JPWO2017038252A1 - Material, composition, curable composition, cured film, optical filter, solid-state imaging device, infrared sensor, camera module, and method for producing material - Google Patents

Abstract

Provided is a material excellent in dispersibility of a pigment in a composition. Also provided are a composition excellent in pigment dispersibility, a curable composition, a cured film, an optical filter, a solid-state imaging device, an infrared sensor, a camera module, and a method for producing the material. A material comprising pigment A and compound B having a structure having an adsorptivity to a resin, wherein X ¹ represented by formula (I) is 0.99 or more. X ² is a solvent having a solubility of Pigment A of 0.02% by mass or less and a solubility of Compound B of 0.2% by mass or more at 25 ° C., and the mass of Compound B in the material after dipping the material And X ³ is the mass of the solid content of the material after being immersed in the solvent. Formula (I); X ¹ = (X ² / X ³ ) × 100

Description

  The present invention relates to a material containing a pigment and a compound having a structure having an adsorptivity to a resin. Moreover, it is related with the manufacturing method of a composition, a curable composition, a cured film, an optical filter, a solid-state image sensor, an infrared sensor, a camera module, and material.

In recent years, with the spread of digital cameras, camera-equipped mobile phones and the like, the demand for solid-state imaging devices such as charge coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements.
In addition, since these solid-state imaging devices use silicon photodiodes having sensitivity to near infrared rays in their light receiving parts, visual sensitivity correction may be performed using an infrared cut filter.

A color filter and an infrared cut filter may be manufactured using a composition containing a pigment.
Patent Document 1 discloses a diketopyrrolopyrrole pigment (A), a dye derivative (B), a water-soluble inorganic salt (C), and a water-soluble organic solvent (D) that does not substantially dissolve the water-soluble inorganic salt (C). It is described that after kneading a mixture containing a water-soluble inorganic salt (C) and a water-soluble organic solvent (D), a pigment for a color filter is produced. In Patent Document 1, a color filter is manufactured using a coloring composition obtained by dispersing this pigment in a transparent resin.

JP 2001-220520 A

  The pigment may be used by being dispersed in a resin, a solvent, or the like. However, if the adsorptivity of the pigment itself to the resin is low, the dispersibility of the pigment in the composition tends to be lowered. According to the study by the present inventors, the color filter pigment obtained by the method described in Patent Document 1 is produced by mixing a diketopyrrolopyrrole pigment and a dye derivative. The pigment for use was found to have poor adhesion between the diketopyrrolopyrrole pigment and the dye derivative, and the dye derivative was easily peeled off from the diketopyrrolopyrrole pigment. Furthermore, it has been found that the color filter pigment described in Patent Document 1 has a low adsorptivity with a resin and insufficient dispersibility of the pigment in the composition.

  Accordingly, an object of the present invention is to provide a material containing a pigment and having excellent dispersibility of the pigment in the composition. Moreover, it is providing the manufacturing method of the composition excellent in the dispersibility of a pigment, a curable composition, a cured film, an optical filter, a solid-state image sensor, an infrared sensor, a camera module, and material.

As a result of intensive studies, the present inventors have synthesized a pigment by reacting a pigment raw material compound in the presence of a compound having a structure having an adsorptive property to a resin. It has been found that a material in which the compound B having a structure having a structure is firmly adsorbed can be obtained. Although the detailed mechanism for obtaining a material in which compound B is firmly attached to pigment A is unknown, pigment A is synthesized by reacting the raw material compound of pigment A in the presence of compound B to produce pigment A. Since the compound B is taken into the particles, it is presumed that a material having the compound B physically and firmly attached to the pigment A was obtained. And when the material manufactured by this method was further examined, the dispersibility of the pigment A in the composition is good in the material in which X ¹ represented by the formula (I) described later is 0.99 or more. As a result, the present invention has been completed. The present invention provides the following.
<1> A material containing Pigment A and Compound B having a structure having adsorptivity to resin,
A material represented by the following formula (I) wherein X ¹ is 0.99 or more;
X ¹ = (X ² / X ³ ) × 100 (I)
X ² in the material after immersing the material in a solvent having a solubility of the pigment A of 0.02% by mass or less and a solubility of the compound B of 0.2% by mass or more at 25 ° C. It is the mass of the compound B, and X ³ is the mass of the solid content of the material after being immersed in the solvent.
<2> The material according to <1>, wherein the pigment A has absorption in the near infrared region.
<3> The material according to <1> or <2>, wherein the maximum absorption wavelength of the pigment A is in the range of 700 to 1200 nm.
<4> Pigment A is at least one selected from a phthalocyanine compound, a naphthalocyanine compound, a perylene compound, a pyrrolopyrrole compound, a cyanine compound, a dithiol metal complex compound, a naphthoquinone compound, an iminium compound, an azo compound, and a squarylium compound. The material according to any one of 1> to <3>.
<5> The material according to any one of <1> to <4>, wherein the pigment A is a pyrrolopyrrole compound.
<6> The material according to <5>, wherein the pyrrolopyrrole compound is a compound represented by the following formula (1);

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ 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 bonded or coordinated, and R ^4A and R ^4B each independently represents a substituent.
<7> The material according to any one of <1> to <6>, wherein compound B has a dye structure.
<8> Dye structure is 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 At least one selected from a structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure, and a benzoxazole dye structure The material according to <7>.
<9> The compound B has at least one selected from an acidic group, a basic group, a hydrogen bonding group, a dipole interacting group, and a π-π interacting group, from <1> to <8> The material according to any one.
<10> A composition comprising the material according to any one of <1> to <9>.
<11> The composition according to <10>, further comprising at least one selected from an organic solvent, a resin, and a pigment derivative.
<12> A curable composition comprising the composition according to <10> or <11> and a curable compound.
<13> A cured film using the curable composition according to <12>.
<14> An optical filter having the cured film according to <13>.
<15> The optical filter according to <14>, which is at least one selected from a color filter, an infrared cut filter, and an infrared transmission filter.
<16> A pixel of the cured film according to <13>,
The optical filter according to <14> or <15>, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.
<17> A solid-state imaging device having the cured film according to <13>.
<18> An infrared sensor having the cured film according to <13>.
<19> A camera module having a solid-state imaging device and the cured film according to <13>.
<20> A method for producing a material comprising a pigment A and a compound B having a structure having an adsorptivity to a resin,
A method for producing a material, wherein the pigment A is synthesized by reacting the raw material compound of the pigment A in the presence of the compound B having a structure having an adsorptivity to the resin when the pigment A is synthesized.

  According to the present invention, it is possible to provide a material containing a pigment and having excellent dispersibility of the pigment in the composition. In addition, it has become possible to provide a composition, a curable composition, a cured film, an infrared cut filter, a solid-state imaging device, an infrared sensor, a camera module, and a material manufacturing method excellent in pigment dispersibility.

It is a schematic sectional drawing which shows the structure of one Embodiment of the infrared sensor of this invention.

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 present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) allyl” means both “allyl” and “methallyl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the near-infrared region refers to a range where the wavelength region is 700 to 2500 nm. Near-infrared light refers to light (electromagnetic wave) having a wavelength region of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
In this specification, solid content means solid content in 25 degreeC.
In this specification, a weight average molecular weight is defined as a polystyrene conversion value by 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 (inner diameter) × 15.0 cm) can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
In the present specification, the pigment means an insoluble compound that is difficult to dissolve in a specific solvent. Typically, it means a compound that exists in a dispersed state as particles in the composition. Here, with a solvent, the solvent illustrated in the column of the solvent mentioned later, for example is mentioned. For example, the pigment used in the present invention preferably has a solubility in propylene glycol monomethyl ether acetate at 25 ° C. of 0.02% by mass or less.

<Material>
The material of the present invention is a material containing the pigment A and the compound B having a structure having an adsorptivity to a resin, and X ¹ represented by the following formula (I) is 0.99 or more.
X ¹ = (X ² / X ³ ) × 100 (I)
X ² is a solvent having a solubility of Pigment A of 0.02% by mass or less and a solubility of Compound B of 0.2% by mass or more at 25 ° C., and the mass of Compound B in the material after dipping the material And X ³ is the mass of the solid content of the material after being immersed in the solvent.
In the material of the present invention, the compound B described above is firmly attached to the pigment A, and the adsorptivity of the pigment A to the resin is excellent. For this reason, the dispersibility of the pigment in a composition can be made favorable.
In the material of the present invention, the pigment A and the compound B exist as separate compounds. Here, “Pigment A and Compound B are present as separate compounds” means that Pigment A is present outside the molecule of Compound B, and the two are not covalently bonded. To do. That is, the material of the present invention is different from a compound (for example, a dye derivative) obtained by introducing a group having adsorptivity to a resin into a part of pigment molecules.

The content of the pigment A in the material of the present invention is preferably 30 to 99% by mass. The lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less.
The content of Compound B in the material of the present invention is preferably 0.99% by mass or more and less than 70% by mass. The lower limit is more preferably 2.91% by mass or more, and particularly preferably 4.76% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. When the content of Compound B is in the above range, the dispersibility of the pigment in the composition is particularly excellent. Moreover, it is preferable that the compound B contains 1-150 mass parts with respect to 100 mass parts of the pigment A in the material of this invention. 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 100 parts by mass or less, and more preferably 70 parts by mass or less.
The content of Compound B in the material is determined by measuring the amount of Compound B contained in the filtrate discharged during the production of the material by high performance liquid chromatography (HPLC), thereby determining the amount of Compound B remaining in the material. It can be calculated. It can also be quantified and calculated by a method such as infrared spectroscopy (IR).

In the material of the present invention, X ¹ represented by the above formula (I) (content ratio of compound B in the material after immersion in the solvent) is 0.99 or more, preferably 3 or more, and particularly preferably 5 or more. . The upper limit can be, for example, 70 or less, 60 or less, or 50 or less. X ¹ is equal to or more than 0.99, compound B has firmly adhered to the pigment A, excellent in adsorptivity to the resin of the pigment. For this reason, the dispersibility of the pigment in a composition can be made favorable.
X ¹ is calculated using, for example, X ² and X ³ measured as follows.
The mass X ³ of the solid content of the material after immersion in the solvent can be obtained by measuring the mass after removing the solvent adhering to the material from the material after immersion in the solvent by a method such as drying. . In addition, the mass at the time when the weight reduction rate of the material after immersion in the solvent is saturated (the mass when the weight reduction rate becomes almost constant) can be obtained by thermal analysis TGA (differential thermal analysis). . Examples of the measuring device include a thermogravimetric measuring device Q500 type ((TE Instruments Japan Co., Ltd.)).
X ² which is the mass of the compound B in the material after the solvent immersion is obtained by measuring the amount of the compound B contained in the filtrate discharged after washing the material with the solvent by high performance liquid chromatography (HPLC). It can be calculated as the amount of compound B remaining therein. Further, the material before and after immersion in the solvent can be quantified and calculated by a method such as infrared spectroscopy (IR).

The solvent is not particularly limited as long as it satisfies the requirement that the solubility of the pigment A is 0.02% by mass or less and the solubility of the compound B is 0.2% by mass or more at 25 ° C. . For example, the organic solvent etc. which the composition mentioned later may contain are mentioned. Specific examples include methanol, ethanol, tetrahydrofuran, acetone and the like. Examples of the immersion method include a method in which 16.6 mL of a solvent is added to 1 g of a sample, heated and refluxed for 30 minutes, and then filtered.
Hereinafter, the material of the present invention will be described.

<< Pigment A >>
The material of the present invention contains pigment A. The type of the pigment A is not particularly limited. It may be a pigment having absorption in the visible region (hereinafter also referred to as a chromatic pigment), or may be a pigment having absorption in the near infrared region (hereinafter also referred to as near infrared absorbing dye).

There is no limitation in particular as a chromatic pigment, The compound which has absorption in a visible region (Preferably the range of wavelength 400-700 nm, More preferably, the range of 400-650 nm) is mentioned. Examples include diketopyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, azo compounds, isoindoline compounds, quinophthalone compounds, benzimidazolone compounds, and perinone compounds. Specific examples of the chromatic pigment include the following.
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, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
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. ,
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
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80

  As the near-infrared absorbing dye, a compound having a maximum absorption wavelength in the range of 700 to 1200 nm is preferable, and a compound having a maximum absorption wavelength in the range of 700 to 1000 nm is more preferable. In the present invention, the pigment A is preferably a near infrared absorbing dye. Many near-infrared absorbing dyes tend to have low dispersibility in the composition, and further improvement in dispersibility is desired, and the effects of the present invention are particularly easily obtained.

  Examples of near-infrared absorbing dyes include phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complex compounds, naphthoquinone compounds, iminium compounds, azo compounds, and squarylium compounds. A naphthalocyanine compound, a pyrrolopyrrole compound, a cyanine compound and a squarylium compound are preferred, and a pyrrolopyrrole compound is more preferred. The pyrrolopyrrole compound is preferably a pyrrolopyrrole boron compound. Since a pyrrolopyrrole compound is excellent in near-infrared absorptivity and invisibility, it is easy to obtain a cured film such as an infrared cut filter excellent in near-infrared shielding and visible transmission. Further, the pyrrolopyrrole compound is a pigment having low dispersibility in the composition, but according to the present invention, the dispersibility of the pigment in the composition can be improved, and the effects of the present invention can be more easily obtained. . Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A No. 2009-263614. As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated. In addition, as for the cyanine compound, for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. .

(Pyrrolopyrrole compound (compound having a pyrrolopyrrole structure))
In the present invention, the pyrrolopyrrole compound is preferably a compound represented by the formula (1). This compound is excellent in near-infrared absorptivity and invisibility.

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.

In formula (1), 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, and 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 a heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom can be 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, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further 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 exemplified 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 ^1a and R ^{1b in} formula (1) may be the same as or different from each other.

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.
The following substituent T can be mentioned as an example of a substituent.
(Substituent T)
An alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably 2 to 30 carbon atoms). Substituted or unsubstituted alkynyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), an amino group (preferably a substituted or unsubstituted amino group having 0 to 30 carbon atoms), An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably carbon A substituted or unsubstituted heteroaryloxy group having 1 to 30 carbon atoms) or an acyl group (preferably a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms). An unsubstituted acyl group), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Group), an acyloxy group (preferably a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably A substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably having a carbon number) 0-30 substitution or no placement Sulfamoyl group), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably A substituted or unsubstituted arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably a substituted or unsubstituted heteroarylthio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably having 1 to 30 carbon atoms). Substituted or unsubstituted alkylsulfonyl group), arylsulfonyl group (preferably substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms), heteroarylsulfonyl group (preferably substituted or unsubstituted group having 1 to 30 carbon atoms) Heteroarylsulfonyl group), alkylsulfinyl group ( Preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, an arylsulfinyl group (preferably a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably having 1 carbon atom) To 30 substituted or unsubstituted heteroarylsulfinyl group), ureido group (preferably substituted or unsubstituted ureido group having 1 to 30 carbon atoms), phosphoric acid amide group (preferably substituted or unsubstituted group having 1 to 30 carbon atoms). Substituted phosphate amide group), hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heteroaryl group (preferably carbon number) 1-30). The carboxy group may be dissociated from a hydrogen atom or may be in a salt state. The sulfo group may be dissociated from a hydrogen atom or in a salt state.
When these groups are further substitutable groups, they may further have a substituent. Examples of the substituent include the groups described above for the substituent T.

At least one of R ² and R ³ is preferably an electron-withdrawing group. A substituent having a positive Hammett σp value (sigma para value) acts as an electron-withdrawing group.
In the present invention, a substituent having a Hammett σp value of 0.2 or more can be exemplified as an electron-withdrawing group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80.
Specific examples include cyano group (0.66), carboxy group (—COOH: 0.45), alkoxycarbonyl group (—COOMe: 0.45), aryloxycarbonyl group (—COOPh: 0.44), carbamoyl. A group (—CONH ₂ : 0.36), an alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh: 0.43), an alkylsulfonyl group (—SO ₂ Me: 0.72), or arylsulfonyl group (-SO ₂ Ph: 0.68) and the like. Particularly preferred is a cyano group. Here, Me represents a methyl group, and Ph represents a phenyl group.
Regarding the Hammett's substituent constant σ value, for example, paragraphs 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 ³ is particularly preferably 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 further 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. 1-30 are preferable and, as for the number of the carbon atoms which comprise a heteroaryl group, 1-12 are more preferable. Specific examples of the heteroaryl group include imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, quinoxalyl group, isoquinolyl group, indolenyl group, furyl group, thienyl group, benzoxazolyl group. Group, benzimidazolyl group, benzthiazolyl group, naphthothiazolyl group, benzoxazolyl group, m-carbazolyl group, azepinyl group, and benzo-fused group or naphtho-fused group of these groups. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T. For example, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned.
Two R ² in the formula (1) may be the same as or different from each other, and two R ³ may be the same as or different from each other.

When R ⁴ represents an alkyl group, an aryl group or a heteroaryl group, the alkyl group, aryl group and heteroaryl group have the same ^meanings 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 difluoroboron, diphenylboron, dibutylboron, dinaphthylboron, and catecholboron. Of these, diphenylboron 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 diphenylboron). Two R ⁴ in the formula (1) may be the same or different.

The dye represented by the formula (1) is more preferably a dye represented by the following formula (1A).

In the formula, each R ¹⁰ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^14A R ^14B or a metal atom. R ¹⁰ may be covalently bonded or coordinated to R ¹² . R ¹¹ and R ¹² each independently represent a hydrogen atom or a substituent, at least one of which is a cyano group, and R ¹¹ and R ¹² may combine to form a ring. R < ¹³ > represents a hydrogen atom or a C3-C30 branched alkyl group each independently.
R ¹⁰ has the same meaning as R ⁴ described in the above formula (1), and the preferred range is also the same. A hydrogen atom or a group represented by —BR ^14A R ^14B (particularly diphenylboron) is preferred, and a group represented by —BR ^14A R ^14B is particularly preferred.
R ¹¹ and R ¹² have the same meanings as R ² and R ³ described in (1) above, and preferred ranges are also the same. More preferably, one of R ¹¹ and R ¹² is a cyano group and the other is a heteroaryl group.
R ^14A and R ^14B have the same ^meanings as R ^4A and R ^4B described in (1) above, and preferred ranges are also the same.
R < ¹³ > represents a hydrogen atom or a C3-C30 branched alkyl group each independently. As for carbon number of a branched alkyl group, 3-20 are more preferable.

Specific examples of the compound represented by the formula (1) include the following compounds. In addition, for example, paragraphs 0037 to 0052 of JP 2011-68731 A (corresponding <0070> of US Patent Application Publication No. 2011/0070407) can be referred to, and the contents thereof are incorporated herein. In the following structural formulas, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Ar-1 to Ar-4 and R-1 to R-7 in the above table are as follows. In the structure shown below, “*” is a bond.

(Squarylium compound (compound having squarylium structure))
In the present invention, the squarylium compound is preferably a compound represented by the formula (11). This compound is excellent in near-infrared absorptivity and invisibility.

In formula (11), A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the following formula (12);

In Formula (12), Z ¹ represents a nonmetallic atomic group that forms a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and a wavy line represents This represents a connecting hand with the formula (11).

A ¹ and A ² in Formula (11) each independently represent an aryl group, a heteroaryl group, or a group represented by Formula (12), and a group represented by Formula (12) is preferable.
The number of carbon atoms of the aryl group represented by A ¹ and A ² is preferably 6-48, more preferably 6 to 24, 6 to 12 are particularly preferred. Specific examples include a phenyl group and a naphthyl group. When the aryl group has a substituent, the carbon number of the aryl group means the number excluding the carbon number of the substituent.
The heteroaryl group represented by A ¹ and A ² 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, more preferably a single ring or a condensed ring having 2 to 4 condensations, a single ring or A condensed ring having a condensation number of 2 or 3 is particularly preferred. As a hetero atom which comprises a heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, and a nitrogen atom and a sulfur atom are preferable. 1-3 are preferable and, as for the number of the hetero atoms which comprise a heteroaryl group, 1-2 are more preferable. Specific examples include a heteroaryl group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered or 6-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
The aryl group and heteroaryl group may have a substituent. Examples of the substituent include the substituent T described in the above-described pyrrolopyrrole compound.

The substituent that the aryl group and heteroaryl group may have is preferably a halogen atom, an alkyl group, a hydroxy group, an amino group, or an acylamino group.
The halogen atom is preferably a chlorine atom.
1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-5 are still more preferable, and 1-4 are the most preferable. The alkyl group is preferably linear or branched.
The amino group is preferably a group represented by —NR ¹⁰⁰ R ¹⁰¹ . R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-10 are still more preferable, and 1-8 are especially preferable. The alkyl group is preferably linear or branched, and more preferably linear.
The acylamino group is preferably a group represented by —NR ¹⁰² —C (═O) —R ¹⁰³ . ^R102 represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom. R ¹⁰³ represents an alkyl group. R ¹⁰² and R ¹⁰³ carbon atoms of the alkyl group represented by is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, 1 to 4 are particularly preferred.
When the aryl group and heteroaryl group have two or more substituents, the plurality of substituents may be the same or different.

Next, the group represented by Formula (12) represented by A ¹ and A ² will be described.
In the formula (12), R ² represents an alkyl group, an alkenyl group or an aralkyl group,
Alkyl groups are preferred.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-12 are still more preferable, and 2-8 are especially preferable.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-12 are still more preferable.
The alkyl group and the alkenyl group may be linear, branched or cyclic, and are preferably linear or branched.
7-30 are preferable and, as for carbon number of an aralkyl group, 7-20 are more preferable.

In the formula (12), the nitrogen-containing heterocycle formed by Z ¹ is preferably a 5-membered ring or a 6-membered ring. Further, the nitrogen-containing heterocycle is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, further preferably a single ring or a condensed ring having 2 to 4 condensations, Is particularly preferably a fused ring of 2 or 3. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom. Moreover, the nitrogen-containing heterocycle may have a substituent. Examples of the substituent include the groups described above for the substituent T. For example, a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-12 are still more preferable. The alkyl group is preferably linear or branched.

The group represented by the formula (12) is preferably a group represented by the following formula (13) or the formula (14).

In formulas (13) and (14), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, R ¹² represents a substituent, and when m is 2 or more, R ¹² are linked to each other. A ring may form, X represents a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and m represents an integer of 0 to 4 The wavy line represents a connecting hand with the formula (11).

R ¹¹ in formula (13) and formula (14) has the same meaning as R ² in formula (12);
The preferable range is also the same.
R ¹² in Formula (13) and Formula (14) represents a substituent. Examples of the substituent include the groups described above for the substituent T. For example, a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-12 are still more preferable. The alkyl group is preferably linear or branched.
When m is 2 or more, R ¹² may be linked to form a ring. Examples of the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, a heterocyclic ring, and the like. The ring may be monocyclic or multicyclic. When the substituents are linked to form a ring, the linking group is a group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. They can be linked by a divalent linking group selected from the above. For example, it is preferable that R ¹² are connected to each other to form a benzene ring.
X in Formula (13) represents a nitrogen atom or CR ¹³ R ¹⁴ , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the groups described above for the substituent T. For example, an alkyl group etc. are mentioned. 1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-5 are still more preferable, 1-3 are especially preferable, and 1 is the most preferable. The alkyl group is preferably linear or branched, and particularly preferably linear.
m represents an integer of 0 to 4, and 0 to 2 is preferable.

In the formula (11), cations are delocalized and exist as follows.

The squarylium compound is preferably a compound represented by the following formula (15).

Ring A and Ring B each independently represent an aromatic ring or a heteroaromatic ring,
X ^A and X ^B each independently represent a substituent,
G ^A and G ^B each independently represent a substituent,
kA is 0 to n _A, kB represents an integer of 0 to n _B,
n _A and n _B each represent the largest integer that can be substituted for ring A or ring B;
X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural may be bonded to form a ring structure .

G ^A and G ^B each independently represent a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl ^{group, -OR 10, -COR 11, -COOR} 12, -OCOR 13, - NR ¹⁴ R ¹⁵ , —NHCOR ¹⁶ , —CONR ¹⁷ R ¹⁸ , —NHCONR ¹⁹ R ²⁰ , —NHCOOR ²¹ , —SR ²² , —SO ₂ R ²³ , —SO ₂ OR ²⁴ , —NHSO ₂ R ²⁵ or —SO ₂ NR ²⁶ R ²⁷ may be mentioned. R ^{10 to} R ²⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ^{12 of} —COOR ¹² is hydrogen (that is, a carboxy group), the hydrogen atom may be dissociated or may be in a salt state. When R ^{24 of} —SO ₂ OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated or may be in a salt state.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-8 are still more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-40 are preferable, as for carbon number of an alkynyl group, 2-30 are more preferable, and 2-25 are especially preferable. The alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. 7-40 are preferable, as for carbon number of an aralkyl group, 7-30 are more preferable, and 7-25 are still more preferable.
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 further preferably a single ring or a condensed ring having 2 to 4 condensations. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heteroaryl group, 3-18 are more preferable, and 3-12 are more preferable. Examples of heteroaryl groups include pyridine ring, piperidine ring, furan ring, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine ring , Indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiadiazole ring.
The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent group T described above.

X ^A and X ^B each independently represent a substituent. The substituent is preferably a group having active hydrogen, —OH, —SH, —COOH, —SO ₃ H, —NR ^X1 R ^X2 , —NHCOR ^X1 , —CONR ^X1 R ^X2 , —NHCONR ^X1 R ^X2 , —NHCOOR _{^{X1, -NHSO 2 R X1, -B}} (OH) 2 and -PO (OH) ₂ are more preferable, -OH, -SH and -NR ^X1 R ^X2 is more preferable.
R ^X1 and R ^X2 each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group. Alkyl groups are preferred. The alkyl group is preferably linear or branched. Alkyl group, an alkenyl group, an alkynyl group, an aryl group and that details of the heteroaryl group, is as defined and ranges described for the G ^A and G ^B.

Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring. The aromatic ring and heteroaromatic ring may be a single ring or a condensed ring. Specific examples of the aromatic ring and heteroaromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring , Chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, Benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenant Phosphorus ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring or a naphthalene ring is preferable.
The aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in G ^A and G ^B.

X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural may be bonded to each other to form a ring. The ring is preferably a 5-membered ring or a 6-membered ring. The ring may be monocyclic or multicyclic.
X ^A and G ^A, X ^B and G ^B, when forming a G ^A or between G ^B are bonded to each other rings, may be they are attached directly to form a ring, an alkylene group, -CO-, A ring may be formed by bonding via a divalent linking group selected from the group consisting of —O—, —NH—, —BR— and combinations thereof. X ^A and G ^A, X ^B and G ^B, G ^A or between G ^B each other, it is preferable to form a ring via -BR-.
R represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described in G ^A and G ^B. An alkyl group or an aryl group is preferred.

  kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA represents the largest integer that can be substituted for ring A, and nB represents the largest integer that can be substituted for ring B. kA and kB are each independently preferably 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the formula (11) include the compounds described below, but are not limited thereto.

(Cyanine compound (compound having a cyanine structure))
In the present invention, the cyanine compound is preferably a compound represented by the formula (A). This compound is excellent in near-infrared absorptivity and invisibility.
Formula (A)

In the formula (A), Z ¹ and Z ² are each independently a nonmetallic atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and R ¹ and R ² are Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, L ¹ represents a methine chain having an odd number of methine groups, and a and b are each independently 0 or 1 Yes,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.

In the formula (A), Z ¹ and Z ² each independently represents a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed.
The nitrogen-containing heterocyclic ring may be condensed with other heterocyclic ring, aromatic ring or aliphatic ring. The nitrogen-containing heterocycle is preferably a 5-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring. Specific examples of the nitrogen-containing heterocycle include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazodibenzobenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, Examples include benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring, quinoxaline ring, quinoline ring, indolenine ring Benzoindolenine ring, benzoxazole ring, benzothiazole ring and benzimidazole ring are preferable, and indolenine ring, benzothiazole ring and benzimidazole ring are particularly preferable.

The nitrogen-containing heterocyclic ring and the ring condensed thereto may have a substituent. Examples of the substituent include the substituents described above for G ^A and G ^B in the formula (15). Specifically, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl ^{group, -OR 10, -COR 11, -COOR} 12, -OCOR 13, - NR ¹⁴ R ¹⁵ , —NHCOR ¹⁶ , —CONR ¹⁷ R ¹⁸ , —NHCONR ¹⁹ R ²⁰ , —NHCOOR ²¹ , —SR ²² , —SO ₂ R ²³ , —SO ₂ OR ²⁴ , —NHSO ₂ R ²⁵ or —SO ₂ NR ²⁶ R ²⁷ may be mentioned. R ^{10 to} R ²⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ^{12 of} —COOR ¹² is hydrogen (that is, a carboxy group), the hydrogen atom may be dissociated or may be in a salt state. When R ^{24 of} —SO ₂ OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated or may be in a salt state. About these details, it is synonymous with the range mentioned above.
The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the above-mentioned substituent group T, preferably a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, an amino group, and the like, more preferably a carboxy group and a sulfo group, and a sulfo group. The group is particularly preferred. The carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.

In the formula (A), R ¹ and R ² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group.
1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-8 are still more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-40 are preferable, as for carbon number of an alkynyl group, 2-30 are more preferable, and 2-25 are especially preferable. The alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. 7-40 are preferable, as for carbon number of an aralkyl group, 7-30 are more preferable, and 7-25 are still more preferable.
The alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group. A carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.

In the formula (A), L ¹ represents a methine chain having an odd number of methine groups. L ¹ is preferably a methine chain having 3, 5, or 7 methine groups, and more preferably a methine chain having 5 or 7 methine groups.
The methine group may have a substituent. The methine group having a substituent is preferably a central (meso-position) methine group. Specific examples of the substituent include a substituent which the nitrogen-containing heterocycle of Z ¹ and Z ² may have, and a group represented by the formula (a). Further, two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.

In formula (a), * represents a connecting part with a methine chain, and A ¹ represents an oxygen atom or a sulfur atom.

a and b are each independently 0 or 1. When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. Both a and b are preferably 0. When a and b are both 0, the formula (A) is expressed as follows.

In the formula (A), when the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, and c represents a number necessary for balancing the charge. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), paratoluenesulfonate ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ or ClO ₄ ⁻ , tris (halogenoalkylsulfonyl) methide anions (eg, , (CF ₃ SO ₂ ) ₃ C ⁻ ), di (halogenoalkylsulfonyl) imide anion (for example, (CF ₃ SO ₂ ) ₂ N ⁻ ), tetracyanoborate anion, and the like.
In the formula (A), when the site represented by Cy in the formula is an anion portion, X ¹ represents a cation, and c represents a number necessary for balancing the charge. As cations, alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ ,
Ba ²⁺ , Sr ^2+, etc.), transition metal ions (Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ etc.), other metal ions (such as Al ³⁺ ), Examples include ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion, tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium and the like. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , and diazabicycloundecenium are preferable.
In the formula (A), when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist. That is, c is 0.
The compound represented by the formula (A) is also preferably a compound represented by the following (A-1) or (A-2), and more preferably a compound represented by the following (A-2).

In the formula, R ^1A , R ^2A , R ^1B and R ^2B each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ^1A and L ^1B each independently represent a methine chain having an odd number of methines;
Y ¹ and Y ² each independently represent —S—, —O—, —NR ^X1 — or —CR ^X2 R ^X3 —
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,
V ^1A , V ^2A , V ^1B and V ^2B are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, —OR ¹⁰ , — ^{COR 11, -COOR 12, -OCOR 13} , -NR 14 R 15, -NHCOR 16, -CONR 17 R 18, -NHCONR 19 R 20, -NHCOOR 21, -SR 22, -SO 2 R 23, -SO 2 Represents OR ²⁴ , —NHSO ₂ R ²⁵ or —SO ₂ NR ²⁶ R ²⁷ , and V ^1A , V ^2A , V ^1B and V ^2B may form a condensed ring;
R ^{10 to} R ²⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group,
When R ^{12 of} —COOR ¹² is a hydrogen atom and R ^{24 of} —SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom may be dissociated or in a salt state,
m1 and m2 each independently represent 0 to 4,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary to balance the charge,
When the site represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c represents a number necessary for balancing the charge,
When the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.

The groups represented by R ^1A , R ^2A , R ^1B and R ^2B are synonymous with the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described for R ¹ and R ² in formula (A), and preferred ranges Is the same. These groups may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group. A carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.
When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, it is more preferably a linear alkyl group.
Y ¹ and Y ² are each independently -S -, - O -, - NR X1 - or -CR ^X2 R ^X3 - represents, -NR ^X1 - is preferred.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear. The alkyl group is particularly preferably a methyl group or an ethyl group.
L ^1A and L ^1B have the same meaning as L ^{1 in} formula (A), and the preferred range is also the same.
The groups represented by V ^1A , V ^2A , V ^1B and V ^2B are synonymous with the ranges described for the substituents that the nitrogen-containing heterocycles of Z ¹ and Z ² in formula (A) may have, and preferred ranges Is the same.
m1 and m2 each independently represent 0 to 4, with 0 to 2 being preferred.
The anion and cation represented by X ¹ have the same meaning as the range described for X ¹ in formula (A), and the preferred range is also the same.

The compound represented by the formula (A) is preferably a compound represented by the following (A-11) to (A-16).

In the formula, R ^1a and R ^2a each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
X ¹ and X ² each independently represent —S—, —O—, —NR ^X1 — or —CR ^X2 R ^X3 —,
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,
R ^3a , R ^4a , V ^1a and V ^2a are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, —OR ¹⁰ , — ^{COR 11, -COOR 12, -OCOR 13} , -NR 14 R 15, -NHCOR 16, -CONR 17 R 18, -NHCONR 19 R 20, -NHCOOR 21, -SR 22, -SO 2 R 23, -SO 2 Represents OR ²⁴ , —NHSO ₂ R ²⁵ or —SO ₂ NR ²⁶ R ²⁷ , and V ^1a and V ^2a may form a condensed ring;
R ^{10 to} R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, and when —COOR ¹² R ¹² is hydrogen and —SO ₂ OR ^When R ^{24 in 24} is a hydrogen atom, the hydrogen atom may be dissociated or in a salt state.
m1 and m2 each independently represent 0-4.

Groups R ^1a and R ^2a represent has the same meaning as R ¹ and R ² of formula (A-1), and preferred ranges are also the same. When R ^1a and R ^2a represent an alkyl group, it is more preferably a linear alkyl group.
X ¹ and X ² has the same meaning as X ¹ and X ² in the formula (A-1), and preferred ranges are also the same.
R ^<3a> and R ^<4a> are synonymous with the range demonstrated by the substituent which L < ¹ > may have which was ^demonstrated in Formula (A), and its preferable range is also the same.
The groups represented by V ^1a and V ^2a are synonymous with the ranges described in the nitrogen-containing heterocycle described in the formula (A) and the substituents that the ring condensed thereto may have, and the preferred ranges are also the same It is.
m1 and m2 each independently represent 0 to 4, with 0 to 2 being preferred.

(Diketopyrrolopyrrole compound (compound having a diketopyrrolopyrrole structure))
In the present invention, examples of the diketopyrrolopyrrole compound include compounds represented by the following formula (DP).
Formula (DP)

In the formula, R ¹ and R ² each independently represents an alkyl group, an aryl group, or a heteroaryl group.
R ¹ and R ² are preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are especially preferable.
6-30 are preferable, as for carbon number of an aryl group, 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 a heteroaryl group, 1-12 are more preferable. As a kind of hetero atom which comprises a heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom can be 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, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further 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. Examples of the substituent include the substituent T described above. For example, a halogen atom is preferable.

Specific examples of the compound represented by the formula (DP) include the compounds shown below.

(Phthalocyanine compound (compound having a phthalocyanine structure))
In the present invention, examples of the phthalocyanine compound include compounds represented by the following formula (PC).

In the formula (PC), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a substituent, and M ¹ represents a metal atom or a metal compound.

Examples of the substituent represented by X ^{1 to} X ¹⁶ include the substituent T described above. Examples include a halogen atom, an alkoxy group, an arylalkoxy group, a heteroarylalkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group, and a halogen atom is preferable.
Examples of the metal atom represented by M ¹ include Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, and Pt. Examples of the metal compound include V = O, Ti = O, and AlCl. M ¹ is preferably Cu, Zn or Ti═O.
Among the above phthalocyanines, a compound (oxotitanyl phthalocyanine) in which M ¹ is represented by Ti═O is excellent in near infrared absorption.
Among the above phthalocyanines, compounds in which M ¹ is Zn or Cu and at least one of X ^{1 to} X ¹⁶ is a halogen atom (halogen zinc phthalocyanine, halogen copper phthalocyanine) have excellent spectral characteristics in the visible region. It can be preferably used as a green pigment.

(Naphthalocyanine compound (a compound having a naphthalocyanine structure))
In the present invention, examples of the naphthalocyanine compound include compounds represented by the following formula (NPC).

In the formula (NPC), X ^{1 to} X ²⁴ each independently represent a hydrogen atom or a substituent, and M ¹ represents a metal atom or a metal compound.
Examples of the substituent represented by X ^{1 to} X ²⁴ include the substituent T described above. Examples include a halogen atom, an alkoxy group, an arylalkoxy group, a heteroarylalkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group, and an alkoxy group is preferable.
Specific examples of the compound represented by the formula (NPC) include the following compounds.

<< Compound B >>
The material of the present invention contains Compound B having a structure having an adsorptivity to a resin. Compound B is preferably a compound having substantially no molecular weight distribution. That is, the compound B is preferably a compound other than the polymer. According to this aspect, since the molecular weight is smaller than that of the polymer, the mobility in the solvent is high, and it can exist uniformly in the system. Therefore, the effect that it can be included efficiently at the time of pigment production can be expected. The molecular weight of Compound B is preferably 50 to 2000, and more preferably 100 to 1500.
In the present invention, the compound B has a solubility in a solvent at 25 ° C. of preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. Is more preferable. As a solvent, the solvent illustrated in the column of the solvent mentioned later is mentioned, One or more types chosen from methanol, ethanol, tetrahydrofuran, and acetone are preferable.
Examples of the structure having the adsorptivity to the resin of Compound B include an acidic group, a basic group, a hydrogen bonding group, a dipole interaction group, and a π-π interaction group. Examples of the group having an acidic group, a basic group, or a salt structure include groups described in the dye derivatives described later. In the present invention, the interaction between dipoles means that polarized molecules interact with other dipoles, and hydrogen bonds are one of them. Specific examples other than hydrogen bonds include nitrile groups, perfluoroalkyl groups, perfluoroaryl groups, and the like. In the present invention, a hydrogen bond is a non-covalent bond formed by a hydrogen atom covalently bonded to an atom having a large electronegativity with a lone electron pair such as nitrogen, oxygen, sulfur, fluorine, or a π electron system located nearby. It is an attractive interaction of sex. The hydrogen bonding group in the present invention is a substituent having at least one of the above hydrogen atom or lone electron pair, and examples thereof include an amide group, an alcohol group, a phenol group, and a carboxy group. In the present invention, π-π interaction is a dispersion force acting between aromatic rings of organic compound molecules, and is also called stacking interaction. For example, aromatic compounds have a strong planar structure and abundant electrons delocalized by the π-electron system, so that the London dispersion force is particularly strong. Therefore, the force attracting each other increases as the number of π electrons increases. Examples of π-π interacting groups include aromatic rings and heteroaromatic rings. Specific examples include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, Fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, Isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring Chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, and benzene ring or a naphthalene ring.

  Compound B preferably has at least one selected from a dye structure, a heterocyclic structure, and an acyclic heteroatom-containing group, and more preferably has at least a dye structure. Since compound B has these structures, compound B is easily included in the particles of pigment A, and a material in which pigment A and compound B are firmly attached is easily obtained.

  As the dye structure, 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 Preferred examples include a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzoimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure, and a benzoxazole dye structure.

  Heterocyclic structures include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, Preferred examples of pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzimidazole, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone and anthraquinone As mentioned.

Examples of the acyclic heteroatom-containing group include a group having a nitrogen atom, and preferred examples include a urea group, an imide group, an amide group, and a sulfonamide group. As the urea group, —NR ¹⁰⁰ CONR ¹⁰¹ R ¹⁰² may be mentioned. R ¹⁰⁰ , R ¹⁰¹ , and R ¹⁰² each independently represents a hydrogen atom, an alkyl group, or an aryl group. 1-30 are preferable and, as for carbon number of an alkyl group, 1-20 are more preferable. The alkyl group may be linear, branched or cyclic. 6-30 are preferable and, as for carbon number of an aryl group, 6-20 are more preferable. R ¹⁰⁰ and R ¹⁰¹ are preferably hydrogen atoms. R ¹⁰² is preferably an alkyl group or an aryl group, and more preferably an aryl group.

  In the present invention, compound B is preferably a pigment derivative. According to this aspect, the compound B is easily included in the particles of the pigment A, and a material in which the compound B is firmly attached to the pigment A is easily obtained. As the dye derivative, a compound having a structure in which a part of the dye is substituted with an acidic group, a basic group or a phthalimidomethyl group is preferable, and a dye derivative represented by the formula (B1) is more preferable. The dye derivative represented by the formula (B1) can improve the dispersibility of the pigment A in the composition because the dye structure P is easily adsorbed on the surface of the pigment A. In the case where the composition contains a resin, the terminal portion X of the dye derivative is adsorbed to the resin by interaction with the adsorbing portion (polar group or the like) of the resin.

In the formula, 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 phthalimide group, m represents 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. When the pigment derivative has these pigment structures, the dispersibility of the pigment A can be further improved.

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. These may be unsubstituted or may further have a substituent. Examples of the substituent include the substituent T described above, and an alkyl group, an aryl group, a hydroxy group, or a halogen atom is preferable.
The linking group is preferably an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, —NR′—, —SO ₂ —, —S—, —O—, —CO— or a combination thereof, an alkylene group, A nitrogen-containing heterocyclic group, —NR′—, —SO ₂ —, or a group consisting of a combination thereof is more preferable. R ′ represents a hydrogen atom, an alkyl group (preferably having 1 to 30 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms).
1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic.
6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, 6-10 are more preferable, and a phenylene group is especially preferable.
The nitrogen-containing heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocyclic 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 further preferably a single ring or a condensed ring having 2 to 4 condensations. 1-3 are preferable and, as for the number of the nitrogen atoms which comprise a nitrogen-containing heterocyclic group, 1-2 are more preferable. The nitrogen-containing heterocyclic group may contain a hetero atom other than the nitrogen atom. Examples of the hetero atom other than the nitrogen atom include an oxygen atom and a sulfur atom. 0-3 are preferable and, as for the number of hetero atoms other than a nitrogen atom, 0-1 are more preferable.
As the nitrogen-containing heterocyclic group, piperazine ring group, pyrrolidine ring group, pyrrole ring group, piperidine ring group, pyridine ring group, imidazole ring group, pyrazole ring group, oxazole ring group, thiazole ring group, pyrazine ring group, morpholine ring Group, thiazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, purine ring group, quinoline ring group, isoquinoline ring group, quinoxaline ring group, cinnoline ring group, carbazole ring group and formula (L-1) Group represented by ~ (L-7).

* In the formula represents a linkage with P, L or X. R represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described above.

Specific examples of the linking group is an alkylene group, an arylene group, -SO ₂ -, the (L-1)
A group represented by the above (L-5), a group composed of a combination of -O- and an alkylene group, a group composed of a combination of -NR'- and an alkylene group, -NR'- and A group consisting of a combination with -CO- (-NR'-CO-, -NR'-CO-NR'-, etc.), a group consisting of a combination of -NR'-, -CO- and an alkylene group, -NR ' A group consisting of a combination of —, —CO—, an alkylene group and an arylene group, a group consisting of a combination of —NR′—, —CO— and an arylene group, a combination of —NR′—, —SO ₂ — and an alkylene group. A group consisting of a combination of —NR′—, —SO ₂ —, an alkylene group and an arylene group, a group consisting of a combination of the group represented by (L-1) and an alkylene group, (L -1) a combination of a group represented by and an arylene group A group consisting of a combination of the group represented by (L-1), -SO ₂ -and an alkylene group, a group represented by (L-1), -S- and an alkylene group, A group consisting of a combination of the above, a group consisting of a combination of the group represented by (L-1), -O- and an arylene group, a group represented by the above (L-1), -NR'- and -CO. A group consisting of a combination of-and an arylene group, a group consisting of a combination of the group represented by (L-3) and an arylene group, and the like.

In the formula (B1), X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide group.
Examples of the acidic group include a carboxy group and a sulfo group.
Examples of the basic group include groups represented by formulas (X-3) to (X-9).
Examples of the group having a salt structure include the above-mentioned acidic group salts, basic group salts, groups represented by the formula (X-1), and groups represented by (X-2). 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 more preferable. Examples of the alkali metal atom include lithium, sodium, potassium and the like. Examples of alkaline earth metal atoms include calcium and magnesium.
The phthalimide group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described acidic group, basic group, group having a salt structure, and the like. Moreover, the substituent T mentioned above may be sufficient. The substituent T may be further substituted with another substituent. Examples of other substituents include a carboxy group and a sulfo group.

X is preferably at least one selected from a carboxy group, a sulfo group, a phthalimide group, and groups represented by the following formulas (X-1) to (X-9).

Wherein (X-1) ~ (X -9), * represents a linking position to L of the formula (B1), R ¹⁰⁰ ~R ¹⁰⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl R ¹⁰⁰ and R ¹⁰¹ may be connected to each other to form a ring, and M represents an atom or an atomic group constituting a salt with an anion.

The alkyl group may be linear, branched or cyclic. 1-20 are preferable, as for carbon number of a linear alkyl group, 1-12 are more preferable, and 1-8 are more preferable. 3-20 are preferable, as for carbon number of a branched alkyl group, 3-12 are more preferable, and 3-8 are more preferable. The cyclic alkyl group may be monocyclic or polycyclic. 3-20 are preferable, as for carbon number of a cyclic | annular alkyl group, 4-10 are more preferable, and 6-10 are more preferable.
2-10 are preferable, as for carbon number of an alkenyl group, 2-8 are more preferable, and 2-4 are more preferable.
6-18 are preferable, as for carbon number of an aryl group, 6-14 are more preferable, and 6-10 are more preferable.
R ¹⁰⁰ and R ¹⁰¹ may be connected to each other to form a ring. The ring may be an aliphatic ring or an aromatic ring. The ring may be monocyclic or multicyclic. Examples of the linking group in the case where R ¹⁰⁰ and R ¹⁰¹ are bonded to form a ring include —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. It can connect with the bivalent coupling group chosen from the group which consists of. Specific examples include, for example, piperazine ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole ring, Examples thereof include a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a cinnoline ring, and a carbazole ring.
M represents an atom or an atomic group constituting an anion and a salt. These include those described above, and the preferred ranges are also the same.

In the formula (B1), m represents an integer of 1 or more. The upper limit of m represents the number of substituents that the dye structure P can take. For example, 10 or less is preferable and 5 or less is more preferable. When m is 2 or more, a plurality of L and X may be different from each other.
n represents an integer of 1 or more, preferably 1 to 3, and more preferably 1 or 2. When n is 2 or more, the plurality of Xs may be different from each other.

  Specific examples of the pigment derivative represented by the formula (B1) include the following (B-1) to (B-62). In the following formulas, m, m1, m2, and m3 each independently represents an integer of 1 or more.

Ar-5, Ar-6, R-1 to R-7, Ra to R-1 in the above table are as follows. In the structure shown below, “*” is a bond.

  In the present invention, as the dye derivative, JP-A-56-118462, JP-A-63-264673, JP-A-1-217077, JP-A-3-9961 and JP-A-3-26767 are disclosed. JP-A-3-153780, JP-A-3-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158, Any of those described in Kaihei 10-30063, JP-A-10-195326, paragraphs 0086 to 0098 of WO 2011/024896, paragraphs 0063 to 0094 of WO 2012/102399, etc. It can be preferably used, the contents of which are incorporated herein.

<Method for producing material of the present invention>
Next, the manufacturing method of the material of this invention is demonstrated. The method for producing a material of the present invention is a method for producing a material containing pigment A and compound B having a structure having an adsorptive property to resin, and has a structure having an adsorptive property to resin when pigment A is synthesized. Pigment A is synthesized by reacting the raw material compound of Pigment A in the presence of Compound B having NO. By thus synthesizing the pigment A, a material in which the compound B is firmly attached to the pigment A is obtained. Even if this material is washed with a solvent or the like, the compound B adheres firmly to the pigment A.

  Although the detailed mechanism by which the material in which Compound B is firmly attached to Pigment A is obtained by the production method of the present invention is not known, Pigment A is obtained by reacting the raw material compound of Pigment A in the presence of Compound B. By synthesizing, since the compound B is taken into the particles of the pigment A, it is presumed that a material in which the compound B is firmly attached to the pigment A is obtained. In addition, when the pigment A and the compound B are simply mixed, the adsorptivity of the compound B to the pigment A is low, and when the mixed material is washed with a solvent having solubility in the compound B, the pigment A Compound B is peeled off from the surface, and compound B hardly remains on the surface of pigment A. Therefore, the material obtained by the production method of the present invention has different characteristics from the material produced by the conventional method.

The material obtained by the production method of the present invention preferably has a pigment A content of 30 to 99% by mass. The lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less.
Further, the content of Compound B is preferably 0.99% by mass or more and less than 70% by mass. The lower limit is more preferably 2.91% by mass or more, and particularly preferably 4.76% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
Further, X ¹ represented by the following formula (I) is preferably 0.99 or more, more preferably 3 or more, and particularly preferably 5 or more. The upper limit can be, for example, 70 or less, 60 or less, or 50 or less.
X ¹ = (X ² / X ³ ) × 100 (I)
X ² is a solvent having a solubility of Pigment A of 0.02% by mass or less and a solubility of Compound B of 0.2% by mass or more at 25 ° C., and the mass of Compound B in the material after dipping the material And X ³ is the mass of the solid content of the material after being immersed in the solvent.
The said solvent and the immersion method are synonymous with the content demonstrated with the material of this invention mentioned above.

<Composition>
Next, the composition of the present invention will be described. The composition of the present invention includes the material of the present invention described above. The content of the material in the composition of the present invention is preferably 1 to 80% by mass in the total solid content, and the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.

<< Chromatic colorant >>
The composition of the present invention may further contain a chromatic colorant in addition to the above-described material of the present invention. 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 a maximum absorption wavelength in the wavelength range of 400 to 650 nm.
The chromatic colorant may be a pigment or a dye. Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Examples of the organic pigment include the chromatic pigment described in the above-described material of the present invention. Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, and U.S. Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115. The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

When the composition of this invention contains a chromatic colorant, it is preferable that content of a chromatic colorant shall be 0.01-70 mass% in the total solid of the composition of this invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
The content of the chromatic colorant is preferably 10 to 1000 parts by mass and more preferably 50 to 800 parts by mass with respect to a total of 100 parts by mass of the material of the present invention and the infrared absorber shown below.
Moreover, it is preferable that the total amount of the material of this invention, an infrared absorber, and a chromatic colorant shall be 1-70 mass% in the total solid of the composition of this invention. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
In addition, the composition of the present invention may be an embodiment that does not substantially contain a chromatic colorant. The term “substantially does not contain a chromatic colorant” means that the content of the chromatic colorant is the present invention. The total solid content of the composition is preferably 0.005% by mass or less, more preferably 0.001% by mass or less, and even more preferably no chromatic colorant.

<< Infrared absorber >>
The composition of the present invention may further contain an infrared absorber in addition to the above-described material of the present invention. An infrared absorber means a compound having absorption in the near infrared region (preferably, a wavelength of 700 to 1200 nm). The maximum absorption wavelength of the infrared absorber is more preferably in the range of 700 to 1000 nm, and particularly preferably in the range of 800 to 1000 nm. The infrared absorber may be a pigment or a dye. Examples of infrared absorbers include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylene compounds, dithiol metal complex compounds, croconium. Compounds, oxole compounds and the like.

When the composition of this invention contains an infrared absorber, 0.1-50 mass parts is preferable with respect to 100 mass parts of materials of the composition of this invention, and the content of an infrared absorber is 0.5- 30 mass parts is more preferable, and 1.0-15 mass parts is still more preferable.
Moreover, it can also be set as the composition which does not contain an infrared absorber substantially. In addition, it is preferable that content of an infrared absorber is 0.1 mass part or less with respect to 100 mass parts of materials, and 0.05 mass part or less is more, for example, that it does not contain an infrared absorber substantially. Preferably, 0.01 mass part or less is still more preferable, and it is still more preferable not to contain.

<< Coloring material that blocks visible light >>
The composition of the present invention can also contain a colorant that blocks visible light. This composition can be preferably used as, for example, a composition for forming an infrared transmission filter. In the present invention, the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits light having a wavelength in the infrared region (infrared).
The color material that shields visible light preferably exhibits black, gray, or a color close to them by a combination of a plurality of color materials. The colorant that blocks visible light is preferably a material that absorbs light in the wavelength range from purple to red. The color material that blocks visible light is preferably a color material that blocks light in the wavelength range of 450 to 650 nm.
In the present invention, the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).
(1): An embodiment containing two or more chromatic colorants.
(2): An embodiment containing an organic black colorant.
In the present invention, the organic black colorant as a colorant that shields visible light means a material that absorbs visible light but transmits at least part of infrared light. 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 compounds include those described in JP-T 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 those described in JP-A-1-170601, JP-A-2-34664, etc., 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.

When two or more kinds of chromatic colorants are included as a colorant that blocks visible light, the chromatic colorants are red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. It is preferable that it is a coloring agent chosen from these. Examples of combinations of chromatic colorants in the case of forming a color material that shields visible light from 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) Embodiment containing yellow colorant, blue colorant and red colorant (3) Embodiment containing yellow colorant, purple colorant and red colorant (4) Embodiment containing yellow colorant and purple colorant (5) Embodiment containing green colorant, blue colorant, purple colorant and red colorant (6) Embodiment containing purple colorant and orange colorant (7) Green colorant, purple colorant and red coloration (8) A mode containing a green colorant and a red colorant

  When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is 0.01 to 70% by mass in the total solid content of the composition of the present invention. It is preferable. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. 10-1000 mass parts is preferable with respect to a total of 100 mass parts of the material of this invention and an infrared absorber, and, as for content of the color material which shields visible light, 50-800 mass parts is more preferable. Moreover, it is preferable that the total amount of the material of this invention, an infrared absorber, and the color material which shields visible light is 1-70 mass% in the total solid of the composition of this invention. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.

<< Dye derivative >>
The composition of the present invention preferably further contains a pigment derivative. By including the pigment derivative, the dispersibility of the pigment in the composition can be enhanced, and the aggregation of the pigment can be efficiently suppressed. Examples of the dye derivative include the dye derivatives described in the compound B of the material of the present invention described above.

  When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment contained in the composition. 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 content of the pigment derivative is in the above range, the dispersibility of the pigment can be increased and the aggregation of particles can be efficiently suppressed. Only one type of pigment derivative 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.

<< Organic solvent >>
The composition of the present invention preferably further contains an organic solvent.
There is no restriction | limiting in particular in the organic solvent, If it can melt | dissolve or disperse | distribute each component uniformly, it can select suitably according to the objective. For example, alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like are preferable. These may be used alone or in combination of two or more.
Specific examples of the alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in paragraph No. 0136 of JP 2012-194534 A, the contents of which are incorporated herein.
Specific examples of the esters, ketones, and ethers include those described in paragraph No. 0497 of JP2012-208494A (corresponding to <0609> in US 2012/0235099). It is done. Furthermore, acetic acid-n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like can be mentioned.
Organic solvents include cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, 2-butanol, ethanol, ethyl lactate and propylene glycol monomethyl ether (1-methoxy-2-propanol) At least one selected from the group consisting of

  In the present invention, the organic solvent is preferably an organic solvent having a low metal content. The metal content of the organic solvent is preferably 10 ppb or less, for example. If necessary, a ppt level solvent may be used, and such a high-purity solvent is provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

  Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter in filtration using a filter 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 a polytetrafluoroethylene, polyethylene, or nylon filter.

  The organic 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.

  The content of the organic solvent is preferably such that the total solid content of the composition of the present invention is 5 to 60% by mass, and more preferably 10 to 40% by mass. Only one type of organic solvent 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.

<< Resin >>
The composition of the present invention preferably further contains a resin. The resin is blended, for example, as a dispersant for dispersing the pigment, the material of the present invention, and the like in the composition.
The resin acting as a dispersant is preferably an acid type resin and / or a basic type resin.
Here, the acid type resin represents a resin having a larger amount of acid groups than that of basic groups. The acid type resin preferably has an acid group content of 70 mol% or more when the total amount of acid groups and basic groups in the resin is 100 mol%. What consists only of group is more preferable. The acid group possessed by the acidic resin is preferably a carboxy group. The acid value of the acid type resin is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
In addition, the basic type resin represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic type resin preferably occupies 50 mol% or more of the basic group when the total amount of the acid group and the basic group in the resin is 100 mol%. The basic group possessed by the basic type resin is preferably an amine.

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 end described in JP-A-3-112992 and JP-T2003-533455, and JP-A-2002-273191. Examples thereof include a polymer having a sulfonic acid 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. Copolymers of polyallylamine and polyester described in JP-A-9-169821 and the like, macromonomers described in JP-A-10-339949, JP-A-2004-37986, etc., and nitrogen atom monomers JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like. Graft type polymers having a partial skeleton or a heterocyclic ring of organic dyes, JP-A-2010-106268 And the like, and the like. Examples of the macromonomer include macromonomer AA-6 (polymethyl methacrylate whose terminal group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S, manufactured by Toagosei Co., Ltd. (A copolymer of styrene and acrylonitrile whose end group is a methacryloyl group), AB-6 (polybutyl acrylate whose end group is a methacryloyl group), Plaxel FM5 (2-hydroxy methacrylate) manufactured by Daicel Chemical Industries, Ltd. Ε-caprolactone 5 mol equivalent addition product of ethyl), FA10L (ε-caprolactone 10 mol equivalent addition product of 2-hydroxyethyl acrylate), and polyester macromonomer described in JP-A-2-272009. .
As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  As the resin, a graft copolymer including a structural unit represented by any one of the following formulas (1) to (4) can also be used.

X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. A hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, preferably an oxygen atom.
R ³ represents a branched or linear alkylene group (the number of carbon atoms is preferably 1-10, more preferably 2 or 3), and —CH ₂ —CH (CH ₃ ) from the viewpoint of dispersion stability. -, a group represented by _{or, -CH (CH 3) -CH 2} - group represented by are preferred.
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group.
Regarding the graft copolymer, the description of paragraph numbers 0025 to 0069 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification.
Specific examples of the graft copolymer include the following. Further, the resins described in paragraph numbers 0072 to 0094 of JP 2012-255128 A can be used.

As the resin, an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used. The oligoimine resin has a repeating unit having a group X containing a partial structure 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 a basic nitrogen atom in at least one of the chains is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
The oligoimine resin is, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeating unit represented by the formula (I-2a). Examples include resins containing units.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a 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 R ⁶ each independently represents 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 ring structure formed together with CR ⁸ CR ⁹ and N, it is preferable together with the carbon atom of CR ⁸ CR ⁹ is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . 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 including a partial structure having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.
The resin (oligoimine-based resin) further contains, as a copolymerization component, one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5). You may do it. When the resin contains such a repeating unit, the dispersion performance of the pigment 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 resin described above, 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 resin include the following. Further, the resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.

As the resin, a resin containing a structural unit represented by the formula (P1) can also be used. The dispersibility of the pigment can be further improved by using the following resins.

In the formula (P1), R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.

The alkylene group represented by R ² is not particularly limited. For example, methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, 2-hydroxypropylene group, methyleneoxy group, ethyleneoxy group, methyleneoxycarbonyl Group, a methylenethio group, etc. are mentioned suitably, A methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, a methylenethio group is more preferable.

  The nitrogen-containing heterocyclic structure represented by Z is, for example, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone Examples thereof include a ring, an anthraquinone ring, a benzimidazole structure, a benztriazole structure, a benzthiazole structure, a cyclic amide structure, a cyclic urea structure, and a cyclic imide structure. Among these, the nitrogen-containing heterocyclic structure represented by Z is preferably a structure represented by the following formula (P2) or formula (P3).

In the formula, X is a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR-, and -C (= O )-. Here, R represents a hydrogen atom or an alkyl group. When R represents an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among these, X is preferably a single bond, a methylene group, —O— or —C (═O) —, and particularly preferably —C (═O) —.

  In the formula, ring A, ring B, and ring C each independently represent an aromatic ring. Examples of the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, phenothiazine. Ring, phenoxazine ring, acridone ring, anthraquinone ring, etc., among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specific examples of the structural unit represented by the formula (P1) include the following. In addition, the description of paragraph number 0023 in Japanese Patent Application Laid-Open No. 2008-009426 can be referred to, and the contents thereof are incorporated in this specification.

The resin including the structural unit represented by the formula (P1) may further include a structural unit represented by any one of the above-described formulas (1) to (4). Moreover, the repeating unit represented by the formula (I-1), the repeating unit represented by the formula (I-2), and / or the repeating unit represented by the formula (I-2a) is further included. You may go out. Specific examples of the resin containing the structural unit represented by the formula (P1) include the following.

  The resin is also available as a commercial product. Specific examples of such resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (acid group-containing co-polymers) manufactured by BYK Chemie. Polymer)), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”, EFKA Corporation “EFKA 4047, 4050-4165 (polyurethane)”, EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid) Polyester), 6745 (phthalocyanine derivatives) , 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 ( Acrylic copolymer) ", manufactured by Enomoto Kasei Co., Ltd." Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705 , DA-725 ", Kao's" Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (High Molecular polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxye) "Rennonyl phenyl ether)", "Acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative)", 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000, manufactured by Nippon Lubrizol Co., Ltd. (Polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft polymer), “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene) manufactured by Nikko Chemicals Monostearate), “Hinoact T-8000E” manufactured by Kawaken Fine Chemical Co., Ltd., “Organosiloxane Polymer KP341” manufactured by Shin-Etsu Chemical Co., Ltd., “EFKA-46, EFKA-47” manufactured by Morishita Sangyo Co., Ltd. EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "(Sannopco) ) "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA, and Sanyo Chemical Co., Ltd. ) “Ionette S-20” and the like.

These resins may be used alone or in combination of two or more. The resin may be an alkali-soluble resin.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more. As the alkali-soluble resin, description in paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to <0700> in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Are incorporated herein.

The alkali-soluble resin is also preferably a resin containing a compound represented by the following formula (ED) as a copolymerization component.

In formula (ED), 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.
The hydrocarbon group having 1 to 25 carbon atoms represented by R ¹ and R ² is not particularly limited. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t -Linear or branched alkyl group such as amyl, stearyl, lauryl, 2-ethylhexyl; aryl group such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, And alicyclic groups such as 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; and the like. Of these, acids such as methyl, ethyl, cyclohexyl, benzyl, etc., and primary or secondary hydrocarbon groups that are difficult to be removed by heat are particularly preferred in terms of heat resistance.
R ¹ and R ² may be the same type of substituent or different substituents.

  As an example of the compound represented by the formula (ED), for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of compound represented by the formula (ED) may be used, or two or more types may be used.

  Regarding the resin containing the compound represented by the formula (ED) as a copolymerization component, the description of paragraph numbers 0079 to 0099 of JP2012-198408A can be referred to, and the contents thereof are incorporated in the present specification.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000. The lower limit is preferably 5,000 or more, and more preferably 7,000 or more. The upper limit is preferably 30,000 or less, and more preferably 20,000 or less.

  As for content of resin in the composition of this invention, 0.1-100 mass parts is preferable with respect to 100 mass parts of pigments. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less. The lower limit is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. When the resin content is in the above range, the dispersibility of the pigment is good.

<Preparation of composition>
The composition of this invention can be prepared by mixing each component mentioned above. In preparing the composition, the components constituting the composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in an organic solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending.
Moreover, it is preferable to include the process of disperse | distributing the material of this invention in a composition. In the process of dispersing the material of the present invention in the composition, the mechanical force used for dispersing the material of the present invention includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. Also, “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)” The process and the dispersing machine described in “Issuance, October 10, 1978” can be preferably used. Moreover, the method of Paragraph 0022 of Unexamined-Japanese-Patent No. 2015-157893 can also be used. Further, in the process of dispersing the material, a refinement process by a salt milling process may be performed. As materials, equipment, processing conditions and the like used in the salt milling process, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.

The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesins such as PTFE (polytetrafluoroethylene), 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) For example). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of 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. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. Further, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.

When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st 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.) can do.
As the second filter, a filter formed of the same material as the first filter described above can be used.

<Curable composition>
Next, the curable composition of this invention is demonstrated. The curable composition of this invention contains the composition mentioned above and a curable compound.
In the curable composition of the present invention, the content of the material of the present invention can be adjusted as necessary. For example, 0.01-50 mass% is preferable in the total solid of a curable composition. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less. When the curable composition of this invention contains 2 or more types of materials of this invention, it is preferable that the total amount exists in the said range.

<< Curable compound >>
The curable composition of the present invention contains a curable compound. In the present invention, as the curable compound, a compound that can be cross-linked by a radical, an acid, or heat can be used. Examples thereof include compounds having a radical polymerizable group, a cyclic ether (epoxy, oxetane) group, a methylol group, and the like. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. In the present invention, a polymerizable or non-polymerizable binder polymer (resin) can also be used as the curable compound.
In the present invention, the curable compound is preferably a polymerizable compound, and more preferably a radical photopolymerizable 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)
In the present invention, the polymerizable compound may be in a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. When the polymerizable compound is a radical photopolymerizable compound, a monomer is preferable.
The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more 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 paragraph numbers [0095] to [0108] of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph number 0254 to JP-A-2008-292970. The compounds described in 0257 can be referred to, the contents of which are incorporated herein.

  The 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; manufactured by Nippon Kayaku Co., Ltd.). Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A -DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, SR454, SR499, commercially available from Sartomer) Is preferredThese oligomer types can also be used. Moreover, KAYARAD RP-1040 and DPCA-20 (made by Nippon Kayaku Co., Ltd.) can also be used.

  The polymerizable compound may have an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group. Examples of commercially available products include M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers 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 particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerizability is good and the curability is excellent.

  A preferable example of the polymerizable compound is a polymerizable compound having a caprolactone structure. As the polymerizable compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

  As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy 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, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, 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. Thus, it is possible to obtain a colored curable composition having an excellent photosensitive speed.
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.

  The polymerizable compound is also preferably isocyanuric acid ethyleneoxy-modified (meth) acrylate. Examples of commercially available products include Aronix M-315, M-313 (manufactured by Toagosei Co., Ltd.), NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR368 (manufactured by Sartomer) and the like.

When a polymerizable compound is used as the curable compound, the content of the polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the 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.
Moreover, 10-100 mass% is preferable with respect to the total mass of a sclerosing | hardenable compound, and, as for content of a polymeric compound, 30-100 mass% is more preferable.

(Compound having an epoxy group)
In the present invention, a compound having an epoxy group can also be used as the curable compound. As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. The upper limit of the number of epoxy groups can be, for example, 100 or less, 10 or less, or 5 or less.

In the present invention, the compound having an epoxy group preferably has a structure having an aromatic ring and / or an aliphatic ring, and more preferably has a structure having an aliphatic ring. The epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group. As the linking group, an alkylene group, an arylene group, -O-, -NR '-(R' is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a group containing at least one selected from a structure represented by —SO ₂ —, —CO—, —O— and —S—.
In the case of a compound having an aliphatic ring, the epoxy group is preferably a compound formed by directly bonding (single bond) to the aliphatic ring. In the case of a compound having an aromatic ring, the epoxy group is preferably a compound formed by bonding to an aromatic ring via a linking group. The linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
Moreover, the compound which has an epoxy group can also use the compound which has a structure which two or more aromatic rings connected with the hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.

  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 macromolecule (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 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.

  Examples of the compound having an epoxy group include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and glycidyl. Ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group, and the like And copolymers with other polymerizable unsaturated compounds.

  As an epoxy resin which is a glycidyl etherified product of a phenol compound, for example, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3- Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl Bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl ) Phenyl] propane, 2,2'-methylene Bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglicinol, diisopropyl Examples thereof include phenols having a redene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of epoxy resins that are glycidyl etherification products of novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. And glycidyl etherified products of various novolac resins such as a novolak resin, a phenol novolak resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolak resin containing a fluorene skeleton.

Examples of the alicyclic epoxy resin include alicyclic compounds having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. An epoxy resin is mentioned.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins composed of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of epoxy resins obtained by glycidylation of halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A. An epoxy resin obtained by glycidylation of halogenated phenols can be mentioned.

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, commercially available products include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758, etc. are mentioned. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of the copolymer of other polymerizable unsaturated compounds include methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane and the like, and particularly methyl (meth) acrylate. , Benzyl (meth) acrylate, and styrene are preferable.

  As a commercial product of a compound having an epoxy group, for example, as a bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (and above, Mitsubishi Chemical Corporation) EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation), and the like. As bisphenol F type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S (Nippon Kayaku Co., Ltd.) and the like. Examples of the phenol novolac type epoxy resin include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. Is mentioned. Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), OXT-221 (manufactured by Toagosei Co., Ltd.) and the like.

  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.

When using the compound which has an epoxy group as a sclerosing | hardenable compound, 0.1-40 mass% is preferable with respect to the total solid of a 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.
Moreover, 1-80 mass% is preferable with respect to the total mass of a curable compound, and, as for content of the compound which has an epoxy group, 1-50 mass% is more preferable.

(Polymerizable or non-polymerizable binder polymer)
In the present invention, a polymerizable or non-polymerizable binder polymer can also be used as the curable compound. Polymerizable or non-polymerizable binder polymers include cyclic olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, poly Examples include ether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, and fluorinated aromatic resin. Specific examples include polymers having the following repeating units. Regarding these details, the description of paragraph numbers 0086 to 0103 in JP-A-2015-040895 can be referred to, and the contents thereof are incorporated in the present specification. Moreover, the resin demonstrated with the composition mentioned above can also be used as a polymeric or nonpolymerizable binder polymer.
As for content of a binder polymer, 0.1-50 mass% is preferable with respect to the total solid of a 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. The binder polymer may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<< Polymerization initiator >>
The curable composition of the present invention may contain a polymerization initiator. When the curable composition of the present invention contains a polymerizable compound as the curable compound, it preferably contains a polymerization initiator. The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light or heat, or both, and can be appropriately selected according to the purpose.
When the polymerizable compound is polymerized by light, a photopolymerization initiator is preferred. The photopolymerization initiator preferably has photosensitivity to light in the ultraviolet region to the visible region.
Further, when the polymerization of the polymerizable compound is initiated by heat, a thermal polymerization initiator is preferable. The thermal polymerization initiator is preferably one that decomposes at 150 to 250 ° C.
Examples of the polymerization initiator include acylphosphine compounds, acetophenone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, Examples include organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, onium salt compounds such as metallocene compounds, organic boron salt compounds, disulfone compounds, and thiol compounds. The polymerization initiator is preferably a compound having at least an aromatic group.
As the polymerization initiator, the description in paragraphs 0218 to 0251 of JP-A-2014-41318 (paragraphs 0220 to 0253 in the corresponding international publication WO 2014/017669) can be referred to, and the contents thereof are incorporated herein. . Moreover, the compound as described in Unexamined-Japanese-Patent No. 2016-21010 can also be used.
The polymerization initiator is preferably an oxime compound, an acetophenone compound or an acylphosphine compound.
Examples of commercially available oxime compounds include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-930 ( ADEKA) and the like.
It is also possible to use an oxime initiator having a fluorine atom. Specific examples of such an initiator include compounds described in JP 2010-262028 A, compounds 24 and 36-40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013. The compound (C-3) described in paragraph 0101 of 164471 is mentioned. Moreover, the oxime multimer described in Japanese translations of PCT publication No. 2010-527339, international publication WO2015 / 004565 etc. can also be used.
It is also possible to use an oxime initiator having a nitro group. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime initiator having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Adeka Arkles NCI-831 (made by ADEKA) is mentioned.
Examples of commercially available acetophenone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379 (trade names: all manufactured by BASF).
Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF).

  In the present invention, the photopolymerization initiator is also preferably used in combination with an acetophenone compound and an oxime compound.

  When the curable composition of this invention contains a polymerization initiator, 0.01-30 mass% is preferable with respect to the total solid of a curable composition. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. Only one type of polymerization initiator 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.

<< Acid anhydride, polyvalent carboxylic acid >>
When the curable composition of this invention contains the compound which has an epoxy group, it is preferable to further contain at least 1 sort (s) chosen from an acid anhydride and polyhydric carboxylic acid.

  Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Is mentioned. In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2,4-diethylglutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2, 1] Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Etc. are preferable from the viewpoint of light resistance, transparency, and workability.

  The polyvalent carboxylic acid is a compound having at least two carboxyl groups. In addition, when a geometric isomer or an optical isomer exists in the following compound, it is not particularly limited. As the polyvalent carboxylic acid, a bifunctional to hexafunctional carboxylic acid is preferable, for example, 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid. Alkyltricarboxylic acids such as acid and citric acid; aliphatic cyclic polyvalents such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid Carboxylic acids; Multimers of unsaturated fatty acids such as linolenic acid and oleic acid, and dimer acids that are reduced products thereof; linear alkyl diacids such as malic acid are preferred; hexanedioic acid, pentanedioic acid, heptane Diacid, octanedioic acid, nonanedioic acid and decanedioic acid are preferred. Sex, more preferable from the viewpoint of transparency of the cured product.

  The content of the acid anhydride and the polyvalent carboxylic acid is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the compound having an epoxy group. 6.0 parts by mass is more preferable.

<< Alkali-soluble resin >>
The curable composition of the present invention may contain an alkali-soluble resin. By containing an alkali-soluble resin, a desired pattern can be formed by alkali development. As alkali-soluble resin, what was demonstrated by the composition is mentioned, A preferable range is also the same.
When the curable composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1% by mass or more, preferably 2% by mass or more in the total solid content of the curable composition of the present invention. It can also be 5 mass% or more, and can also be 10 mass% or more. Moreover, content of alkali-soluble resin can also be 80 mass% or less in the total solid of the curable composition of this invention, can also be 65 mass% or less, and shall be 60 mass% or less. It can also be made into 15 mass% or less.
In addition, when not forming a pattern by alkali image development using the curable composition of this invention, it cannot be overemphasized that it can also be set as the aspect which does not contain alkali-soluble resin.

<< Surfactant >>
The curable composition of the present invention may contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably 0.0001 to 2% by mass with respect to the solid content of the curable composition of the present invention. The lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. The upper limit is preferably 1.0% by mass or less, and more preferably 0.1% by mass or less.
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. The curable composition of the present invention preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. According to this, the interfacial tension between the coated surface and the coating liquid is lowered, and the wettability to the coated surface is improved. For this reason, the liquid characteristic (especially fluidity | liquidity) of a curable composition improves, and the uniformity of coating thickness and liquid-saving property improve more. As a result, even when a thin film of about several μm is formed with a small amount of liquid, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. When the fluorine content is within the above-described range, it is effective in terms of uniformity of coating film thickness and liquid-saving properties, and good solubility.
Specific examples of the fluorosurfactant include surfactants described in paragraphs 0060 to 0064 of JP 2014-41318 A (paragraphs 0060 to 0064 of pamphlet of international publication WO 2014/17669), JP 2011 The surfactants described in paragraphs 0117 to 0132 of JP-A-132503 are listed, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, R30, F-437, F-475, F-479, F-482, F-554, F-780 (above, manufactured by DIC Corporation) , FLORARD FC430, FC431, FC171 (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) Etc. The.
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.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. As specific examples, compounds described in JP2010-164965A paragraphs 0050-0090 and 0289-0295, for example, Megafac RS-101, RS-102, RS-718K, RS-72K manufactured by DIC, etc. Is mentioned.
As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.

Specific examples of nonionic surfactants include nonionic surfactants described in paragraph No. 0553 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to US Patent Application Publication No. 2012/0235099 [0679]). The contents of which are incorporated herein by reference.
Specific examples of the cationic surfactant include a cationic surfactant described in paragraph No. 0554 of JP2012-208494A (corresponding to [0680] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
Examples of the silicone surfactant include silicone surfactants described in paragraph No. 0556 of JP 2012-208494 A (corresponding US Patent Application Publication No. 2012/0235099 [0682]). The contents of which are incorporated herein by reference.

<< Substrate adhesion agent >>
The curable composition of the present invention can contain a substrate adhesion agent. As the substrate adhesion agent, it is preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
Examples of silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and hexyltri. Methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Lysidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, parastyryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl Pyrtrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltriethoxysilane, 3-mercapto Examples include propylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane. In addition to the above, alkoxy oligomers can be used. Also, the following compounds can be used.

  Commercially available products include Shin-Etsu Silicone's KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM- 403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, K M-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X- 41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40- 9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238, and the like.

  0.1-30 mass% is preferable with respect to the total solid of a curable composition, as for content of a board | substrate adhesion agent, 0.5-20 mass% is more preferable, and 1-10 mass% is especially preferable.

<< Polymerization inhibitor >>
The curable composition of the present invention may contain a small amount of a polymerization inhibitor in order to prevent unnecessary reaction of the curable compound during production or storage. Examples of the polymerization inhibitor include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, Examples include cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, phosphorus compounds, lactone compounds, and transition metal compounds (FeCl ₃ , CuCl _2, etc.). In addition, these compounds may be composite compounds in which a plurality of structures that exhibit a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton are present in the same molecule. For example, compounds described in JP-A-10-46035 are also preferably used. Specific examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol). 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like, and paramethoxyphenol is preferred.
When the curable composition of this invention contains a polymerization inhibitor, 0.01-5 mass% of content of a polymerization inhibitor is preferable with respect to the total solid of the curable composition of this invention.

<< UV absorber >>
The curable composition of the present invention may contain an ultraviolet absorber. A well-known compound can be used for a ultraviolet absorber. As a commercial item, UV503 (Daito Chemical Co., Ltd.) etc. are mentioned, for example. As the ultraviolet absorber, aminodiene-based, salicylate-based, benzophenone-based, benzotriazole-based, acrylonitrile-based, triazine-based ultraviolet absorbers, and the like can be used. Specific examples include compounds described in JP2013-68814A. As the benzotriazole series, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil and Fat may be used.
The content of the ultraviolet absorber is preferably 0.01 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the curable composition.

<< Organic solvent >>
The curable composition of the present invention may contain an organic solvent. As an organic solvent, what was demonstrated by the said composition is mentioned, A preferable range is also the same.
The content of the organic solvent in the curable composition of the present invention is preferably such that the total solid content of the curable composition of the present invention is 5 to 90% by mass, more preferably 10 to 80% by mass. The amount of 20 to 75% by mass is more preferable.

<< Other ingredients >>
As long as the effect of this invention is not impaired, the curable composition of this invention may select and use another component suitably according to the objective.
For example, the curable composition of the present invention can contain one or more selected from a chromatic colorant, an infrared absorber, and a colorant that blocks visible light, in addition to the above-described material of the present invention. About these details, the chromatic color agent demonstrated with the composition mentioned above, an infrared absorber, and the coloring material which shields visible light are mentioned. These can be appropriately selected depending on the use of the curable composition.
Examples of other components that can be used in combination include a sensitizer, a crosslinking agent (crosslinking agent aqueous solution), acetic anhydride, a silane compound, a curing accelerator, a filler, a plasticizer, and other auxiliary agents (for example, conductive Particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding <0237> to <0309> of US 2013/0034812 specification), JP2008-250074. Paragraph Nos. 0101 to 0102, Paragraph Nos. 0103 to 0104 of JP 2008-250074, Paragraphs 0107 to 0109 of JP 2008-250074, Paragraphs 0159 to 0184 of JP 2013-195480, etc. The contents of which are incorporated herein by reference.
By appropriately containing these components, properties such as the stability and film properties of the intended infrared cut filter can be adjusted.

<Preparation of curable composition>
The curable composition of this invention can be prepared by mixing each component mentioned above. Moreover, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. About the kind of filter and the filtration method, what was demonstrated by the composition is mentioned, A preferable range is also the same.

<Use of curable composition>
Since the curable composition of the present invention can be in a liquid state, for example, by applying the curable composition of the present invention to a substrate and drying it, a color filter, an infrared cut filter, an infrared transmission filter, etc. Can be easily produced.
For example, when the pigment A in the material of the present invention is a near infrared absorbing dye, an infrared cut filter can be produced by using a curable composition containing the material of the present invention. Further, in this embodiment, when the curable composition of the present invention further contains an infrared absorber in addition to the material of the present invention, a wider wavelength than can be cut with the pigment A contained in the material of the present invention. An infrared cut filter capable of absorbing light in the near infrared region of the region is obtained. In this embodiment, when the curable composition of the present invention further contains a colorant that blocks visible light in addition to the material of the present invention, an infrared transmission filter can be produced. In this embodiment, when the curable composition of the present invention further contains a chromatic colorant in addition to the material of the present invention, an infrared cut filter having a function as a color filter can be produced. .
For example, when the pigment A in the material of the present invention is a chromatic pigment, a color filter can be produced by using a curable composition containing the material of the present invention.
In the present invention, the 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 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. It may be a thing. In the present invention, the color filter means a filter that transmits a specific wavelength range of visible light and shields the specific wavelength range.

The viscosity of the curable composition of the present invention is preferably 1 to 3000 mPa · s when a cured film is formed by coating. The lower limit is preferably 2 mPa · s or more, and more preferably 3 mPa · s or more. The upper limit is preferably 100 mPa · s or less, more preferably 50 mPa · s or less, still more preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
Although the total solid content of the curable composition of this invention is changed by the apply | coating method, it is preferable that it is 1-50 mass%, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.

  The use of the curable composition of the present invention is not particularly limited. For example, an infrared cut filter on the light receiving side of the solid-state image sensor (for example, for an infrared cut filter for a wafer level lens), a back surface side (light receiving) It can be preferably used for an infrared cut filter on the side opposite to the side). In particular, it can be preferably used as an infrared cut filter on the light receiving side of the solid-state imaging device.

<Curing film>
Next, the cured film of the present invention will be described.
The cured film of the present invention is formed by curing the above-described curable composition of the present invention. The cured film of the present invention can be used as an infrared cut filter, an infrared transmission filter, a color filter, or the like. The cured film of the present invention may have a pattern or may be a film (flat film) having no pattern.

  When the cured film of the present invention is used as an infrared transmission filter, it preferably has the following spectral characteristics (1) or (2). According to this aspect, a film that can transmit infrared rays (preferably, light having a wavelength of 900 nm or more) can be obtained in a state where there is little noise derived from visible light.

  (1): The maximum value of the light transmittance in the thickness direction of the film is 20% or less in the wavelength range of 400 to 830 nm, and the minimum of the light transmittance in the thickness direction of the film is in the range of wavelength 1000 to 1300 nm. The value is preferably 70% or more. The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is preferably 20% or less, and more preferably 10% or less. The minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more, and more preferably 80% or more.

  (2): The maximum value of the light transmittance in the film thickness direction in the wavelength range of 450 to 650 nm is 20% or less, and the light transmittance of the wavelength 835 nm in the film thickness direction is 20% or less. The minimum value of light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more. The maximum value of light transmittance in the thickness direction of the film in the wavelength range of 450 to 650 nm is preferably 20% or less, and more preferably 10% or less. The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 650 to 835 nm is preferably 50% or less, and more preferably 30% or less. The transmittance of light having a wavelength of 835 nm in the thickness direction of the film is preferably 20% or less, and more preferably 10% or less. The minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is preferably 70% or more, and more preferably 80% or more.

  The spectral characteristic of the cured film of the present invention 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).

  When using the cured film of this invention as an infrared cut filter or an infrared transmission filter, it can also be used in combination with an infrared cut filter and an infrared transmission filter. By using a combination of an infrared cut filter and an infrared transmission filter, the filter can be preferably used for an infrared sensor that detects infrared rays having a specific wavelength. When both filters are used in combination, one of the infrared cut filter and the infrared transmission filter is a cured film (cured film of the present invention) formed using the curable composition of the present invention, and the other is the curable film of the present invention. It is good also as a cured film formed using curable compositions other than a composition. Moreover, you may comprise both with the cured film of this invention.

  In addition, when the cured film of the present invention is used as a color filter or an infrared cut filter, the infrared cut filter may or may not be adjacent to the color filter in the thickness direction. When the infrared cut filter and the color filter are not adjacent to each other in the thickness direction, the infrared cut filter may be formed on a base material different from the base material on which the color filter is formed. Other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state imaging device may be interposed between the filter and the filter.

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

  The cured film of 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.

<Optical filter>
Next, the optical filter of the present invention will be described. The optical filter of the present invention has the above-described cured film of the present invention. The optical filter of the present invention can be preferably used as at least one selected from a color filter, an infrared cut filter, and an infrared transmission filter. In addition, an embodiment in which the optical filter of the present invention includes a pixel using the cured film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferable embodiment.

<Pattern formation method>
The pattern forming method of the present invention comprises a step of forming a curable composition layer on a support using the curable composition of the present invention, and a photolithography method or a dry etching method on the curable composition layer. Forming a pattern.

The pattern formation method may be a pattern formation method by photolithography or a pattern formation method by dry etching.
When the pattern forming method is based on photolithography, a dry etching process is unnecessary, and thus the number of processes can be reduced.
When the pattern forming method is performed by dry etching, the curable composition does not need a photolithographic function, so that an effect of increasing the concentration of a pigment or the like can be obtained.

Pattern formation by the photolithography method includes a step of forming a curable composition layer on a support using a curable composition, a step of exposing the curable composition layer in a pattern, and developing and removing unexposed portions. And a step of forming a pattern. As needed, you may provide the process (prebaking process) of baking a curable composition layer, and the process (post-baking process) of baking the developed pattern.
In addition, pattern formation by a dry etching method includes a step of forming a curable composition layer on a support using a curable composition and curing to form a cured product layer, and a photoresist layer on the cured product layer. A step of patterning a photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the cured product layer using the resist pattern as an etching mask to form a pattern. preferable. Hereinafter, each step will be described.

<< Step of Forming Curable Composition Layer >>
In the step of forming the curable composition layer, the curable 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 in the present invention 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 on the support, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be used.

The curable 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. Drying can be performed with a hot plate, oven, or the like.
When patterning a plurality of layers at the same time, it is preferable to apply the curable composition for forming each layer on the curable composition layer to form another curable composition layer.

(When forming a pattern by photolithography)
<< Exposure process >>
Next, the curable composition layer is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the curable 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.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). The irradiation amount (exposure amount) is preferably, for example, 30 to 5000 mJ / cm ² . The upper limit is preferably 3000 mJ / cm ² or less, more preferably 2000 mJ / cm ² or less, more preferably 1500 mJ / cm ² or less. The lower limit is more preferably 50 mJ / cm ² or more, 80 mJ / cm ² or more is particularly preferable.
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 or less, preferably 5% by volume or less, more The exposure may be performed preferably in a substantially oxygen-free manner) in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume or more, preferably 30% by volume or more, more preferably 50% by volume or more). May be exposed. The exposure illuminance can be appropriately set, and is usually 1000 W / m ^{2 to} 100,000 W / m ² (for example, 5000 W / m ² or more, preferably 15000 W / m ² or more, more preferably 35000 W / m ² or more). You can choose from a 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 curable composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. , Organic alkaline agents such as choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, dimethylbis (2-hydroxyethyl) ammonium hydroxide. 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.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
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, generally 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-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. . Further, when a pattern is formed by a low temperature process, post baking is not necessary.

(When pattern is formed by dry etching method)
Pattern formation by dry etching is performed by curing a curable composition layer formed on a support to form a cured product layer, and then using the patterned photoresist layer as a mask for the resulting cured product layer. Etching gas can be used.
Specifically, it is preferable to form a photoresist layer by applying a positive or negative radiation sensitive composition on the cured product layer and drying it. In the formation of 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.

As the photoresist layer, for example, a positive radiation sensitive composition sensitive to radiation such as ultraviolet rays (g-rays, h-rays, i-rays), excimer lasers, deep ultraviolet rays, electron beams, ion beams and X-rays. Is preferably used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by light irradiation with a wavelength of 500 nm or less to produce a carboxy group, resulting in becoming alkali-soluble from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. As a commercial item, "FHi622BC" (made by FUJIFILM Electronics Materials) etc. are mentioned, for example.

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and further preferably 0.3 to 2 μm. In addition, the application method of a positive radiation sensitive composition can be suitably performed using the application | coating method of the curable composition mentioned above.

  Next, by exposing and developing the photoresist layer, a resist pattern (patterned photoresist layer) provided with a group of resist through holes is formed. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the cured product layer.

  The exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

  Any developer can be used as long as it does not affect the cured product layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, dimethylbis (2-hydroxyethyl) ammonium hydroxide. When an alkaline aqueous solution is used, a washing treatment with water is generally performed after development.

  Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that a through hole group is formed in the cured product layer.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first-stage etching is performed according to the etching time calculated in (2) above.
(4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.

The mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed. Further, in the second stage etching process and the over etching process, after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.

  Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

  Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.

  Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

  Examples of the process of removing the resist pattern using the cleaning water include a process of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.

  The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of the organic solvent include (1) hydrocarbon compounds, (2) halogenated hydrocarbon compounds, (3) alcohol compounds, (4) ether or acetal compounds, (5) ketones or aldehyde compounds, (6) ester compounds, (7) polyhydric alcohol compounds, (8) carboxylic acids or acid anhydride compounds, (9) phenol compounds, (10) nitrogen compounds, (11) sulfur compounds, (12) Fluorine-containing compounds are exemplified. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxy group. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine. Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

  The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably contains at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with a stripping solution, it is sufficient that the resist pattern formed on the pattern has been removed, and even if deposits that are etching products adhere to the side walls of the pattern, the deposits are completely removed. It does not have to be. A deposit means an etching product deposited and deposited on the side wall of a cured product layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

<Solid-state imaging device, camera module>
The solid-state imaging device of the present invention has the above-described cured film of the present invention.
Moreover, the camera module of this invention has a solid-state image sensor and the cured film (preferably infrared cut filter) of this invention. The configuration of the solid-state imaging element is not particularly limited as long as it is a configuration having the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

A transfer electrode made of a plurality of photodiodes, polysilicon, etc. constituting a light receiving area of a solid-state imaging device (charge coupled device (CCD) image sensor, complementary metal oxide semiconductor (CMOS) image sensor, etc.) on a support. Silicon nitride or the like having a light-shielding film made of tungsten or the like that is opened only on the light-receiving portion of the photodiode on the photodiode and the transfer electrode, and covering the entire surface of the light-shielding film and the photodiode light-receiving portion on the light-shielding film A device protective film comprising the film of the present invention such as an infrared cut filter or an infrared transmission filter on the device protective film.
Furthermore, on the device protective film, the structure having a light collecting means (for example, a microlens, etc., the same shall apply hereinafter) under the cured film of the present invention (side closer to the support), or on the cured film of the present invention. The structure etc. which have a condensing means may be sufficient.

<Infrared sensor>
The infrared sensor of the present invention has the above-described cured film of the present invention. The configuration of the infrared sensor of the present invention is not particularly limited as long as it is a configuration having the cured film of the present invention and functions as an infrared sensor.

Hereinafter, an embodiment of an infrared sensor of the present invention will be described with reference to the drawings.
In the infrared sensor 100 shown in FIG. 1, reference numeral 110 denotes a solid-state image sensor.
The imaging area provided on the solid-state imaging device 110 includes an infrared cut filter 111 and a color filter 112. The infrared cut filter 111 can be formed using, for example, the curable composition of the present invention.
A region 114 is provided between the infrared transmission filter 113 and the solid-state image sensor 110. In the region 114, a resin layer (for example, a transparent resin layer) that can transmit light having a wavelength that has passed through the infrared transmission filter 113 is disposed. In the embodiment shown in FIG. 1, the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
A micro lens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 113. A planarization layer 116 is formed so as to cover the microlens 115.
In the embodiment shown in FIG. 1, the film thickness of the color filter 112 and the film thickness of the infrared transmission filter 113 are the same, but the film thicknesses of both may be different.
In the embodiment shown in FIG. 1, the color filter 112 is provided on the incident light hν side with respect to the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 is changed to cut the infrared filter. The filter 111 may be provided closer to the incident light hν than the color filter 112.
In the embodiment shown in FIG. 1, the infrared cut filter 111 and the color filter 112 are stacked adjacent to each other, but the filters do not necessarily have to be adjacent to each other, and other layers are provided between them. Also good.
In the embodiment shown in FIG. 1, the infrared cut filter 111 and the color filter 112 are provided as separate members. However, the color filter 112 contains the composition of the present invention, and the color filter 112 is used as an infrared cut filter. You may give the function of. In this case, the infrared cut filter 111 can be omitted.

  The characteristics of the infrared cut filter 111 are selected according to the emission wavelength of an infrared light emitting diode (infrared LED) described later. For example, the infrared cut filter 111 transmits visible light (for example, light having a wavelength of 400 to 650 nm) and is in the near infrared region (preferably in the range of wavelength 700 to 1300 nm, more preferably in the range of wavelength 700 to 1000 nm). It is preferable that the filter shields at least a part of the light. The infrared cut filter 111 can be composed of a cured film using the curable composition of the present invention.

  The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible 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 paragraphs 0214 to 0263 in JP 2014-043556 A can be referred to, and the contents thereof are incorporated in the present specification. The color filter 112 can also be formed of a cured film using the curable composition of the present invention.

The characteristics of the infrared transmission filter 113 are selected according to the emission wavelength of an infrared LED described later.
For example, when the emission wavelength of the infrared LED is 850 nm, the infrared transmission filter 113 preferably has a light transmittance in the thickness direction of the film having a maximum value of 30% or less in the wavelength range of 400 to 650 nm. % 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 113, the minimum value of the light transmittance in the thickness direction of the film 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 113 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 113 will be described 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).
The infrared transmission filter 113 having the spectral characteristics described above can be manufactured using a curable composition containing a colorant that blocks visible light. The details of the coloring material that blocks visible light are the same as those described in the above-described composition of the present invention.

  Further, for example, when the emission wavelength of the infrared LED is 940 nm, the infrared transmission filter 113 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 infrared transmission filter 113 having the spectral characteristics described above can be manufactured using a curable composition containing a colorant that blocks visible light and a compound having a maximum absorption wavelength in the wavelength range of 750 to 950 nm. The details of the coloring material that blocks visible light are the same as those described in the above-described composition of the present invention. Examples of the compound having the maximum absorption wavelength in the wavelength range of 750 to 950 nm include the material of the present invention using a near infrared absorbing dye as the pigment A and the infrared absorbent described in the composition of the present invention described above. .

<Image display device>
The cured film of the present invention (preferably an infrared cut filter) can also be used for image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices. For example, when used with each colored pixel (for example, red, green, blue), the infrared light contained in the backlight of the display device (for example, white light emitting diode (white LED)) is blocked, and malfunction of peripheral devices is prevented. It can be used for the purpose of forming an infrared pixel in addition to each colored display pixel.

  For the definition of the image display device and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Sangyo Tosho Co., Ltd.) ) "Issued in 1989"). 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, “Frontier 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.

  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.

<Production method of material>
Example 1
Stir 8.74 parts by mass of diphenylborinic acid ester, 10 parts by mass of the following compound (A-1-a), 4.27 parts by mass of the following compound (B-30), and 100 mL of toluene at 40 ° C. 7.36 parts by mass of titanium was dropped and reacted for 30 minutes. The mixture was heated to reflux at an external temperature of 130 ° C. for 3 hours, then cooled to room temperature, 57 mL of toluene was added, and this was filtered off. To the obtained crude crystals, 88 mL of methanol was added, and the mixture was heated to reflux at an external temperature of 80 ° C. for 1 hour. After cooling to room temperature, this was filtered off, and 88 mL of methanol was added again to the obtained crystals, and the mixture was heated to reflux at an external temperature of 80 ° C. for 1 hour. The material (C-1) containing a pigment (A-1) and the following compound (B-30) was obtained by cooling to room temperature and filtering this.

(Examples 2-8, 11-25)
At the time of synthesis of each compound (pigment A), the compound (C-2) was prepared in the same manner as in Example 1 except that the compounds shown in the following table were added as compound B in the final step to synthesize each pigment. ) To (C-8) and (C-11) to (C-25).

Example 9
Compound (A-2-b)
Compound (A-2-b) was synthesized according to the following scheme.

Using 4- (1-methylheptoxy) benzonitrile as a starting material, compound (A-2-a) was synthesized according to the method described in US Pat. No. 5,969,154.
¹ H-NMR (DMSO (dimethyl sulfoxide): 28% by mass methanol solution of sodium methoxide = 95: 5 (mass ratio) mixed solution): δ 0.82 (t, 6H), 1.15-1.70 ( m, 26H), 4.40 (m, 2H), 6.78 (d, 4H), 8.48 (d, 2H)
20.0 parts by mass of the compound (A-2-a) and 15.4 parts by mass of 2- (2-benzothiazolyl) acetonitrile were stirred in 230 parts by mass of toluene, and then 45. 0 parts by mass was added dropwise and heated to reflux for 3.5 hours. After completion of the reaction, the internal temperature was cooled to 25 ° C, and 200 parts by mass of methanol was added dropwise over 60 minutes while maintaining the internal temperature at 30 ° C or lower. After completion of dropping, the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were separated by filtration and washed with 100 parts by mass of methanol. To the obtained crystals, 200 parts by mass of methanol was added, heated to reflux for 30 minutes, allowed to cool to 30 ° C., and the crystals were filtered off. The obtained crystal was blown and dried at 40 ° C. for 12 hours to obtain 8.8 parts by mass of the compound (A-2-b).
¹ H-NMR (CDCl ₃ ): δ 0.90-1.90 (m, 32H), 4.54 (m, 2H), 7.12 (d, 4H), 7.20-7.40 (m, 2H), 7.43 (t, 2H), 7.75 (d, 4H), 7.81 (t, 4H)

Synthesis of Material (C-9) In Example 1, (A-2-b) was used instead of Compound (A-1-a), and Compound (B-61) was used instead of Compound (B-30). A material (C-9) containing the pigment (A-2) and the compound (C-61) was obtained in the same manner as in the synthesis of the material (C-1) except that it was used.

(Example 10)
Synthesis of Compound (A-3-c) Compound (A-3-c) was synthesized according to the following scheme.

50.0 parts by mass of 2-amino-6-methoxybenzothiazole and 93.4 parts by mass of potassium hydroxide were heated to reflux in 200 parts by mass of water for 24 hours and cooled to 10 ° C. or lower. 6 mol / L hydrochloric acid and acetic acid were added while maintaining the temperature at 10 ° C. or lower so that the pH of the reaction solution was 6. The precipitated crystals were separated by filtration and washed with 200 parts by mass of water. The total amount of crystals obtained, 18.3 parts by weight of malononitrile, 19.3 parts by weight of acetic acid, and 172 parts by weight of methanol were mixed, stirred at 60 ° C. for 1 hour, and then cooled to 10 ° C. or less. The precipitated crystals were separated by filtration and washed with 200 parts by mass of methanol. The obtained crystal was blown and dried at 40 ° C. for 12 hours to obtain 38.7 parts by mass of the compound (A-3-b).
¹ H-NMR (CDCl ₃ ): δ 3.85 (s, 3H), 4.22 (s, 2H), 7.16 (d, 1H), 7.38 (s, 1H), 7.97 (d , 1H)
Using compound (A-1-a) and compound (A-3-b) as raw materials, compound (A-3-c) is synthesized in the same manner as compound (A-2-b). did.
¹ H-NMR (DMSO (dimethyl sulfoxide): 28% by mass methanol solution of sodium methoxide = 95: 5 (mass ratio) mixed solution): δ 0.98 (t, 6H), 1.12 (d, 6H) , 1.30 (m, 2H), 1.63 (m, 2H), 1.95 (m, 2H), 3.89 (m, 4H), 6.88 (d, 2H), 6.98 ( d, 4H), 7.42 (m, 4H), 7.67 (s, 2H), 7.85 (d, 4H)

Synthesis of Material (C-10) A method similar to the synthesis of Material (C-9) except that Compound (A-3-c) was used instead of Compound (A-2-b) in Example 9. The material (C-10) containing a pigment (A-3) and a compound (B-61) was obtained.

(Comparative Example 1)
10 parts by mass of pigment (NPC-1) and 3 parts by mass of compound (B-30) were added to a mortar, stirred with a pestle and mixed uniformly to obtain material (C′-1).

(Comparative Example 2)
10 parts by mass of the pigment (DP-1) and 3 parts by mass of the compound (B-30) were added to a mortar and mixed with stirring with a pestle to obtain a material (C′-2).

<Evaluation>
The amount of Compound B contained in the filtrate discharged during the synthesis of the pigment was measured by high performance liquid chromatography (HPLC), and the amount of Compound B extracted from each material was calculated. From the amount of compound B eluted from each material, the amount of compound B contained in each material was calculated.
Subsequently, 16.6 mL of methanol was added to 1 g of each material obtained above, followed by stirring and washing at 80 ° C. for 30 minutes. The washed filtrate was collected, the amount of Compound B contained in the filtrate was measured by high performance liquid chromatography (HPLC), and the amount of Compound B extracted from each material was calculated. From the amount of compound B eluted from each material, the mass X ² of compound B in the material after washing with methanol was calculated. Further, the material after washing with methanol was blown and dried at 45 ° C. for 12 hours, and the mass X ³ of the solid content of the material after washing with methanol was measured.
The resulting material, the mass X ² of the compound B in the material after washing with methanol, washing the material after a solid content mass X ³ Metropolitan of methanol, the following equation to determine the X ^1.
X ¹ = (X ² / X ³ ) × 100
Methanol is a solvent satisfying the requirement that the solubility of the pigment A described in the following table is 0.02% by mass or less and the solubility of the compound B described in the following table is 0.2% by mass or more at 25 ° C. It is.

As is clear from the above results, in the examples, the value of X ¹ satisfied the requirement of 0.99 or more, and it was confirmed that the compound B was firmly attached to the pigment A.
On the other hand, in Comparative Examples 1 and 2, the value of X ¹ was less than 0.99, and the compound B was easily peeled from the pigment A.

The materials listed in the above table are as follows.
Pigment A: The following compound. Compound A-122 was synthesized with reference to the method described in WO09 / 060573. Compound A-123 was synthesized with reference to the method described in JP2012-8532A.


Compound B: the following compound

Synthesis of Compound (B-61) Compound (B-61) was synthesized according to the following scheme.

3.9 parts by mass of diphenylborinic acid 2-aminoethyl ester and 6.0 parts by mass of compound (A-2-b) were stirred in 60 parts by mass of toluene, and at a circumscribed temperature of 40 ° C., titanium tetrachloride. Was added dropwise over 10 minutes and stirred for 30 minutes. The external temperature was raised to 130 ° C. and heated to reflux for 3 hours. The mixture was allowed to cool until the internal temperature reached 30 ° C, and 40 parts by mass of methanol was added dropwise while maintaining the internal temperature at 30 ° C or lower. After dropping, the mixture was stirred for 30 minutes, and the precipitated crystals were collected by filtration and washed with 35 parts by mass of methanol. An operation of adding 50 parts by mass of methanol to the obtained crystal, heating to reflux for 30 minutes, allowing to cool to 30 ° C., and filtering the crystal twice was performed. The obtained crystal was blown and dried at 40 ° C. for 12 hours to obtain 4.6 parts by mass of the compound (A-2). ¹ H-NMR (DMSO): δ 6.20-6.30 (dd, 8H), 6.91 (d, 2H), 7.12-7.21 (m, 24H), 7.92 (d, 2H) ), 9.54 (s, 2H)
After stirring 3.0 parts by mass of compound (A-2) and 3.45 parts by mass of potassium carbonate in 28.2 parts by mass of dimethylacetamide (DMAc), 3.40 parts by mass of butane sultone Then, 5.6 parts by mass of DMAc was added and stirred at room temperature for 10 minutes. The external temperature was raised to 105 ° C. and heated for 4 hours. Next, it was allowed to cool to an internal temperature of 30 ° C., and the precipitated crystals were separated by filtration. While maintaining an internal temperature of 30 ° C. or less to 30 parts by mass of a 4 mol / L hydrochloric acid aqueous solution, the obtained crystals were added little by little, stirred for 30 minutes at room temperature, and the precipitated crystals were filtered off twice. It was. The operation of adding 60 parts by mass of ethyl acetate to the obtained crystals, heating to reflux for 30 minutes, allowing to cool to 30 ° C., and filtering the crystals three times was performed. The obtained crystal was blown and dried at 50 ° C. for 24 hours to obtain 2.74 parts by mass of the compound (B-61).
¹ H-NMR (DMSO): δ 1.76 (m, 8H), 3.42 (m, 4H), 3.93 (m, 4H), 6.34-6.47 (dd, 8H), 6. 89 (d, 2H), 7.12-7.21 (m, 24H), 7.93 (d, 2H)

Synthesis of Compound (B-113) Compound (B-113) was obtained by using the same procedure as for Compound (B-61) except that propane sultone was used instead of butane sultone.

Synthesis of compound (B-81)

4.6 parts by mass of pigment (A-2), 10 parts by mass of 4-[(diethylamino) methyl] -benzoic acid chloride, 87 parts by mass of DMAc, and 16.7 parts by mass of triethylamine were added. Stir for 5 minutes. The external temperature was raised to 110 ° C. and heated for 4 hours. The mixture was allowed to cool to an internal temperature of 30 ° C., and the precipitated crystals were separated by filtration. Subsequently, it was washed with 100 parts by mass of methanol and 100 parts by mass of water. 200 parts by mass of distilled water was added to the obtained crystal, heated to reflux for 30 minutes, allowed to cool to 30 ° C., and the precipitated crystal was filtered off. To the obtained crystal, 200 parts by mass of dimethyl sulfoxide was added and heated at 80 ° C. for 30 minutes. After heating, the mixture was allowed to cool to 30 ° C., and the precipitated crystals were filtered off. To the obtained crystals, 200 parts by mass of methanol was added, heated to reflux for 30 minutes, allowed to cool to 30 ° C., and the precipitated crystals were filtered off. The obtained crystal was blown and dried at 50 ° C. for 24 hours to obtain 5.5 parts by mass of the compound (B-81).
¹ H-NMR (CDCl ₃ ): 1.07 (t, 12H), 2.56 (q, 8H), 3.67 (s, 4H), 6.60 (d, 4H), 6.85 (d , 4H), 6.91-7.40 (m, 26H), 7.51 (m, 6H), 8.19 (d, 4H)

Synthesis of Compounds (B-114) and (B-115) Compound (B-81) except that isonicotinic acid chloride and nicotinic acid chloride were used instead of 4-[(diethylamino) methyl] -benzoic acid chloride. By using the same method, compounds (B-114) and (B-115) were obtained.

Synthesis of compound (B-119)

4.5 parts by mass of N- (3-bromopropyl) phthalimide, 2.0 parts by mass of pigment (A-2), 37.6 parts by mass of DMAc, and 4.7 parts by mass of potassium carbonate Added and stirred for 5 minutes. The external temperature was raised to 100 ° C. and heated for 1 hour. Next, 2.3 parts by mass of N- (3-bromopropyl) phthalimide and 2.5 parts by mass of potassium carbonate were added to the reactor, followed by stirring for 6 hours. The mixture was allowed to cool to an internal temperature of 30 ° C, and 40 parts by mass of a 1 mol / L sodium hydroxide aqueous solution was added dropwise while maintaining the internal temperature at 30 ° C or lower. After dropping, the mixture was stirred for 30 minutes, and the precipitated crystals were separated by filtration and washed with 35 parts by mass of distilled water. The obtained crystals were blown and dried at 50 ° C. for 24 hours to obtain 2.1 parts by mass of the compound (B-119).
¹ H-NMR (CDCl ₃ ): 2.21 (quin, 4H), 3.96 (t, 4H), 4.02 (t, 4H), 6.35 (d, 4H), 6.40 (d , 4H), 7.00-7.25 (m, 28H) 7.73 (m, 4H), 7.89 (m, 4H)

<Preparation of composition (dispersion)>
10 parts by mass of the materials shown in the following table, 3.0 parts by mass of the dye derivatives shown in the following table, 7.8 parts by mass of the resin shown in the following table, 109 parts by mass of the organic solvent shown in the following table, and 0.5 mm Dispersion treatment was performed for 520 parts by mass of zirconia beads with a paint shaker for 30 minutes. Thereafter, filtration was performed using DFA4201NXEY (0.45 μm nylon filter) manufactured by Nippon Pole, and the beads were separated by filtration to prepare a composition (dispersion).

<Evaluation of dispersibility>
The viscosity of each composition at 25 ° C. and 1000 rpm was measured using an E-type viscometer, and the dispersibility was evaluated according to the following criteria.
A: 20 mPa · s or less B: Over 20 mPa · s, 100 mPa · s or less C: Over 100 mPa · s

From the above results, the examples had good dispersibility. On the other hand, the comparative example which does not contain the material of this invention was inferior in the dispersibility.
In Examples 101-127, the same effect can be obtained even if materials before washing with methanol are used as the materials C-1 to C-25.

The components shown in the above table are as follows.
(Materials, pigments, dye derivatives)
C-1 to C-25, C-1 ′, C-2 ′: The above-mentioned materials C-1 to C-25, C-1 ′, C-2 ′ after calculating X ¹ (after methanol washing)
DP-1, B-1, B-30, B-61: The above structure (resin)
D-1: The following structure (a resin produced using macromonomer AA-6 manufactured by Toagosei Co., Ltd. as a raw material, x / y / z = 10/78/12 (mass%), Mw: 19700 .)
D-2: The following structure (Mw = 38900)
D-3: The following structure (Mw = 7950)
D-4: The following structure (Mw = 11833)
D-5: The following structure (Mw = 22900)

PGMEA: Propylene glycol methyl ether acetate PGME: 1-methoxy-2-propanol

<Preparation of curable composition>
(Examples 201-225, Comparative Examples 201-203)
The following components were mixed to prepare the curable composition of Example 201. Moreover, in the curable composition of Example 201, the dispersion liquid of Example 101 was changed to the dispersion liquids of Examples 102 to 125 and Comparative Examples 101 to 103, and Examples 202 to 225 and Comparative Examples 201 to 203 were changed. A near-infrared absorbing composition was prepared.
-Dispersion liquid of Example 101: 28.0 parts by mass-Polymerizable compound 1: 6.83 parts by mass-Alkali-soluble resin 1: 6.73 parts by mass-Polymerization initiator 1: 1.96 parts by mass-Polymerization inhibitor 1: 0.003 parts by mass-Surfactant 1: 0.04 parts by mass-Organic solvent 1: 56.44 parts by mass Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Alkali-soluble resin 1: following structure (Mw: 11000)

Polymerization initiator 1: following structure

Polymerization inhibitor 1: Paramethoxyphenol (manufactured by Mitsuru Chemie)
Surfactant 1: The following mixture (Mw = 14000)

Organic solvent 1: Propylene glycol methyl ether acetate

(Example 226)
In a glass separable flask equipped with a stirrer and a thermometer, 50.0 parts by mass of an epoxy group-containing compound (manufactured by NOF Corporation, Marproof G-0150M weight average molecular weight 10,000), propylene glycol methyl ether acetate 100 A mass part was added and dissolved by stirring at 20 to 35 ° C. for 2 hours. Next, 0.75 parts by mass of the composition (dispersion liquid) of Example 126 was added, and the mixture was stirred at 20 to 35 ° C. until uniform. Furthermore, 0.500 parts by mass of butanedioic acid (1 part by mass with respect to 100 parts by mass of the epoxy group-containing compound) was added and stirred at 20 to 35 ° C. for 1 hour to obtain a curable composition.

(Example 227)
In a container, 100 parts by mass of the following resin A (binder polymer), 0.08 parts by mass of the composition of Example 127 (dispersion), and propylene glycol methyl ether acetate are added to bring the concentration of the resin A to 20% by mass. It adjusted and obtained the curable composition.
Resin A: The following structure (synthesized with reference to the method described in paragraphs 0141 to 0143 of JP-A-2015-40895, Mw = 137,000)

<Evaluation of in-plane uniformity>
Each curable composition of Examples 201-225 and Comparative Examples 201-203 was spin-coated on an 8 inch (200 mm) glass wafer and dried on a hot plate at 100 ° C. for 120 seconds to produce a cured film.
Also, the curable composition of Example 226 was dropped on a glass substrate placed on a spin coater, the substrate surface was coated by rotating the substrate at 1000 rpm for 30 seconds, and then dried at 80 ° C. for 10 minutes. The solvent was removed and heat cured at 150 ° C. for 3 hours to obtain a cured film.
The curable composition of Example 227 was cast on a smooth glass substrate, dried at 20 ° C. for 8 hours, and then peeled from the glass substrate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a cured film having a thickness of 0.1 mm.
About the obtained cured film, the film thickness measurement of a total of five points was measured by Dektak (made by Bruker) at intervals of 2 cm from the center to the end, and the in-plane uniformity was evaluated according to the following criteria.
A: (Max-Min) / Min <3%
B: 3 ≦ (Max−Min) / Min ≦ 7%
C: (Max-Min) / Min> 7%
Note that “Min” is the thickness of the thinnest portion, and “Max” is the thickness of the thickest portion.

From the above results, the examples had good in-plane uniformity. Since the dispersion used in the curable compositions of Examples had good pigment dispersibility, the viscosity of the curable composition was low and the coating property was good. Therefore, in the examples, it is considered that unevenness is less likely to occur in the coating film, and the in-plane uniformity is improved. On the other hand, the comparative example which does not contain the material of this invention was inferior in-plane uniformity.
In an Example, an infrared rays transmission filter is obtained by further mix | blending the coloring material which shields visible light.

DESCRIPTION OF SYMBOLS 100 Infrared sensor, 110 Solid-state image sensor, 111 Infrared cut filter, 112 Color filter, 113 Infrared transmission filter, 114 area | region, 115 microlens, 116 Flattening layer

Claims (20)

A material containing Pigment A and Compound B having a structure having an adsorptivity to a resin;
A material represented by the following formula (I) wherein X ¹ is 0.99 or more;
X ¹ = (X ² / X ³ ) × 100 (I)
X ² is a material obtained by immersing the material in a solvent in which the solubility of the pigment A is 0.02% by mass or less and the solubility of the compound B is 0.2% by mass or more at 25 ° C. The mass of the compound B in the medium,
X ³ is the mass of the solid content of the material after being immersed in the solvent.   The material according to claim 1, wherein the pigment A has absorption in the near infrared region.   The material according to claim 1 or 2, wherein the maximum absorption wavelength of the pigment A is in the range of 700 to 1200 nm.   The pigment A is one or more selected from phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complex compounds, naphthoquinone compounds, iminium compounds, azo compounds, and squarylium compounds. The material of any one of -3.   The material according to any one of claims 1 to 4, wherein the pigment A is a pyrrolopyrrole compound. The material according to claim 5, wherein the pyrrolopyrrole compound is a compound represented by the following formula (1);

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ 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 bonded or coordinated, and R ^4A and R ^4B each independently represents a substituent.   The material according to any one of claims 1 to 6, wherein the compound B has a dye structure.   The dye structure is 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, The material according to claim 7. The said compound B has at least 1 sort (s) chosen from an acidic group, a basic group, a hydrogen bond group, a dipole interaction group, and a (pi)-(pi) interaction group, The any one of Claims 1-8. Materials described in.
  The composition containing the material of any one of Claims 1-9.   Furthermore, the composition of Claim 10 containing 1 or more types chosen from an organic solvent, resin, and a pigment derivative.   A curable composition comprising the composition according to claim 10 or 11 and a curable compound.   A cured film formed using the curable composition according to claim 12.   An optical filter having the cured film according to claim 13.   The optical filter according to claim 14, which is at least one selected from a color filter, an infrared cut filter, and an infrared transmission filter. A pixel of the cured film according to claim 13;
At least one pixel selected from red, green, blue, magenta, yellow, cyan, black and colorless;
The optical filter according to claim 14, comprising:   A solid-state imaging device having the cured film according to claim 13.   An infrared sensor having the cured film according to claim 13.   A camera module comprising a solid-state imaging device and the cured film according to claim 13. A method for producing a material comprising a pigment A and a compound B having a structure having an adsorptivity to a resin,
A method for producing a material, wherein the pigment A is synthesized by reacting the raw material compound of the pigment A in the presence of the compound B having a structure having an adsorptivity to a resin.