JP2018048217A - Method for producing pigment dispersion and method for producing curable composition - Google Patents

Abstract

The present invention provides a method for producing a pigment dispersion and a method for producing a curable composition, which can produce a film with good visible transparency and reduced roughness of the brightness of transmitted light. The method for producing a pigment dispersion comprises a step of kneading and polishing a near-infrared absorbing organic pigment in the presence of a water-soluble organic solvent and a water-soluble inorganic salt 7 to 18 times the mass of the near-infrared absorbing organic pigment. And a step of washing the near-infrared absorbing organic pigment after kneading and polishing, and a step of dispersing the washed near-infrared absorbing organic pigment in the presence of a pigment derivative, a resin and a solvent. Moreover, the manufacturing method of this curable composition contains the manufacturing method of the above-mentioned pigment dispersion liquid. [Selection figure] None

Description

  The present invention relates to a method for producing a pigment dispersion and a method for producing a curable composition.

  Video cameras, digital still cameras, mobile phones with camera functions, and the like use CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state imaging devices for color images. Since these solid-state imaging devices use silicon photodiodes having sensitivity to infrared rays in their light receiving portions, visual sensitivity correction may be performed using a near-infrared cut filter.

  As a manufacturing method of a near-infrared cut filter, the method of manufacturing using the curable composition containing near-infrared absorbers, such as a near-infrared absorption organic pigment, is known (for example, patent document 1, 2).

  On the other hand, organic pigments after synthesis (also referred to as crude pigments) are often used after being pulverized and refined. For example, in the field of chromatic organic pigments, a method for obtaining a finer pigment in a uniformly dispersed state has been studied from the viewpoint of improving the coloring effect. As one method for refining organic pigments, a method is known in which organic pigments, water-soluble inorganic salts, water-soluble solvents, and the like are kneaded with a kneader or the like to refine organic pigments. Such a method is called a salt milling method.

  For example, Patent Document 3 discloses that a mixture containing an organic pigment, a dispersion stabilizing solvent and a dispersing agent, and a mixture containing a water-soluble inorganic salt is kneaded and ground, washed, dehydrated, and finely divided. A refining step for obtaining a pigmented pigment composition, a solvent phase changing step for charging the finer pigment composition and a solvent into a flasher, phase-inverting the pigment from an aqueous phase to an oil phase, and then removing the water by decantation. The invention relates to a method for producing a pigment dispersion in which the dispersion stabilizing solvent and dispersant contained in the mixture in the refinement step have the same or equivalent functions as the solvent and dispersant used in the solvent phase inversion step. ing.

JP 2014-191190 A International Publication WO2014 / 185518 JP 2010-106260 A

Near-infrared absorbers such as near-infrared absorbing organic pigments are required to have excellent infrared shielding properties and excellent visible transparency.
Further, the near-infrared absorbing organic pigment tends to be coarsened due to aggregation of primary particles of the near-infrared absorbing organic pigment in the dispersion or the curable composition. When a film such as a near-infrared cut filter is manufactured using a curable composition containing a coarsened near-infrared absorbing organic pigment, the brightness of the transmitted light may be locally low or high. Roughness was likely to occur in the brightness.

  Patent Document 3 does not describe or suggest a near infrared absorbing organic pigment.

  Therefore, an object of the present invention is to provide a method for producing a pigment dispersion and a method for producing a curable composition, which can produce a film having good visible transparency and suppressed roughness of the brightness of transmitted light. It is in.

Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the above object can be achieved by producing a pigment dispersion by the method described later, and the present invention has been completed. The present invention provides the following.
<1> Kneading and polishing the near-infrared absorbing organic pigment in the presence of a water-soluble organic solvent and a water-soluble inorganic salt 7 to 18 times the mass of the near-infrared absorbing organic pigment;
Cleaning the near infrared absorbing organic pigment after kneading and polishing;
And a step of dispersing the washed near-infrared absorbing organic pigment in the presence of a pigment derivative, a resin and a solvent.
<2> The pigment dispersion liquid according to <1>, wherein the near-infrared absorbing organic pigment is kneaded and polished in the presence of a water-soluble organic solvent and a water-soluble inorganic salt 9 to 16 times the mass of the near-infrared absorbing organic pigment. Production method.
<3> The method for producing a pigment dispersion according to <1> or <2>, wherein the water-soluble organic solvent has a solubility in 100 g of water at 23 ° C. of 20 g or more.
<4> The method for producing a pigment dispersion according to any one of <1> to <3>, wherein the water-soluble inorganic salt is at least one selected from sodium chloride and sodium sulfate.
<5> The method for producing a pigment dispersion according to any one of <1> to <4>, wherein the average particle diameter D50 of the water-soluble inorganic salt is 15 μm or more.
<6> The method for producing a pigment dispersion according to any one of <1> to <5>, wherein kneading and polishing are performed at a temperature of 50 ° C. or higher.
<7> The method for producing a pigment dispersion according to any one of <1> to <6>, wherein kneading and polishing are performed so that the average primary particle diameter of the near-infrared absorbing organic pigment is 10 to 100 nm.
<8> The method for producing a pigment dispersion according to any one of <1> to <7>, wherein the near-infrared absorbing organic pigment is at least one selected from a pyrrolopyrrole compound and a squarylium compound.
<9> A method for producing a curable composition, comprising the method for producing a pigment dispersion according to any one of <1> to <8>.

  According to the present invention, it is possible to provide a method for producing a pigment dispersion and a method for producing a curable composition, which can produce a film having good visible transparency and suppressed roughness of the brightness of transmitted light. Became.

It is the schematic which shows one Embodiment of an infrared sensor.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the notation of a group (atomic group) in the present specification, the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include an emission line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, and electron beams.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID (inner diameter) × 15.0 cm) and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
In this specification, near-infrared light refers to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
In the present specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In the present specification, the pigment means a compound that is difficult to dissolve 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.

<Method for producing pigment dispersion>
The method for producing the pigment dispersion of the present invention comprises:
A step of kneading and polishing the near-infrared absorbing organic pigment in the presence of a water-soluble organic solvent and a water-soluble inorganic salt 7 to 18 times the mass of the near-infrared absorbing organic pigment;
A step of cleaning the near infrared absorbing organic pigment after kneading and polishing (cleaning step);
And a step of dispersing the washed near-infrared absorbing organic pigment in the presence of a pigment derivative, a resin and a solvent (dispersing step). Hereinafter, the near-infrared absorbing organic pigment before kneading and polishing is also referred to as a crude pigment. The near-infrared absorbing organic pigment after kneading and polishing is also referred to as a milling pigment.

According to the present invention, it is possible to obtain a pigment dispersion that can produce a film having good visible transparency and suppressed lightness roughness of transmitted light.
Near-infrared absorbing organic pigments are softer than chromatic organic pigments, and tend to decrease crystallite size, crystallinity, and crystal structure changes during visible kneading. However, by kneading and polishing the near-infrared absorbing organic pigment of the crude pigment under the above conditions, the near-infrared absorbing organic pigment can be miniaturized while suppressing the change in the near-infrared absorbing organic pigment as much as possible. For this reason, the milling pigment of the near-infrared absorption organic pigment with a small particle diameter and excellent visible transparency can be obtained. And after washing | cleaning the near-infrared absorption organic pigment (milling pigment) after kneading | polishing grinding | polishing, a near-infrared absorption organic pigment is stably disperse | distributed in a dispersion liquid by disperse | distributing in presence of a pigment derivative, resin, and a solvent. be able to. For this reason, aggregation of the near-infrared absorbing organic pigment in the dispersion can be suppressed. For these reasons, by using the dispersion liquid obtained according to the present invention, a film with good visible transparency and suppressed lightness roughness of transmitted light can be produced. Each step will be described below.

(Kneading polishing process)
In the method for producing a pigment dispersion of the present invention, first, the near-infrared absorbing organic pigment is kneaded and polished in the presence of a water-soluble organic solvent and a water-soluble inorganic salt. At this time, the water-soluble inorganic salt is used in an amount 7 to 18 times the mass of the near-infrared absorbing organic pigment.

  The type of the near-infrared absorbing organic pigment 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 is a pigment composed of an organic compound. The near-infrared absorbing organic pigment is preferably at least one selected from a pyrrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, and a diimonium compound, and more preferably a pyrrolopyrrole compound or a squarylium compound. Preferably, it is a pyrrolopyrrole compound. In particular, in the case of a pyrrolopyrrole compound, the visible transparency can be improved more effectively. Furthermore, it is easy to obtain a milling pigment having excellent heat resistance. Since the heat resistance of the milling pigment itself can be enhanced, coloring by heating can be effectively suppressed, and a film having excellent visible transparency even after heating can be produced.

式中、Ｒ^1aおよびＲ^1bは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²およびＲ³は、各々独立に水素原子または置換基を表し、Ｒ²およびＲ³は、互いに結合して環を形成してもよく、Ｒ⁴は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、−ＢＲ^4AＲ^4B、または金属原子を表し、Ｒ⁴は、Ｒ^1a、Ｒ^1bおよびＲ³から選ばれる少なくとも一つと、共有結合もしくは配位結合していてもよく、Ｒ^4AおよびＲ^4Bは、各々独立に置換基を表す。 The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ are They may be bonded to each other to form a ring, and each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^4A R ^4B , or a metal atom, and R ⁴ represents R ^At least one selected from ^1a , R ^1b and R ³ may be covalently or coordinately bonded, and R ^4A and R ^4B each independently represent a substituent.

R ^1a and R ^1b each independently represents an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group.
1-30 are preferable, as for carbon number of the alkyl group which R ^{< 1a>} , R ^<1b> represents, 1-20 are more preferable, and 1-10 are especially preferable.
6-30 are preferable, as for carbon number of the aryl group which R ^{< 1a>} , R ^<1b> represents, 6-20 are more preferable, and 6-12 are especially preferable.
1-30 are preferable and, as for the number of the carbon atoms which comprise the heteroaryl group which R ^{< 1a>} , R ^<1b> represents, 1-12 are more preferable. As a kind of hetero atom which comprises heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 is preferable, and 1 to 2 is more preferable. The heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
The alkyl group, aryl group, and heteroaryl group described above may have a substituent or may be unsubstituted. It preferably has a substituent. Examples of the substituent include the groups described for the substituent T described later. Of these, an alkoxy group and a hydroxy group are preferable. The alkoxy group is preferably an alkoxy group having a branched alkyl group. The group represented by R ^1a or R ^1b is preferably an aryl group having an alkoxy group having a branched alkyl group as a substituent or an aryl group having a hydroxy group as a substituent. 3-30 are preferable and, as for carbon number of a branched alkyl group, 3-20 are more preferable.

R ² and R ³ each independently represents a hydrogen atom or a substituent. R ² and R ³ may combine to form a ring. At least one of R ² and R ³ is preferably an electron withdrawing group. R ² and R ³ preferably each independently represent a cyano group or a heteroaryl group. Examples of the substituent include substituents described in paragraph numbers 0020 to 0022 of JP-A-2009-263614. The above contents are incorporated in the present specification. Examples of the substituent include the following substituent T.
(Substituent T)
Alkyl group (preferably 1-30 carbon atoms), alkenyl group (preferably 2-30 carbon atoms), alkynyl group (preferably 2-30 carbon atoms), aryl group (preferably 6-30 carbon atoms), amino group (Preferably 0-30 carbon atoms), alkoxy group (preferably 1-30 carbon atoms), aryloxy group (preferably 6-30 carbon atoms), heteroaryloxy group (preferably 1-30 carbon atoms), acyl A group (preferably having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), an acyloxy group (preferably having 2 to 30 carbon atoms), Acylamino group (preferably having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms), aryloxycarbonylamino group Preferably 7-30 carbon atoms, sulfamoyl group (preferably 0-30 carbon atoms), carbamoyl group (preferably 1-30 carbon atoms), alkylthio group (preferably 1-30 carbon atoms), arylthio group (preferably 6-30 carbon atoms), heteroarylthio group (preferably 1-30 carbon atoms), alkylsulfonyl group (preferably 1-30 carbon atoms), arylsulfonyl group (preferably 6-30 carbon atoms), heteroarylsulfonyl Group (preferably having 1 to 30 carbon atoms), alkylsulfinyl group (preferably having 1 to 30 carbon atoms), arylsulfinyl group (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably having 1 to 30 carbon atoms) Ureido group (preferably having 1 to 30 carbon atoms), phosphoramide group (preferably having 1 to 30 carbon atoms), hydro Shi group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxy group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a heteroaryl group (preferably having 1 to 30 carbon atoms).
When these groups are further substitutable groups, they may further have a substituent. Examples of the further substituent include the groups described for the substituent T described above.

At least one of R ² and R ³ is preferably an electron withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-attracting group. Here, the substituent constant obtained by Hammett's rule includes a σp value and a σm value. These values can be found in many common books. In the present invention, substituents having Hammett's substituent constant σ value of 0.2 or more can be exemplified as electron-attracting groups. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (σp value = 0.66), a carboxy group (—COOH: σp value = 0.45), and an alkoxycarbonyl group (—COOMe: σp value = 0.45). An aryloxycarbonyl group (for example, —COOPh: σp value = 0.44), a carbamoyl group (for example, —CONH ₂ : σp value = 0.36), an alkylcarbonyl group (for example, —COMe: σp value = 0.50) An arylcarbonyl group (for example, —COPh: σp value = 0.43), an alkylsulfonyl group (for example, —SO ₂ Me: σp value = 0.72), an arylsulfonyl group (for example, —SO ₂ Ph: σp value = 0) .68). Here, Me represents a methyl group, and Ph represents a phenyl group. Regarding the Hammett's substituent constant σ value, for example, paragraph numbers 0017 to 0018 of JP 2011-68731 A can be referred to, and the contents thereof are incorporated herein.

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). The ring formed is preferably a merocyanine dye that is used as an acidic nucleus, and specific examples thereof can include, for example, paragraphs 0019 to 0021 of JP 2011-68731 A, the contents of which are incorporated herein. It is.

R ² represents an electron withdrawing group (preferably a cyano group), and R ³ preferably represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations. 1-3 are preferable and, as for the number of the hetero atoms which comprise a heteroaryl group, 1-2 are more preferable. 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, aryl group and heteroaryl group are the same as those described for 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 substituent represented by R ^4A and R ^4B include the substituent T described above, and a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, and an alkyl group, an aryl group, or a hetero group is preferable. An aryl group is more preferable, and an aryl group is particularly preferable. Specific examples of the group represented by —BR ^4A R ^4B include a difluoroboron group, a diphenylboron group, a dibutylboron group, a dinaphthylboron group, and a catecholboron group. Of these, a diphenylboron group 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, and platinum, and aluminum, zinc, vanadium. 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 , and it is particularly preferable that R ⁴ is coordinated to R ³ . R ⁴ is preferably a hydrogen atom or a group represented by —BR ^4A R ^4B (particularly a diphenylboron 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.

  The water-soluble inorganic salt serves as an attritor 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, sodium hydrogen carbonate and the like, preferably sodium chloride and sodium sulfate. These water-soluble inorganic salts can be pulverized. These water-soluble inorganic salts can be used alone or in a mixture of two or more.

  The average particle diameter D50 (50% diameter based on volume) 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. Near-infrared absorbing organic pigments have low hardness compared to chromatic organic pigments and inorganic pigments, and when kneaded and polished using a water-soluble inorganic salt with a small particle diameter, Although the crystallite size decreases, the crystallinity of the near-infrared absorbing organic pigment decreases, or the crystal structure of the near-infrared absorbing organic pigment changes, the visible transparency tends to decrease. By using a water-soluble inorganic salt having a reasonably large size, the near-infrared absorbing organic pigment can be made finer (for example, an average primary particle diameter of 10 to 100 nm) while suppressing the above-described change of the near-infrared absorbing organic pigment as much as possible. In addition, a milling pigment having the characteristics described later in the powder X-ray diffraction spectrum is easily obtained. Furthermore, the visible transparency and heat resistance of the milling pigment itself can be further improved.

  The amount of the water-soluble inorganic salt is 7 to 18 times, more preferably 8 to 17 times, and still more preferably 9 to 16 times the mass of the near infrared absorbing organic pigment. The lower limit is particularly preferably 10 times or more, and most preferably 11 times or more. The upper limit is particularly preferably 15 times or less, and most preferably 14 times or less. When the amount of the water-soluble inorganic salt is in the above-described range, the crystallinity (crystallinity) can be adjusted appropriately while suppressing the distortion of the crystal structure of the near-infrared absorbing organic pigment. Furthermore, the near-infrared absorbing organic pigment can be miniaturized. For this reason, it is easy to obtain a milling pigment having the characteristics described later in the powder X-ray diffraction spectrum. Furthermore, the visible transparency and heat resistance of the milling pigment itself can be further improved.

  The water-soluble organic solvent acts as a binder for the near-infrared absorbing organic pigment and the water-soluble inorganic salt, and the mixture containing the near-infrared absorbing organic pigment, the water-soluble inorganic salt and the water-soluble organic solvent is hardened and sticky. In addition, the crystal growth and crystal transition of the near-infrared absorbing organic pigment can be suppressed. The solubility of the water-soluble organic solvent in 100 g of water at 23 ° C. is preferably 10 g or more, more preferably 20 g or more, still more preferably 50 g or more, and particularly preferably 100 g or more. According to this aspect, the water-soluble inorganic salt can be efficiently washed in the next step. Specific examples of the water-soluble organic solvent include alkylene glycols such as ethylene glycol and propylene glycol, condensates of alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, and polyethylene-propylene glycol, methoxyethanol, and polyethylene glycol. Examples include (poly) alkylene glycol alkyl ethers such as monomethyl ether, glycerin, and the like, and because the mixture containing a near-infrared absorbing organic pigment, a water-soluble inorganic salt and a water-soluble organic solvent gives an appropriate hardness and viscosity. Highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol, and polyethylene glycol are preferred. One type of water-soluble organic solvent can be used alone, or a mixture of two or more types can be used. The amount of the water-soluble organic solvent varies depending on the amount of the near-infrared absorbing organic pigment, the amount of the water-soluble inorganic salt, the kneading conditions (temperature, kneading speed, etc.), the characteristics of the kneader used, etc. It is preferably 0.10 to 0.35 times, more preferably 0.12 to 0.30 times, still more preferably 0.15 to 0.25 times the total mass of the pigment and the water-soluble inorganic salt. If the amount of the water-soluble organic solvent is within the above range, it is possible to give an appropriate hardness and stickiness to the mixture containing the near-infrared absorbing organic pigment, the water-soluble inorganic salt and the water-soluble organic solvent.

  As the kneader, it is only necessary to have the ability to knead the above mixture, and a double-arm kneader, a flasher, a planetary mixer, or the like can be used. For miniaturization, a double-arm kneader having a strong shearing force is more preferable.

  The temperature at the time of kneading (milling temperature) is set according to the temperature dependence and crystal transition of the crystal growth rate of the near infrared absorbing organic pigment. In general, the lower the temperature, the lower the crystal growth rate. On the other hand, the wettability of the water-soluble organic solvent to the pigment surface and the penetration rate of the water-soluble organic solvent into the pigment mass are faster as the temperature is higher. The sizing of near-infrared absorbing organic pigments proceeds by a balance between both miniaturization and crystal growth. As kneading | mixing temperature, 0 degreeC or more is preferable, for example, 10 degreeC or more is more preferable, 20 degreeC or more is further more preferable, 30 degreeC or more is still more preferable, 40 degreeC or more is still more preferable. Especially, 50 degreeC or more is especially preferable from the reason that it is easy to manufacture the near-infrared absorption organic pigment excellent in visible transparency and heat resistance, adjusting an average primary particle diameter in the range of 1-100 nm. The upper limit is preferably 120 ° C. or lower, and more preferably 100 ° C. or lower.

  In the kneading and polishing step, a water-soluble inorganic salt or a water-soluble organic solvent can be added in accordance with the progress of refinement and sizing of the near-infrared absorbing organic pigment. Further, the discharge and re-kneading of the pigment kneaded material is not limited to once, and may be performed a plurality of times.

  In the kneading and polishing step, crystal transition can be performed together with the refinement of the near-infrared absorbing organic pigment. In addition, a pigment derivative or a surface treatment agent can be added for the purpose of miniaturizing the near-infrared absorbing organic pigment or controlling the crystal form.

  In the kneading and polishing step, it is preferable to perform kneading and polishing so that the average primary particle diameter of the near-infrared absorbing organic pigment is 10 to 100 nm. That is, the average primary particle diameter of the near-infrared absorbing organic pigment that is a milling pigment is preferably 10 to 100 nm. The lower limit is more preferably 15 nm or more, further preferably 20 nm or more, particularly preferably 25 nm or more, and most preferably 30 nm or more. The upper limit is preferably 90 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less, and particularly preferably 45 nm or less. When the average primary particle size of the milling pigment is 100 nm or less, the visible transparency is excellent. Further, when the average primary particle diameter of the milling pigment is 10 nm or more, the dispersion stability of the near infrared absorbing organic pigment in the dispersion is good.

The coefficient of variation of the primary particle diameter of the near-infrared absorbing organic pigment that is a milling pigment 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, still more preferably 29% or less, and even more preferably 28% or less. If the variation coefficient of the primary particle diameter of the milling pigment is within the above range, the visible transparency of the milling pigment itself can be further improved. 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 primary particle diameter of near-infrared absorbing organic pigment = (standard deviation of primary particle diameter of near-infrared absorbing organic pigment / arithmetic average value of primary particle diameter of near-infrared absorbing organic pigment) × 100

  The average long / short side ratio of the near-infrared absorbing organic pigment which is a milling pigment 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. If the average long / short side ratio of the milling pigment is within the above range, an effect of improving heat resistance can be expected.

The variation coefficient of the long-short side ratio of the near-infrared absorbing organic pigment which is a milling pigment 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. If the variation coefficient of the long / short side ratio of the milling pigment is within the above range, the effect of improving the visible transparency can be expected. The coefficient of variation of the long / short side ratio of the near infrared absorbing organic pigment is defined by the following equation.
Variation coefficient of long-short side ratio of near-infrared absorbing organic pigment = (standard deviation of long-short side ratio of near-infrared absorbing organic pigment / arithmetic average value of long-short side ratio of near-infrared absorbing organic pigment) × 100

  In the present invention, the primary particle diameter and the long / short side ratio of the near-infrared absorbing organic pigment can be determined from a photograph obtained by observing the primary particles of the near-infrared absorbing organic pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the near-infrared absorbing organic pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle size of the near-infrared absorbing organic pigment. Further, the ratio of the short side to the long side (short side / long side) of the primary particle is obtained from the projected photograph, and the long / short side ratio is calculated. Moreover, let the average primary particle diameter and average long-short side ratio in this invention be an arithmetic mean value of the primary particle diameter and long-short side ratio about the primary particle of 400 near-infrared absorption organic pigments. The longest diameter of the primary particles is called the long side, and the shortest diameter is called the short side. That is, in the case of an ellipse, the long axis is the long side and the short axis is the short side. Moreover, the primary particle | grains of a near-infrared absorption organic pigment mean the independent particle | grains without aggregation.

  The near-infrared absorbing organic pigment, which is a milling pigment, has a diffraction intensity peak in the region where the diffraction angle 2θ is 5 to 12 ° in the powder X-ray diffraction spectrum, and the full width at half maximum of the peak having the highest diffraction intensity in the aforementioned region. Is preferably 0.3 to 0.6 °.

  As a result of intensive studies by the present inventors, the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment has a diffraction intensity peak in the region where the diffraction angle 2θ is 5 to 12 °, and the diffraction intensity in the region described above. The near-infrared absorbing organic pigment having a full width at half maximum of 0.3 to 0.6 ° was found to be excellent in visible transparency and heat resistance. Although the detailed reason is unknown, the full width at half maximum of the peak having the highest diffraction intensity is 0.3 to 0.6 °, so that the near-infrared absorbing organic pigment crystallite has an appropriate size, and the scattering is On the other hand, the proportion of pigment molecules forming aggregates is increased, and as a result, it is assumed that visible transparency and heat resistance can be improved. As the average primary particle diameter of the near infrared absorbing organic pigment decreases, the heat resistance tends to decrease, but the near infrared absorbing organic pigment having the above-described characteristics is small even if the average primary particle diameter is small. Excellent heat resistance.

The peak having the highest diffraction intensity is preferably in the region where the diffraction angle 2θ is 6 to 10 °, more preferably in the region of 6 to 9 °, and in the region of 6.5 to 8.5 °. More preferably, it has. According to this aspect, the visible transparency and heat resistance of the milling pigment itself 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 embodiment, the visible transparency and heat resistance of the milling pigment itself are particularly good. In the present invention, the full width at half maximum of the peak having the highest diffraction intensity in the powder X-ray diffraction spectrum represents the peak having the highest diffraction intensity in the region where the diffraction angle 2θ is 5 to 12 ° as the Lorentz function [y = A / (1 + ((x−x0) / w) ² ) + h]. Here, y is the intensity, A is the peak height, x is 2θ, x0 is the peak position, w is the peak width (half width at half maximum), and h is the baseline. Moreover, as a measuring method of the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment, a Rigaku sample horizontal type strong X-ray diffractometer RINT-TTR III is used as a measuring device, and a diffraction angle 2θ = 5 ° to 55 °. , Voltage 50 kV, current 300 mA, scan speed 4 ° / min, step interval 0.1, slit (scattering 0.05 mm, divergence 10 mm, light receiving 0.15 mm).

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

  In addition, the peak derived from the crystal | crystallization in this invention means the sharp peak whose full width at half maximum in the peak of diffraction intensity is 1 degrees or less. In addition, the peak derived from amorphous means a peak whose full width at half maximum exceeds 3 ° in the peak of diffraction intensity. In the present invention, the values of Ic and Ia are such that the diffraction intensity in the region where the diffraction angle 2θ of the powder X-ray diffraction spectrum of the near-infrared absorbing organic pigment is 5 to 15 ° is the lowest and 25 to 35 °. This is a value calculated using a spectrum correction value obtained by subtracting the baseline value from the measured spectrum value of the powder X-ray diffraction spectrum, with the straight line connecting the lowest diffraction intensity in the region as the baseline.

(Washing process)
Next, the near infrared absorbing organic pigment (milling pigment) after kneading and polishing is washed. Examples of the cleaning method include a cleaning method using water, acid, alkali or the like. A water washing treatment is preferable for the reason of reducing environmental load. After the water washing treatment, the near-infrared absorbing organic pigment containing water may be used as it is, or a water treatment may be performed by performing a drying treatment. The drying method is not particularly limited, but it is preferably performed by hot air drying for the purpose of improving productivity. Moreover, when performing a drying process, it is preferable to make the moisture content of a near-infrared absorption organic pigment into 5% or less, and it is more preferable to set it as 2% or less.

(Dispersion process)
Next, the washed near-infrared absorbing organic pigment (milling pigment) is dispersed in the presence of a pigment derivative, a resin and a solvent to prepare a pigment dispersion. First, the pigment derivative, resin and solvent used for preparing the pigment dispersion will be described.

  Examples of the pigment derivative used for preparing the pigment dispersion 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 phthalimidomethyl group. The pigment derivatives represented are preferred.

式（Ｂ１）中、Ｐは色素構造を表し、Ｌは単結合または連結基を表し、Ｘは酸性基、塩基性基、塩構造を有する基またはフタルイミドメチル基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。

In formula (B1), P represents a dye 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 phthalimidomethyl group, and m is an integer of 1 or more. N represents an integer of 1 or more. When m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.

  In formula (B1), P represents a dye structure, and pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzoisoindole dye structure, thiazine indigo dye structure Azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, benzothiazole dye structure, benzimidazole dye structure and benzoxazole dye structure And at least one selected from pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure and benzimidazolone dye structure is more preferable. Roll dye structure is particularly preferred.

In formula (B1), L represents a single bond or a linking group. The linking group is preferably 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. , May be unsubstituted or 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 combination thereof. 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 phthalimidomethyl group. Examples of the acidic group include a carboxyl group and a sulfo group. As the basic group, an amino group is preferable, and a tertiary amino group is particularly preferable. Examples of the group having a salt structure include the above-mentioned acidic group salts and basic group salts. Examples of the atoms or atomic groups constituting the salt include metal atoms and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is preferable. Examples of the alkali metal atom include lithium, sodium, potassium and the like. Examples of alkaline earth metal atoms include calcium and magnesium.

  Specific examples of the pigment derivative include the following compounds. JP-A 56-118462, JP-A 63-264474, JP-A 1-217077, JP-A 3-9961, JP-A 3-26767, JP-A 3-153780. JP, 3-45662, JP 4-285669, JP 6-145546, JP 6-212088, JP 6-240158, JP 10-30063, JP-A-10-195326, International Publication WO2011 / 024896, Paragraph Nos. 0086 to 0098, International Publication WO2012 / 102399, Paragraph Nos. 0063 to 0094, etc., International Publication No. WO2016 / 035695, Paragraph The compounds described in No. 0053 can also be used, the contents of which are described herein. It is incorporated seen. 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 preferred.

  The addition amount of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the near infrared absorbing organic pigment. The lower limit 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. If the addition amount of a pigment derivative is the said range, the dispersibility of a near-infrared absorption organic pigment can be improved and aggregation of a near-infrared absorption organic pigment can be suppressed efficiently. Only one type of pigment derivative may be used, or two or more types may be used, and in the case of two or more types, the total amount is preferably within the above range.

  In the pigment dispersion, the resin is blended for the purpose of dispersing the near infrared absorbing organic pigment. In addition, a resin mainly used for dispersing a near infrared absorbing organic pigment or the like is also referred to as a dispersant.

  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.

The resin used as the dispersant is preferably at least one selected from acidic resins, basic resins and amphoteric resins, and more preferably at least one selected from acidic resins and amphoteric resins.
In the present invention, the acidic resin means a resin having an acid group and having an acid value of 5 mgKOH / g or more and an amine value of less than 5 mgKOH / g. The acidic resin preferably does not have a basic group. As an acid group which acidic resin has, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable. The acid value of the acidic resin is preferably 5 to 200 mgKOH / g. The lower limit is more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more. The upper limit is more preferably 100 mgKOH / g or less, and still more preferably 60 mgKOH / g or less. Further, 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 having an amine value of 5 mgKOH / g or more and an acid value of less than 5 mgKOH / g. The basic resin preferably does not have an acid group. As a basic group which basic resin has, an amino group is preferable. 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, the amphoteric resin means a resin having an acid group and a basic group and 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 those described above, and a carboxyl group is preferable. As the basic group, an amino group is preferable. 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 further preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, and even 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 further preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. The ratio between the acid value and the amine value of the amphoteric resin is preferably acid value: amine value = 1: 4 to 4: 1, more preferably 1: 3 to 3: 1.

  The resin preferably contains a repeating unit having an acid group. By using a resin including a repeating unit having an acid group, residue generated on the base of the pixel can be further reduced when a pattern is formed by photolithography.

  Resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures. Examples of the terminal-modified polymer include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, etc., and JP-A-2002-273191. Examples thereof include a polymer having a sulfo group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability. Examples of the graft polymer include reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. Reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, macromonomers described in JP-A-10-339949, JP-A-2004-37986, and the like, and a monomer having a nitrogen atom Copolymers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc., JP-A 2010- Examples thereof include a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-106268. As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

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

In Formula (11) to Formula (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 represents a hydrogen 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 represents a monovalent group, R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a monovalent group, and n, m, p, and q are each independently an integer of 1 to 500. J and k each independently represents an integer of 2 to 8. In formula (13), when p is 2 to 500, a plurality of R ³ may be the same or different from each other. In formula (14), when q is 2 to 500, a plurality of R ³ are present. ⁵ and R ⁴ may be the same or different from each other.

  Regarding the graft copolymer, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the above contents are incorporated in the present specification. Specific examples of the graft copolymer include the following resins. Further, resins described in paragraph numbers 0072 to 0094 of JP 2012-255128 A can be mentioned, and the contents thereof are incorporated in the present specification.

In addition, as the resin, an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can also be used. The oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain. A resin having at least one basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
The oligoimine dispersant is represented by, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or the formula (I-2a). Examples thereof include a resin containing a repeating unit.

Ｒ¹及びＲ²は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１〜６が好ましい）を表す。ａは、各々独立に、１〜５の整数を表す。＊は繰り返し単位間の連結部を表す。Ｒ⁸及びＲ⁹はＲ¹と同義の基である。Ｌは単結合、アルキレン基（炭素数１〜６が好ましい）、アルケニレン基（炭素数２〜６が好ましい）、アリーレン基（炭素数６〜２４が好ましい）、ヘテロアリーレン基（炭素数１〜６が好ましい）、イミノ基（炭素数０〜６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは−ＣＲ⁵Ｒ⁶−ＮＲ⁷−（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ⁵、Ｒ⁶は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１〜６が好ましい）を表す。Ｒ⁷は水素原子または炭素数１〜６のアルキル基である。
Ｌ^aはＣＲ⁸ＣＲ⁹とＮとともに環構造を形成する構造部位であり、ＣＲ⁸ＣＲ⁹の炭素原子と合わせて炭素数３〜７の非芳香族複素環を形成する構造部位であることが好ましい。さらに好ましくは、ＣＲ⁸ＣＲ⁹の炭素原子及びＮ（窒素原子）を合わせて５〜７員の非芳香族複素環を形成する構造部位であり、より好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。この構造部位はさらにアルキル基等の置換基を有していてもよい。
ＸはｐＫａ１４以下の官能基を有する基を表す。
Ｙは原子数４０〜１０，０００の側鎖を表す。
オリゴイミン系分散剤は、さらに式（Ｉ−３）、式（Ｉ−４）、および、式（Ｉ−５）で表される繰り返し単位から選ばれる１種以上を共重合成分として含有していてもよい。オリゴイミン系分散剤が、このような繰り返し単位を含むことで、分散性能を更に向上させることができる。

R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units. R ⁸ and R ⁹ are the same groups as R ¹ . L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms). Are preferred), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, or a linking group thereof. Among these, a single bond or —CR ⁵ R ⁶ —NR ⁷ — (imino group is X or Y) is preferable. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
L ^a is a structural site to form a ring structure together with CR ⁸ CR ⁹ and N, be combined with the carbon atoms of CR ⁸ CR ⁹ is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms preferable. More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR ⁸ CR ⁹ and N (nitrogen atom), more preferably a 5-membered non-aromatic heterocyclic ring. It is a structural part to be formed, and a structural part to form pyrrolidine is particularly preferable. This structural part 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 oligoimine-based dispersant further contains at least one selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5) as a copolymerization component. Also good. When the oligoimine dispersant contains such a repeating unit, the dispersion performance can be further improved.

R ¹ , R ² , R ⁸ , R ⁹ , L, La, a and * are as defined in the formulas (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) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.

Regarding the oligoimine-based dispersant, the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. Specific examples of the oligoimine dispersant include the following. Further, the resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.

  The resin is also available as a commercial product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie). In addition, pigment dispersants described in paragraph numbers 0041 to 0130 of JP 2014-130338 A can also be used, the contents of which are incorporated herein. Moreover, alkali-soluble resin etc. which are demonstrated by curable composition mentioned later can also be used for resin.

  As addition amount of resin, 0.1-100 mass parts is preferable with respect to 100 mass parts of near-infrared absorption organic pigments. The upper limit is more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less. The lower limit is more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more. When the resin content is within the above range, the dispersibility of the near-infrared absorbing organic pigment is good.

  Examples of the solvent used for preparing the pigment dispersion include organic solvents. Examples of the organic solvent include the following organic solvents. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyloxyacetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Til, ethyl 3-ethoxypropionate, etc.), alkyl esters of 2-alkyloxypropionic acid (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.) Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Acetoacetate Le, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol Examples thereof include monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons (for example, 50 ppm by weight per part of organic solvent). (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, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone A mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.

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

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

  The solvent may contain isomers (compounds having the same number of atoms and different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.

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

  The addition amount of the solvent is preferably 60 to 92% by mass, more preferably 70 to 90% by mass, and still more preferably 75 to 89% by mass with respect to the total amount of the pigment dispersion. Only one type of solvent may be used, or two or more types of solvents may be used. When two or more types of solvents are included, the total amount is preferably within the above range.

  Examples of the mechanical force used for dispersing the near-infrared absorbing organic pigment (milling pigment) in the dispersing step include compression, pressing, impact, shearing, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion. Also, the process and disperser for dispersing near-infrared absorbing organic pigments (milling pigments) are centered on “Suspension of Dispersion Technology, Issued by Information Technology Corporation, July 15, 2005” and “Suspension (solid / liquid dispersion)”. The process and disperser described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893, “Distribution technology and industrial application in practice” Can be used.

In preparing the pigment dispersion, it is preferable to filter the pigment dispersion with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the pore diameter of the filter is in the above range, fine foreign matters can be reliably removed. It is also preferable to use a fiber-shaped filter medium. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber. Specifically, filter cartridges of SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno Co., Ltd. may be mentioned.

When using the filters, different filters (for example, a first filter and a second filter) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
Moreover, you may combine the filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as the first filter can be used.

  The pigment dispersion obtained by the present invention is excellent in the dispersion stability of the near infrared absorbing organic pigment. The viscosity of the pigment dispersion is preferably low. The viscosity (23 ° C.) of the pigment dispersion 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 pigment dispersion obtained by the present invention preferably has a low thixotropic property. The thixotropic property 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), η (20 rpm) / η when the rotation speeds are 20 rpm and 50 rpm, respectively, are η (20 rpm) and η (50 rpm) Let the value of (50 rpm) be Ti value. The closer the Ti value is to 1, the lower the thixotropic property. Regarding the Ti value obtained by such a measuring method, the Ti value at 23 ° C. is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, 0.9 More preferably, it is -1.1.

  The pigment dispersion obtained by the present invention preferably has a maximum absorption wavelength in the wavelength range of 700 to 1000 nm. Absorbance A550 / absorbance Amax, which is the ratio of absorbance A550 at a wavelength of 550 nm to absorbance Amax at a maximum absorption wavelength, is preferably 0.002 to 0.040, and preferably 0.003 to 0.030. More preferably, it is still more preferably 0.004 to 0.020. The absorbance A400 / absorbance Amax, which is the ratio of the absorbance A400 at a wavelength of 400 nm and the absorbance Amax at the maximum absorption wavelength, is preferably 0.005 to 0.150, more preferably 0.020 to 0.100. Preferably, it is 0.050-0.070. The maximum absorption wavelength in the pigment dispersion of the present invention is more preferably in the range of 720 to 980 nm, and further preferably in the range of 740 to 960 nm.

  The content of the near-infrared absorbing organic pigment in the pigment dispersion obtained by the present invention is preferably 30 to 99% by mass and more preferably 50 to 99% by mass with respect to the total solid content of the pigment dispersion. Preferably, it is 60-99 mass%.

  The solid content concentration of the pigment dispersion obtained by the present invention is preferably 8 to 40% by mass, more preferably 10 to 30% by mass, and still more preferably 11 to 25% by mass.

<Method for producing curable composition>
Next, the manufacturing method of the curable composition of this invention is demonstrated.
The manufacturing method of the curable composition of this invention includes the manufacturing method of the pigment dispersion liquid of this invention mentioned above. More specifically, it can be produced by mixing the pigment dispersion obtained by the above-described method for producing a pigment dispersion of the present invention with other components constituting the curable composition such as a curable compound. it can. Moreover, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. With respect to the type of filter and the filtration method, those described in the column for preparing the pigment dispersion can be mentioned, and the preferred ranges are also the same. The curable composition in the present invention may be a photocurable composition or a thermosetting composition. In the case of a photocurable composition, it is preferably a composition containing a polymerizable compound (preferably a radically polymerizable compound) and a photopolymerization initiator (preferably a photoradical polymerization initiator).

  As for content of the near-infrared absorption organic pigment in a curable composition, 0.1-60 mass% is preferable with respect to the total solid of a 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.

  When forming a film | membrane by application | coating, for example, it is preferable that the viscosity (23 degreeC) of a curable composition exists in the range of 1-3000 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 at 23 ° C. of the curable composition is preferably 0.8 to 1.4, more preferably 0.9 to 1.2, and 0.9 to 1.1. Further preferred. Ti value of a curable composition can be measured by the method demonstrated in the column of the pigment dispersion liquid mentioned above.

  The curable composition manufactured by this invention can be preferably used for formation of a near-infrared cut filter, an infrared transmission filter, etc. Hereinafter, each component used for preparation of a curable composition is demonstrated.

<< Resin >>
The curable composition preferably further contains a resin in addition to the above-described pigment dispersion of the present invention. That is, in the manufacturing method of the curable composition in this invention, it is preferable to manufacture a curable composition by mixing a pigment dispersion, resin, and other components as needed.

  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 those described in the pigment dispersion described above. Also, (meth) acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, It is also preferable to use a resin such as a polyolefin resin, a cyclic olefin resin, a polyester resin, or a styrene resin. One of these resins may be used alone, or two or more thereof may be mixed and used.

  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 used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins. It can also be used as a dispersant.

  As for the weight average molecular weight (Mw) of alkali-soluble resin, 5000-100,000 are preferable. The number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 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 still more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

  The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

  As the alkali-soluble resin, a polymer having a carboxyl group in the 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 alkali-soluble resins such as novolac resins. Examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

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

式（ＥＤ２）中、Ｒは、水素原子または炭素数１〜３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０−１６８５３９号公報の記載を参酌できる。 In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

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

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- Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl and the like An alkyl group substituted with an aryl group of Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

式（Ｘ）において、Ｒ₁は、水素原子またはメチル基を表し、Ｒ₂は炭素数２〜１０のアルキレン基を表し、Ｒ₃は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。 The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).

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 a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

  Examples of the alkali-soluble resin include those described in paragraph Nos. 0558 to 0571 of JP2012-208494A (paragraph Nos. 0865 to 0700 of US 2012/0235099 corresponding), JP2012-198408A. Paragraphs 0076 to 0099, which are incorporated herein by reference.

  As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. The alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin having a polymerizable group in the side chain. Examples of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscote R-264, KS resist 106 All are manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Acrycure RD-F8 Nippon Shokubai Co., Ltd.).

  In the curable composition, the content of the resin (the total content of the resin in the pigment dispersion and the resin added in addition to the pigment dispersion) is from 14 to 14 based on the total solid content of the curable composition. 70 mass% is preferable. 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 with respect to the total solid content of the curable composition. 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. Moreover, as for content of alkali-soluble resin, 14-70 mass% is preferable with respect to the total solid of a curable composition. 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 >>
In the production of the curable composition of the present invention, a solid content concentration of the curable composition may be prepared by further adding a solvent in addition to the pigment dispersion. Examples of the solvent include organic solvents. The solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the curable composition, but is preferably selected in consideration of applicability and safety of the curable composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. About these details, the organic solvent demonstrated with the pigment dispersion liquid mentioned above can be used. Examples of the organic solvent include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol. Acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred.

  The content of the solvent in the curable composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 25 to 75% by mass with respect to the total amount of the curable composition. More preferably. The curable composition may contain only one type of solvent, or may contain two or more types. When two or more types of solvents are included, the total amount is preferably within the above range.

<< Curable compound >>
The curable composition preferably contains a curable compound. That is, in the manufacturing method of the curable composition in this invention, it is preferable to manufacture a curable composition by mixing a pigment dispersion, a curable compound, and other components as needed. As the curable compound, known compounds that can be cross-linked 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) acryloyl group. The polymerizable compound is preferably a radical polymerizable compound.

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

(Polymerizable compound)
The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, and an oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.
The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. Specific examples of these compounds include those described in paragraph Nos. 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph numbers 0254 to 0257 of JP-A 2008-292970. Compounds, the contents of which are incorporated herein.

Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku ( Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, Sartomer) (SR454, SR499, commercially available from the company) Is preferred. These oligomer types can also be used.
In addition, as a polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Examples of commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.

  A polymerizable compound having an acid group can also be used as the polymerizable compound. By using the polymerizable compound having an acid group, the unexposed portion of the polymerizable compound is easily removed during development, and the generation of development residues can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable. Examples of commercially available polymerizable compounds having acid groups include Aronix M-510 and M-520 (manufactured by Toagosei Co., Ltd.).

  A 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 production and handling. Furthermore, it is excellent in curability.

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

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58. Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Is also preferable.
Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H. UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

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

(Compound having an epoxy group)
As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. 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 compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. / Equivalent is more preferable.

  The compound having an epoxy group may be either a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). . 200-100000 are preferable and, as for the weight average molecular weight of the compound which has an epoxy group, 500-50000 are more preferable. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

  Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein. Further, compounds having an epoxy group (epoxy resin) are Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100. G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer) is also preferably used.

When the curable composition contains a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass relative to the total solid content of the curable composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. The compound which has an epoxy group may be single 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.
The mass ratio of the polymerizable compound to the compound having an epoxy group is preferably the mass of the polymerizable compound: the mass of the compound having an epoxy group = 100: 1 to 100: 400, and 100: 1 to 100: 100. More preferably, 100: 1 to 100: 50 is even more preferable.

<< photopolymerization initiator >>
The curable composition can contain a photopolymerization initiator. In particular, when the curable composition contains a polymerizable compound, it is preferable to contain a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a radical photopolymerization initiator.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, a US patent And the compounds described in the specification of No. 42122976.

  Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryls from the viewpoint of exposure sensitivity. Compounds selected from the group consisting of imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.

  As the photopolymerization initiator, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds can also be suitably used. For example, an α-aminoketone compound described in JP-A-10-291969 and an acylphosphine compound described in Japanese Patent No. 4225898 can also be used. As the α-hydroxyketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (manufactured by BASF) can be used. As the α-aminoketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF) can be used. As the α-aminoketone compound, the compounds described in JP2009-191179A can be used. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (manufactured by BASF), which are commercially available products, can be used.

  The photopolymerization initiator is preferably an oxime compound. Specific examples of the oxime compound include a compound described in JP-A No. 2001-233842, a compound described in JP-A No. 2000-80068, a compound described in JP-A No. 2006-342166, and JP-A No. 2006-21012. The description is given in the publication. Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2- Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In addition, J.H. C. S. Perkin II (1979, pp. 1653-1660), J. MoI. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP 2000-66385 A, JP 2000-80068 A, Special Table 2004 Examples thereof include compounds described in JP-A-534797 and JP-A-2006-342166. IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF) are also preferably used as commercial products. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 (manufactured by ADEKA Corporation), Adeka Arcles NCI-930 (manufactured by ADEKA Corporation), Adeka Optomer N -1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP2012-14052A) can also be used.

  Further, as oxime compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton In the same molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, and the like. Also good.

  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 oxime N—O bond is an (E) isomer, or the oxime N—O bond may be a (Z) oxime compound. Z) It may be a mixture with the body.

  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. Regarding the details of the formula (OX-1), the description of paragraph numbers 0276 to 0304 in JP 2013-029760 A can be referred to, and the contents thereof are incorporated in the present specification.

  In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.

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

  In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP2013-114249A, paragraph numbers 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles 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 thereto.

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

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

  0.1-50 mass% is preferable with respect to the total solid of a curable composition, content of a photoinitiator has more preferable 0.5-30 mass%, and 1-20 mass% is still more preferable. If the content of the photopolymerization initiator is within the above range, better sensitivity and pattern formability can be obtained. The curable composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types of photopolymerization initiators are included, the total amount is preferably within the above range.

<< Other near-infrared absorbing compounds >>
The curable composition can contain a near-infrared absorbing compound other than the above-described near-infrared absorbing organic pigment (also referred to as other near-infrared absorbing compound). Examples of other near infrared absorbing compounds include dyes. Examples of compound species include phthalocyanine compounds, naphthalocyanine compounds, rylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diiminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, and dibenzofuranone compounds. Is mentioned. As the phthalocyanine compound, naphthalocyanine compound, diiminium compound and croconium compound, compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used, the contents of which are incorporated herein. Moreover, IRA868 (made by Exiton), IRG-068 (made by Nippon Kayaku Co., Ltd.), etc. can also be used.

Moreover, inorganic particles can also be used as other near infrared absorbing compounds. The inorganic particles are preferably metal oxide particles or metal particles in terms of better infrared shielding properties. 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 dioxide (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. Moreover, a tungsten oxide compound can be used as the inorganic fine particles. The tungsten oxide compound is preferably cesium tungsten oxide. Regarding the details of the tungsten oxide compound, paragraph number 0080 of JP-A-2006-006476 can be referred to, and the contents thereof are incorporated in the present specification. The shape of the inorganic particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.

  The average particle size 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 such a range, the visible transparency is good. From the viewpoint of avoiding light scattering, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the inorganic particles is usually 1 nm or more.

  When the curable composition contains another near-infrared absorbing compound, the content of the other near-infrared absorbing compound is preferably 0.1 to 80 parts by mass with respect to 100 parts by mass of the near-infrared absorbing organic pigment, 60 mass parts is more preferable, and 10-40 mass parts is further more preferable.

<< Chromatic colorant >>
The curable composition can contain a chromatic colorant. In the present invention, the chromatic colorant means a colorant other than the white colorant and the black colorant. The chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.

In the present invention, the chromatic colorant may be a pigment or a dye. The pigment is preferably an organic pigment. The following can be mentioned as an organic pigment.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 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 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange pigment)
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment),
These organic pigments can be used alone or in various combinations.

  There is no restriction | limiting in particular as dye, A well-known dye can be used. Chemical structures include pyrazole azo, anilino azo, triaryl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes. Moreover, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

When the curable composition contains a chromatic colorant, the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the curable composition. 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, more preferably 50% by mass or less.
10-1000 mass parts is preferable with respect to 100 mass parts of a near-infrared absorption organic pigment, and, as for content of a chromatic colorant, 50-800 mass parts is more preferable.
Moreover, it is preferable that the total amount of a chromatic colorant and a near-infrared absorption organic pigment shall be 1-80 mass% with respect to the total solid of a curable composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by 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 contains two or more chromatic colorants, the total amount is preferably within the above range.

<< Coloring material that transmits infrared rays and blocks visible light >>
The curable composition can contain a colorant that transmits infrared rays and shields visible light (hereinafter also referred to as a colorant that blocks visible light).
In the present invention, the color material that blocks visible light is preferably a color material that absorbs light in the wavelength range from purple to red. In the present invention, the color material that blocks visible light is preferably a color material that blocks light in the wavelength region 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, the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2).
(1): Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants.
(2): Contains an organic black colorant. In the aspect (2), it is also preferable to further contain a chromatic colorant.

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

  Examples of the chromatic colorant include those described above. Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable. Examples of the bisbenzofuranone compound include compounds described in JP 2010-534726, JP 2012-515233, JP 2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available. Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-1-170601, JP-A-2-34664 and the like, and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.

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

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

Examples of the ratio (mass ratio) of each colorant include the following.

When the curable composition contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 30% by mass or less, and 20% by mass with respect to the total solid content of the curable composition. The following is more preferable, and 15% by mass or less is still more preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, the curable composition in this invention can also be set as the aspect which does not contain the coloring material which light-shields visible light substantially. The phrase “substantially free of a colorant that blocks visible light” means that the content of the colorant that blocks visible light is preferably 0.005% by mass or less in the total solid content of the curable composition, and 0.001 It is more preferable that the content is not more than mass%, and it is even more preferable not to contain a colorant that blocks visible light.
<< Chain transfer agent >>
The curable composition can contain a chain transfer agent. According to this aspect, curing of the film surface (pattern surface) can be promoted by exposure. For this reason, it is possible to suppress a decrease in film thickness during exposure, and it is easy to form a pattern with more excellent rectangularity.

Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, with thiol compounds being preferred. The thiol compound is preferably a compound having 2 or more (preferably 2 to 8, 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-mercaptobutyloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, thiol compounds having a heterocyclic ring, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) And aliphatic thiol compounds such as butyryloxy) butane. Moreover, it is also preferable to use the following compound. Commercially available chain transfer agents include PEMP (manufactured by Nagase Sangyo Co., Ltd., thiol compound), Sunseller M (manufactured by Sanshin Chemical Industry Co., Ltd., thiol compound), Karenz MT BD1 (Showa Denko Co., Ltd.) And thiol compounds).

  0.2-5.0 mass% is preferable with respect to the total solid of a curable composition, and, as for content of a chain transfer agent, 0.4-3.0 mass% is more preferable. Moreover, 1-40 mass parts is preferable with respect to 100 mass parts of a polymeric compound, and, as for content of a chain transfer agent, 2-20 mass parts is more preferable.

<< Polymerization inhibitor >>
The curable composition can contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) can be mentioned. Of these, p-methoxyphenol is preferred. As for content of a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a curable composition. Moreover, it is preferable that content of a polymerization inhibitor is 0.001-1 mass part with respect to 100 mass parts of a polymeric 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 may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds of polymerization inhibitors are included, the total amount is preferably within the above range.

<< UV absorber >>
The curable composition preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds and diketone compounds. Examples of the conjugated diene compound include a compound represented by the formula (UV-1).

In 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 or different from each other, but do not represent a hydrogen atom at the same time.

  For the description of the substituent of the compound represented by the formula (UV-1), the description of paragraph numbers 0024 to 0033 of International Publication WO2009 / 123109 can be referred to, and the contents thereof are incorporated herein. Specific examples of the compound represented by the formula (UV-1) include Exemplified Compounds (1) to (14) in Paragraph Nos. 0034 to 0037 of International Publication WO2009 / 123109. Incorporated into. As a commercial item of the ultraviolet absorber shown by a formula (UV-1), UV503 (made by Daito Chemical Co., Inc.) etc. are mentioned, for example.

式（ＵＶ−２）において、Ｒ¹⁰¹及びＲ¹⁰²は、各々独立に、置換基を表し、ｍ１およびｍ２は、それぞれ独立して０〜４を表す。置換基は、アルキル基、アルケニル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロアリールオキシカルボニル基、アシルオキシ基、アミノ基、アシルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、ヘテロアリールオキシカルボニルアミノ基、スルホニルアミノ基、スルファモイル基、カルバモイル基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アルキルスルホニル基、アリールスルホニル基、ヘテロアリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、ヘテロアリールスルフィニル基、ウレイド基、リン酸アミド基、メルカプト基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、シリル基、ヒドロキシル基、ハロゲン原子、シアノ基などが挙げられ、アルキル基およびアルコキシ基が好ましい。
アルキル基の炭素数は、１〜２０が好ましい。アルキル基は、直鎖、分岐、環状が挙げられ、直鎖または分岐が好ましく、分岐がより好ましい。
アルコキシ基の炭素数は、１〜２０が好ましい。アルコキシ基は、直鎖、分岐、環状が挙げられ、直鎖または分岐が好ましく、分岐がより好ましい。
Ｒ¹⁰¹及びＲ¹⁰²の一方がアルキル基で、他方がアルコキシ基である組み合わせが好ましい。
ｍ１およびｍ２は、それぞれ独立して０〜４を表す。ｍ１およびｍ２は、それぞれ独立して０〜２が好ましく、０〜１がより好ましく、１が特に好ましい。 Examples of the diketone compound include compounds represented by the following formula (UV-2).

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. Substituents are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, acyloxy groups, Amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl group, aryl Sulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfinyl, ureido, phosphate amide, mercapto, E group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, or a cyano group, an alkyl group and alkoxy group are preferred.
As for carbon number of an alkyl group, 1-20 are preferable. Examples of the alkyl group include linear, branched, and cyclic, and linear or branched is preferable, and branched is more preferable.
As for carbon number of an alkoxy group, 1-20 are preferable. Examples of the alkoxy group include straight chain, branched, and cyclic, and straight chain or branched is preferable, and branched 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 0-4. m1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.

Examples of the compound represented by the formula (UV-2) include the following compounds.

  Ubinal A (manufactured by BASF) can also be used as the ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, or a triazine compound can be used, and specific examples thereof include compounds described in JP2013-68814A. Is mentioned. As the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil and Fat may be used.

  0.01-10 mass% is preferable with respect to the total solid of a curable composition, and, as for content of a ultraviolet absorber, 0.01-5 mass% is more preferable. Moreover, it is preferable that content of a ultraviolet absorber is 5-100 mass parts with respect to 100 mass parts of a polymeric 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 can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, the functional group other than the hydrolyzable group is preferably a group that exhibits affinity by forming an interaction or bond with the resin. Examples thereof include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, and an isocyanate group, and a (meth) acryloyl group and an epoxy group are preferable. As silane coupling agents, compounds described in JP-A 2009-288703, paragraphs 0018 to 0036, compounds described in JP-A 2009-242604, paragraphs 0056 to 0066, and international publication WO2015 / 166679. Examples include the compounds described in paragraphs 0229-0236, the contents of which are incorporated herein.

  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 with respect to the total solid content of the curable composition. . The curable composition may contain only one type of silane coupling agent, or may contain two or more types. When two or more types of silane coupling agents are included, the total amount is preferably within the above range.

<<< surfactant >>>
The curable composition may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. As for the surfactant, paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, and the contents thereof are incorporated herein.

  By including a fluorosurfactant in the curable composition, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the coating thickness uniformity and liquid-saving properties are further improved. Can do. In the case of forming a film using a coating liquid to which a curable composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability | paintability to a coated surface improves. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a curable composition.

  Specific examples of the fluorosurfactant include surfactants described in paragraph Nos. 0060 to 0064 of JP 2014-41318 A (paragraph Nos. 0060 to 0064 of international publication 2014/17669), and the like. Examples include surfactants described in paragraph numbers 0117 to 0132 of Kokai 2011-132503, the contents of which are incorporated herein. Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (and above, DIC). Manufactured by Co., Ltd.), FLORARD FC430, FC431, FC171 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC- 381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

  In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heated is suitably used. Can be used. Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21, and these can be used.

上記の化合物の重量平均分子量は、好ましくは３，０００〜５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％は質量％である。 As the fluorosurfactant, a block polymer can be used. For example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. % Which shows the ratio of a repeating unit in said compound is the mass%.

  In addition, as the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. RS-72-K and the like. As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

  Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BASF) ), Solsperse 20000 (manufactured by Nihon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D- 6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

  Only one type of surfactant may be used, or two or more types may be combined. 0.001-2.0 mass% is preferable with respect to the total solid of a curable composition, and, as for content of surfactant, 0.005-1.0 mass% is more preferable.

<< Other ingredients >>
The curable composition may be a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, and other auxiliary agents (for example, conductive particles, A filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, a surface tension adjusting agent, a chain transfer agent, and the like). As for these components, descriptions in paragraph numbers 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074 can be referred to, and the contents thereof are incorporated in the present 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 thioether compound having a molecular weight of 500 or more is more preferable. You may use these in mixture of 2 or more types. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. In particular, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, methyl group, ethyl group, propionyl group, isopropionyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl. Group, t-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, phosphorus antioxidant can also be used suitably for antioxidant. As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl And at least one compound selected from the group consisting of) oxy] ethyl] amine and ethylbisphosphite (2,4-di-tert-butyl-6-methylphenyl). These are available as commercial products. For example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330 (stock) ADEKA) and the like. It is preferable that content of antioxidant is 0.01-20 mass% with respect to the total solid of a composition, and it is more preferable that it is 0.3-15 mass%. Only one type of antioxidant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<Membrane, near-infrared cut filter>
A film (also referred to as a film in the present invention) obtained using the curable composition described above can be preferably used as an optical filter such as a near infrared cut filter or an infrared transmission filter. In addition, an aspect in which the optical filter includes a pixel using the film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferable aspect. Moreover, the film | membrane in this invention can also be used as a heat ray shielding filter. The film in the present invention may have a pattern, or may be a film without a pattern (flat film). In addition, the film in the present invention may be used by being laminated on a support, or may be used after being peeled off from the support. Moreover, when using the film | membrane in this invention as an infrared rays permeable filter, the infrared rays transmissive filter light-shields visible light and the filter which transmits the light of wavelength 900nm or more is mentioned, for example. When the film according to the present invention is used as an infrared transmission filter, a near-infrared absorbing organic pigment and a colorant that shields visible light (preferably a colorant containing two or more chromatic colorants, or an organic black coloration) A filter using a curable composition containing at least an agent), or a filter having a layer of a color material that blocks visible light in addition to a layer containing a near infrared absorbing organic pigment. Preferably there is. When using the film | membrane in this invention as an infrared rays transmission filter, the near-infrared absorption organic pigment has a role which limits the light (near-infrared rays) which permeate | transmits to a longer wavelength side.

  The thickness of the film in 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 further preferably 0.3 μm or more.

  The film in the present invention can also be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using the coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the curable composition. 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. About these details, the material demonstrated by the curable composition is mentioned, These can be used. Moreover, it is good also as a filter provided with the function as a near-infrared cut filter and a color filter by making the film | membrane in this invention contain a chromatic colorant.

  In the present invention, the near-infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and shields at least a part of light having a wavelength in the near-infrared region (near-infrared light). . The near-infrared cut filter may transmit all light having a wavelength in the visible region, and transmits light in a specific wavelength region out of light having a wavelength in the visible region, and blocks light in the specific wavelength region. You may do. In the present invention, the color filter means a filter that allows light in a specific wavelength region to pass and blocks light in a specific wavelength region out of light having a wavelength in the visible region. The infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least part of light having a wavelength in the near infrared region (near infrared).

  When using the film | membrane in this invention as a near-infrared cut off filter, it is preferable that the film | membrane in this invention has a maximum absorption wavelength in the range of 700-1000 nm. Absorbance A550 / absorbance Amax, which is a ratio of absorbance A550 at a wavelength of 550 nm to absorbance Amax at a maximum absorption wavelength, is preferably 0.002 to 0.040, more preferably 0.003 to 0.030. Preferably, it is 0.004 to 0.020. The absorbance A400 / absorbance Amax, which is the ratio of the absorbance A400 at a wavelength of 400 nm and the absorbance Amax at the maximum absorption wavelength, is preferably 0.005 to 0.150, more preferably 0.020 to 0.100. Preferably, it is 0.050-0.070. The maximum absorption wavelength of the film is more preferably in the range of 720 to 980 nm, and further preferably in the range of 740 to 960 nm. Further, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

The near-infrared cut filter preferably satisfies at least one of the following (1) to (4) with respect to the light transmittance, and more preferably satisfies all the conditions (1) to (4). .
(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.
(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.

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

  The near-infrared cut filter may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorption layer, and the like in addition to the film in the present invention. When the near-infrared cut filter further has a copper-containing layer and / or a dielectric multilayer film, a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be easily obtained. Moreover, it can be set as the near-infrared cut filter excellent in ultraviolet-shielding property because a near-infrared cut filter has an ultraviolet absorption layer further. As the ultraviolet absorbing layer, for example, the absorbing layer described in Paragraph Nos. 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 090960 can be referred to, and the contents thereof are incorporated herein. As the dielectric multilayer film, the description of paragraph numbers 0255 to 0259 of JP 2014-41318 A can be referred to, and the contents thereof are incorporated in the present specification. As a layer containing copper, the glass substrate (copper containing glass substrate) comprised with the glass containing copper and the layer (copper complex containing layer) containing a copper complex can also be used. Examples of the copper-containing glass substrate include a phosphate glass containing copper and a fluorophosphate glass containing copper. Examples of commercially available products of copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Shot Corporation), CD5000 (manufactured by HOYA Corporation), and the like. As a copper complex content layer, the layer formed using the composition containing a copper complex is mentioned. The copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1200 nm. The maximum absorption wavelength of the copper complex is more preferably in the wavelength region of 720 to 1200 nm, and further preferably in the wavelength region of 800 to 1100 nm.

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

<Laminate>
The film of the present invention and a color filter can be laminated to be used as a laminate. In this laminate, the film and the color filter in the present invention may be adjacent to each other in the thickness direction or may not be adjacent. When the film in the present invention and the color filter are not adjacent in the thickness direction, the film in the present invention may be formed on a support different from the support on which the color filter is formed. Other members (for example, a microlens, a flattening layer, etc.) constituting a solid-state imaging device may be interposed between the film and the color filter.

<Pattern formation method>
Next, the pattern formation method using a curable composition is demonstrated. The pattern forming method includes a step of forming a composition layer on a support using a curable composition, and a step of forming a pattern on the composition layer by a photolithography method or a dry etching method. Is preferred.

  The pattern forming method by the photolithography method includes a step of forming a composition layer on a support using a curable composition, a step of exposing the composition layer in a pattern, and developing and removing an unexposed portion. Forming a pattern. If necessary, a step of baking the composition layer (pre-bake step) and a step of baking the developed pattern (post-bake step) may be provided. The pattern formation method by the dry etching method includes a step of forming a composition layer on a support using a curable composition and curing to form a cured product layer, and forming a photoresist layer on the cured product layer. It is preferable to include a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask. Hereinafter, each step will be described.

<< Step of Forming Composition Layer >>
In the step of forming the composition layer, the composition layer is formed on the support using the curable composition.

  As the support, for example, a solid-state image sensor substrate in which a solid-state image sensor (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 image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface). If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the curable composition to the support, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A). Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer methods using a mold or the like; nanoimprint methods and the like. The application method in the ink jet is not particularly limited. For example, the method described in the patent gazette shown in “Expanded and usable ink jet-unlimited possibilities seen in patents, issued in February 2005, Sumibe Techno Research”. (Especially pages 115 to 133), JP2003-262716A, JP2003-185831A, JP2003-261627A, JP2012-126830A, JP2006-169325A, etc. The method of description is mentioned.

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

(When forming a pattern by photolithography)
<< Exposure process >>
Next, the composition layer is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
Radiation (light) that can be used for exposure is preferably ultraviolet rays such as g-line and i-line, and i-line is more preferable. Irradiation dose (exposure dose), for example, preferably 0.03~2.5J / cm ^2, more preferably 0.05~1.0J / cm ^2, and most preferably 0.08~0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) with an oxygen concentration exceeding 21% by volume. The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) can be selected from the range of . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.

<< Development process >>
Next, the unexposed portion is developed and removed to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains on a support body.
The developer is preferably an alkaline developer that does not damage the underlying solid-state imaging device or circuit.
As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

  Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate And inorganic alkaline compounds such as. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Further, a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described curable composition, and a nonionic surfactant is preferable. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) with a pure water after image development.

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

  Moreover, after developing and removing an unexposed part (after image development), you may have the process (Hereafter, exposure after image development is also called post-exposure.). When a curable composition containing an oxime compound and an α-aminoketone compound is used as the photopolymerization initiator, post-exposure is preferably performed. By exposing the composition layer in two stages before and after the pattern formation, the composition can be appropriately cured by the first exposure (exposure before forming the pattern), and the next exposure (after forming the pattern) The entire composition can be almost cured by the above exposure). As a result, even if the post-bake temperature is 180 ° C. or lower, the curable composition can be effectively cured. Even when the exposure is performed in two stages, post-baking may be further performed after the post-exposure. As for post-baking temperature, 100-240 degreeC is preferable, for example.

(When pattern is formed by dry etching method)
The pattern formation by the dry etching method is performed by curing the composition layer formed on the support to form a cured product layer, and then using the patterned photoresist layer as a mask for the obtained cured product layer. Etching gas can be used. In forming the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable. Regarding the pattern formation by the dry etching method, the description of paragraph numbers 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in the present specification.

<Solid-state imaging device>
The film in the present invention can be used for a solid-state imaging device. The configuration of the solid-state imaging device is not particularly limited as long as the configuration functions as a solid-state imaging device. For example, the following configurations can be mentioned.

  On the support, there are a plurality of photodiodes that constitute the light receiving area of the solid-state imaging device, and transfer electrodes made of polysilicon, etc., and light shielding made of tungsten or the like that opens only the light receiving part of the photodiodes on the photodiodes and transfer electrodes. A device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light shielding film and the photodiode light receiving portion on the light shielding film, and the film in the present invention on the device protective film. is there. Furthermore, it is on the device protective film and has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) under the film in the present invention (on the side close to the support), or on the film in the present invention. The structure etc. which have a means may be sufficient. In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the imaging apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

<Image display device>
The film in the present invention can also be used for image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices. For example, the film according to the present invention is added to each colored pixel for the purpose of blocking infrared light contained in a backlight (for example, a white light emitting diode (white LED)) of an image display device, for the purpose of preventing malfunction of peripheral devices. Can be used for the purpose of forming infrared pixels.

  For the definition and details of image display devices, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute, 1990)”, “Display Device (written by Junaki Ibuki, published in 1989 by Sangyo Tosho). ) "Etc. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

  The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, “The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. The spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.

<Infrared sensor>
The film in the present invention can be used for an infrared sensor. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.

Hereinafter, an embodiment of an infrared sensor will be described with reference to the drawings.
In FIG. 1, reference numeral 110 denotes a solid-state image sensor. The imaging region provided on the solid-state imaging device 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. A micro lens 115 is 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 microlens 115. The near-infrared cut filter 111 can be formed using the curable composition obtained by the manufacturing method of the curable composition of this invention.

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

  The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the infrared transmission filter 114 preferably has a maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm of 30% or less. % Or less, more preferably 10% or less, and particularly preferably 0.1% or less. This transmittance preferably satisfies the above conditions throughout the wavelength range of 400 to 650 nm. The maximum value in the wavelength range of 400 to 650 nm is usually 0.1% or more.

  In the infrared transmission filter 114, the minimum value of the light transmittance in the film thickness direction in the wavelength range of 800 nm or more (preferably 800 to 1300 nm) is preferably 70% or more, and more preferably 80% or more. More preferably, it is 90% or more. This transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and preferably satisfies the above condition at a wavelength corresponding to the emission wavelength of the infrared LED. The minimum value of the light transmittance in the wavelength 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, further preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. When the film thickness is in the above range, a film satisfying the above-described spectral characteristics can be obtained.
A method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.
The film thickness was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the dried substrate having the film.
The spectral characteristic of the film is a value obtained by measuring the 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).

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

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass. In the following structural formulas, Me represents a methyl group, and Ph represents a phenyl group.

<Kneading and polishing of near-infrared absorbing organic pigment (production of milling pigment)>
The pigment, milling agent and binder described in the following table are added to Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the temperature of the kneaded material in the apparatus is the temperature described in the following table (milling temperature). The mixture was kneaded at the milling time described in the following table under temperature control.
The kneaded product after kneading and polishing is washed with 10 L of water at 24 ° C. to remove the milling agent and the binder, and dried in a heating oven at 80 ° C. for 24 hours. A pigment was obtained. The average primary particle size of the milling pigment was 10 to 100 nm.
The average primary particle size of the milling pigment was measured by the following method. The primary particles of the milling pigment were observed with a transmission electron microscope and determined from the obtained photographs. Specifically, the projected area of the primary particles was obtained from the obtained photograph, and the corresponding circle equivalent diameter was calculated as the primary particle diameter. The arithmetic average value of the primary particle diameters for 400 primary particles was taken as the average primary particle diameter of the milling pigment.

顔料２：下記構造の化合物（近赤外線吸収有機顔料である）

顔料３：下記構造の化合物（近赤外線吸収有機顔料である）

（摩砕剤）
摩砕剤１：中性無水芒硝Ｅ（硫酸ナトリウム、平均粒子径（体積基準の５０％径（Ｄ５０））＝２０μｍ、三田尻化学製）
摩砕剤２：ナクルＵＭ（塩化ナトリウム、平均粒子径（体積基準の５０％径（Ｄ５０））＝５０μｍ、ナイカイ塩業製）
（粘結剤）
ＤＥＧ：ジエチレングリコール
ＥＧ：エチレングリコール The materials described in the above table are as follows.
(Pigment)
Pigment 1: Compound having the following structure (near infrared absorbing organic pigment)

Pigment 2: Compound having the following structure (near infrared absorbing organic pigment)

Pigment 3: Compound having the following structure (near infrared absorbing organic pigment)

(Abrasive)
Milling agent 1: neutral anhydrous sodium sulfate E (sodium sulfate, average particle size (50% diameter (D50) based on volume) = 20 μm, manufactured by Mitajiri Chemical)
Milling agent 2: Nakuru UM (sodium chloride, average particle diameter (50% diameter (D50) based on volume) = 50 μm, manufactured by Naikai salt industry)
(Binder)
DEG: Diethylene glycol EG: Ethylene glycol

<Preparation of pigment dispersion>
The raw materials shown in the following table and 66 parts by mass of zirconia beads having a diameter of 0.5 mm were subjected to a dispersion treatment with a paint shaker for 120 minutes, and then the zirconia beads were separated by decantation to prepare a dispersion.

分散剤１：下記構造の樹脂（重量平均分子量＝２１０００）。主鎖に付記した数値は繰り返し単位のモル比を表し、側鎖に付記した数値は、繰り返し単位の数を表す。

Pigment derivative 1:

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

<Evaluation of spectral characteristics>
Spectral characteristics were evaluated using a sample solution obtained by mixing 10 parts by mass of each dispersion obtained above and 10 parts by mass of resin (Cyclomer P (ACA) 230AA manufactured by Daicel Corporation).

(Spectral characteristics)
The sample solution was applied onto a glass wafer by spin coating so that the film thickness after application was 0.3 μm, and then heated at 100 ° C. for 2 minutes using a hot plate. Next, it exposed at 1000 mJ / cm < ² > using i line | wire stepper exposure apparatus FPA-3000i5 + (made by Canon Inc.). Furthermore, it heated at 220 degreeC for 5 minute (s) using the hotplate, and formed the film | membrane. Using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), the maximum absorption wavelength, the absorbance Amax at the maximum absorption wavelength, the absorbance A550 at a wavelength of 550 nm, and the absorbance at a wavelength of 400 nm are applied to the substrate on which the film is formed. A400 is obtained, and the ratio of absorbance A550 at the wavelength of 550 nm to absorbance Amax at the maximum absorption wavelength (absorbance A550 / absorbance Amax), and the ratio of absorbance A400 at wavelength 400 nm to absorbance Amax at the maximum absorption wavelength (absorbance A400 / absorbance Amax) Calculated.

Moreover, the roughness of the brightness of the transmitted light was evaluated by the following method.
An optical microscope in which a substrate on which the film is formed is placed between an observation lens and a light source of an optical microscope to irradiate light toward the observation lens, and the transmitted light state is installed with a digital camera having a magnification of 1000 times Observed by. The digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels and photographed the film surface in the transmitted light state. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format. Imaging of the film surface was performed on 20 arbitrarily selected regions. In addition, the digitally converted data was digitized and stored as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of red, green, and blue. Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged. In this evaluation method, an image with a magnification of 1000 is taken with a 1.28 million pixel digital camera, so 2 μm on the actual substrate is 2 mm on the taken image. Since the image size on the display was 452 mm × 352 mm, the total number of sections in one area was 39776.
For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A section having a difference of 5 or more from the average brightness of the adjacent section was recognized as a significant difference section, and the ratio of the average total number of significant difference sections in all the regions to the total number (39976) of each region was calculated. The results are shown in the table below. In addition, it has shown that the roughness of the brightness of transmitted light is so small that the ratio which the average total number of the significant difference division of all the said areas occupies with respect to the total number of divisions of each area | region is small.

As shown in the above table, in the examples, the absorbance A400 and the absorbance A550 were low, and the visible transparency was excellent. Moreover, the roughness of the brightness of the transmitted light was also suppressed.
In the examples, even when a cyanine compound or squarylium compound is used as the pigment, the same excellent effects as in the examples can be obtained.
In the examples, even when the pigment derivative described in this specification is used in place of the pigment derivative 1 as the pigment derivative, the same excellent effect as in the example can be obtained.

110: Solid-state imaging device, 111: Near-infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Micro lens, 116: Flattening layer

Claims (9)

Kneading and polishing the near-infrared absorbing organic pigment in the presence of a water-soluble organic solvent and a water-soluble inorganic salt 7 to 18 times the mass of the near-infrared absorbing organic pigment;
Washing the near infrared absorbing organic pigment after the kneading and polishing;
And a step of dispersing the washed near-infrared absorbing organic pigment in the presence of a pigment derivative, a resin and a solvent.   The method for producing a pigment dispersion according to claim 1, wherein the near-infrared absorbing organic pigment is kneaded and polished in the presence of a water-soluble organic solvent and a water-soluble inorganic salt 9 to 16 times the mass of the near-infrared absorbing organic pigment. .   The method for producing a pigment dispersion according to claim 1, wherein the water-soluble organic solvent has a solubility in 100 g of water at 23 ° C. of 20 g or more.   The method for producing a pigment dispersion according to any one of claims 1 to 3, wherein the water-soluble inorganic salt is at least one selected from sodium chloride and sodium sulfate.   The manufacturing method of the pigment dispersion liquid of any one of Claims 1-4 whose average particle diameter D50 of the said water-soluble inorganic salt is 15 micrometers or more.   The manufacturing method of the pigment dispersion liquid of any one of Claims 1-5 which performs the said kneading | polishing grinding | polishing under the temperature of 50 degreeC or more.   The manufacturing method of the pigment dispersion liquid of any one of Claims 1-6 which performs the said kneading | polishing and making the average primary particle diameter of the said near-infrared absorption organic pigment into 10-100 nm.   The method for producing a pigment dispersion according to any one of claims 1 to 7, wherein the near-infrared absorbing organic pigment is at least one selected from a pyrrolopyrrole compound and a squarylium compound.   The manufacturing method of a curable composition containing the manufacturing method of the pigment dispersion liquid of any one of Claims 1-8.

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