absorbance A400 / absorbance Amax is preferably 0.005 to 0.150, more preferably 0.020 to 0.100, and still more preferably 0.050 to 0.070. The maximum absorption wavelength of the film is more preferably in the range of 720 to 980 nm, and more preferably in the range of 740 to 960 nm.

With regard to the near-infrared cut filter of the present invention, it is preferable that at least one of the following conditions (1) to (4) be satisfied with respect to the transmittance of light, and it is more preferable to satisfy all the conditions (1) to (4). (1) The transmittance at a wavelength of 400 nm is preferably 70% or more, 80% or more is more preferable, 85% or more is further preferable, and 90% or more is particularly preferable. (2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, 90% or more is further preferable, and 95% or more is particularly preferable. (3) The transmittance at a wavelength of 600 nm is preferably 70% or more, 80% or more is more preferable, 90% or more is further preferable, and 95% or more is particularly preferable. (4) The transmittance at a wavelength of 650 nm is preferably 70% or more, 80% or more is more preferable, 90% or more is further preferable, and 95% or more is particularly preferable.

In the present invention, the film thickness of the near-infrared cut filter is 20 μm or less, and the transmittance in the entire range of wavelengths of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. The transmittance is preferably 20% or less at at least one point in the wavelength range of 700 to 1000 nm.

The near-infrared cut filter of the present invention may further include a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, and the like in addition to the film of the present invention. The near-infrared cut filter further includes a copper-containing layer and / or a dielectric multilayer film, so that a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be easily obtained. In addition, the near-infrared cut filter further includes an ultraviolet absorbing layer, so that a near-infrared cut filter having excellent ultraviolet shielding properties can be produced. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 099060 can be referred to, and the contents are incorporated into this specification. As the dielectric multilayer film, the descriptions of paragraph numbers 0255 to 0259 of Japanese Patent Application Laid-Open No. 2014-41318 can be referred to, and the contents are incorporated into this specification. As the copper-containing layer, a glass substrate (copper-containing glass substrate) made of glass containing copper, or a copper complex (layer containing copper complex) can also be used. Examples of the copper-containing glass substrate include copper-containing phosphate glass and copper-containing fluorophosphate glass. Examples of commercial products of copper-containing glass include NF-50 (manufactured by AGC TECHNO GLASS Co., Ltd.), BG-60, BG-61 (manufactured by Schott), and CD5000 (manufactured by HOYA CORPORATION). Examples of the copper complex-containing layer include a layer formed using a composition containing a copper complex. The copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1200 nm. Regarding the maximum absorption wavelength of the copper complex, it is more preferable to have a wavelength range of 720 to 1200 nm, and it is more preferable to have a wavelength range of 800 to 1100 nm.

The film and the near-infrared cut filter of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.

<Laminate> The laminated body of the present invention includes the film of the present invention and a color filter containing a colorant. In the laminated body of the present invention, the film and the color filter of the present invention may or may not be adjacent to each other in the thickness direction. When the film and the color filter of the present invention are not adjacent in the thickness direction, the film of the present invention may be formed on a support different from the support on which the color filter is formed, or the film and the filter of the present invention may be formed. Other components (for example, microlenses, flattening layers, etc.) that constitute the solid-state image sensor are interposed between the color devices.

<Pattern formation method> Next, the pattern formation method using the curable composition of this invention is demonstrated. The pattern forming method preferably includes the following processes: a process of forming a composition layer on a support using the curable composition of the present invention; and a process of forming a pattern on the composition layer by a photolithography method or a dry etching method .

The photolithography-based pattern formation method preferably includes the following processes: a process of forming a composition layer on a support using a hardening composition; a process of exposing the composition layer into a pattern; and developing an unexposed portion Removal to form a pattern. According to requirements, a process for baking the composition layer (pre-baking process) and a process for baking developed patterns (post-baking process) can be set. It is preferable that the pattern forming method based on the dry etching method includes the following processes: a process of forming a composition layer on a support using a curable composition and hardening it to form a cured product layer; forming a photoresist on the cured product layer Process of forming a photoresist layer; process of obtaining a resist pattern by patterning a photoresist layer through exposure and development; and process of forming a pattern by dry-etching a hardened layer using the resist pattern as an etching mask . Hereinafter, each process will be described.

<<< Process of Forming a Composition Layer >> In the process of forming a composition layer, a hardening composition is used to form a composition layer on a support.

As the support body, for example, a substrate for a solid-state imaging element in which a solid-state imaging element (light-receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used. The pattern may be formed on the solid-state imaging element formation surface side (front surface) of the solid-state imaging element substrate, or may be formed on the solid-state imaging element non-formation surface side (back surface). In order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, an undercoat layer may be provided on the support as necessary.

As a method of applying the curable composition to the support, a known method can be used. For example, a dropwise addition method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating method); a cast coating method; a slit spin coating method; a pre-wet method (For example, the method described in Japanese Patent Application Laid-Open No. 2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle spray, and other ejection system printing, flexographic printing, screen printing, gravure Various printing methods such as printing, reverse offset printing, and metal mask printing; transfer methods using molds; nano-imprinting methods. The application method based on inkjet is not particularly limited. For example, "Inkjet that can be promoted and used-unlimited possibilities as seen in patents-, issued in February 2005, SB RESEARCH CO., LTD." The method described in the patent publication (especially pages 115 to 133), or Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, and Japanese Patent Application Publication No. The methods described in Japanese Unexamined Patent Publication No. 2012-126830 and Japanese Unexamined Patent Publication No. 2006-169325.

The composition layer formed on the support can be dried (pre-baked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When performing pre-baking, the pre-baking temperature is preferably below 150 ° C, more preferably below 120 ° C, and even more preferably below 110 ° C. The lower limit can be set to, for example, 50 ° C or higher, and can also be set to 80 ° C or higher. By performing it at a pre-baking temperature of 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, such characteristics can be more effectively maintained. The pre-baking time is preferably from 10 seconds to 300 seconds, more preferably from 40 to 250 seconds, and even more preferably from 80 to 220 seconds. The pre-baking can be performed using a hot plate, an oven, or the like.

(Case where pattern is formed by photolithography method) << Exposure Process >> Next, the composition layer is exposed to a pattern (exposure process). For example, pattern exposure can be performed by exposing the composition layer with a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed part can be hardened. As the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferred, and i-rays are more preferred. Irradiation amount (exposure amount) based, for example, 0.03 ~ 2.5J / cm ² is preferred, 0.05 ~ 1.0J / cm ² is more preferably, 0.08 ~ 0.5J / cm ² is optimal. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed in the atmosphere, for example, under a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, and substantially free of oxygen) The exposure may be performed under a high-oxygen environment (for example, 22% by volume, 30% by volume, and 50% by volume) in an oxygen concentration exceeding 21% by volume. In addition, the exposure illuminance can be appropriately set, and can usually be selected from a range of 1000 W / m ² to 100,000 W / m ² (for example, 5000 W / m ² , 15000 W / m ² , and 35000 W / m ² ). The oxygen concentration and exposure illuminance conditions may be appropriately combined, for example, to an oxygen concentration of 10 vol% and the illuminance 10000W / m ^2, an oxygen concentration of 35% by volume and illuminance 20000W / m ² and the like.

<< Development Process >> Next, the unexposed part is developed and removed to form a pattern. The development and removal of the unexposed portion can be performed using a developing solution. Thereby, the composition layer of the unexposed portion in the exposure process is dissolved in the developing solution, and only the light-hardened portion remains on the support. As the developing solution, an alkali developing solution that does not cause damage to the solid-state imaging element or circuit of the substrate is preferred. The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removal ability of the residue, the process of throwing off the developing solution every 60 seconds and supplying a new developing solution may be repeated several times.

Examples of the alkaline agent used in the developing solution include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, and tetramethyl hydroxide Ammonium, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, Organic basic compounds such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate , Sodium metasilicate and other inorganic basic compounds. As the developing solution, an alkaline aqueous solution obtained by diluting these alkaline agents in 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. A surfactant may be used in the developing solution. Examples of the surfactant include the surfactants described in the above-mentioned curable composition, and nonionic surfactants are preferred. In addition, when a developing solution including such an alkaline aqueous solution is used, it is preferable to wash (rinse) with pure water after development.

After development, heat treatment (post-baking) can also be performed after drying. Post-baking is a heat treatment after development for completely curing the film. When performing the post-baking, the post-baking temperature is preferably, for example, 100 to 240 ° C. From the viewpoint of film hardening, 200 to 230 ° C is more preferable. In the case of using an organic electroluminescence (organic EL) element as a light source, or in the case of a photoelectric conversion film of an image sensor made of an organic material, the post-baking temperature is preferably 150 ° C or lower, and 120 ° C or lower. More preferably, it is more preferably below 100 ° C, and particularly preferably below 90 ° C. The lower limit can be set to, for example, 50 ° C or higher. In order to satisfy the above conditions, post-baking of the developed film can be performed continuously or intermittently using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater.

In addition, the pattern forming method of the present invention may further include a process of performing exposure after the unexposed portion is developed and removed (after development) (hereinafter, the exposure after development is also referred to as post exposure). When a curable composition containing an oxime compound and an α-amino ketone compound is used as a photopolymerization initiator, post-exposure is preferably performed. By exposing the composition layer in two stages before and after pattern formation, the composition can be appropriately hardened by the initial exposure (exposure before pattern formation) and the subsequent exposure (exposure after pattern formation). The entire composition is substantially hardened. As a result, even if the post-baking temperature is 180 ° C. or lower, the curable composition can be effectively cured. Even in the case where exposure is performed in two stages, post-baking can be performed after the post-exposure. The post-baking temperature is preferably, for example, 100 to 240 ° C.

(When a pattern is formed by a dry etching method) Regarding pattern formation by a dry etching method, a composition layer formed on a support can be hardened to form a hardened layer. Then, the obtained hardened layer can be patterned. The photoresist layer is used as a mask and an etching gas is used. When the photoresist layer is formed, it is preferable to further perform a pre-baking treatment. In particular, as the formation process of the photoresist, it is preferable to perform a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, reference can be made to the descriptions of paragraph numbers 0010 to 0067 of Japanese Patent Application Laid-Open No. 2013-064993, which are incorporated into this specification.

<Solid-state imaging element> The solid-state imaging element of the present invention includes the film of the present invention described above. The structure of the solid-state imaging element of the present invention is a structure having the film of the present invention, and is not particularly limited as long as the structure functions as a solid-state imaging element. For example, the following configuration is mentioned.

The structure is as follows: a plurality of photodiodes and a transmission electrode including polycrystalline silicon are provided on a support body to constitute a light-receiving area of a solid-state imaging element; The light-shielding film includes a device protection film including silicon nitride and the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portion of the photodiode. The device protection film includes the film of the present invention. In addition, it may be a structure that is provided on the device protection film and has a light condensing mechanism (for example, a micro lens, etc. below) on the lower side (the side near the support) of the film of the present invention, or on the film of the present invention. It has the structure of a light-concentrating mechanism. In addition, the color filter may have a structure in which a hardened film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid shape. In this case, it is preferable that the partition wall has a low refractive index with respect to each pixel system. Examples of the imaging device having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577.

<Image display device> The film of the present invention can also be used for an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device. For example, it is possible to form infrared pixels in addition to the colored pixels for the purpose of blocking the infrared light included in the backlight of the image display device (for example, a white light emitting diode (white LED)), the purpose of preventing malfunction of peripheral devices, and the like. The purpose is to use the film of the present invention.

The definition or details of the image display device are described in, for example, "Electronic Display Device (Asa Sasaki, Kogyo Chosakai Publishing Co., Ltd. 1990)", "Display Device (Ibuki Shun, Sangyo Tosho Publishing Co. ., Ltd., issued in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., issued in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology" described above.

The image display device may include a white organic EL element. As a white organic EL element, a tandem structure is preferable. Regarding the tandem structure of organic EL elements, it is described in Japanese Patent Application Laid-Open No. 2003-45676, supervised by Miyoshi Akira, "Forefront of Organic EL Technology Development-High Brightness, High Precision, Long Life, Skill Set-", Technical Information Association, pp. 326-328, 2008, etc. The spectrum of the white light emitted by the organic EL element has a strong maximum emission peak in the blue region (430nm-485nm), the green region (530nm-580nm), and the yellow region (580nm-620nm). In addition to these emission peaks, it is more preferable to have a further maximum emission peak in the red region (650nm-700nm).

<Infrared sensor> The infrared sensor of the present invention includes the film of the present invention described above. The configuration of the infrared sensor of the present invention is a configuration including the film of the present invention, and is not particularly limited 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 drawings. In FIG. 1, reference numeral 110 is a solid-state imaging element. An imaging region provided on the solid-state imaging element 110 includes a near-infrared cut filter 111 and an infrared transmission filter 114. A color filter 112 is laminated on the near-infrared cut filter 111. Microlenses 115 are disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlenses 115. The near-infrared cut filter 111 can be formed using the composition of the present invention.

The color filter 112 is a color filter in which a pixel that transmits and absorbs light of a specific wavelength in a visible region is formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed can be used. For example, Japanese Patent Application Laid-Open No. 2014-043556 can refer to the descriptions of paragraph numbers 0214 to 0263, which are incorporated into this specification.

The infrared transmission filter 114 can select its characteristics according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the maximum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film in the range of wavelength 400 to 650 nm is preferably 30% or less, and 20% or less More preferably, 10% or less is further preferable, and 0.1% or less is particularly preferable. This transmittance preferably satisfies the above conditions in the entire region in the wavelength range of 400 to 650 nm. The maximum value in the range of 400 to 650 nm is usually 0.1% or more.

The minimum transmittance of the infrared transmission filter 114 in the thickness direction of the film in the range of a wavelength of 800 nm or more (preferably 800 to 1300 nm) is preferably 70% or more, more preferably 80% or more, and 90% The above is further preferred. It is preferable that the transmittance satisfies the above conditions in a part of a wavelength range of 800 nm or more, and it is preferable to satisfy the above conditions at a wavelength corresponding to the emission wavelength of the infrared LED. The minimum value of the light transmittance in the range of 900 to 1300 nm is usually 99.9% or less.

The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, even more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit value is preferably 0.1 μm. When the film thickness is within the above range, a film satisfying the above-mentioned spectral characteristics can be produced. A method for measuring the spectral characteristics and film thickness of the infrared transmission filter 114 is shown below. The film thickness was measured using a stylus-type surface shape measuring device (DEKTAK150 manufactured by ULVAC, Inc.) on a substrate having a film after drying. The spectroscopic characteristics of the film are values obtained by measuring transmittance in a wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

For example, when the emission wavelength of the infrared LED is 940 nm, the maximum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film in the range of the wavelength of 450 to 650 nm is 20% or less and the thickness of the film The transmittance of light with a wavelength of 835 nm in the direction is preferably 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film with a wavelength in the range of 1000 to 1300 nm is preferably 70% or more. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, usage amounts, proportions, processing contents, processing steps and the like shown in the following examples can be appropriately changed as long as they do not depart from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "%" and "part" are mass standards. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group.

<Production of near-infrared-absorbing organic pigments> Pigments, grinders, and binders described in the following table were added to LABO PLASTOMILL (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to make the kneaded product in the device The temperature was controlled so that the temperature (milling temperature) described in the following table, and kneading was performed for the milling time described in the following table. 10L of water at 24 ° C was used to wash and wash the kneaded mixture to remove the grinding agent and binder, and then treated at 80 ° C for 24 hours in a heating oven to obtain a near-infrared absorbing organic pigment. . The average primary particle diameter, the coefficient of variation of the primary particle diameter, the average length-to-edge ratio, the coefficient of variation of the length-to-edge ratio, and the powder X-ray diffraction spectrum of the near-infrared-absorbing organic pigment obtained were measured. Further, based on the powder X-ray diffraction spectrum, the values of the full width at half maximum and the crystallinity of the peak with the highest diffraction intensity in the region with a diffraction angle 2θ of 5 to 12 ° were obtained.

[Table 2]

The materials listed in the above table are as follows. (Pigment) Pigment 2: A compound having the following structure (a near-infrared absorbing organic pigment) [Chemical Formula 21] Pigment 4: a compound of the following structure (a near-infrared absorbing organic pigment) [Chemical Formula 22] (Grinding agent) Grinding agent 1: Neutral anhydrous thenardite E (sodium sulfate, average particle size (50% diameter (D50) on a volume basis)) = 20 μm, manufactured by MITAJIRI Chemical Industry Co., Ltd., grinding agent 2 : Nacl UM (sodium chloride, average particle size (50% diameter (D50) on a volume basis) = 50 μm, manufactured by Naikai Salt Industries Co., LTD.) Grinding agent 3: OSHIO MICRON T-0 (sodium chloride, Average particle size (50% diameter (D50) on a volume basis) = 10 μm, manufactured by Ako Kasei Co., Ltd. (Binder) DEG: Diethylene glycol

<Evaluation> (Measurement of the average primary particle diameter and the coefficient of variation of the primary particle diameter of the near-infrared absorbing organic pigment) The primary particles of the near-infrared absorbing organic pigment were observed with a transmission electron microscope, and were obtained from the obtained photos. Specifically, the projected area of the primary particles of the near-infrared-absorbing organic pigment was determined, and the equivalent circle diameter corresponding thereto was set as the primary particle diameter of the near-infrared-absorbing organic pigment. The arithmetic mean value of the primary particle diameters of the 400 primary particles of the near-infrared-absorbing organic pigment was taken as the average primary particle diameter. The coefficient of variation of the primary particle diameter was obtained based on the following formula. Coefficient of variation of the primary particle size of the near-infrared absorbing organic pigment = (standard deviation of the primary particle size of the near-infrared absorbing organic pigment / the arithmetic mean of the primary particle size of the near-infrared absorbing organic pigment) × 100

(Measurement of the average aspect ratio of the near-infrared-absorbing organic pigment and the coefficient of variation of the long-to-short-side ratio) The primary particles of the near-infrared-absorbing organic pigment were observed with a transmission electron microscope, and were obtained from the obtained photos. Specifically, the ratio of the short side to the long side (short side / long side) of the primary particles of the near-infrared absorbing organic pigment is obtained according to the projected photograph, and the length to short side ratio is calculated. The coefficient of variation of the aspect ratio was obtained based on the following formula. Coefficient of variation of the aspect ratio of the near-infrared-absorbing organic pigment = (standard deviation of the aspect ratio of the near-infrared-absorbing organic pigment / the arithmetic mean of the aspect ratio of the near-infrared-absorbing organic pigment) × 100

(Measurement of powder X-ray diffraction spectrum of near-infrared-absorbing organic pigments) A sample horizontal powerful X-ray diffraction device RINT-TTR III manufactured by Rigaku Corporation was used as a measurement device at a diffraction angle of 2θ = 5 ° to 55 ° The powder X-ray diffraction of near-infrared-absorbing organic pigments was measured under the conditions of a voltage of 50 kV, a current of 300 mA, a scanning speed of 4 ° / min, a step interval of 0.1, and a slit (0.05 mm scattering, 10 mm divergence, and 0.15 mm light reception). spectrum.

(Measurement of the full width at half maximum) In the obtained powder X-ray diffraction spectrum, a peak having a diffraction intensity with a diffraction angle of 2θ of 5 to 12 ° was fitted to the Lorentz function [y = A / ( 1 + ((x-x0) / w) ² ) + h] to obtain the full width at half maximum of the peak. Among them, y is intensity, A is peak height, x is 2θ, x0 is peak position, w is peak width (half-peak half-width), and h is baseline.

(Measurement of Crystallinity) In the powder X-ray diffraction spectrum, a straight line connecting the lowest point in the region with a diffraction angle 2θ of 5 to 15 ° and the lowest point in the region of 25 to 35 ° is used as a baseline. Using the spectrum correction value obtained by subtracting the value of the baseline from the measured value of the powder X-ray diffraction spectrum, the crystallinity was measured using the following formula. Crystallinity = [Ic / (Ia + Ic)] In the formula, Ic is in the region where the diffraction angle 2θ is 15 ° or more. The maximum value of the diffraction intensity from the peak of the crystal in the powder X-ray diffraction spectrum, Ia It is the maximum value of the diffraction intensity derived from the amorphous peak in the powder X-ray diffraction spectrum. In addition, a peak having a full width at half maximum of 1 ° or less was defined as a peak derived from a crystal. In addition, a peak whose full width at half maximum exceeds 3 ° is referred to as an amorphous-derived peak.

[table 3]

<Preparation of Dispersion Liquid> 3.13 parts by mass of the near-infrared-absorbing organic pigments of Examples 1 to 9 and Comparative Examples 1 to 3, 0.63 parts by mass of the pigment derivative 1, 2.25 parts by mass of the dispersant 1, and 44 parts by mass of propylene glycol monomethyl ether After the acetate (PGMEA) and 66 parts by mass of zirconia beads with a diameter of 0.5 mm were dispersed in a paint mixer for 120 minutes, the zirconia beads were separated by decantation to prepare a dispersion.

Pigment derivative 1: the following compound [Chemical Formula 23] Dispersant 1: Resin of the following structure (weight average molecular weight = 21,000). The numerical value attached to the main chain represents the mole ratio of repeating units, and the numerical value attached to the side chain represents the number of repeating units. [Chemical Formula 24]

<Evaluation of spectral characteristics and heat resistance> A sample solution obtained by mixing 10 parts by mass of a dispersion solution using the near-infrared absorbing organic pigment of the examples and comparative examples obtained above and 10 parts by mass of resin 1 was evaluated. Spectral characteristics and heat resistance. Resin 1: CYCLOMER P (ACA) 230AA manufactured by Daicel Corporation

(Spectral characteristics) The sample solution was applied to a glass wafer by a spin coating method so that the film thickness after coating became 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-ray stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). In addition, a film was formed by heating at 220 ° C for 5 minutes using a hot plate. For the substrate on which the film was formed, a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) was used to determine the maximum absorption wavelength, the absorbance Amax at the maximum absorption wavelength, the absorbance A550 at the wavelength 550nm, and the wavelength at 400nm. Absorbance A400, and calculate the ratio of the absorbance A550 at a wavelength of 550nm to the absorbance Amax at a maximum absorption wavelength (absorbance A550 / absorbance Amax), the ratio of the absorbance A400 at a wavelength of 400nm to the absorbance Amax at a maximum absorption wavelength ( Absorbance A400 / Amax).

(Heat resistance) Further, the substrate evaluated by the above-mentioned spectral characteristics was heated at 220 ° C. for 60 minutes using a hot plate, and the transmittance was measured using a spectro hardness tester U-4100 (manufactured by Hitachi High-Technologies Corporation). A change in transmittance (maximum transmittance change) at a wavelength at which the transmittance changes the most before and after the heating in a transmittance in a wavelength range of 400 to 1000 nm was calculated using the following formula. The change in the maximum transmittance is close to zero, indicating excellent heat resistance. Maximum transmittance change = transmittance before heating-transmittance after heating [Table 4]

As shown in the above table, the absorbance A400 and the absorbance A550 of the examples were low, and the transparency was excellent. Moreover, heat resistance is also good.

In the examples, the same effect can be obtained as the dispersant even if it is replaced with the dispersant described in this specification.

In addition, even when a squaraine compound or a cyanine compound is used as the near-infrared absorbing organic pigment, the same effects as in the examples can be obtained by satisfying the following characteristics. In the powder X-ray diffraction spectrum of the near-infrared-absorbing organic pigment, there is a peak of diffraction intensity in a region with a diffraction angle of 2θ of 5 to 12 °, and the full width at half maximum of the peak with the highest diffraction intensity in this region It is 0.3 to 0.6 °.

110‧‧‧ solid-state imaging element

111‧‧‧Near infrared cut-off filter

112‧‧‧ Color Filter

114‧‧‧ Infrared Transmission Filter

115‧‧‧ micro lens

116‧‧‧ flattening layer

hν‧‧‧ incident light

FIG. 1 is a schematic diagram showing an embodiment of an infrared sensor.

Claims (18)

A near-infrared absorbing organic pigment having a diffraction intensity peak in a region with a diffraction angle of 2θ of 5 to 12 ° in a powder X-ray diffraction spectrum, and a half-peak full of a peak with the largest diffraction intensity in the foregoing region. The width is 0.3 to 0.6 °. The near-infrared-absorbing organic pigment according to item 1 of the patent application range, wherein the full width at half maximum of the aforementioned half-value is 0.3 to 0.45 °. The near-infrared absorbing organic pigment according to item 1 or 2 of the scope of the patent application, wherein the average primary particle diameter of the near-infrared absorbing organic pigment is 10 to 100 nm. The near-infrared-absorbing organic pigment according to item 1 or 2 of the scope of the patent application, wherein the average primary particle diameter of the near-infrared-absorbing organic pigment is 20 to 45 nm. The near-infrared-absorbing organic pigment according to item 1 or 2 of the scope of the patent application, wherein the coefficient of variation of the primary particle diameter of the near-infrared-absorbing organic pigment is 20 to 35%. The near-infrared-absorbing organic pigment according to item 1 or 2 of the scope of the patent application, wherein the average near-to-short side ratio of the near-infrared-absorbing organic pigment is 0.5 to 0.9. The near-infrared-absorbing organic pigment according to item 1 or 2 of the scope of application for a patent, wherein the coefficient of variation of the aspect ratio of the near-infrared-absorbing organic pigment is 10 to 30%. The near-infrared absorbing organic pigment according to item 1 or 2 of the scope of the patent application, wherein the value of the crystallinity represented by the following formula of the near-infrared absorbing organic pigment is 0.9 to 0.99; crystallinity = [Ic / ( Ia + Ic)] In the formula, Ic is in the region where the diffraction angle 2θ is 15 ° or more, the maximum value of the diffraction intensity derived from the peak of the crystal in the powder X-ray diffraction spectrum, and Ia is the powder X-ray diffraction spectrum The maximum value of the diffraction intensity derived from the amorphous peak in. The near-infrared absorbing organic pigment according to item 1 or 2 of the scope of the patent application, wherein the near-infrared absorbing organic pigment is at least one selected from the group consisting of a pyrrolopyrrole compound and a squarylium compound. A pigment dispersion liquid comprising a near-infrared-absorbing organic pigment, a resin, and a solvent as described in any one of claims 1 to 9 of the scope of patent application. The pigment dispersion according to item 10 of the patent application scope, further comprising a pigment derivative. A hardenable composition comprising the near-infrared-absorbing organic pigment, resin, hardenable compound, and solvent described in any one of claims 1 to 9 of the scope of patent application. A film using the curable composition described in claim 12 of the scope of patent application. A near-infrared cut-off filter having the film described in claim 13 of the scope of patent application. A laminated body having the film described in claim 13 of the scope of patent application and a color filter containing a colorant. A solid-state imaging element having the film described in claim 13 of the scope of patent application. An image display device having the film described in claim 13 of the scope of patent application. An infrared sensor having the film described in claim 13 of the scope of patent application.