TWI746450B - Material, composition, curable composition, cured film, optical filter, solid-state imaging element, infrared sensor, camera module, and material manufacturing method - Google Patents

Abstract

The present invention provides a material with excellent dispersibility of the pigment in the composition. In addition, it provides a composition, a curable composition, a cured film, an optical filter, a solid-state imaging element, an infrared sensor, a camera module, and a material manufacturing method with excellent pigment dispersibility. A material comprising pigment A and a compound B having a structure that is adsorbable to resin, and X ¹ represented by formula (I) is 0.99 or more. X ² is the mass of compound B in the material after immersing the material in a solvent with 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 X ³ is the mass of compound B after immersing in the above solvent The quality of the solid content of the material. Formula (I); X ¹ =(X ² /X ³ )×100

Description

Material, composition, curable composition, cured film, optical filter, solid-state imaging element, infrared sensor, camera module, and material manufacturing method

The present invention relates to a material containing a pigment and a compound having a structure that is adsorbable to resin. In addition, it relates to a method of manufacturing a composition, a curable composition, a cured film, an optical filter, a solid-state imaging element, an infrared sensor, a camera module, and materials.

In recent years, due to the popularization of digital cameras and mobile phones with cameras, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key components of displays and optical components.

In addition, since these solid-state imaging elements use silicon photodiodes that are sensitive to near-infrared rays in their light-receiving parts, an infrared cut filter is sometimes used for visibility correction.

Sometimes a color filter or infrared cut filter is made using a composition containing a pigment.

Patent Document 1 describes the following: kneaded containing diketopyrrolopyrrole pigment (A), pigment derivative (B), water-soluble inorganic salt (C) and substantially insoluble After the mixture of the water-soluble inorganic salt (C) and the water-soluble organic solvent (D), the water-soluble inorganic salt (C) and the water-soluble organic solvent (D) are removed to produce the color filter pigment. In Patent Document 1, a color filter is manufactured using a coloring composition obtained by dispersing the pigment in a transparent resin.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1]: Japanese Patent Application Publication No. 2001-220520

The pigment may be used after being dispersed in a resin or a solvent. However, if the pigment itself has low adsorbability to the resin, the dispersibility of the pigment in the composition tends to decrease. According to research conducted by the inventors, the color filter pigment obtained by the method described in Patent Document 1 is manufactured by mixing diketopyrrolopyrrole pigments and pigment derivatives, but the color filter pigment is diketone The adhesion of the pyrrolopyrrole pigment to the pigment derivative is poor and the pigment derivative is easily peeled off from the diketopyrrolopyrrole pigment. In addition, it has been found that the color filter pigment described in Patent Document 1 has low adsorptivity to resin, and the dispersibility of the pigment in the composition is insufficient.

Therefore, the object of the present invention is to provide a material containing a pigment and having excellent dispersibility of the pigment in the composition. In addition, there is provided a composition, a curable composition, a cured film, an optical filter, a solid-state imaging element, an infrared sensor, a camera module, and a material manufacturing method with excellent pigment dispersibility.

The inventors of the present invention have conducted in-depth research and found that in the presence of a compound having a structure that is adsorbable to the resin, the raw material compound of the pigment is reacted to synthesize the pigment. As a result, the pigment A and the resin having an adsorbent structure can be obtained. The compound B of the sexual structure is a material that is firmly adsorbed. Although the detailed mechanism for obtaining the material in which the compound B is firmly attached to the pigment A is unknown, it is inferred that pigment A is synthesized by reacting the raw material compound of the pigment A in the presence of the above-mentioned compound B, and the compound B is absorbed into the pigment A In the inside of the particles, the compound B is physically and firmly attached to the pigment A material. In addition, as a result of further research on the material produced by this method, it was found that in ^{the material in which X 1} represented by the formula (I) described below is 0.99 or more, the dispersibility of the pigment A in the composition is good, thereby completing the present invention invention. The present invention provides the following.

<1> A material comprising a pigment A and a compound B having a structure that is adsorbable to resin, and X ¹ represented by the following formula (I) is 0.99 or more, wherein X ¹ (X ² /X ³ )× 100...(I)

X ² is the mass of compound B in the material after the material is immersed in a solvent with 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 X ³ is the mass of compound B after immersing in the above solvent The quality of the solid content of the material.

<2> The material according to <1>, wherein the pigment A has absorption in the near infrared region.

<3> The material as described in <1> or <2>, wherein the maximum absorption wavelength of pigment A is in the range of 700 to 1200 nm.

<4> The material according to any one of <1> to <3>, wherein the pigment A is selected from a phthalocyanine compound, a naphthalocyanine compound, a perylene compound, a pyrrolopyrrole compound, One or more of cyanine compounds, dithiol metal complexes, naphthoquinone compounds, iminium compounds, azo compounds, and squaraine ylide compounds.

<5> The material according to any one of <1> to <4>, wherein the pigment A is a pyrrolopyrrole compound.

<6> The material as described in <5>, 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, R ² and R ³ may be bonded to each other to form a ring, R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, and R ⁴ may be covalently bonded to at least one selected from R ^1a , R ^1b and R ^{3 or} Coordination bonding, R ^4A and R ^4B each independently represent a substituent.

<7> The material according to any one of <1> to <6>, wherein the compound B has a dye structure.

<8> The material according to <7>, wherein the pigment structure is selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, and bianthraquinone pigment structure , Benzoisoindole pigment structure, thiazide indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, peruranone Pigment structure, benzimid At least one of oxazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure, and benzoxazole pigment structure.

<9> The material according to any one of <1> to <8>, wherein the compound B has an acidic group, a basic group, a hydrogen bonding group, a dipole interaction group, and a π-π At least one of the interaction groups.

<10> A composition comprising the material described in any one of <1> to <9>.

<11> The composition according to <10>, which further contains one or more selected from organic solvents, resins, and pigment derivatives.

<12> A curable composition comprising the composition described in <10> or <11> and a curable compound.

<13> A cured film using the curable composition described in <12>.

<14> An optical filter having the cured film described in <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> The optical filter according to <14> or <15>, which has: pixels of the hardened film according to <13>; and selected from red, green, blue, magenta, yellow, cyan, black, and colorless At least one type of pixel.

<17> A solid-state imaging device having the cured film described in <13>.

<18> An infrared sensor having the cured film described in <13>.

<19> A camera module having a solid-state imaging element and the aforementioned <13> The hardened film.

<20> A method of manufacturing a material comprising pigment A and a compound B having an adsorbent structure to the resin, wherein when the pigment A is synthesized, there is a compound B having an adsorbent structure to the resin , The raw material compound of pigment A reacts to synthesize pigment A.

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 is possible to provide a composition, a curable composition, a cured film, an infrared cut filter, a solid-state imaging element, an infrared sensor, a camera module, and a material manufacturing method with excellent pigment dispersibility.

100: infrared sensor

110: solid-state image sensor

111: Infrared cut filter

112: Color filter

113: Infrared transmission filter

114: area

115: Micro lens

116: Planarization layer

Fig. 1 is a schematic cross-sectional view showing the structure of an embodiment of the infrared sensor of the present invention.

Hereinafter, the content of the present invention will be described in detail. In addition, in this manual, "~" is used to include the numerical values described before and after it as the lower limit and the upper limit.

In this manual, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means both or either of "acrylic" and "methacrylic" The square "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".

In the label of a group (atomic group) in this specification, the label which does not describe a substitution and an unsubstituted includes the thing which does not have a substituent, and the thing which has a substituent is included. For example, "alkane "Group" includes not only an unsubstituted alkyl group (unsubstituted alkyl), but also a substituted alkyl group (substituted alkyl).

In this 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 the wavelength range of 700 to 2500 nm. In addition, near-infrared rays refer to light (electromagnetic waves) having a wavelength range 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 components of the composition.

In this specification, the solid content refers to the solid content at 25°C.

In this specification, the weight average molecular weight is defined as a polystyrene conversion value measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and using TSKgel Super AWM-H (TOSOH CORPORATION) as the column. Manufactured, 6.0 mm (inner diameter) × 15.0 cm), and a 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution was used as a washing solution.

In this specification, a pigment means an insoluble compound that is not easily soluble in a specific solvent. Typically, it means a compound that exists in a state of being dispersed into particles in the composition. Among them, the solvent includes, for example, the solvents exemplified in the column of solvents described later. The pigment used in the present invention preferably has a solubility of 0.02% by mass or less with respect to propylene glycol monomethyl ether acetate at 25°C, for example.

<material>

The material of the present invention is a material containing a pigment A and a compound B having a structure that is adsorbable to 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 the mass of compound B in the material after the material is immersed in a solvent with 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 X ³ is the mass of compound B after immersing in the above solvent The quality of the solid content of the material.

In the material of the present invention, the above-mentioned compound B firmly adheres to the pigment A, and the pigment A has excellent adsorbability to the resin. Therefore, the dispersibility of the pigment in the composition can be improved.

In addition, in the material of the present invention, the pigment A and the compound B exist as independent compounds. Among them, "pigment A and compound B exist as independent compounds" means that the pigment A exists outside the molecule of compound B, and the two are not bonded by covalent bonding. That is, the material of the present invention is different from a compound (for example, a pigment derivative) in which a resin-adsorbent group is introduced into a part of a pigment molecule.

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 the 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 more 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. If the content of compound B is in the above range, the pigment in the composition The dispersibility is particularly excellent. In addition, in the material of the present invention, the compound B preferably contains 1 to 150 parts by mass relative to 100 parts by mass of the pigment A. 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.

Regarding the content of compound B in the material, the amount of compound B contained in the liquid discharged during the manufacture of the material can be measured by high performance liquid chromatography (HPLC), and the amount of compound B remaining in the material can be calculated and obtained . In addition, it can also be quantitatively calculated by infrared spectroscopy (IR) and other methods.

In the material of the present invention, X ¹ (content of compound B in the material after solvent immersion) represented by the above formula (I) is 0.99 or more, preferably 3 or more, and particularly preferably 5 or more. The upper limit can be set to 70 or less, for example, 60 or less, or 50 or less. When X ¹ is 0.99 or more, the compound B is firmly attached to the pigment A, and the pigment has excellent adsorbability to the resin. Therefore, the dispersibility of the pigment in the composition can be improved.

X ^{1 is} calculated ^{using X 2} and X ³ measured as follows, for example.

^{The mass X 3} of the solid content of the material after the solvent immersion can be obtained by removing the solvent adhering to the material from the material after immersion in the solvent by a method such as drying, and then measuring the mass. In addition, the mass at the point when the weight loss rate of the material after solvent immersion is saturated (the mass at the point when the weight loss rate is approximately constant) can also be measured and determined by thermal analysis TGA (differential thermal analysis). As a measuring device, for example, a thermogravimetric measuring device Q500 model (TA Instruments Japan Inc.) etc. can be mentioned.

Regarding the mass of compound B in the material after solvent immersion, that is, X ² , the amount of compound B contained in the liquid discharged after washing the material with the solvent can be measured as the amount of compound B remaining in the material by high performance liquid chromatography (HPLC) Calculate the amount of compound B in the material. In addition, it is also possible to quantitatively calculate the material before and after solvent immersion by infrared spectroscopy (IR) and other methods.

The solvent is not particularly limited as long as it satisfies the requirements 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, an organic solvent which can contain the composition mentioned later, etc. are mentioned. Specific examples include methanol, ethanol, tetrahydrofuran, acetone, and the like. As the above-mentioned immersion method, a method of adding 16.6 mL of a solvent to 1 g of a sample, heating and refluxing for 30 minutes, and then performing filtration treatment can be mentioned.

Hereinafter, the material of the present invention will be described.

<<Pigment A>>

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

The color pigment is not particularly limited, and a compound having absorption in the visible region (preferably in the range of 400 to 700 nm in wavelength, more preferably in the range of 400 to 650 nm) can be mentioned. For example, a diketopyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, an azo compound, an isoindoline compound, a quinophthalone compound, a benzimidazolone compound, a purpurone compound, etc. are mentioned. As a specific example of a color pigment, the following can be mentioned.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 etc.

CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 Wait

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279

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 a 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 pigment. There are many near-infrared absorbing dyes whose dispersibility in the composition tends to decrease, and it is desired to further improve the dispersibility, and it is easy to obtain the effects of the present invention particularly notably.

Examples of near-infrared absorbing dyes include phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complexes, naphthoquinone compounds, iminium compounds, and azo compounds As well as squaraine ylide compounds, etc., phthalocyanine compounds, naphthalocyanine compounds, pyrrolopyrrole compounds, cyanine compounds, and squaraine ylide compounds are preferred, and pyrrolopyrrole compounds are more preferred. The pyrrolopyrrole compound is preferably a boron pyrrolopyrrole compound. The pyrrolopyrrole compound is excellent in near-infrared absorption and invisibility, so it is easy to obtain a cured film such as an infrared cut filter having excellent near-infrared shielding properties and visible transmittance. In addition, the pyrrolopyrrole compound is a pigment with low dispersibility in the composition. 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 easily obtained more significantly. As the pyrrolopyrrole compound, for example, the compounds described in paragraph numbers 0016 to 0058 of JP 2009-263614 A, etc. can be cited. As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squaraine compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 can be used. This content Included in this manual. In addition, cyanine compounds can be referred to, for example, "Functional Pigments, Ogawara Nobuyuki/Matsuoka Ken/ Kitao Tejiro/Hirashima Hengliang‧ Works, Kodansha Ltd.", this content is incorporated into this manual.

(Pyrrolopyrrole compound (compound with pyrrolopyrrole structure))

In the present invention, the pyrrolopyrrole compound is preferably a compound represented by formula (1). This compound is excellent in near-infrared absorption 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, R ² and R ³ may be bonded to each other to form a ring, R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, and R ⁴ may be covalently bonded to at least one selected from R ^1a , R ^1b and R ^{3 or} Coordination bonding, R ^4A and R ^4B each independently represent a substituent.

In formula (1), R ^1a and R ^1b each independently represent an alkyl group, an aryl group, or a heteroaryl group, and an aryl group or a heteroaryl group is preferable, and an aryl group is more preferable.

The ^{number of carbon atoms of the alkyl group represented by R 1a} and R ^1b is preferably 1-30, more preferably 1-20, and particularly preferably 1-10.

The ^{number of carbon atoms of the aryl group represented by R 1a} and R ^1b is preferably 6-30, more preferably 6-20, and particularly preferably 6-12.

The number of carbon atoms constituting ^{the heteroaryl group represented by R 1a} and R ^1b is preferably 1-30, and more preferably 1-12. Examples of the types of heteroatoms constituting the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 are preferred, and 1 to 2 are more preferred. The heteroaryl group is preferably a single ring or a condensed ring, a single ring or a condensed ring with a condensation number of 2 to 8 is more preferred, and a single ring or a condensed ring with a condensation number of 2 to 4 is even more preferred.

The above-mentioned alkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted. It is preferable to have a substituent. As a substituent, the group mentioned in the substituent T mentioned later can be mentioned. Among them, alkoxy and hydroxyl are preferred. The alkoxy group is preferably an alkoxy group having a branched alkyl group. As the group represented by R ^1a and R ^1b , an aryl group having an alkoxy group having a branched alkyl group as a substituent or an aryl group having a hydroxyl group as a substituent is preferable. The number of carbon atoms of the branched alkyl group is preferably 3-30, more preferably 3-20.

^{R 1a} and R ^1b in formula (1) may be the same or different.

R ² and R ³ each independently represent a hydrogen atom or a substituent. R ² and R ³ may be bonded to form a ring. At least one of R ² and R ³ is preferably an electron withdrawing group. Preferably, R ² and R ³ each independently represent a cyano group or a heteroaryl group.

Examples of the substituent include the substituents described in paragraph numbers 0020 to 0022 of JP 2009-263614 A. The above content is included in this manual.

As an example of the substituent, the following substituent T can be given as an example.

(Substituent T)

Alkyl (preferably substituted or unsubstituted alkyl having 1 to 30 carbon atoms), alkenyl (preferably substituted or unsubstituted alkenyl having 2 to 30 carbon atoms), alkynyl (preferably A substituted or unsubstituted alkynyl group with 2 to 30 carbon atoms), an aryl group (preferably a substituted or unsubstituted aryl group with 6 to 30 carbon atoms), an amino group (preferably a substituted or unsubstituted aryl group with carbon atoms of 0 to 30 The substituted or unsubstituted amine group), alkoxy (preferably substituted or unsubstituted with 1 to 30 carbon atoms) Unsubstituted alkoxy), aryloxy (preferably substituted or unsubstituted aryloxy with 6 to 30 carbon atoms), heteroaryloxy (preferably substituted or unsubstituted with 1 to 30 carbon atoms) (Substituted heteroaryloxy), acyl (preferably substituted or unsubstituted with 1 to 30 carbon atoms), alkoxycarbonyl (preferably substituted or unsubstituted with 2 to 30 carbon atoms) Oxycarbonyl), aryloxycarbonyl (preferably substituted or unsubstituted aryloxycarbonyl with 7 to 30 carbon atoms), acyloxy (preferably substituted or unsubstituted with 2 to 30 carbon atoms) ), amide group (preferably substituted or unsubstituted amide group with 2 to 30 carbon atoms), alkoxycarbonyl amine group (preferably substituted or unsubstituted alkoxy group with 2 to 30 carbon atoms) Carbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonylamino group with 7 to 30 carbon atoms), sulfasulfonyl group (preferably with 0 to 30 carbon atoms) The substituted or unsubstituted sulfamoyl group), the carbamoyl group (preferably a substituted or unsubstituted carbamoyl group with 1 to 30 carbon atoms), and an alkylthio group (preferably with 1 to 30 carbon atoms) 30 substituted or unsubstituted alkylthio), arylthio (preferably substituted or unsubstituted arylthio with 6 to 30 carbon atoms), heteroarylthio (preferably 1 to 30 carbon atoms) Substituted or unsubstituted heteroarylthio), alkylsulfonyl (preferably substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms), arylsulfonyl (preferably carbon A substituted or unsubstituted arylsulfonyl group with 6 to 30 atoms), a heteroarylsulfonyl group (preferably a substituted or unsubstituted heteroarylsulfonyl group with 1 to 30 carbon atoms), an alkyl group Sulfinyl (preferably substituted or unsubstituted alkylsulfinyl with 1 to 30 carbon atoms), arylsulfinyl (preferably substituted or unsubstituted with 6 to 30 carbon atoms) Arylsulfinyl), heteroarylsulfinyl (preferably substituted or unsubstituted heteroarylsulfinyl having 1 to 30 carbon atoms), ureido (preferably carbon atom number 1 ~30 substituted or unsubstituted ureido groups), amide phosphate Group (preferably a substituted or unsubstituted phosphoamido group having 1 to 30 carbon atoms), hydroxyl group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfinyl group, A hydrazine group, an imino group, and a heteroaryl group (preferably having 1 to 30 carbon atoms). In the carboxyl group, the hydrogen atom can be dissociated, or it can be in the form of a salt. In addition, in the sulfo group, the hydrogen atom may be dissociated, or it may be in the form of a salt.

When these groups are groups that can be further substituted, they may have further substituents. Examples of the substituent include the groups described in the above-mentioned substituent T.

At least one of R ² and R ³ is preferably an electron withdrawing group. The substituent whose σp value (sigma palla value) of Hammett is positive functions as an electron withdrawing group.

In the present invention, a substituent having Hammett's 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 it is preferably 0.80.

Specific examples include cyano group (0.66), carboxyl group (-COOH: 0.45), alkoxycarbonyl group (-COOMe: 0.45), aryloxycarbonyl group (-COOPh: 0.44), aminomethanyl group (-CONH ₂ : 0.36), alkylcarbonyl (-COMe: 0.50), arylcarbonyl (-COPh: 0.43), alkylsulfonyl (-SO ₂ Me: 0.72), or arylsulfonyl (-SO ₂ Ph: 0.68) etc. Especially preferred is cyano. Here, Me represents a methyl group, and Ph represents a phenyl group.

Regarding the value of the Hammett substituent constant σ, for example, paragraphs 0017 to 0018 of JP 2011-68731 A can be referred to, and this content is incorporated in this specification.

When R ² and R ³ are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered ring (preferably a 5- or 6-membered ring). The ring formed is usually used as an acidic nucleus in merocyanine pigments. As a specific example, refer to paragraphs 0019 to 0021 of Japanese Patent Application Publication No. 2011-68731, which are incorporated in this specification. .

R ³ is particularly preferably heteroaryl. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. In addition, the heteroaryl group is preferably a single ring or a condensed ring, a single ring or a condensed ring having a condensation number of 2 to 8 is more preferred, and a single ring or a condensed ring having a condensation number of 2 to 4 is more preferred. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom can be illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. The number of carbon atoms constituting the heteroaryl group is preferably 1-30, more preferably 1-12. Specific examples of heteroaryl groups include, for example, imidazolyl, pyridyl, pyrazyl, pyrimidinyl, pyridazinyl, triazyl, quinolinyl, quinoxalinyl, and isoquinyl. Linyl, indolenyl, furan, thienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, naphththiazolyl, benzoxazole, m-carbazolyl group, azepinyl group, benzo-condensed group or naphtho-condensed group of these groups, etc. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the above-mentioned substituent T. For example, an alkyl group, an alkoxy group, a halogen atom, etc. can be mentioned.

^{The two R 2} in the formula (1) may be the same or different, and the two R ³ may be the same or different.

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

When R ⁴ represents -BR ^4A R ^4B , R ^4A and R ^4B each independently represent a substituent. Examples of the substituent represented by R ^4A and R ^4B include the aforementioned substituent T. A halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group is preferred, and an alkyl group, an aryl group or a heteroaryl group is more preferred. Best, aryl is particularly good. Specific examples of the group represented by -BR ^4A R ^4B include boron difluoro, biphenyl boron, dibutyl boron, dinaphthyl boron, and catechol boron. Among them, biphenylboron is particularly preferred.

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

R ⁴ may be covalently bonded or coordinately bonded to at least one of ^{R 1a} , R ^1b and R ^{3 , and R 4} and R ^{3 are} particularly preferably coordinately bonded. R ⁴ is preferably a hydrogen atom or a ^{group represented by -BR 4A} R ^4B (especially biphenylboron). ^{Two R 4} in the formula (1) may be the same or different.

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

In the formula, R ¹⁰ each 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 coordinately bonded ^{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 be bonded to form a ring. R ¹³ each independently represents a hydrogen atom or a branched alkyl group having 3 to 30 carbon atoms.

The meaning of R ^{10 is the same as that of R 4} described in the above formula (1), and the preferred range is also the same. A hydrogen atom or a group (especially boron biphenyl) and indicated with -BR ^14A R ^14B is preferred, in the group represented -BR ^14A R ^14B is particularly preferred.

The meanings of R ¹¹ and R ^{12 are the same as R 2} and R ³ described in (1) above, and the preferred ranges are also the same. It is ^{more preferable that any one of R 11} and R ¹² is a cyano group and the other is a heteroaryl group.

The meanings of R ^14A and R ^{14B are the same as R 4A} and R ^4B described in (1) above, and the preferred ranges are also the same.

R ¹³ each independently represents a hydrogen atom or a branched alkyl group having 3 to 30 carbon atoms. The number of carbon atoms of the branched alkyl group is more preferably 3-20.

As specific examples of the compound represented by formula (1), the following compounds can be given. In addition, for example, paragraphs 0037 to 0052 of JP 2011-68731 A (corresponding to <0070> of the specification of U.S. Patent Application Publication No. 2011/0070407) can be referred to, and this content is incorporated in this specification. In the following structural formulae, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

【Chemical formula 4】

【Table 1】

【Table 2】

Ar-1~Ar-4 and R-1~R-7 in the above table are as follows. The "*" in the structure shown below represents a bonding key.

【Chemical formula 5】

(Squaraine ylide compound (compound with squaraine ylide structure))

In the present invention, the squaraine ylide compound is preferably a compound represented by formula (11). This compound is excellent in near-infrared absorption 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 the formula (12), Z ¹ represents a non-metal atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and the wave line represents a bond with the formula (11).

^{A 1} and A ² in the formula (11) each independently represent an aryl group, a heteroaryl group, or a group represented by the formula (12), and a group represented by the formula (12) is preferred.

The ^{number of carbon atoms of the aryl group represented by A 1} and A ² is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. As a specific example, a phenyl group, a naphthyl group, etc. are mentioned. In addition, when the aryl group has a substituent, the number of carbon atoms of the aryl group means the number excluding the number of carbon atoms of the substituent.

As ^{the heteroaryl group represented by A 1} and A ² , a 5-membered ring or a 6-membered ring is preferable. In addition, the heteroaryl group is preferably a single ring or a condensed ring. A single ring or a condensed ring with a condensation number of 2 to 8 is more preferred. A single ring or a condensed ring with a condensation number of 2 to 4 is more preferred. Or a condensed ring with a condensation number of 2 or 3 is particularly preferred. As the hetero atom constituting the heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom can be exemplified, and a nitrogen atom and a sulfur atom are preferable. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Specifically, a heteroaryl group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered ring or a 6-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned.

The aryl group and heteroaryl group may have a substituent. As a substituent, the substituent T demonstrated in the said pyrrolopyrrole compound is mentioned.

The substituent which the aryl group and heteroaryl group may have is preferably a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an amido group.

The halogen atom is preferably a chlorine atom.

The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 5, and most preferably from 1 to 4. The alkyl group is preferably straight or branched.

The amino group is preferably a group represented ^{by -NR 100} R ^101. R100 and R101 each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 8. The alkyl group is straight chain, preferably branched, and more preferably straight chain.

The amide group is preferably a group represented by -NR ¹⁰² -C(=O)-R ¹⁰³ . R ¹⁰² represents a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. R ¹⁰³ represents an alkyl group. The ^{number of carbon atoms of the alkyl group represented by R 102} and R ¹⁰³ is preferably from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 4.

When the aryl group and the heteroaryl group have two or more substituents, the plural substituents may be the same or different.

Next, the group represented by the formula (12) represented by ^{A 1} and A ^{2 will be explained.}

In formula (12), R ² represents an alkyl group, an alkenyl group or an aralkyl group, and an alkyl group is preferred.

The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, more preferably from 1 to 12, and particularly preferably from 2 to 8.

The number of carbon atoms of the alkenyl group is preferably 2-30, more preferably 2-20, and still more preferably 2-12.

The alkyl group and the alkenyl group may be any of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the aralkyl group is preferably 7-30, more preferably 7-20.

In the formula (12), as ^{the nitrogen-containing heterocyclic ring formed by Z 1} , a 5-membered ring or a 6-membered ring is preferable. In addition, the nitrogen-containing heterocyclic ring is preferably a single ring or a condensed ring. A single ring or a condensed ring with a condensation number of 2 to 8 is more preferred. A single ring or a condensed ring with a condensation number of 2 to 4 is even more preferred. Condensed rings with a number of 2 or 3 are particularly preferred. In addition to nitrogen atoms, nitrogen-containing heterocycles may also contain sulfur atoms. In addition, the nitrogen-containing heterocyclic ring may have a substituent. Examples of the substituent include the groups described in the above-mentioned substituent T. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an amide group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, and still more preferably 1-12. The alkyl group is preferably straight or branched.

The group represented by the formula (12) is preferably a group represented by the following formula (13) or 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 can be connected to each other to form a ring, and X represents a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, m represents an integer from 0 to 4, and the wave line represents a bond with formula (11).

^{The meaning of R 11} in formula (13) and formula (14) is the ^{same as that of R 2} in formula (12), and the preferred range is also the same.

^{R 12 in} formula (13) and formula (14) represents a substituent. Examples of the substituent include the groups described in the above-mentioned substituent T. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an amide group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, and still more preferably 1-12. The alkyl group is preferably straight or branched.

When m is 2 or more, R ¹² may be connected to each other to form a ring. Examples of the ring include aliphatic rings (non-aromatic hydrocarbon rings), aromatic rings, heterocyclic rings, and the like. The ring can be a single ring or multiple rings. As the linking group when the substituents are linked to each other to form a ring, it can be selected from -CO-, -O-, -NH-, divalent aliphatic groups, divalent aromatic groups, and combinations of these The group's 2-valent link base link. For example, R ¹² is preferably connected to each other to form a benzene ring.

X in the 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 in the above-mentioned substituent T. For example, an alkyl group etc. can be mentioned. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, and 1 is the most preferred. The alkyl group is preferably straight or branched, and straight chain is particularly preferred.

m represents an integer of 0 to 4, preferably 0 to 2.

In addition, the cation in the formula (11) exists in a non-localized manner as follows.

【Chemical formula 9】

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

Rings A and B each independently represent an aromatic ring or a heteroaromatic ring, X ^A and X ^B each independently represent a substituent group, G ^A and G ^B independently represents a substituent group, kA represents an integer of 0 ~ n _A a, kB Represents an integer from 0 to n _{B , n A} and n _B respectively represent the largest integer that can be substituted for ring A or ring B. X ^A and G ^A , X ^B and G ^B can be bonded to each other to form a ring, G ^A and G ^When there are plural B respectively, they can be bonded to each other to form a ring structure.

G ^A and G ^B independently represents a substituent group. Examples of the substituent include halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , and -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 . R ¹⁰ to R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. In addition, when R ^{12 of -COOR 12} is hydrogen (that is, a carboxyl group), the hydrogen atom may be dissociated, or it may be in the form of a salt. In addition, when R ²⁴ _{of -SO 2} OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated, or it may be in the form of a salt.

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

The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1-8. The alkyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the alkenyl group is preferably 2-20, more preferably 2-12, and particularly preferably 2-8. The alkenyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the alkynyl group is preferably 2-40, more preferably 2-30, and particularly preferably 2-25. The alkynyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12.

The alkyl part of the aralkyl group is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group is the same as the above-mentioned aryl group. The number of carbon atoms of the aralkyl group is preferably 7-40, more preferably 7-30, and even more preferably 7-25.

The heteroaryl group is preferably a single ring or a condensed ring, a single ring or a condensed ring with a condensation number of 2 to 8 is more preferred, and a single ring or a condensed ring with a condensation number of 2 to 4 is even more preferred. 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. The number of carbon atoms constituting the heteroaryl ring is preferably 3-30, more preferably 3-18, 3-12 is 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. As a substituent, the group demonstrated in the above-mentioned substituent T group is mentioned.

X ^A and X ^B each independently represent a substituent. The substituent is preferably a group with active hydrogen, -OH, -SH, -COOH, -SO3H, -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 preferred, and -OH, -SH and -NR ^X1 R ^X2 are further preferred.

R ^X1 and R ^X2 each independently represent a hydrogen atom or a substituent. As a substituent, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group can be mentioned. Alkyl is preferred. The alkyl group is preferably straight or branched. For details on the alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group, and the description of G ^A and G ^B in the same range of meaning.

(chrysene)環、聯伸三苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑 環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪(quinolizine)環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹噁唑啉(quinoxazoline)環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉(phenanthroline)環、噻嗯環、苯并哌喃(chromene)環、呫噸(xanthene)環、啡噁噻(phenoxathiine)環、啡噻嗪環及啡嗪(phenazine)環，苯環或萘環為較佳。 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 aromatic rings and heteroaromatic rings include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, and indecene ring. , Perylene ring, fused pentabenzene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

(chrysene) ring, biphenyl ring, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxa Quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thien ring, chromene ring, xanthene ring , Phenoxathiine ring, phenothiazine ring and phenazine ring, benzene ring or naphthalene ring is preferred.

The aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include G ^A and G ^B described in the substituent group.

X ^A and G ^A , X ^B and G ^B may be bonded to each other to form a ring, ^{and when there are plural G A} and G ^B , they may be bonded to each other to form a ring. As the ring, a 5-membered ring or a 6-membered ring is preferable. The ring can be a single ring or multiple rings.

When X ^A and G ^A , X ^B and G ^B , G ^A or G ^B are bonded to each other to form a ring, these may be directly bonded to form a ring, or may be selected from alkylene, -CO-,- The divalent linking group of the group constituted by O-, -NH-, -BR- and the combination thereof is bonded to form a ring. X ^A and G ^A, X ^B and G ^B, G ^A or G ^B to each other to form a ring is preferably bonded via a -BR-.

R represents a hydrogen atom or a substituent. Examples of the substituent include G ^A and G ^B described in the substituent group. Alkyl or aryl is preferred.

kA represents an integer from 0 to nA, kB represents an integer from 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 independently 0~4, preferably 0~2, 0~1 especially Better.

As specific examples of the compound represented by formula (11), the compounds described below may be mentioned, but are not limited to these.

【Chemical formula 12】

(Cyanine compounds (compounds with cyanine structure))

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

Formula (A)【Chemical formula 13】

In formula (A), Z ¹ and Z ² are each independently a non-metallic atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring of a condensable ring, and R ¹ and R ² each independently represent an alkyl group, an alkenyl group, Alkynyl, aralkyl, or aryl, L ¹ represents a methine chain with an odd number of methine groups, a and b are each independently 0 or 1, and when the part represented by Cy in the formula is a cation part, X ¹ represents an anion, and c represents a number required to balance the charge. When the part represented by Cy in the formula is an anion part, X ¹ represents a cation, and c represents a number required to balance the charge, where When the charge of the part represented by Cy is neutralized in the molecule, c is 0.

In the formula (A), Z ¹ and Z ² each independently represent a non-metallic atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring of a condensable ring.

In the nitrogen-containing heterocyclic ring, other heterocyclic rings, aromatic rings or aliphatic rings may be condensed. The nitrogen-containing heterocyclic ring is preferably a 5-membered ring. It is more preferable that the 5-membered nitrogen-containing heterocyclic ring is condensed with a benzene ring or a naphthalene ring. Specific examples of nitrogen-containing heterocycles include oxazole ring, isoxazole ring, benzoxazole ring, naphthoxazole ring, oxazocarbazole ring, oxazolodibenzofuran ring, and thiazole ring. Ring, benzothiazole ring, naphthiazole ring, indole ring, benzoindole ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furan Pyrrole ring, indazine ring, imidazoquinoxaline ring, quinoxaline ring, etc., quinoline ring, indole ring, benzoindole ring, benzoxazole ring, benzothiazole ring, benzo Imidazole ring is more Preferably, an indole ring, a benzothiazole ring, and a benzimidazole ring are particularly preferred.

The nitrogen-containing heterocyclic ring and the ring condensed therein may have a substituent. Examples of the substituent include G ^A and G ^B of the formula (15) described in the substituent group. Specifically, halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , and -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 . R ¹⁰ to R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. In addition, when R ^{12 of -COOR 12} is hydrogen (that is, a carboxyl group), the hydrogen atom may be dissociated, or it may be in the form of a salt. In addition, when R ²⁴ _{of -SO 2} OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated, or it may be in the form of a salt. The detailed meaning of these is the same as the above range.

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 T group. A halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amine group, etc. are preferred, a carboxyl group and a sulfo group are more preferred, and a sulfo group is more preferred. Especially good. In the carboxyl group and sulfo group, the hydrogen atom can be dissociated, or it can be in the form of a salt.

In formula (A), R ¹ and R ² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group.

The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1-8. The alkyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the alkenyl group is preferably 2-20, more preferably 2-12, especially 2-8 good. The alkenyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the alkynyl group is preferably 2-40, more preferably 2-30, and particularly preferably 2-25. The alkynyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred.

The number of carbon atoms of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12.

The alkyl part of the aralkyl group is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group is the same as the above-mentioned aryl group. The number of carbon atoms of the aralkyl group is preferably 7-40, more preferably 7-30, and even more preferably 7-25.

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 hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amino group, etc., a carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. In the carboxyl group and sulfo group, the hydrogen atom can be dissociated, or it can be in the form of a salt.

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 (middle) methine group. Specific examples of the substituent include ^{substituents that the nitrogen-containing heterocycle of Z 1} and Z ² may have, and groups represented by the following formula (a). In addition, the two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.

【Chemical formula 14】

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

a and b are independently 0 or 1, respectively. 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. It is preferable that both a and b are 0. In addition, when both a and b are 0, the formula (A) is expressed as follows.

In the formula (A), when the part represented by Cy in the formula is a cation part, X ¹ represents an anion, and c represents a number required to achieve a balance of charges. Examples of the anion include a halide ion ^{(Cl -, Br -, I} -), p-toluenesulfonic acid ion, an ethylsulfate ion, PF ₆ ^-, BF ₄ ^- or ClO ₄ ^-, tris (haloalkyl sulfonamide acyl) methide anion _{(e.g., (CF 3 SO 2) 3} C -), bis (sulfo-haloalkyl acyl) acyl imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetracyanoborate Salt anions, etc.

In the formula (A), when the part represented by Cy in the formula is an anion part, X ¹ represents a cation, and c represents a number required to achieve a balance of charges. Examples of cations include 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 (Al ³⁺ etc.), ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion , Tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, diazabicyclo undecenium (diazabicyclo undecenium) and so on. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , and diazabicycloundecene are preferred.

In the formula (A), when the charge at the part 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 preferably a compound represented by the following (A-1) or (A-2), and a compound represented by the following (A-2) is more preferred.

In the formula, R ^1A , R ^2A , R ^1B and R ^2B each independently represent an alkyl, alkenyl, alkynyl, aralkyl or aryl group, and L ^1A and L ^1B each independently represent an odd number of methine groups. Methylene chain, 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 alkane Group, V ^1A , V ^2A , V ^1B and V ^2B each independently represent a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a 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 OR ²⁴ , -NHSO ₂ R ²⁵ or -SO ₂ NR ²⁶ R ²⁷ , V ^1A , V ^2A , V ^1B and V ^2B can form a condensed ring, R ¹⁰ ~ R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group when an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, -COOR R ¹² is a hydrogen atom and ¹² -SO ₂ oR ²⁴ when R ²⁴ is a hydrogen atom, a hydrogen atom may be dissociated, it may also be a salt state , M1 and m2 each independently represent 0~4. When the part represented by Cy in the formula is a cation part, X ¹ represents an anion, c represents a number required to achieve a balance of charges, and the formula is represented by Cy when the sites of the anion portion, X ¹ represents a cation, c denotes a number in order to obtain the desired charge balancing, the charge to the formula Cy represents a portion of the molecule is neutralized, c is 0.

The meanings of the groups represented by R ^1A , R ^2A , R ^1B and R ^2B are the same as the alkyl, alkenyl, alkynyl, aralkyl and aryl groups described ^{in R 1} and R ^{2 of formula (A).} The optimal range is also the same. These groups may be unsubstituted or have substituents. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amino group, etc., a carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. In the carboxyl group and sulfo group, the hydrogen atom can be dissociated, or it can be in the form of a salt.

When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, a straight-chain alkyl group is more preferred.

Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 -or -CR ^X2 R ^X3 -, ^{preferably -NR X1} -.

R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferred. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. The alkyl group may be any one of linear, branched, and cyclic, and linear or branched is preferred, and linear is particularly preferred. The alkyl group is particularly preferably a methyl group or an ethyl group.

The meanings of L ^1A and L ^1B are the same as L1 in formula (A), and the preferred ranges are also the same.

The groups represented by V ^1A , V ^2A , V ^1B and V ^2B are the same as those described in the substituents that the nitrogen-containing heterocycle ^{of Z 1} and Z ^{2 of formula (A) may have, and the preferred ranges are also the same.}

m1 and m2 each independently represent 0-4, preferably 0-2.

X X ¹ represented by the anions and cations meaning as in formula (A) is the same as the ^one described range, the preferred range is also the same.

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

【Chemical formula 17】

In the formula, R ^1a and R ^2a each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, and 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 each independently represent a halogen atom, a cyano group, a nitro group, an alkane Group, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, -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 , V ^1a and V ^2a can form a condensed ring , R ¹⁰ ~ R ²⁷ R 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, -COOR ^12, R ¹² is hydrogen and the -SO ₂ oR ^{24 When 24} is a hydrogen atom, the hydrogen atom can be dissociated, or it can be in the state of a salt, and m1 and m2 each independently represent 0~4.

The meanings of the groups represented by R ^1a and R ^{2a are the same as those of R 1} and R ^{2 in the} formula (A-1), and the preferred ranges are also the same. When R ^1a and R ^2a represent an alkyl group, a linear alkyl group is more preferred.

X X the same meaning as in formula (A-1) ^{1 1} and X ² and X ^2, the preferred range is also the same.

The meanings of R ^3a and R ^{4a are the same as the ranges described in the substituents that L 1} described in formula (A) may have, and the preferred ranges are also the same.

The meanings of the groups represented by V ^1a and V ^2a are the same as those described in the nitrogen-containing heterocyclic ring described in formula (A) and the substituents that the ring condensed therein may have, and the preferred ranges are also the same.

m1 and m2 each independently represent 0-4, preferably 0-2.

(Diketopyrrolopyrrole compound (compound with diketopyrrolopyrrole structure))

In the present invention, the diketopyrrolopyrrole compound may be a compound represented by the following formula (DP).

In the formula, R ¹ and R ² each independently represent an alkyl group, an aryl group, and a heteroaryl group.

R ¹ and R ² are preferably aryl or heteroaryl, more preferably aryl.

The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, and particularly preferably 1-10.

The number of carbon atoms of the aryl group is preferably 6-30, more preferably 6-20, and particularly preferably 6-12.

The number of carbon atoms constituting the heteroaryl group is preferably 1-30, more preferably 1-12. Examples of the types of heteroatoms constituting the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 are preferred, and 1 to 2 are more preferred. The heteroaryl group is preferably a single ring or a condensed ring, a single ring or a condensed ring with a condensation number of 2 to 8 is more preferred, and a single ring or a condensed ring with a condensation number of 2 to 4 is even more preferred.

The above-mentioned alkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted. As a substituent, the above-mentioned substituent T can be mentioned. For example, halogen atoms are preferred.

As specific examples of the compound represented by the formula (DP), for example, the compounds shown below can be given.

(Phthalocyanine compound (compound with phthalocyanine structure))

In the present invention, the phthalocyanine compound may be a compound 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 aforementioned substituent T.} For example, a halogen atom, an alkoxy group, an aralkoxy group, a heteroaralkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group can be mentioned, 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 metal compounds include V=O, Ti=O, AlCl, and the like. Preferably, M ¹ is Cu, Zn or Ti=O.

Among the above-mentioned phthalocyanines, ^{compounds in which M 1} is represented by Ti=O (oxo-titanyl phthalpcyanine) have excellent near-infrared absorption.

In addition, among the above-mentioned phthalocyanines, M ¹ is Zn or Cu, and ^{at least one of X 1} to X ^{16 is} a compound represented by a halogen atom (halogen zinc phthalocyanine, halogen copper phthalocyanine). It is preferably used as a green pigment.

(Naphthalocyanine compound (compound with 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 aforementioned substituent T.} For example, a halogen atom, an alkoxy group, an aralkoxy group, a heteroaralkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group can be mentioned, and an alkoxy group is preferable.

As specific examples of the compound represented by the formula (NPC), the compounds shown below can be given.

<<Compound B>>

The material of the present invention includes compound B having a structure that has an adsorbent property to resin. Compound B is preferably a compound having substantially no molecular weight distribution. That is, it is preferable that compound B is a compound other than a polymer. According to this aspect, the molecular weight is smaller than that of the polymer, so the mobility in the solvent is high, and it can exist uniformly in the system. Therefore, it is expected that the effect can be effectively contained in the production of pigments. The molecular weight of compound B is preferably 50-2000, more preferably 100-1500.

In the present invention, the solubility of the compound B with respect to the solvent at 25°C is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. As the solvent, the solvents exemplified in the column of the solvent mentioned later can be mentioned, and preferably one or more selected from methanol, ethanol, tetrahydrofuran, and acetone.

環、三亞苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹噁唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻嗯環、苯并哌喃環、呫噸環、啡噁噻環、啡噻嗪環及啡嗪環，可舉出苯環或萘環等。 Examples of the structure possessed by the compound B that are adsorbable to the resin include an acidic group, a basic group, a hydrogen bonding group, a dipole interaction group, and a π-π interaction group. As an acidic group, a basic group, or the group which has a salt structure, the group demonstrated in the pigment derivative mentioned later can be mentioned. In the present invention, the interaction between dipoles refers to the interaction of polarized molecules with other dipoles, and hydrogen bonding is also one of them. As specific examples other than the hydrogen bond, a nitro group, a perfluoroalkyl group, a perfluoroaryl group, and the like can be given. In the present invention, hydrogen bond refers to a non-covalent bond formed by a covalent bond and a more electronegative atom combined with a hydrogen atom and nearby solitary electron pairs such as nitrogen, oxygen, sulfur, fluorine, and π electron systems. Valence of gravitational interaction. The hydrogen-bonding group in the present invention refers to a substituent having at least one of the above-mentioned hydrogen atom or lone electron pair, such as an amino group, an alcohol group, a phenol group, a carboxyl group, and the like. In the present invention, π-π interaction refers to the dispersion force acting between the aromatic rings of organic compound molecules, which is also called stacking interaction. For example, aromatic compounds have a solid planar structure, and there are abundant electrons that are not localized by the π-electron system, so the London dispersion force is particularly strong. Therefore, the more π electrons increase, the stronger the mutual attraction force. Examples of the π-π interaction group include aromatic rings and heteroaromatic rings. Specific examples include benzene ring, naphthalene ring, pentacyclopentadiene ring, indene ring, azulene ring, heptene ring, decene ring, perylene ring, fused pentabenzene ring, ethane naphthalene ring, phenanthrene ring Ring, anthracene ring, fused tetraphenyl ring,

Ring, triphenylene ring, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indazine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline Ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiamine ring, benzopyran ring, xanthene ring, phenoxathi ring, phenanthrazine ring and phenanthrazine ring, including benzene Ring or naphthalene ring, etc.

The compound B preferably has one or more selected from the group consisting of a dye structure, a heterocyclic structure, and a non-cyclic heteroatom-containing group, and it is more preferable to have at least a dye structure. Since the compound B has these structures, it is easy to contain the compound B in the particles of the pigment A, and it is easy to obtain a material to which the pigment A and the compound B adhere firmly.

Examples of the pigment structure include pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, bianthraquinone pigment structure, benzisoindole pigment structure, thiazide indigo Pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, perylene pigment structure, benzimidazolone pigment structure, benzo Thiazole pigment structure, benzimidazole pigment structure, and benzoxazole pigment structure are preferred examples.

As the heterocyclic structure, thiophene, furan, xanthene, pyrrole, pyrophosphorus, Pyrrolidine, dioxolane, pyrazole, pyrazoline, Pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxy Heterocyclic ethane, mopholine, pyridazine, pyrimidine, piperazine, triazine, trithia, isoindoline, isoindolinone, benzimidazolone, benzimidazole, benzothiazole, butadiene Imine, phthalimide, naphthalene phthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridinone, and anthraquinone are preferred examples.

Examples of the acyclic heteroatom-containing group include a group having a nitrogen atom, and preferable examples include a ureido group, an imino group, an amide group, and a sulfonamide group. As the ureido group, -NR ¹⁰⁰ CONR ¹⁰¹ R ¹⁰² can be mentioned. R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² may each independently include a hydrogen atom, an alkyl group, or an aryl group. The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20. The alkyl group may be any of linear, branched, and cyclic. The number of carbon atoms of the aryl group is preferably 6-30, more preferably 6-20. 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 contained in the particles of the pigment A, and it is easy to obtain a material in which the compound B is firmly attached to the pigment A. As the pigment derivative, a compound having a structure in which a part of the pigment is substituted by an acidic group, a basic group, or a phthaliminomethyl group is preferred, and a pigment derivative represented by formula (B1) is more preferred. In the pigment derivative represented by the formula (B1), the pigment structure P is easily adsorbed on the surface of the pigment A, and therefore the dispersibility of the pigment A in the composition can be improved. In addition, when the composition contains a resin, the end portion X of the pigment derivative is adsorbed to the resin due to the interaction with the adsorption portion (polar group etc.) of the resin, so the dispersibility of the pigment A can be further improved.

In the formula, P represents a pigment structure, L represents a single bond or a linking group, X represents an acidic group, a basic group, a group with a salt structure or a phthalimide group, m represents an integer of 1 or more, and n represents An integer of 1 or more, and 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 the pigment structure, selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, bianthraquinone pigment structure, benzisoindole Pigment structure, thiazide indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, perylene pigment structure, benzimidazole At least one of keto pigment structure, benzothiazole pigment structure, benzimidazole pigment structure and benzoxazole pigment structure is preferably selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone At least one of the pigment structure and the benzimidazolone pigment structure is more preferred, and the pyrrolopyrrole pigment structure is particularly preferred. Since the pigment derivative has these pigment structures, the dispersibility of the pigment A can be further improved.

In the formula (B1), L represents a single bond or a linking group.

As the linking group, a group composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms is preferred, and may be without It may be substituted and may further have a substituent. Examples of the substituent include the above-mentioned substituent T, and an alkyl group, an aryl group, a hydroxyl group, or a halogen atom is preferred.

The linking group is an alkylene group, an aryl group, a nitrogen-containing heterocyclic group, -NR'-, -SO ₂ -, -S-, -O-, -CO-, or a group composed of a combination of these. Preferably, an alkylene group, a nitrogen-containing heterocyclic group, -NR'-, -SO ₂ -or a group composed of these are more preferred. R'represents a hydrogen atom, an alkyl group (preferably with 1 to 30 carbon atoms) or an aryl group (preferably with 6 to 30 carbon atoms).

The number of carbon atoms of the alkylene group is preferably 1-30, more preferably 1-15, and still more preferably 1-10. The alkylene group may have a substituent. The alkylene group may be any of linear, branched, and cyclic. In addition, the cyclic alkylene group may be monocyclic or polycyclic.

The number of carbon atoms of the aryl group is preferably 6 to 18, more preferably 6 to 14, more preferably 6 to 10, and particularly preferably phenyl group.

The nitrogen-containing heterocyclic group is preferably a 5-membered ring or a 6-membered ring. In addition, the nitrogen-containing heterocyclic group is preferably a monocyclic ring or a condensed ring, a monocyclic ring or a condensed ring with a condensation number of 2 to 8 is more preferred, and a monocyclic ring or a condensed ring with a condensation number of 2 to 4 is more preferred. The number of nitrogen atoms constituting the nitrogen-containing heterocyclic group is preferably 1 to 3, more preferably 1 to 2. The nitrogen-containing heterocyclic group may contain heteroatoms other than nitrogen atoms. Examples of heteroatoms other than nitrogen atoms include oxygen atoms and sulfur atoms. The number of heteroatoms other than nitrogen atoms is preferably 0 to 3, more preferably 0 to 1.

Examples of nitrogen-containing heterocyclic groups include piperazine ring groups, pyrrolidin ring groups, pyrrol ring groups, piperidin ring groups, pyridine ring groups, imidazole ring groups, pyrazole ring groups, oxazole ring groups, and thiazole ring groups. , Pyrazinyl, mophorin, thiazinyl, indole, isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoline Oxaline ring group, cinnoline ring group, carbazole ring group, and groups represented by formulas (L-1) to (L-7).

【Chemical formula 24】

The * in the formula represents the bond with P, L or X. R represents a hydrogen atom or a substituent. As a substituent, the above-mentioned substituent T can be mentioned.

Specific examples of the linking group include an alkylene group, an arylene group, -SO ₂ -, the group represented by the above (L-1), the group represented by the above (L-5), and the group represented by -O -A group consisting of a combination with an alkylene group, a group consisting of a combination of -NR'- and an alkylene group, a group consisting of a combination of -NR'- and -CO- (-NR'-CO- , -NR'-CO-NR'- etc.), a group consisting of a combination of -NR'-, -CO- and alkylene, and a group consisting of -NR'-, -CO-, alkylene and arylalkylene A group consisting of a combination of -NR'-, -CO- and a combination of an aryl group, a group consisting of a combination of -NR'-, -SO ₂ -and an alkylene group, a group consisting of a combination of- NR'-, -SO ₂ -, a group composed of a combination of an alkylene group and an aryl group, a group composed of a combination of a group represented by the above (L-1) and an alkylene group, a group composed of the above ( L-1) A group consisting of a combination of a group represented by (L-1), _{a combination of -SO 2} -and an alkylene group, a group consisting of a combination of the group represented by (L-1), and a combination of The group represented by (L-1), the group composed of the combination of -S- and the alkylene group, the group composed of the group represented by the above (L-1), the combination of -O- and the alkylene group , A group consisting of the group represented by the above (L-1), a combination of -NR'-, -CO- and an aryl group, a group consisting of the group represented by the above (L-3) and an aryl group Combination of groups, etc.

In the formula (B1), X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide group.

As an acidic group, a carboxyl group, a sulfo group, etc. are mentioned.

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 salt of the above-mentioned acidic group, the salt of the basic group, the group represented by the formula (X-1), and the group represented by (X-2). Examples of the atoms or atomic groups constituting the salt include metal atoms, tetrabutylammonium, and the like. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Examples of alkali metal atoms include lithium, sodium, potassium, and the like. Examples of alkaline earth metal atoms include calcium, magnesium, and the like.

The phthalimino group may be unsubstituted or may have a substituent. As a substituent, the above-mentioned acidic group, a basic group, the group which has a salt structure, etc. are mentioned. In addition, it may be the above-mentioned substituent T. The substituent T may be further substituted by other substituents. As other substituents, a carboxyl group, a sulfo group, etc. can be mentioned.

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

In formulas (X-1) to (X-9), * represents a bond with L of formula (B1), R ¹⁰⁰ to R ¹⁰⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, R ¹⁰⁰ It can be connected with R ¹⁰¹ to form a ring, and M represents an atom or an atom group that forms a salt with an anion.

The alkyl group may be linear, branched, or cyclic. The number of carbon atoms of the linear alkyl group is preferably 1-20, more preferably 1-12, and still more preferably 1-8. The number of carbon atoms of the branched alkyl group is preferably 3-20, more preferably 3-12, and still more preferably 3-8. The cyclic alkyl group may be either monocyclic or polycyclic. The number of carbon atoms of the cyclic alkyl group is preferably 3-20, more preferably 4-10, and still more preferably 6-10.

The number of carbon atoms of the alkenyl group is preferably 2-10, more preferably 2-8, and still more preferably 2-4.

The number of carbon atoms of the aryl group is preferably 6-18, more preferably 6-14, and still more preferably 6-10.

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 can be a single ring or multiple rings. As ^{the linking group when R 100} and R ^{101 are} bonded to form a ring, it can be selected from -CO-, -O-, -NH-, divalent aliphatic groups, divalent aromatic groups and these The divalent linking base link of the group constituted by the combination. As specific examples, for example, piperazine ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, moforine ring, thiol Oxazine ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring, etc.

M represents an atom or group of atoms forming a salt with an anion. These can include the above, The preferred range is also the same.

In formula (B1), m represents an integer of 1 or more. The upper limit of m represents the number of substituents that the pigment 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 greater than or equal to 1, preferably 1 to 3, and more preferably 1 to 2. When n is 2 or more, a plurality of Xs may be different from each other.

As specific examples of the dye derivative represented by the formula (B1), the following (B-1) to (B-62) can be given. In addition, in the following chemical formulae, m, m1, m2, and m3 each independently represent an integer of 1 or more.

【Chemical formula 26】

【Chemical formula 27】

【Chemical formula 28】

【Chemical formula 29】

【Chemical formula 30】

【Chemical formula 31】

【table 3】

Ar-5, Ar-6, R-1~R-7, R-a~R-1 in the above table are as follows. The "*" in the structure shown below is a bonding key.

【Chemical formula 32】

In the present invention, as the pigment derivative, Japanese Patent Application Publication No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 1-217077, and Japanese Patent Application Publication No. 3-9961 can be preferably used. No. 3-26767, Japanese Patent Publication No. 3-26767, Japanese Patent Application Publication No. 3-153780, Japanese Patent Application Publication No. 3-4-5662, Japanese Patent Application Publication No. 4-285669, Japanese Patent Application Publication No. 6-145546, Japanese Patent Application Publication No. Kaiping No. 6-212088, Japanese Patent Application Publication No. 6-240158, Japanese Patent Application Publication No. 10-30063, Japanese Patent Application Publication No. 10-195326, International Publication WO2011/024896 Pamphlet No. 0086~0098, International Publication For those described in paragraph numbers 0063 to 0094 of the pamphlet No. WO2012/102399, this content is incorporated into this specification.

<Production method of the material of the present invention>

Next, the manufacturing method of the material of the present invention will be described. The manufacturing method of the material of the present invention is a compound containing pigment A and a structure that has resin adsorption The method for producing the material of the substance B, wherein when synthesizing the pigment A, in the presence of the compound B having a structure that has an adsorbability to the resin, the raw material compound of the pigment A is reacted to synthesize the pigment A. By synthesizing the pigment A in this way, a material in which the compound B is firmly attached to the pigment A can be obtained. Even if the material is washed with a solvent or the like, the compound B adheres to the pigment A firmly.

Although the detailed mechanism of obtaining the material of the compound B firmly attached to the pigment A according to the manufacturing method of the present invention is not clear, it is inferred that pigment A is synthesized by reacting the raw material compound of the pigment A in the presence of the above-mentioned compound B , The compound B is attracted to the inside of the pigment A particles, so 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 adsorption of the compound B to the pigment A is relatively low. The surface of the pigment is peeled off, and the compound B is not easy to remain on the surface of the pigment A. Therefore, the material obtained by the manufacturing method of the present invention has different characteristics from the material manufactured by the conventional method.

In the material obtained by the manufacturing method of the present invention, the content of the pigment A 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.

In addition, the content of the 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 more 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.

^{In addition, 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 set to 70 or less, for example, 60 or less, or 50 or less.

X ¹ =(X ² /X ³ )×100......(I)

X ² is the mass of compound B in the material after the material is immersed in a solvent with 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 X ³ is the mass of compound B after immersing in the above solvent The quality of the solid content of the material.

The meanings of the above-mentioned solvent and dipping method are the same as those described in the above-mentioned material of the present invention.

<Composition>

Next, the composition of the present invention will be described. The composition of the present invention includes the above-mentioned material of the present invention. The content of the above-mentioned materials 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.

<<Color Colorant>>

The composition of the present invention may contain a coloring agent in addition to the above-mentioned material of the present invention. In addition, in the present invention, the color coloring agent means a coloring agent other than a white coloring agent and a black coloring agent. The coloring agent is preferably a coloring agent having a maximum absorption wavelength in the wavelength range of 400 to 650 nm.

The coloring agent can be a pigment or a dye. As a pigment, one can cite A variety of well-known inorganic or organic pigments. Examples of organic pigments include the color pigments described in the above-mentioned material of the present invention. As the dye, for example, Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 1-94301, Japanese Patent Application Publication No. 6-11614, Japanese Patent Publication No. 2592207, Specification of U.S. Patent No. 4808501, Specification of U.S. Patent No. 5,67,920, Specification of U.S. Patent No. 505950, Specification of U.S. Patent No. 5,669,920, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115 , The pigment disclosed in Japanese Patent Laid-Open No. 6-194828, etc. If distinguished as a chemical structure, pyrazole azo compounds, pyrrole phenylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxacyanine compounds, pyrazolo three compounds can be used. Azole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazol azomethine compounds, and the like. In addition, as a dye, a dye multimer can also be used. Examples of the dye multimer include compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097.

When the composition of the present invention contains a color colorant, the content of the color colorant is preferably 0.01 to 70% by mass in the total solid content of the composition of the present 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 coloring agent is preferably 10 to 1000 parts by mass, and more preferably 50 to 800 parts by mass relative to the total of 100 parts by mass of the material of the present invention and the infrared absorber shown below.

In addition, the total amount of the material of the present invention, the infrared absorber, and the color colorant is preferably 1 to 70% by mass in the total solid content of the composition of the present 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 can also be set to a state that does not substantially contain a color colorant. Substantially not containing a color colorant means that the content of the color colorant is 0.005 mass in the total solid content of the composition of the present invention. % Or less is preferable, 0.001 mass% or less is more preferable, and it is more preferable not to contain a coloring agent.

<<Infrared Absorber>>

The composition of the present invention may contain an infrared absorber in addition to the above-mentioned material of the present invention. The infrared absorber means a compound that has absorption in the near infrared region (preferably with 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 can 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, squaraine ylide compounds, and naphthalenephthalein compounds. Cyanine compounds, quaterrylene compounds, dithiol metal complexes, croconium compounds, oxole compounds, etc.

When the composition of the present invention contains an infrared absorber, the content of the infrared absorber is preferably 0.1-50 parts by mass relative to 100 parts by mass of the material of the composition of the present invention, preferably 0.5-30 parts by mass, and 1.0-15 Parts by mass are further preferred.

Moreover, it can also be set as the composition which does not contain an infrared absorber substantially. In addition, the fact that the infrared absorber is not substantially included means that, for example, relative to 100 parts by mass of the material, the content of the infrared absorber is preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and 0.01 parts by mass or less is more preferred. Preferably, it is more preferable not to contain it.

<<Colored materials shielding visible light>>

The composition of the present invention can also contain a colored material that shields visible light. This composition can be suitably used as a composition for forming an infrared transmission filter, for example. In addition, in the present invention, the infrared transmission filter means a filter that blocks light of wavelengths in the visible region and transmits light (infrared rays) of wavelengths in the infrared region.

The colored material that shields visible light is preferably black, gray, or a color close to these by a combination of a plurality of colored materials. In addition, a colored material that shields visible light is preferably a material that absorbs light in the violet to red wavelength range. In addition, the colored material that shields visible light is preferably a colored material that shields light in the wavelength range of 450 to 650 nm.

In the present invention, it is preferable that the colored material for shielding visible light satisfies at least one of the following requirements (1) and (2), and it is more preferable to satisfy the requirement (1).

(1): Contains two or more color colorants.

(2): Contains organic black colorant.

In addition, in the present invention, the organic black colorant as a colored material that shields visible light means a material that absorbs visible light but transmits at least a part of infrared rays. Therefore, in the present invention, the organic black colorant as a colored material that shields visible light does not include black colorants that absorb both visible light and infrared rays, such as carbon black and Titanium black.

As a coloring agent, the above-mentioned are mentioned.

Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, and the like, and bisbenzofuranone compounds and perylene compounds are preferred.

Examples of the bisbenzofuranone compound include those described in Japanese Patent Application No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234. For example, they may be manufactured by BASF Corporation. "Irgaphor Black" to get it.

Examples of the perylene compound include C.I. Pigment Black 31, 32 and the like.

Examples of the azomethine compound include those described in Japanese Unexamined Patent Publication No. 1-170601, Japanese Unexamined Patent Publication No. 2-34664, etc., for example, "CHROMOFINEBLACK A1103 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. "To get.

In the present invention, in the colored material that shields visible light, for example, the ratio of the minimum absorbance value A in the wavelength range of 450 to 650 nm to the minimum absorbance value B in the wavelength range of 900 to 1300 nm, that is, A/B of 4.5 or more is Better. The above-mentioned characteristics can be satisfied by one kind of raw material, or by a combination of multiple kinds of raw materials. For example, in the case of the aspect (1) above, it is preferable to combine a plurality of color colorants to satisfy the above-mentioned spectral characteristics.

When two or more kinds of color colorants are included as a colored material that shields visible light, the color colorants are selected from the group consisting of red colorants, green colorants, blue colorants, Coloring agents of yellow coloring agent, purple coloring agent and orange coloring agent are preferred. Examples of the combination of color colorants in the case of combining two or more color colorants to form a colored material that shields visible light include the following.

(1) Containing yellow coloring agent, blue coloring agent, purple coloring agent and red coloring agent

(2) Containing yellow coloring agent, blue coloring agent and red coloring agent

(3) Containing yellow coloring agent, purple coloring agent and red coloring agent

(4) Contains yellow coloring agent and purple coloring agent

(5) Containing green coloring agent, blue coloring agent, purple coloring agent and red coloring agent

(6) Containing purple coloring agent and orange coloring agent

(7) Containing green coloring agent, purple coloring agent and red coloring agent

(8) Containing green coloring agent and red coloring agent

When the composition of the present invention contains a colored material that shields visible light, the content of the colored material that shields visible light is preferably 0.01 to 70% by mass in the total solid content of the composition of the present 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 colored material that shields visible light is preferably 10 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass relative to 100 parts by mass of the total of the material of the present invention and the infrared absorber. In addition, it is preferable that the total amount of the material of the present invention, the infrared absorber, and the colored material shielding visible light is 1 to 70% by mass in the total solid content of the composition of the present 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.

<<Pigment Derivatives>>

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 improved and the aggregation of the pigment can be effectively suppressed. As the pigment derivative, the pigment derivative described in the compound B of the above-mentioned material of the present invention can be exemplified.

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1-50 parts by mass relative 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 improved and the aggregation of particles can be effectively suppressed. The dye derivative may be one type or two or more types. When there are two or more types, the total amount is preferably in the above-mentioned range.

<<Organic Solvent>>

The composition of the present invention preferably further contains an organic solvent.

The organic solvent is not particularly limited, and as long as it can uniformly dissolve or disperse each component, it can be appropriately selected according to the purpose. For example, alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfene, and tetrahydrothiophene can be preferably cited.碸 etc. These may be used individually by 1 type, and may use 2 or more types together.

As specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons, those described in paragraph 0136 of JP 2012-194534 A, etc. can be cited, and this content is incorporated in this specification.

Specific examples of esters, ketones, and ethers include those described in paragraph 0497 of JP 2012-208494 A (corresponding to <0609> of US Patent Application Publication No. 2012/0235099). Furthermore, n-pentyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl Ether acetate and so on.

As an organic solvent, selected from cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, 2-butanol, ethanol, ethyl lactate and propylene glycol monomethyl At least one type of ether (1-methoxy-2-propanol) is preferred.

In the present invention, it is better to use an organic solvent with less metal content as the organic solvent. The metal content of the organic solvent is preferably 10 ppb or less, for example. A ppt-level solvent can be used as needed, and this high-purity solvent is provided by, for example, Toyo Gosei Co., Ltd (Chemical Industry Daily, November 13, 2015).

As a method of removing impurities such as metals from the organic solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration with a filter can be cited. As the pore size of the filter in filtration with a filter, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.

The organic solvent may also contain isomers (compounds with the same number of atoms and different structures). In addition, the isomer may include only one type, or may include a plurality of types.

Regarding the content of the organic solvent, the total solid content of the composition of the present invention is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass. The organic solvent may be only one type, or two or more types. When there are two or more types, the total The amount is preferably in the above-mentioned range.

<<Resin>>

The composition of the present invention preferably further contains a resin. The resin is formulated as a dispersant for dispersing a pigment or the material of the present invention in the composition, for example.

The resin that functions as a dispersant is preferably an acid type resin and/or a basic type resin.

Here, the acidic resin means one having more acid groups than basic groups. For acidic resins, when the total amount of the amount of acid groups and the amount of basic groups in the resin is set to 100 mol%, the amount of acid groups is preferably 70 mol% or more, and it is essentially composed of only acid groups. The composer is better. The acid group possessed by the acidic resin is preferably a carboxyl group. The acid value of the acidic resin is preferably 40-105 mgKOH/g, more preferably 50-105 mgKOH/g, and still more preferably 60-105 mgKOH/g.

In addition, the base-type resin means one having more basic groups than acid groups. In the basic resin, when the total amount of the amount of acid groups and the amount of basic groups in the resin is 100 mol%, it is preferable that the amount of basic groups account for 50 mol% or more. The basic group possessed by the basic resin is preferably an amine.

Resins can be further classified into linear polymers, end-modified polymers, grafted polymers, and block polymers based on their structure.

As the terminal modified polymer, for example, the polymer having a phosphate group at the terminal described in Japanese Patent Laid-Open No. 3-112992, Japanese Patent Publication No. 2003-533455, etc., and Japanese Patent Laid-Open No. 2002-273191 The polymer having a sulfonic acid group at the end is described in the bulletin, etc., and it is described in the Japanese Patent Laid-Open No. 9-77994, etc. Part of the skeleton of organic pigments or heterocyclic polymers, etc. In addition, Japanese Unexamined Patent Publication No. 2007-277514 describes the introduction of two or more fixed sites (acid groups, basic groups, partial skeletons or heterocycles of organic pigments, etc.) on the surface of the pigment into the end of the polymer. The dispersion stability is also excellent, so it is preferable.

As the graft type polymer, for example, the poly(lower alkylimine) described in JP 54-37082 A, JP 8-507960 A, JP 2009-258668 A, etc. ) Reaction product with polyester, reaction product of polyallylamine and polyester described in Japanese Patent Application Publication No. 9-169821, etc., described in Japanese Patent Application Publication No. 10-339949, Japanese Patent Application Publication No. 2004-37986, etc. Copolymers of macromonomers and nitrogen atom monomers, JP 2003-238837 A, JP 2008-9426 A, JP 2008-81732 A, etc., have a partial skeleton or an organic pigment described in Heterocyclic graft polymers, copolymers of macromonomers and acid group-containing monomers described in JP 2010-106268 A, etc. As the macromonomer, for example, TOAGOSEI CO., LTD macromonomer AA-6 (polymethyl methacrylate whose end group is methacrylic acid group), AS-6 (end group is methyl methacrylate) can be mentioned. Polystyrene based on methacrylic acid group), AN-6S (copolymer of styrene and acrylonitrile with methacrylic acid end group), AB-6 (polybutyl acrylate with methacrylic acid end group) ), PLACCEL FM5 (2-hydroxyethyl methacrylate ε-caprolactone 5-mole equivalent adduct), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10-mole equivalent) manufactured by Daicel Corporation Adduct), and polyester-based macromonomers described in JP Hei 2-272009 A, etc.

As a block type polymer, Japanese Patent Application Publication No. 2003-49110, Japanese Patent Application Publication No. 2003-49110 The block type polymer described in 2009-52010 publication etc. is preferable.

The resin can also use a graft copolymer containing a structural unit represented by any one of the following formulas (1) to (4).

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, and an oxygen atom is preferred.

R ³ represents a branched or straight-chain alkylene group (the number of carbon atoms is preferably 1 to 10, and 2 or 3 is more preferable). From the viewpoint of dispersion stability, -CH ₂ -CH(CH ₃ )- The group represented or the group represented by -CH(CH ₃ )-CH ₂ -is preferred.

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group.

Regarding the above-mentioned graft copolymer, refer to the description of paragraph numbers 0025 to 0069 of JP 2012-255128 A, which are incorporated in this specification.

As a specific example of the said graft copolymer, the following can be mentioned, for example. In addition, the paragraph numbers 0072~0094 of JP 2012-255128 A can be used. Resin.

As the resin, an oligoimine-based resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used. As an oligoimine-based resin, it has a repeating unit including a partial structure of the group X and a side chain including a side chain Y with a number of atoms of 40 to 10,000, and has a basic nitrogen atom in at least one of the main chain and the side chain The resin is preferable, and the partial structure has a partial structure of a functional group with a pKa14 or less. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

The oligoimine-based dispersant may include, for example, a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2) and/or a repeating unit represented by the formula (I-2a) The resin and so on.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group (the number of carbon atoms is preferably 1 to 6). a represents an integer of 1 to 5 independently, respectively. * Indicates the connection between the repeating units.

R ⁸ and R ⁹ have the same meaning as R ^1.

L represents a single bond, an alkylene group (the number of carbon atoms is preferably 1 to 6), an alkenylene group (the number of carbon atoms is preferably 2 to 6), an arylene group (the number of carbon atoms is preferably 6 to 24), Heteroaryl groups (1 to 6 carbon atoms are preferred), imino groups (0 to 6 carbon atoms are preferred), ether groups, thioether groups, carbonyl groups or linking groups involving a combination of these. Among them, a single bond or -CR ⁵ R ⁶ -NR ^7- (the side where the imino group becomes X or Y) is preferred. Here, R ⁵ R ⁶ each independently represents a hydrogen atom, a halogen atom, and an alkyl group (the number of carbon atoms is preferably 1 to 6). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

La is ^a structural part that forms a ring structure together with CR ⁸ CR ^{9 and N, and it is preferably a structural part that combines with the carbon atom of CR 8} CR ⁹ to form a non-aromatic heterocyclic ring with 3 to 7 carbon atoms. It ^{is more preferable to combine the carbon atom of CR 8} CR ⁹ and N (nitrogen atom) to form a 5- to 7-membered non-aromatic heterocyclic structure, and it is more preferable to form a 5-membered non-aromatic heterocyclic structure. The structural part forming pyrrolidine is particularly preferred. This structural part may further have substituents, such as an alkyl group.

X represents a group containing a partial structure of a functional group having pKa14 or less.

Y represents a side chain with 40 to 10,000 atoms.

The above-mentioned resin (oligoimine-based resin) may further contain one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5) as a copolymerization component. The above-mentioned resin containing this type of repeating unit can further improve the dispersibility of the pigment.

The meanings of R ¹ , R ² , R ⁸ , R ⁹ , L, La, a, and * are the same as those defined in formulas (I-1), (I-2), and (I-2a).

Ya represents a side chain having an anion group with 40 to 10,000 atoms. The repeating unit represented by the formula (I-3) can be added to a resin having a primary or secondary amine group in the main chain part, an oligomer or polymer having a group that reacts with the amine group to form a salt And react to form.

Regarding the above-mentioned oligoimine-based resin, refer to the description of paragraph numbers 0102 to 0166 of JP 2012-255128 A, which are incorporated in this specification. As a specific example of an oligoimine resin, the following can be mentioned, for example. In addition, 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 formula (P1) can also be used. By using the following resins, the dispersibility of the pigment can be further improved.

【Chemical formula 38】

In formula (P1), R ¹ represents hydrogen or methyl, 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, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and a 2-hydroxy propylene group , Methyleneoxy, ethyleneoxy, methyleneoxyhydroxy, methylenethio, etc., methylene, methyleneoxy, methyleneoxyhydroxy, methylenethio are more preferred.

The nitrogen-containing heterocyclic structure represented by Z includes, for example, those having the following structures: pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, Acridine ring, phenanthrazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, cyclic urea structure and Cyclic imine structure. Among these, as the nitrogen-containing heterocyclic structure represented by Z, a structure represented by the following formula (P2) or formula (P3) is preferred.

In the formula, X is selected from single bond, alkylene (for example, methylene, ethylene Group, propylene, trimethylene, tetramethylene, etc.), -O-, -S-, -NR- and -C(=O)-. In addition, where R represents a hydrogen atom or an alkyl group, examples of the alkyl group when R represents an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, and n-hexyl. , N-octyl, 2-ethylhexyl, n-octadecyl, etc.

Among these, X is a single bond, methylene, -O-, -C(=O)- is preferred, and -C(=O)- is particularly preferred.

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, pyridine ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, Acridine ring, phenoxazine ring, phenoxazine ring, acridone ring, anthraquinone ring, etc., among which, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine A ring, a phenoxazine ring, an acridone ring, and an anthraquinone ring are preferred, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferred.

As a specific example of the structural unit represented by Formula (P1), the following can be mentioned, for example. In addition, refer to the description of paragraph 0023 of JP 2008-009426 A, which is incorporated into this specification.

The resin containing the structural unit represented by formula (P1) may further contain the structural unit represented by any one of the above-mentioned formula (1) to formula (4). In addition, the repeating unit represented by the above formula (I-1), the repeating unit represented by the formula (I-2), and/or the repeating unit represented by the formula (I-2a) may also be included. As a specific example of the resin containing the structural unit represented by formula (P1), the following can be mentioned.

Resins can also be obtained as commercially available products. As a specific example of this type, "Disperbyk-101 (polyamide-amine phosphate), 107 (carboxylate), 110, 111 (containing acid group) manufactured by BYK Chemie Copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA 4047, 4050-4165 (polyurethane series), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 ( High molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)'', AJISPER PB821, PB822, PB880 manufactured by Ajinomoto Fine-Techno Co., Inc. , PB881", "FLOWLEN TG-710 (urethane oligomer)" made by KYOEISHA CHEMICAL Co., LTD, "POLYFLOW No.50E, No. 300 (acrylic copolymer), Kusumoto Chemicals, Ltd., "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703- 50, DA-705, DA-725", Kao Corporation "DEMOL RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonate formalin polycondensate)", "Homogenol L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN 86 (stearyl amine acetate)", made by Lubrizol Japan SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer with a functional part at the end), 24000, 28000, 32000, 38500 ( Grafted polymer)”, “Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)” manufactured by NIKKO CHEMICALS CO., LTD., Kawaken Fine Chemicals "Hinoact T-8000E" manufactured by Co., Ltd., "Organosiloxane polymer KP341" manufactured by Shin-Etsu Chemica. Co., Ltd., "EFKA-46, EFKA-47 manufactured by MORISHITA & CO., LTD. , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid6, Disperse Aid8, Disperse Aid15, Disperse Aid9100" manufactured by SAN NOPCO LIMITED, "Adeka pluronic" manufactured by ADEKA CORPORATION L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123'', and ``Ionet S manufactured by Sanyo Chemical Industries, Ltd. -20" and so on.

These resins may be used alone or in combination of two or more kinds. and, As the resin, an alkali-soluble resin can also be used.

As the alkali-soluble resin, it can be appropriately selected from the following alkali-soluble resins. The alkali-soluble resin is a linear organic polymer and is in the molecule (preferably a molecule with an acrylic copolymer or a styrene copolymer as the main chain). ) Has at least one group that promotes alkali solubility. From the viewpoint of heat resistance, polyhydroxystyrene-based resins, polysiloxane-based resins, acrylic resins, acrylamide-based resins, and acrylic/acrylamide copolymer resins are preferable, and from the viewpoint of controlling developability, Acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred.

Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, phenolic hydroxyl groups, etc., which are soluble in organic solvents and can be developed by weakly alkaline aqueous solutions. It is preferable, and as a particularly preferable one, (meth)acrylic acid can be mentioned. There may be only one type of these acid groups, or two or more types. As the alkali-soluble resin, refer to paragraphs 0558 to 0571 of JP 2012-208494 (corresponding to [0685] to [0700] of the specification of US Patent Application Publication No. 2012/0235099), and these contents are incorporated herein. In the manual.

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

In the formula (ED), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

The hydrocarbon group having 1 to 25 carbon atoms represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Linear or branched alkyl groups such as tertiary butyl, tertiary pentyl, stearyl, lauryl, 2-ethylhexyl, etc.; aryl groups such as phenyl; cyclohexyl, tertiary butyl cyclohexyl, two Cyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and other alicyclic groups; 1-methoxyethyl, 1-ethoxyethyl Such as alkyl substituted by alkoxy; benzyl and other alkyl substituted by aryl. Among these, from the viewpoint of heat resistance, a first- or second-class hydrocarbon group such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group that is not easily removed by acid or heat is particularly preferable.

In addition, R ¹ and R ² may be the same kind of substituents or different substituents.

As an example of the compound represented by the formula (ED), for example, paragraph 0317 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification. The compound represented by the formula (ED) may be only one type or two or more types.

Regarding the resin containing the compound represented by the formula (ED) as a copolymerization component, refer to the description of paragraph numbers 0079 to 0099 of JP 2012-198408 A, and this content is incorporated in this 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 30,000 The following are preferable, and 20,000 or less is more preferable.

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

<Preparation of composition>

The composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, the components of the composition may be uniformly blended, or the components may be dissolved and dispersed in an organic solvent and then blended sequentially. In addition, the order of input and operating conditions at the time of deployment are not particularly limited.

In addition, a process including dispersing the material of the present invention and the like in the composition is preferable. In the process of dispersing the material and the like of the present invention in the composition, the mechanical force used for the dispersion of the material and the like of the present invention includes compression, extrusion, impact, shear, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, high-speed impellers, sand mills, jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. In addition, the "Dispersion Technology Encyclopedia, issued by the Information Agency Co., Ltd., July 15, 2005" and "suspension (solid/liquid dispersion system)-centered dispersion technology and actual industrial applications The process and dispersing machine described in "Comprehensive data collection, issued by the Publishing Department of the Management Development Center, October 10, 1978". In addition, the method described in paragraph 0022 of JP 2015-157893 A can also be used. And, in the process of dispersing the material, it can be carried out by the salt milling process Micronization processing. The raw materials, equipment, processing conditions, etc. used in the salt milling process can be those described in Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629, for example.

In order to remove foreign matter and reduce defects, etc., it is preferable to filter the composition of the present invention with a filter. As the filter, as long as it is previously used for filtering purposes, etc., it can be used without particular limitation. For example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon (such as nylon-6, nylon-6, 6), polyolefin resins such as polyethylene and polypropylene (PP) (including High-density, ultra-high molecular weight) and other filters. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it in this range, it is possible to reliably remove fine foreign matter that hinders the preparation of a uniform and smooth composition in the subsequent process. Furthermore, it is also preferable to use a fibrous filter material. Examples of the filter material include polypropylene fiber, nylon fiber, glass fiber, etc., specifically, the SBP type series manufactured by ROKI GROUP CO., LTD. (SBP008 etc.) can be used. , TPR type series (TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.) filter element.

When using filters, different filters can also be combined. At this time, the filtration by the first filter may be performed only once, or may be performed two or more times.

In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, available from Pall Corporation (DFA4201NXEY etc.), ADVANTEC TOYO KAISHA, LTD., Nihon Entegris K.K. Nihon Entegris K.K. (formerly Choose from various filters provided by Nippon Mykrolis Corporation) or KITZ MICRO FILTER CORPORATION.

The second filter can be formed of the same material as the above-mentioned first filter.

<Curable composition>

Next, the curable composition of the present invention will be described. The curable composition of the present invention includes the above-mentioned composition 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, the curable composition is preferably 0.01-50% by mass in the total solid content. 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 the present invention contains two or more of the materials of the present invention, the total amount thereof is preferably within the above-mentioned range.

<<hardening 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 crosslinked by free radicals, acid, or heat can be used. For example, compounds having a radical polymerizable group, a cyclic ether (epoxy, oxetane) group, a methylol group, and the like can be mentioned. 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. Furthermore, 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 a photoradical polymerizable compound is more preferred.

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

(Polymerizable compound)

In the present invention, the polymerizable compound may be, for example, monomers, prepolymers, that is, dimers, trimers, and oligomers, or mixtures of these, and any of these multimers. When the polymerizable compound is a photo-radical polymerizable compound, a monomer is preferred.

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 to 15 functional (meth)acrylate compound, and a 3 to 6 functional (meth)acrylate compound is more preferred. As these specific compounds, refer to Paragraph Nos. [0095]~[0108] of JP 2009-288705 A, Paragraph 0227 of JP 2013-29760 A, Paragraph of JP 2008-292970 A The contents of the compounds described in Nos. 0254 to 0257 are incorporated in this specification.

The polymerizable compound is dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as Commercially available products include KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acrylic acid groups via ethylene glycol residues The structure in which the propylene glycol residue is bonded to the propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer Co. Inc.) is preferred. These oligomer types can also be used. In addition, KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of commercially available products include M-305, M-510, M-520, etc., which are polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD.

The preferred acid value of the polymerizable compound having an acid group is 0.1-40 mgKOH/g, and particularly preferably 5-30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development dissolution characteristic is good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Moreover, it has good photopolymerization properties and excellent curability.

It is also preferable that the polymerizable compound is a compound having a caprolactone structure. As a compound having a caprolactone structure, reference can be made to the description of paragraphs 0042 to 0045 of JP 2013-253224 A, which are incorporated in this specification. Polymerizable compounds having a caprolactone structure are, for example, commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

Polymerizable compounds can also use polymerizable compounds with alkyleneoxy groups Things. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or an ethyleneoxy group, and a polymerizable compound having an ethyleneoxy group is more preferable, having 4-20 A 3-6 functional (meth)acrylate compound having an ethyleneoxy group is further preferred. Commercial products of polymerizable compounds having alkyleneoxy groups include, for example, SR-494, Nippon Kayaku Co., which is a 4-functional acrylate having 4 ethyleneoxy groups, manufactured by Sartomer Co., Inc. , Ltd., as a 6-functional acrylate with 6 pentyloxy groups, DPCA-60, as a 3-functional acrylate with 3 isobutyloxy groups, TPA-330, etc.

As the polymerizable compound, urethane acrylic acid described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765, etc. Esters (Urethane acrylate) or, ethylene oxide described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Carbamate compounds that form a skeleton are also preferred. In addition, by using the additions described in JP 63-277653, JP 63-260909, and Hei 1-105238, which have an amine group structure or a thioether structure in the molecule Polymerizable compounds can obtain a color-hardening composition with a very excellent photosensitive speed.

Commercial products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), and 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 (KYOEISHA CHEMICAL Co., LTDorporation system) and so on.

As the polymerizable compound, vinyloxy isocyanurate modified (meth)acrylate is also preferred. As commercially available products, 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 Co. Inc.), 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 relative to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and more preferably 40% by mass or less. The curable compound may be one type alone or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably within the above-mentioned range.

In addition, the content of the polymerizable compound is preferably from 10 to 100% by mass, and more preferably from 30 to 100% by mass relative to the total mass of the curable compound.

(Compounds with epoxy groups)

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 also be set to 100 or less, for example, 10 or less, or 5 or less.

In the present invention, the compound having an epoxy group is preferably a structure having an aromatic ring and/or an aliphatic ring, and a structure having an aliphatic ring is more preferable. The epoxy group is preferably bonded to the aromatic ring and/or aliphatic ring via a single bond or a linking group. Examples of the linking group include an alkyl group selected from an alkylene group, an arylene group, -O-, a hydrogen atom represented by -NR'-(R', an alkyl group which may have a substituent, or an aryl group which may have a substituent. A hydrogen atom is preferably a structure represented by), _{a group of at least one of -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 the aromatic ring via a linking group. The linking group is preferably an alkylene group or a group composed of a combination of an alkylene group and -O-.

In addition, as the compound having an epoxy group, a compound having a structure in which two or more aromatic rings are connected via a hydrocarbon group can also be used. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. The epoxy group is preferably connected via the above-mentioned linking group.

Among the compounds with epoxy groups, the epoxy equivalent (= the molecular weight of the compound with epoxy groups/the number of epoxy groups) is preferably 500g/equivalent or less, more preferably 100~400g/equivalent, 100~300g/ The equivalent is more preferable.

The compound with epoxy group may be a low molecular compound (for example, a molecular weight less than 1000), or a macromolecule compound (for example, a molecular weight of 1000 or more, when it is a polymer, the weight average molecular weight is 1000 or more). One. The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less.

Examples of compounds having epoxy groups include epoxy resins as glycidyl ether compounds of phenol compounds, epoxy resins as glycidyl ether compounds of various novolak resins, alicyclic epoxy resins, and aliphatic rings. Oxygen resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, halogenated Glycilated epoxy resins with phenolic compounds, condensates of silicon compounds with epoxy groups and other silicon compounds, copolymers of polymerizable unsaturated compounds with epoxy groups and other polymerizable unsaturated compounds, etc. .

As the epoxy resin that is the glycidyl etherate 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, tetramethyl bisphenol 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 Base-bis(4-methyl-6-tertiary butylphenol), 4,4'-butylene-bis(3-methyl-6-tertiary butylphenol), trihydroxyphenylmethane, m-benzene Diphenols, hydroquinone, pyrogallol, phloroglucinol, phenols with a diisopropylene skeleton; 1,1-di-4-hydroxyphenyl phenols with a skeleton; phenols Polybutadiene, etc. as the glycidyl ether of polyphenol compounds, epoxy resins, etc.

As the epoxy resin that is the glycidyl etherate of novolak resin, for example, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, and bisphenol Phenol S and other bisphenols, naphthols and other phenols as raw materials, novolac resins, phenol novolac resins containing xylene skeleton, phenol novolac resins containing dicyclopentadiene skeleton, and biphenyl skeleton Glycidyl ether products of various novolac resins, such as phenol novolac resins and phenol novolac resins containing a sulphur skeleton.

Examples of alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl -(3,4-epoxy)cyclohexyl carboxylate, bis(3,4-epoxycyclohexylmethyl)adipate and other alicyclic epoxy resins having an aliphatic ring skeleton.

Examples of aliphatic epoxy resins include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.

As a heterocyclic epoxy resin, the heterocyclic epoxy resin which has a heterocyclic ring, such as an isocyanuride ring and a hydantoin ring, is mentioned, for example.

Examples of glycidyl ester-based epoxy resins include epoxy resins composed of carboxylic acid esters such as diglycidyl hexahydrophthalate.

Examples of glycidylamine epoxy resins include epoxy resins obtained by glycidylating amines such as aniline and toluidine.

Examples of epoxy resins that glycidyl halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol phenol, brominated cresol phenol, and chlorinated bisphenol Phenol S, chlorinated bisphenol A and other halogenated phenolic glycidyl epoxy resins.

As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, as products available on the market, Marr proof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758, etc. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-ethylene-1-cyclohexene-1,2-epoxide, and the like. In addition, examples of copolymers of other polymerizable unsaturated compounds include methyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, styrene, and vinyl ring. Hexane, etc., especially methyl (meth)acrylate, benzyl (meth) Acrylate and styrene are preferred.

As a commercially available product of a compound having an epoxy group, for example, as a bisphenol A epoxy resin, there may be mentioned jER 825, jER 827, jER 828, jER 834, jER 1001, jER 1002, jER 1003, jER 1055, and jER 1007 , JER 1009, jER 1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, manufactured by DIC CORPORATION), etc. Examples of bisphenol F epoxy resins include jER 806, jER 807, jER 4004, jER 4005, jER 4007, jER 4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (above, manufactured by DIC CORPORATION), LCE -21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of phenol novolak type epoxy resins 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. . As the cresol novolak type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, DIC CORPORATION), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of aliphatic epoxy resins include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, manufactured by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above, manufactured by Daicel Corporation), DENACOL EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase Chemtex Corporation), etc. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN 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), etc.

For compounds having epoxy groups, paragraph numbers 0034 to 0036 of JP 2013-011869 A, paragraph numbers 0147 to 0156 of JP 2014-043556, and paragraph numbers of JP 2014-089408 can also be used. Compounds described in 0085~0092. These contents are incorporated into this manual.

When a compound having an epoxy group is used as the curable compound, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass relative to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and more preferably 20% by mass or less. The compound having an epoxy group may be one type alone or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably within the above-mentioned range.

In addition, the content of the compound having an epoxy group is preferably 1 to 80% by mass, and more preferably 1 to 50% by mass relative to the total mass of the curable compound.

(Polymerizable or non-polymerizable binder polymer)

In the present invention, as the curable compound, a polymerizable or non-polymerizable binder polymer can also be used. As a polymerizable or non-polymerizable binder polymer, there can be mentioned Cyclic olefin resins, aromatic polyether resins, polyimide resins, polycarbonate resins, polyester resins, polycarbonate resins, polyamide (aramide) resins, polyarylate resins, polyamide resins Chlorine resin, polyether resin, poly-p-phenylene resin, polyamide imide resin, polyethylene naphthalate resin, fluorinated aromatic resin, etc. As a specific example, the polymer etc. which have the following repeating unit are mentioned. For the details of these, please refer to the description of paragraph numbers 0086 to 0103 of JP 2015-040895 A, which are incorporated into this manual. In addition, as the polymerizable or non-polymerizable binder polymer, the resin described in the above composition can also be used.

The content of the binder polymer is preferably 0.1-50% by mass relative to the total solid content of the curable composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and more preferably 40% by mass or less. The binder polymer may be one type alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably within the above-mentioned 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 is preferable to contain a polymerization initiator. As a polymerization initiator, as long as it has the ability to initiate polymerization of a polymerizable compound by either light or heat, or both, it is not particularly limited, and it can be used according to the purpose. Choose appropriately.

When the polymerizable compound is polymerized by light, a photopolymerization initiator is preferred. The photopolymerization initiator is preferably one having sensitivity to light from the ultraviolet region to the visible region.

In addition, when the polymerizable compound is polymerized by heat, a thermal polymerization initiator is preferred. The thermal polymerization initiator is preferably one that decomposes at 150-250°C.

Examples of polymerization initiators include phosphine compounds, acetophenone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, and oxime compounds. , Hexaaryl bisimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, metallocene compounds and other onium salt compounds, organic boron Salt compounds, disulfite compounds, thiol compounds, etc. The polymerization initiator is preferably a compound having at least an aromatic group.

As the polymerization initiator, reference can be made to the description of paragraphs 0218 to 0251 of JP 2014-41318 (corresponding to paragraphs 0220 to 0253 of the pamphlet of International Publication WO2014/017669), and these contents are incorporated into this specification. In addition, the compounds described in JP 2016-21012 A can also be used.

The polymerization initiator is preferably an oxime compound, an acetophenone compound, or an acylphosphine compound.

Commercial products of oxime compounds include IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), and Adeka arc Luz NCI -930 (Manufactured by ADEKA CORPORATION) and so on.

In addition, an oxime initiator having a fluorine atom can also be used. Specific examples of the initiator include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40, and the compounds described in paragraph 0345 of JP 2014-500852 A. The compound (C-3) described in paragraph 0101 of the 2013-164471 Bulletin. In addition, the oxime polymer described in Japanese Patent Application Publication No. 2010-527339, International Publication WO2015/004565, etc. can also be used.

In addition, an oxime initiator having a nitro group can also be used. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of the oxime initiator having a nitro group include paragraphs 0031 to 0047 of JP 2013-114249 and paragraphs 0008 to 0012, 0070 to 0079 of JP 2014-137466. Compound or Adeka arc Luz NCI-831 (manufactured by ADEKA CORPORATION).

Examples of commercially available products of the acetophenone compound include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (brand names: all manufactured by BASF Corporation).

Examples of commercially available products of the phosphine compound include IRGACURE-819, DAROCUR-TPO (brand names: all manufactured by BASF Corporation), and the like.

In the present invention, it is also preferable to use an acetophenone compound and an oxime compound together as a polymerization initiator.

When the curable composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass relative to the total solid content of the curable composition. The lower limit is preferably 0.1% by mass or more. The upper limit is less than 20% by mass, which is relatively Better, more preferably 15% by mass or less. The polymerization initiator may be only one type or two or more types. When there are two or more types, the total amount is preferably in the above-mentioned range.

<<Anhydrides, polycarboxylic acids>>

When the curable composition of the present invention contains an epoxy compound, it is preferable to further contain at least one selected from acid anhydrides and polycarboxylic acids.

Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic anhydride. , Nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethylglutaric anhydride, 3,3-dimethylglutaric anhydride, butane Alkyltetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexyl-1, Acid anhydrides such as 3,4-tricarboxylic acid-3,4-acid anhydride. From the viewpoints of light resistance, transparency, and handling, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2,4-Diethylglutaric anhydride, butanetetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2 ,3-Dicarboxylic anhydride, cyclohexyl-1,3,4-tricarboxylic acid-3,4-anhydrate, etc. are particularly preferred.

Polycarboxylic acid is a compound having at least two carboxyl groups. In addition, there are no particular restrictions on the presence of geometric isomers or optical isomers in the following compounds. As the polycarboxylic acid, 2 to 6 functional carboxylic acids are preferred, for example, 1,2,3,4-butane tetracarboxylic acid, 1,2,3-propane tricarboxylic acid, 1,3,5-pentane Alkyl tricarboxylic acid, citric acid and other alkyl tricarboxylic acids; phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid , Cyclohexyl tricarboxylic acid, nadic acid, methyl nadic acid, etc. Aliphatic cyclic polycarboxylic acids; polymers of unsaturated fatty acids such as linolenic acid or oleic acid and dimer acids as reduction products of these; linear alkyl diacids such as malic acid are preferred, adipic acid , Pentanedioic acid, heptanedioic acid, suberic acid, azelaic acid, and sebacic acid are more preferred. In particular, butanedioic acid is more preferred from the viewpoint of heat resistance and transparency of the cured product.

The content of the acid anhydride and the polycarboxylic acid is preferably 0.01-20 parts by mass relative to 100 parts by mass of the compound having an epoxy group, more preferably 0.01-10 parts by mass, and still more preferably 0.1-6.0 parts by mass.

<<Alkali-soluble resin>>

The curable composition of the present invention may contain alkali-soluble resin. By containing alkali-soluble resin, a desired pattern can be formed by alkali development. Examples of the alkali-soluble resin include those described in the composition, and the preferred 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 in the total solid content of the curable composition of the present invention is preferably 1% by mass or more, and can also be 2% by mass or more. It can also be 5 mass% or more, and it can also be 10 mass% or more. In addition, the content of the alkali-soluble resin can be set to 80% by mass or less in the total solid content of the curable composition of the present invention, can also be set to 65% by mass or less, or can be set to 60% by mass or less. It is 15% by mass or less.

In addition, when the curable composition of the present invention is used and the pattern is not formed by alkali development, of course, it can also be a state that does not contain alkali-soluble resin.

<<Surface Active Agent>>

The curable composition of the present invention may contain a surfactant. Surfactant may use only 1 type, and may combine 2 or more types. The content of the surfactant is preferably 0.0001 to 2% by mass relative 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 fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants 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. Thereby, the interfacial tension between the coated surface and the coating liquid is reduced, and the wettability to the coated surface is improved. Therefore, the liquid properties (especially, fluidity) of the curable composition are improved, and the uniformity of the coating thickness and the liquid-saving properties are further improved. As a result, even when a thin film of about several μm is formed with a small amount of liquid, a film of uniform thickness with small thickness unevenness can be formed more appropriately.

The fluorine content of the fluorine-based surfactant is preferably 3-40% 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 range, it is effective in terms of uniformity of the thickness of the coating film and liquid-saving properties, and the solubility is also good.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of JP 2014-41318 (corresponding to paragraphs 0060 to 0064 of International Publication WO2014/17669 pamphlet). The surfactants described in paragraphs 0117 to 0132 of JP 2011-132503 A are incorporated into this specification. As commercial products of fluorine-based surfactants, for example, Megafac F-171, Megafac F-172, Megafac F-173, Megafac F-176, Megafac F-177, Megafac F-141, Megafac F-142, Megafac F-143, Megafac F-144, Megafac R30, Megafac F -437, Megafac F-475, Megafac F-479, Megafac F-482, Megafac F-554, Megafac F-780 (above, manufactured by DIC CORPORATION), FLUORAD FC430, FLUORAD FC 431, FLUORAD FC 171 (above, Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (above, manufactured by OMNOVA SOLUTIONS INC.).

In addition, the following compounds can also be exemplified as fluorine-based surfactants 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.

In addition, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. As a specific example, Japanese Patent Application Publication No. 2010-164965 The compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 include, for example, Megafac RS-101, RS-102, RS-718K, RS-72K manufactured by DIC CORPORATION, and the like.

As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A can also be used.

Specific examples of nonionic surfactants include the nonionic surfactants described in paragraph 0553 of JP 2012-208494 (corresponding to US Patent Application Publication No. 2012/0235099 [0679]). Ionic surfactants, these contents are incorporated into this specification.

Specific examples of the cationic surfactant include the cationic interface described in paragraph 0554 of JP 2012-208494 (corresponding to US Patent Application Publication No. 2012/0235099 Specification [0680]). Active agent, these contents are incorporated into this specification.

Examples of silicone-based surfactants include the silicone-based interface described in paragraph 0556 of JP 2012-208494 A (corresponding to US Patent Application Publication No. 2012/0235099 Specification [0682]). Active agent, these contents are incorporated into this specification.

<<Substrate Adhesive>>

The curable composition of the present invention can contain a substrate adhesive. As the substrate adhesion agent, it is preferable to use a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.

As the silane coupling agent, for example, methyl trimethoxy silane, dimethyl dimethoxy silane, methyl triethoxy silane, dimethyl diethoxy silane, phenyl trimethoxy silane, Ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-Bis(trimethoxysilane)hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3 , 4-Epoxycyclohexyl) ethyl trimethoxysilane, 3-glycidyl ether propyl methyl dimethoxy silane, 3-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether propyl methyl Diethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methyl 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane Oxyoxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tri-( Trimethoxysilylpropyl) isocyanurate, 3-ureapropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, double (Triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. In addition, alkoxy oligomers can be used in addition to the above. In addition, the following compounds can also be used.

【Chemical formula 45】

Commercial products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, and KBE-3033 manufactured by Shin-Etsu Chemical Co., Ltd. , 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, KBM-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, KBM-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, etc.

The content of the substrate adhesive relative to the total solid content of the curable composition is preferably 0.1-30% by mass, more preferably 0.5-20% by mass, and particularly preferably 1-10% by mass.

<<Polymerization inhibitor>>

The curable composition of the present invention may contain a small amount of a polymerization inhibitor in order to prevent unnecessary reactions of the curable compound during production or storage. Examples of polymerization inhibitors include phenol-based hydroxyl-containing compounds, N-oxide compounds, piperidine 1-oxy radical compounds, pyrrolidine 1-oxy radical compounds, and N-nitrosophenyl groups. Hydroxylamines, diazonium compounds, cationic dyes, sulfide-containing compounds, nitro-containing compounds, phosphorus-based compounds, lactone-based compounds, transition metal compounds (FeCl3, CuCl2, etc.). In addition, among these compounds, the polymerization inhibitor may be a composite compound in which a plurality of phenol skeletons or phosphorus-containing skeletons are present in the same molecule and exhibit a polymerization-inhibiting function. For example, the compounds described in Japanese Patent Application Laid-Open No. 10-46035 etc. can also be preferably used. Specific examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butylcatechol, p-benzoquinone, 4 ,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N-nitroso Among them, p-methoxyphenol is preferred.

When the curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the curable composition of the present invention.

<<Ultraviolet absorber>>

The curable composition of the present invention may contain an ultraviolet absorber. Known compounds can be used as the ultraviolet absorber. As a commercial item, UV503 (DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example. In addition, the ultraviolet absorber can use aminodiene-based, salicylate-based, benzophenone-based, benzotriazole-based, acrylonitrile-based, and triazine-based And other ultraviolet absorbers. As a specific example, the compound described in JP 2013-68814 A can be mentioned. As the benzotriazole series, Miyoshi Oil & Fat Co, Ltd.'s MYUA series (Chemical Industry Daily, February 1, 2016) can 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 relative to the total solid content of the curable composition.

<<Organic Solvent>>

The curable composition of the present invention may contain an organic solvent. Examples of the organic solvent include those described in the above composition, and the preferred range is also the same.

The content of the organic solvent in the curable composition of the present invention is that the total solid content of the curable composition of the present invention is preferably 5 to 90% by mass, and 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 the present invention is not impaired, the curable composition of the present invention can appropriately select other components according to the purpose.

For example, the curable composition of the present invention can contain one or more selected from the group consisting of coloring agents, infrared absorbers, and colored materials that shield visible light in addition to the materials of the present invention described above. The details of these include the colored colorants, infrared absorbers, and colored materials that shield visible light described in the above-mentioned composition. These can be appropriately selected according to the use of the curable composition.

In addition, as other components that can be used in combination, for example, a sensitizer, a crosslinking agent (aqueous solution of a crosslinking agent), acetic anhydride, a silane compound, a hardening accelerator, a filler, a plasticizer, and other auxiliary agents (for example, Conductive particles, fillers, defoamers, flame retardants, Levelling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.).

For these ingredients, refer to paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (corresponding to <0237> to <0309> of the specification of U.S. Patent Application Publication No. 2013/0034812), Japanese Patent Application Publication No. 2008-250074 Paragraph No. 0101 to 0102 of the Bulletin, Paragraph No. 0103 to 0104 of JP 2008-250074, Paragraph No. 0107 to 0109 of JP 2008-250074, Paragraph No. 0159 of JP 2013-195480 ~0184 and other records, these contents are incorporated into this manual.

By appropriately containing these components, the stability of the target infrared cut filter and the properties of the film can be adjusted.

<Preparation of curable composition>

The curable composition of the present invention can be prepared by mixing the above-mentioned components. In addition, in order to remove foreign matter and reduce defects, it is better to filter with a filter. Regarding the type of filter and the filtering method, those described in the composition can be cited, and the preferred range is also the same.

<Use of curable composition>

The curable composition of the present invention can be made into a liquid form. Therefore, for example, by applying the curable composition of the present invention to a substrate and drying it, it is possible to easily manufacture a color filter, an infrared cut filter, and an infrared transmission. Hardened film for filters, etc.

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 manufactured by using a curable composition containing the material of the present invention. And, in this aspect, the curable composition of the present invention is in addition to the material of the present invention. When an infrared absorber is included in addition to the material, an infrared cut filter capable of absorbing light in the near-infrared region of a wider wavelength region than the region that can be cut by the pigment A contained in the material of the present invention can be obtained. Furthermore, in this aspect, when the curable composition of the present invention contains a colored material that shields visible light in addition to the material of the present invention, an infrared transmission filter can be manufactured. Furthermore, in this aspect, when the curable composition of the present invention contains a color colorant in addition to the material of the present invention, it is possible to manufacture an infrared cut filter having a function as a color filter.

And, for example, when the pigment A in the material of the present invention is a color pigment, a color filter can be manufactured by using a curable composition containing the material of the present invention.

In addition, in the present invention, the infrared cut filter refers to a filter that transmits light with a wavelength in the visible region (visible light) and shields at least a part of light with a wavelength in the near-infrared region (near infrared). The infrared cut filter may transmit all light of wavelengths in the visible region, or may transmit light of a specific wavelength region among light of wavelengths of the visible region and shield light of a specific wavelength region. In addition, in the present invention, the color filter refers to a filter that passes a specific wavelength range in visible light and shields the specific wavelength range.

Regarding the viscosity of the curable composition of the present invention, when a cured film is formed by coating, it is 1~3000mPa. s is better. The lower limit is 2mPa. s or more is better, 3mPa. s or more is more preferable. The upper limit is 100mPa. s or less is better, 50mPa. s or less is better, 30mPa. s or less is further preferred, 15mPa. s or less is particularly good.

The total solid content of the curable composition of the present invention is changed depending on the coating method, and for example, 1 to 50% by mass is preferable. 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, it can be preferably used for infrared cut filters on the light-receiving side of solid-state imaging devices (for example, infrared cut filters for wafer-level lenses, etc.), solid An infrared cut filter on the back side of the imaging element (the side opposite to the light-receiving side), etc. In particular, it can be suitably used as an infrared cut filter on the light-receiving side of a solid-state imaging element.

<Cured film>

Next, the cured film of the present invention will be described.

The cured film of the present invention is obtained by curing the curable composition of the present invention described above. The cured film of the present invention can be used as an infrared cut filter, an infrared transmission filter, a color filter, and the like. The cured film of the present invention may have a pattern or a film without a pattern (flat film).

When the cured film of the present invention is used as an infrared transmission filter, it is preferable to have the following spectral characteristics (1) or (2). According to this aspect, it can be set as a film capable of transmitting infrared light (preferably light with a wavelength of 900 nm or more) with less noise caused by visible light.

(1): The light transmittance in the thickness direction of the film has a maximum value of 20% or less in the wavelength range of 400 to 830 nm, and the light transmittance in the thickness direction of the film is the smallest in the wavelength range of 1000 to 1300 nm The value is preferably 70% or more. The maximum value of the transmittance of light 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 transmittance of light 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 transmittance of light in the thickness direction of the film is 20% or less at the maximum value in the wavelength range of 450 to 650 nm, and the transmittance of light with a wavelength of 835 nm in the thickness direction of the film is 20% or less, and the thickness of the film The light transmittance in the direction preferably has a minimum value of 70% or more in the wavelength range of 1000 to 1300 nm. The transmittance of light in the thickness direction of the film is preferably 20% or less in the wavelength range of 450 to 650 nm, and more preferably 10% or less. The transmittance of light in the thickness direction of the film is preferably 50% or less in the wavelength range of 650 to 835 nm, and more preferably 30% or less. The transmittance of light with 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 transmittance of light 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 characteristics of the cured film of the present invention are measured by the value of the transmittance in the range of wavelength 300 to 1300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

When the cured film of the present invention is used as an infrared cut filter or an infrared transmission filter, it is also possible to use an infrared cut filter and an infrared transmission filter in combination. By using an infrared cut filter and an infrared transmission filter in combination, it can be preferably used as an infrared sensor for detecting infrared rays of a specific wavelength. When two filters are used in combination, one of the infrared cut filter and the infrared transmission filter can be set as a cured film formed using the curable composition of the present invention (cured film of the present invention), and the other can be set It is a cured film formed using a curable composition other than the curable composition of the present invention. In addition, both of them may be constituted by the cured film of the present 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 in the thickness direction, the infrared cut filter can be formed on a substrate different from the substrate on which the color filter is formed. Other components (for example, microlens, planarization layer, etc.) constituting the solid-state imaging element are interposed.

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 even more preferably 0.3 μm or more.

The cured film of the present invention can be used in various devices such as solid-state imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Film Semiconductor), infrared sensors, and image display devices.

<Optical Filter>

Next, the optical filter of the present invention will be described. The optical filter of the present invention has the cured film of the present invention described above. 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, it is also preferable that the optical filter of the present invention has pixels using the cured film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black, and colorless.

<Pattern Formation Method>

The pattern forming method of the present invention includes: using the curable composition of the present invention in The process of forming the hardenable composition layer on the support; and the process of patterning the hardenable composition layer by photolithography or dry etching is preferred.

The pattern formation method may be a pattern formation method based on the photolithography method, or a pattern formation method based on a dry etching method.

If it is a pattern forming method based on the photolithography method, the dry etching process is not required, so the effect of reducing the number of processes can be obtained.

In the case of a pattern formation method based on a dry etching method, the curable composition does not require a photolithography function, so the effect of increasing the concentration of pigments and the like can be obtained.

The pattern formation based on the photolithography method includes a process of forming a curable composition layer on a support using a curable composition, a process of exposing the curable composition layer into a pattern, and developing and removing the unexposed part to form a pattern. The manufacturing process is better. A process of baking the hardenable composition layer (pre-baking process) and a process of baking the developed pattern (post-baking process) can be set according to needs.

In addition, the pattern formation based on the dry etching method includes a process of forming a curable composition layer on a support with a curable composition and hardening to form a hardened layer, a process of forming a photoresist layer on the hardened layer, The process of patterning the photoresist layer by exposure and development to obtain the photoresist pattern and the process of dry etching the hardened layer to form the pattern using the photoresist pattern as an etching mask are preferable. Hereinafter, each manufacturing process will be described.

<<The process of forming the curable composition layer>>

In the process of forming the curable composition layer, the curable composition is used to form the curable composition layer on the support.

As the support, for example, a solid-state imaging element substrate in which a solid-state imaging element (light-receiving element) such as 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 imaging device forming surface side (front surface) of the solid-state imaging device substrate, or may be formed on the solid-state imaging device non-forming surface side (back surface).

A primer layer can be provided on the support body as needed to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.

As a method of applying the curable composition to the support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

The hardenable composition layer formed on the support can be dried (pre-baked). When the pattern is formed by a low-temperature process, pre-baking may not be performed.

When performing the pre-baking, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be set to 50°C or higher, for example, and can also be set to 80°C or higher. By setting the pre-baking temperature to 150°C or lower, for example, when the photoelectric conversion film of the image sensor is composed of organic materials, these characteristics can be maintained more effectively.

The pre-baking time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and more preferably 80 to 220 seconds. Drying can be performed by a hot plate, an 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.

(In the case of pattern formation by photolithography method)

<<Exposure Process>>

Next, the curable composition layer is exposed in a pattern (exposure process). For example, by exposing the curable composition layer using an exposure device such as a stepper through a mask having a predetermined mask pattern, pattern exposure can be performed. Thereby, the exposed part can be hardened.

As the radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays can be preferably used (i-rays are particularly preferred). The irradiation amount (exposure amount) ^{is preferably 30 to 5000 mJ/cm 2,} for example. The upper limit is ^{preferably 3000 mJ/cm 2} or less, more preferably 2000 mJ/cm ² or less, and even more ^{preferably 1500 mJ/cm 2} or less. The lower limit is ² or more good 50mJ / cm, 80mJ / cm ² or more is particularly good.

The oxygen concentration during exposure can be appropriately selected. In addition to performing it in the atmosphere, for example, it can be in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume or less, preferably 5% by volume or less, more preferably Substantially oxygen-free) exposure can also be exposed in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume or more, preferably 30% by volume or more, more preferably 50% by volume or more). Further, exposure illuminance can be appropriately set, typically from ^{1000W / m 2 ~ 100000W / m} 2 ( e.g., 5000W / m ² or more, preferably 15000W / m ² or more, more preferably 35000W / m ² or more) selected from the range . The oxygen concentration and the exposure illuminance can be combined with appropriate conditions. For example, the oxygen concentration can be 10% by ^{volume and the illuminance is 10,000 W/m 2} , the oxygen concentration is 35% by volume, and the illuminance is 20,000 W/m ² .

<<Development process>>

Next, the unexposed part is removed by development to form a pattern. Development and removal of unexposed areas It can be done with a developer. Thereby, the curable composition layer of the unexposed part in the exposure process is dissolved in the developing solution, and only the light-hardened part remains.

As the developer, an organic alkaline developer that does not cause damage to the solid-state imaging element or circuit of the substrate is preferable.

The temperature of the developer is preferably 20 to 30°C, for example. The developing time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal, the following process can be repeated several times: the developer is shaken off every 60 seconds, and the developer is further supplied again.

As the alkali agent used in the developer, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide Ammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, dimethylbis(2- Hydroxyethyl) ammonium hydroxide and other organic alkali agents. As the developer, it is preferable to use an alkaline aqueous solution obtained by diluting these alkaline agents with pure water. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.

In addition, an inorganic base can be used as a developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. are preferred.

In addition, a surfactant can be used as the developer. As an example of the surfactant, the surfactant described in the above-mentioned curable composition can be mentioned, and a nonionic surfactant is preferred. In addition, when a developer composed of such an alkaline aqueous solution is used, it is generally preferable to wash (rinse) with pure water after development.

After development, heat treatment (post-baking) can also be performed after drying. Post-baking is a post-development heat treatment to complete the hardening of the film. Post-bake In this case, the post-baking temperature is preferably 100 to 240°C, for example. From the viewpoint of film hardening, 200~230°C is more preferable. In addition, when organic electroluminescence (organic EL) elements are used as the light source, or when the photoelectric conversion film of the image sensor is composed of organic materials, the post-baking temperature is preferably 150°C or less, and more preferably 120°C or less. Preferably, 100°C or lower is more preferred, and 90°C or lower is particularly preferred. The lower limit can be set to 50°C or higher, for example.

Regarding post-baking, the developed film can be continuously or intermittently performed using a heating mechanism such as a heating plate, a convection oven (hot air circulation type dryer), and a high-frequency heater so as to meet the above-mentioned conditions. Moreover, when the pattern is formed by a low-temperature process, post-baking may not be performed.

(In the case of pattern formation by dry etching)

For pattern formation by dry etching, the hardenable composition layer formed on the support is hardened to form a hardened layer, and then the obtained hardened layer is used as a mask with the patterned photoresist layer. Use etching gas to do it.

Specifically, it is preferable to coat a positive or negative radiation-sensitive composition on the hardened material layer and dry it to form a photoresist layer. In the formation of the photoresist layer, it is preferable to further perform a pre-baking treatment. In particular, as a photoresist forming process, a form in which heat treatment after exposure and heat treatment after development (post-baking treatment) are performed is preferable.

As the photoresist layer, for example, positive-type radiation that induces ultraviolet rays (g-rays, h-rays, i-rays), extreme ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays can be preferably used. Sexual composition. Among the radiations, g-rays, h-rays, and i-rays are preferred, and i-rays are particularly preferred.

Specifically, as a positive radiation-sensitive composition, it contains quinone diazide compound The composition of an alkali-soluble resin and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is irradiated with light with a wavelength of 500 nm or less, and the quinonediazide group is decomposed to generate a carboxyl group, and as a result, the quinonediazide group is changed from an alkali-insoluble state to alkali-soluble. The resolution of the positive photoresist is remarkably excellent, so it is used to make collective circuits such as IC (integrated circuit) or LSI (Large Scale Integration). Examples of the quinonediazide compound include naphthoquinonediazide compounds. Examples of commercially available products include "FHi622BC" (manufactured by FUJIFILM Value from innovation).

As the thickness of the photoresist layer, 0.1 to 3 μm is preferable, 0.2 to 2.5 μm is more preferable, and 0.3 to 2 μm is still more preferable. In addition, the coating method of the positive radiation-sensitive composition can be preferably performed by the above-mentioned coating method of the curable composition.

Then, by exposing and developing the photoresist layer, a photoresist pattern (patterned photoresist layer) provided with a resist through hole group is formed. The formation of the photoresist pattern is not particularly limited, and the conventionally known photolithography technology can be appropriately optimized. A resist through hole group is provided in the photoresist layer by exposure and development, whereby the photoresist pattern as an etching mask used in the next etching is provided on the hardened layer.

The photoresist layer can be exposed via a predetermined mask pattern, using g-rays, h-rays, i-rays, etc., preferably i-rays, to expose the positive or negative radiation-sensitive composition. After exposure, a developing solution is used for developing treatment, thereby removing the photoresist corresponding to the area where the colored pattern is to be formed.

As the developer, any solution can be used as long as it does not affect the cured layer and dissolves the exposed part of the positive resist and the uncured part of the negative resist. For example, a combination of various solvents or an alkaline aqueous solution can be used. As an alkaline aqueous solution, An alkaline aqueous solution prepared by dissolving the alkaline compound so that the concentration becomes 0.001 to 10% by mass, preferably 0.01 to 5% by mass. Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl Base ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, dimethylbis(2-hydroxyethyl)ammonium hydroxide, etc. In addition, when an alkaline aqueous solution is used, the washing process is usually performed with water after development.

Next, using the photoresist pattern as an etching mask, patterning is performed by dry etching in a manner of forming a through hole group in the hardened layer.

As dry etching, from the viewpoint of forming the pattern cross section closer to a rectangular shape or the viewpoint of reducing damage to the support, it is preferable to perform the following form.

It is preferable to include the following form: _{a mixed gas of fluorine-based gas and oxygen (O 2} ) is used to perform the first step of etching to the area (depth) where the support is not exposed; after the first step of etching, use The mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) is preferably the second stage of etching until the area (depth) where the support is exposed; and over etching after the support is exposed . Hereinafter, a specific method of dry etching, first-stage etching, second-stage etching, and over-etching will be described.

Dry etching is performed by determining the etching conditions in advance by the following method.

(1) Calculate the etching rate (nm/min) in the first stage of etching and the etching rate (nm/min) in the second stage of etching, respectively.

(2) Calculate the time required for the etching in the first stage of etching and the second stage respectively The time required to etch the required thickness in the segment etching.

(3) Perform the first stage etching based on the etching time calculated in (2) above.

(4) Perform the second stage etching based on the etching time calculated in (2) above. Alternatively, the etching time may be determined by end point detection, and the second stage etching may be performed according to the determined etching time.

(5) Calculate the over-etching time with respect to the total time of (3) and (4) above, and perform over-etching.

As the mixed gas used in the first-stage etching process, it is preferable to _{include a fluorine-based gas and oxygen (O 2} ) from the viewpoint of processing the organic material as the film to be etched into a rectangular shape. In addition, the first stage of the etching process can avoid damage to the support by setting it to be etched to the area where the support is not exposed. In addition, in the first stage of the etching process, the mixed gas of fluorine-based gas and oxygen is used to etch to the area where the support is not exposed. From the viewpoint of avoiding damage to the support, the second stage of the etching process and the over-etching process use nitrogen. It is preferable to perform the etching process with a mixed gas of oxygen and oxygen.

The ratio of the etching amount in the first-stage etching process to the etching amount in the second-stage etching process is preferably determined in a manner that does not damage the rectangularity based on the etching process in the first-stage etching process. In addition, the ratio of the latter 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 less than 50%, 10~ 20% is better. The amount of etching is an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

In addition, it is preferable that the etching includes an over-etching process. The over-etching process is preferably performed by setting the over-etching ratio. In addition, it is better to calculate the over-etching ratio based on the etching treatment time performed first. The over-etching ratio can be set arbitrarily, but from the perspective of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched, 30% or less of the etching treatment time in the etching process is preferred, and 5-25% is more preferred. 10 ~15% is particularly good.

Then, the photoresist pattern remaining after the etching (ie, the etching mask) is removed. The removal of the photoresist pattern preferably includes a process of applying a stripping liquid or a solvent to the photoresist pattern to set the photoresist pattern into a removable state, and a process of removing the photoresist pattern by washing water.

As a process for applying a stripper or solvent to the photoresist pattern to make the photoresist pattern in a removable state, for example, it is possible to add at least a stripper or solvent to the photoresist pattern and let it stay for a predetermined period of time to make puddles. The process of paddle development. There is no particular limitation on the time for stagnation of the peeling liquid or the solvent, but several tens of seconds to several minutes are preferred.

In addition, as a process of removing the photoresist pattern by using cleaning water, for example, a process of spraying cleaning water from a spray nozzle or spray nozzle to the photoresist pattern to remove the photoresist pattern can be cited. As washing water, pure water can be preferably used. In addition, examples of the spray nozzle include a spray nozzle whose spray range encompasses the entire support body, or a movable spray nozzle whose movable range encompasses the entire support body. When the spray nozzle is movable, the photoresist pattern can be removed more effectively by moving the cleaning water from the center of the support body to the end of the support body more than two times during the process of removing the photoresist pattern.

The peeling liquid usually contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include (1) hydrocarbon compounds, (2) halogenated hydrocarbon compounds, (3) alcohol compounds, (4) ether or formaldehyde compounds, (5) ketone or aldehyde compounds, (6) Ester compound, (7) Polyol compound, (8) Carboxylic acid or its anhydride compound, (9) Phenol compound, (10) Nitrogen compound, (11) Sulfur compound, (12) Fluorine-containing compounds. As the peeling liquid, it is preferable to contain a nitrogen-containing compound, and it is more preferable to contain a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

As the acyclic nitrogen-containing compound, an acyclic nitrogen-containing compound having a hydroxyl group is preferred. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine , Diethanolamine, triethanolamine, etc., preferably monoethanolamine, diethanolamine, triethanolamine, more preferably monoethanolamine (H2NCH2CH2OH). In addition, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, Pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorphine, 2,4-lutidine, 2,6-lutidine, etc., preferably N-methyl- 2-pyrrolidone, N-ethyl mopholin, more preferably N-methyl-2-pyrrolidone (NMP) is more preferable.

The peeling liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among them, at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as the acyclic nitrogen-containing compound and as a cyclic nitrogen-containing compound The nitrogen compound is preferably at least one selected from N-methyl-2-pyrrolidone and N-ethyl mopholin, including monoethanolamine and N-methyl Al-2-pyrrolidone is further preferred.

When removing with a stripping solution, the photoresist pattern formed on the pattern can be removed. When the storage material as the etching product is attached to the sidewall of the pattern, the storage material may not be completely removed. The storage material refers to the part where the etching product adheres to and accumulates on the side wall of the hardened material layer.

As the peeling liquid, the content of the acyclic nitrogen-containing compound is 9 parts by mass or more and 11 parts by mass or less relative to 100 parts by mass of the peeling liquid, and the content of the cyclic nitrogen-containing compound is 65 parts by mass or more relative to 100 parts by mass of the peeling liquid And 70 parts by mass or less of peeling liquid is preferable. In addition, the peeling liquid is preferably a peeling liquid obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

<Solid-state imaging element, camera module>

The solid-state imaging element of the present invention has the cured film of the present invention described above.

In addition, the camera module of the present invention has a solid-state imaging element and the cured film of the present invention (preferably an infrared cut filter). The structure of the solid-state imaging element is a structure having the cured film of the present invention, and it is not particularly limited as long as it functions as a solid-state imaging element. For example, the following structures can be mentioned.

The structure is as follows: on the support, there are a plurality of photoelectric devices that constitute the light-receiving area of a solid-state imaging element (charge coupled device (CCD) image sensor, complementary metal oxide film semiconductor (CMOS) image sensor, etc.) Diodes and transfer electrodes made of polysilicon, etc., on the photodiodes and transfer electrodes, there is a shielding film made of tungsten, etc., with only the light-receiving part of the photodiode opening, and the shielding film has a shielding film to cover the entire shielding film The surface and the photodiode light-receiving part are formed by silicon nitride, etc. A protective film is prepared, and the film of the present invention such as an infrared cut filter or an infrared transmission filter is provided on the device protective film.

In addition, it may be a structure having a light-concentrating mechanism (for example, a micro lens, etc., the same below) on the device protective film and below the cured film of the present invention (near the support side), or on the cured film of the present invention It has the structure of concentrating mechanism, etc.

<Infrared Sensor>

The infrared sensor of the present invention has the cured film of the present invention described above. The structure of the infrared sensor of the present invention is a structure having the cured film of the present invention, and it is not particularly limited as long as it functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.

In the infrared sensor 100 shown in FIG. 1, the symbol 110 is a solid-state imaging element.

The imaging area provided on the solid-state imaging element 110 has 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 imaging element 110. The region 114 is provided with a resin layer (for example, a transparent resin layer, etc.) through which light of the wavelength of the infrared transmission filter 113 can be transmitted. In the embodiment shown in FIG. 1, the resin layer is arranged on the area 114, but the infrared transmission filter 113 may be formed in the area 114. That is, the infrared transmission filter 113 can be formed on the solid-state imaging element 110.

The color filter 112 and the infrared transmission filter 113 are arranged on the hν side of the incident light. Lens 115. A planarization layer 116 is formed to cover the microlens 115.

In addition, 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 the two may be different.

In addition, in the embodiment shown in FIG. 1, the color filter 112 is provided on the side of the incident light hν than the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 can be changed to filter the infrared cut The filter 111 is arranged closer to the incident light hν side than the color filter 112.

In addition, 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 two filters do not necessarily have to be adjacent, and other layers may be provided between the two filters.

In addition, in the embodiment shown in FIG. 1, the infrared cut filter 111 and the color filter 112 are provided as independent components, but the color filter 112 may contain the composition of the present invention so that the color filter 112 has the function of The function of the infrared cut filter. In this case, the infrared cut filter 111 can be omitted.

The infrared cut filter 111 selects its characteristics according to the emission wavelength of the infrared light diode (infrared LED) described later. For example, the infrared cut filter 111 transmits visible light (for example, light with a wavelength of 400 to 650 nm) and shields light in the near-infrared region (preferably in the range of 700 to 1300 nm, more preferably in the range of 700 to 1000 nm). At least a part of the filter is preferable. 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 formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and can be formed using conventionally known pixels. Use color filters. For example, a color filter formed with pixels of red (R), green (G), and blue (B) can be used. For example, refer to the description of paragraphs 0214 to 0263 of JP 2014-043556 A, which are incorporated into this specification. The color filter 112 can also be composed of a cured film using the curable composition of the present invention.

The infrared transmission filter 113 selects its characteristics according to the emission wavelength of the infrared LED described later.

For example, when the emission wavelength of an infrared LED is 850nm, in the infrared transmission filter 113, the light transmittance in the thickness direction of the film is preferably 30% or less, and more preferably 20% or less. Preferably, 10% or less is more preferable, and 0.1% or less is particularly preferable. It is preferable that the transmittance satisfies the aforementioned conditions in the entire wavelength range of 400 to 650 nm. The maximum value of 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 range of a wavelength of 800 nm or more (preferably 800 to 1300 nm) is preferably 70% or more, more preferably 80% or more, and 90% The above is further preferred. The transmittance preferably satisfies the above-mentioned condition in a part of the wavelength range of 800 nm or more, and preferably satisfies the above-mentioned 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, more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. If the film thickness is in the above-mentioned range, it can be set as a film satisfying the above-mentioned spectral characteristics.

The methods for measuring the spectral characteristics, film thickness, and the like of the infrared transmission filter 113 are shown below.

Regarding the film thickness, the dried substrate with the film was measured with a stylus-type surface profile measuring instrument (DEKTAK150 manufactured by ULVAC, INC.).

Regarding the spectral characteristics of the film, the value of the transmittance was measured in a wavelength range of 300 to 1300 nm using an ultraviolet-visible light-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

The infrared transmission filter 113 having the above-mentioned spectral characteristics can be manufactured using a curable composition containing a colored material that shields visible light. The detailed content of the colored material that shields visible light is the same as that described in the above-mentioned composition of the present invention.

And, for example, when the emission wavelength of an infrared LED is 940 nm, the transmittance of light in the thickness direction of the film in the infrared transmission filter 113 is 20% or less at the maximum value of the wavelength range of 450 to 650 nm. The transmittance of light with a wavelength of 835nm is 20% or less, and the transmittance of light in the thickness direction of the film is preferably 70% or more at the minimum value of the wavelength range of 1000 to 1300 nm.

The infrared transmission filter 113 having the above-mentioned spectral characteristics can be manufactured using a curable composition containing a colored material that shields visible light and a compound having a maximum absorption wavelength in the wavelength range of 750 to 950 nm. The detailed content of the colored material that shields visible light is the same as that described in the above-mentioned composition of the present invention. Examples of the compound having a 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 or the infrared absorber described in the composition of the present invention described above.

<Image display device>

The cured film (preferably an infrared cut filter) of the present invention can also be used in image display devices such as liquid crystal display devices or organic electroluminescence (organic EL) display devices. For example, by using together with each colored pixel (e.g. red, green, blue) to shield the infrared light contained in the backlight of the display device (e.g. white light emitting diode (white LED)), it can prevent the malfunction of peripheral equipment It is used for the purpose of forming infrared pixels in addition to the colored display pixels.

The definition of display devices and the details of each display device are described in, for example, "Electronic Display Equipment (Akio Sasaki, issued by the Industrial Research Council of Co., Ltd. in 1990)", "Display Equipment (Jun Akio Ibuki, Industrial Books (Co., Ltd.) ) Issued in the first year of Heisei)” and so on. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, issued by the Industrial Research Council of Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

The image display device may be an image display device having a white organic EL element. As a white organic EL element, a tandem structure is preferable. Regarding the tandem structure of organic EL elements, it is described in Japanese Patent Laid-Open No. 2003-45676, Supervised by Akoyoshi Mikami, "The Frontline of Organic EL Technology Development-High Brightness, High Accuracy, Longer Lifetime, Technology Collection -", Technical Information Association, pages 326-328, 2008, etc. The spectrum of the white light emitted by the organic EL element has a strong maximum emission in the blue region (430nm-485nm), green region (530nm-580nm) and yellow region (580nm-620nm) The light peak is better. In addition to these luminescence peaks, it is better to have a very large luminescence peak in the red region (650nm-700nm).

[Example]

Examples are given below to illustrate the present invention in more detail. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "%" and "parts" are quality standards.

<Material manufacturing method>

(Example 1)

Stirring 8.74 parts by mass of diphenyl borinic 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 chloride was added dropwise and allowed to react for 30 minutes. After heating and refluxing at an external temperature of 130°C for 3 hours, it was cooled to room temperature, and 57 mL of toluene was added and filtered. 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. It was cooled to room temperature and filtered, 88 mL of methanol was added to the obtained crystal again, and it was heated to reflux at an external temperature of 80° C. for 1 hour. It was cooled to room temperature and filtered, thereby obtaining a material (C-1) containing the pigment (A-1) and the following compound (B-30).

【Chemical formula 46】

(Examples 2~8, 11~25)

When synthesizing each compound (pigment A), in the final process, the compound described in the following table was added as compound B to synthesize each pigment, except that the same method as in Example 1 was used to produce (C-2 )~(C-8), (C-11)~(C-25).

(Example 9)

Compound (A-2-b)

The compound (A-2-b) was synthesized according to the following scheme.

Using 4-(1-methylpentyl)benzonitrile as a raw material, the compound (A-2-a) was synthesized according to the method described in the specification of U.S. Patent No. 5,969,154.

¹ H-NMR (DMSO (dimethyl sulfite): 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 compound (A-2-a) and 15.4 parts by mass of 2-(2-benzothiazole)acetonitrile were stirred in 230 parts by mass of toluene, and then 45.0 parts by mass of phosphatidyl chloride were added dropwise, and the mixture was heated to reflux 3.5 hours. After 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 the dropwise addition, it was stirred at room temperature for 30 minutes. The precipitated crystals were filtered, and washed with 100 parts by mass of methanol. 200 parts by mass of methanol was added to the obtained crystals, heated to reflux for 30 minutes, allowed to cool to 30°C, and the crystals were filtered. The obtained crystal was air-dried at 40°C for 12 hours to obtain 8.8 parts by mass of the compound (A-2-b).

¹ H-NMR (CDCl3): 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 in place of compound (A-1-a), and compound (B-61) was used in place of compound (B-30). In addition, it was used with material (C-1 In the same way as the synthesis of ), the material (C-9) containing the pigment (A-2) and the compound (C-61) was obtained.

【Chemical formula 48】

(Example 10)

Synthesis of compound (A-3-c)

The compound (A-3-c) was synthesized according to the following scheme.

In 200 parts by mass of water, 50.0 parts by mass of 2-amino-6-methoxybenzothiazole and 93.4 parts by mass of potassium hydroxide were heated to reflux for 24 hours, and cooled to 10°C or lower. 6 mol/L hydrochloric acid and acetic acid were added while maintaining the pH of the reaction liquid to 6 at 10°C or lower. The precipitated crystals were filtered, and washed with 200 parts by mass of water. After mixing all the obtained crystals, 18.3 parts by mass of malononitrile, 19.3 parts by mass of acetic acid, and 172 parts by mass of methanol, the mixture was stirred at 60°C for 1 hour, and then cooled to 10°C or lower. The precipitated crystals were filtered, and washed with 200 parts by mass of methanol. The obtained crystal was air-dried at 40°C for 12 hours to obtain 38.7 parts by mass of compound (A-3-b).

¹ H-NMR (CDCl3): 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) was synthesized in the same manner as the synthesis of compound (A-2-b).

¹ H-NMR (DMSO (dimethyl sulfide): 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)

In Example 9, the compound (A-3-c) was used instead of the compound (A-2-b), except that the pigment (A-3) was obtained by the same method as the synthesis of the material (C-9) And compound (B-61) material (C-10).

【Chemical formula 50】

(Comparative example 1)

10 parts by mass of the pigment (NPC-1) and 3 parts by mass of the compound (B-30) were added to a mortar, stirred with a mortar hammer and mixed until uniform, thereby obtaining a 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, stirred with a mortar hammer and mixed until uniform, thereby obtaining 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. The amount of compound B contained in each material was calculated from the eluted amount of compound B from each material.

Next, 16.6 mL of methanol was added to 1 g of each material obtained above, and the mixture was stirred and washed at 80°C for 30 minutes. The washed filtrate was taken, and 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. ^{The mass X 2} of the compound B in the material after washing with methanol was calculated from the elution amount of the compound B from each material. In addition, the material washed with methanol was air-dried for 12 hours at 45°C, and the mass X ³ of the solid content of the material washed with methanol was measured.

Regarding the obtained material, ^{X 1 was} obtained by the following formula ^{based on the mass X 2 of the compound B in the material after washing with methanol and the mass X 3} of the solid content of the material after washing with methanol.

X ¹ =(X ² /X ³ )×100

In addition, methanol is a solvent that satisfies the requirements 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.

From the above results, it was confirmed that in Examples, the requirement ^{that the value of X 1} is 0.99 or more is satisfied, and the compound B is 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 off from the pigment A.

The materials described 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 JP 2012-8532 A.

【Chemical formula 52】

Compound B: The following compound

【Chemical formula 53】

【Chemical formula 54】

Synthesis of compound (B-61)

The compound (B-61) was synthesized according to the following scheme.

Stir 3.9 parts by mass of 2-aminoethyl diphenyl hypoborate and 6.0 parts by mass of compound (A-2-b) in 60 parts by mass of toluene, and add 10.6 parts dropwise over 10 minutes at an external temperature of 40°C. Parts by mass of titanium tetrachloride and stirred for 30 minutes. The external temperature was increased to 130°C and heated to reflux for 3 hours. It was left to cool until the internal temperature became 30°C, and 40 parts by mass of methanol was added dropwise while maintaining the internal temperature at 30°C or lower. After dripping, it was stirred for 30 minutes, and the precipitated crystal was filtered and washed with 35 parts by mass of methanol. 50 parts by mass of methanol was added to the obtained crystals, heated under reflux for 30 minutes, allowed to cool to 30°C, and the crystal was filtered twice. The obtained crystal was air-dried at 40°C for 12 hours to obtain 4.6 parts by mass of 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 butanesulfonic acid and 5.6 parts by mass of DMAc were added, And stirred at room temperature for 10 minutes. The external temperature was increased to 105°C and heated for 4 hours. Then, it was left to cool to an internal temperature of 30°C, and the precipitated crystal was filtered. To 30 parts by mass of 4mol/L hydrochloric acid aqueous solution, the obtained crystals were added in small amounts while maintaining the internal temperature below 30°C, and stirred at room temperature for 30 minutes, and the precipitated crystals were filtered twice. To the obtained crystal, 60 parts by mass of ethyl acetate was added, heated under reflux for 30 minutes, allowed to cool to 30°C, and the crystal was filtered three times. The obtained crystal was blow-dried at 50°C for 24 hours to obtain 2.74 parts by mass of the compound (B-61).

¹ H-NMR(DMSO): δ1.76(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)

Except that propanesulfonic acid was used instead of butanesulfonic acid, the compound (B-113) was obtained by the same method as the compound (B-61).

Synthesis of compound (B-81)

Add 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, 16.7 parts by mass of triethylamine, and Stir for 5 minutes. The external temperature was increased to 110°C and heated for 4 hours. Leave to cool until the internal temperature becomes 30°C, and filter the precipitated crystals. Then, washing was performed 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 crystals, heated to reflux for 30 minutes, allowed to cool to 30°C, and the precipitated crystals were filtered. 200 parts by mass of dimethyl sulfoxide was added to the obtained crystal, and heated at 80°C for 30 minutes. After heating, it was allowed to cool to 30°C, and the precipitated crystals were filtered. 200 parts by mass of methanol was added to the obtained crystals, heated under reflux for 30 minutes, allowed to cool to 30°C, and the precipitated crystals were filtered. The obtained crystal was dried by blowing air 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)

Use isonicotinic acid chloride and nicotinic acid chloride instead of 4-[(diethylamino)methyl]-benzoic acid chloride, except that the same method as compound (B-81) is used, Compounds (B-114) and (B-115) were obtained.

Synthesis of compound (B-119)

Add 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, and stir for 5 minutes . Increase the external temperature to 100°C and heat 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. It was left to cool until the internal temperature became 30°C, and 40 parts by mass of 1 mol/L sodium hydroxide aqueous solution was added while maintaining the internal temperature at 30°C or lower. After the dripping, it was stirred for 30 minutes, the precipitated crystal was filtered, and washed with 35 parts by mass of distilled water. The obtained crystal was dried by blowing air at 50°C for 24 hours to obtain 2.1 parts by mass of the compound (B-119).

¹ H-NMR (CDCl3): 2.21 (quintet, 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)>

To 10 parts by mass of the material shown in the following table, 3.0 parts by mass of the pigment derivative shown in the following table, 7.8 parts by mass of the resin shown in the following table, 109 parts by mass The organic solvent shown in the table and 520 parts by mass of 0.5 mm diameter zirconia beads were subjected to a 30-minute dispersion treatment with a paint shaker. After that, filtration was performed using DFA4201NXEY (0.45 μm nylon filter) manufactured by NIHON PALL LTD., and the beads were separated by filtration to prepare a composition (dispersion liquid).

<Evaluation of Dispersibility>

Using an E-type viscometer, the viscosity of each composition was measured at 25°C and 1000 rpm, and the dispersibility was evaluated based on the following criteria.

A: 20mPa. s or less

B: More than 20mPa. s and 100mPa. s or less

C: More than 100mPa. s

According to the above results, the dispersibility of the examples is good. In contrast, the comparative example that does not include the material of the present invention has poor dispersibility.

In Examples 101 to 127, the same effect can be obtained even if the material before cleaning with methanol is used as the materials C-1 to C-25.

The ingredients shown in the above table are as follows.

(Materials, pigments, pigment derivatives)

C-1~C-25, C-1', C-2': The above materials C-1~C-25, C-1', C-2' after ^{calculating X 1 (after methanol cleaning)}

DP-1, B-1, B-30, B-61: the above structure

(Resin)

D-1: The following structure (resin manufactured by using the macromonomer AA-6 manufactured by TOAGOSEI CO., LTD as a raw material, and 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=11483)

D-5: The following structure (Mw=22900)

【Chemical formula 58】

PGMEA: Propylene Glycol Methyl Ether Acetate

PGME: 1-methoxy-2-propanol

<Preparation of curable composition>

(Examples 201 to 225, Comparative Examples 201 to 203)

The following components were mixed to prepare a curable composition of Example 201. In addition, in the curable composition of Example 201, the dispersion of Example 101 was changed to the dispersion of Examples 102 to 125 and Comparative Examples 101 to 103, thereby preparing Examples 202 to 225 and Comparative Examples 201 to 203. The near-infrared absorbing composition.

‧The dispersion 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: The following structure (Mw: 11000)

Polymerization initiator 1: The following structure

Polymerization inhibitor 1: p-methoxyphenol (manufactured by SANRITSU CHEMICALS)

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 stirring device and a thermometer, 50.0 parts by mass of a compound having an epoxy group (manufactured by NOF CORPORATION, Marr proof G-0150M weight average molecular weight 10000) and 100 parts by mass of propylene glycol methyl ether acetic acid are added Ester, stir and dissolve at 20~35℃ for 2 hours. Next, 0.75 parts by mass of the composition (dispersion liquid) of Example 126 was added and stirred at 20 to 35°C until uniform. Furthermore, 0.500 parts by mass of succinic acid (1 part by mass relative to 100 parts by mass of the epoxy group-containing compound) was added, and the mixture was stirred at 20 to 35°C for 1 hour to obtain a curable composition.

(Example 227)

100 parts by mass of the following resin A (binder polymer), 0.08 parts by mass of the composition (dispersion liquid) of Example 127, and propylene glycol methyl ether acetate were added to the container, and the concentration of resin A was adjusted to 20 mass %, thereby obtaining a curable composition.

‧Resin A: The following structure (referring to the method described in paragraphs 0141 to 0143 of Japanese Patent Application Laid-Open No. 2015-40895 to synthesize. Mw=137,000)

<Evaluation of in-plane uniformity>

Each curable composition of Examples 201 to 225 and Comparative Examples 201 to 203 was spin-coated on an 8 inch (200 mm) glass wafer, and dried under conditions of 100° C., 120 seconds, and a hot plate to obtain a cured film.

In addition, the curable composition of Example 226 was dropped on a glass substrate placed on a spin coater, and the substrate surface was coated by rotating the substrate at 1000 rpm for 30 seconds, and then performing a 10 minute process at 80°C. It was dried to remove the solvent, and thermally cured at 150°C for 3 hours to obtain a cured film.

In addition, the curable composition of Example 227 was applied 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 for 8 hours under reduced pressure to obtain a cured film with a thickness of 0.1 mm.

The obtained cured film was measured by Dektak (manufactured by Bruker Corporation) at 5 points in total at 2 cm intervals from the center to the end, and the in-plane uniformity was evaluated based on the following criteria.

A: (Max-Min)/Min<3%

(Max-Min)/Min

7% B: 3

(Max-Min)/Min

7%

C: (Max-Min)/Min>7%

In addition, "Min" is the film thickness of the thinnest part, and "Max" is the film thickness of the thickest part.

According to the above results, the in-plane uniformity of the examples is good. The dispersion used in the curable composition of the example has good pigment dispersibility, so the curable composition Low viscosity and good coating properties. Therefore, it is considered that in the examples, unevenness is less likely to occur on the coating film, and the in-plane uniformity is improved. In contrast, the comparative example that does not include the material of the present invention has poor in-plane uniformity.

In the embodiment, by further deploying colored materials that shield visible light, an infrared transmission filter can be obtained.

100‧‧‧Infrared sensor

110‧‧‧Solid-state image sensor

111‧‧‧Infrared cut filter

112‧‧‧Color filter

113‧‧‧Infrared transmission filter

114‧‧‧Region

115‧‧‧Micro lens

116‧‧‧Planarization layer

Claims (19)

A material comprising a pigment A and a compound B having an adsorbent structure for resin, wherein the solubility of the pigment A with respect to the solvent C at 25° C. is 0.02% by mass or less, and the compound B is of the formula (B1) The indicated pigment derivatives have a solubility of 0.2% by mass or more with respect to solvent C at 25°C. The solvent C is methanol, ethanol, tetrahydrofuran, acetone, n-propanol, isopropanol, n-butanol, and second butanol , N-hexanol, toluene, xylene, benzene, ethylbenzene, carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene, dimethylformamide Amine, dimethyl acetamide, dimethyl sulfide, tetrahydrothiophene, n-pentyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, methyl iso Butyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, 2- Butanol, ethyl lactate or propylene glycol monomethyl ether, the compound B in the material is attracted to the inside of the particles of the pigment A, and X ¹ represented by the following formula (I) of the material is 0.99 Above, X ¹ =(X ² /X ³ )×100...(I) X ² is the mass of the compound B in the material after the material is immersed in the solvent C, X ³ is the mass of the solid content of the material after being immersed in the solvent C,

In the formula, P represents a pigment structure, L represents a single bond or a linking group, X represents an acidic group, a basic group, a group with a salt structure or a phthalimide group, m represents an integer of 1 or more, and n represents An integer of 1 or more, and 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. The material described in item 1 of the scope of patent application, wherein the pigment A has absorption in the near-infrared region. The material described in item 1 of the scope of patent application, wherein the maximum absorption wavelength of the pigment A is in the range of 700 to 1200 nm. The material described in item 1 of the scope of patent application, wherein the pigment A is selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, pyrrolopyrrole compounds, cyanine compounds, dithiol metal complexes, naphthalene One or more of quinone compounds, iminium compounds, azo compounds, and squaraine ylide compounds. The material described in item 1 of the scope of patent application, wherein the pigment A is a pyrrolopyrrole compound. The material described in item 5 of the scope of patent application, 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, R ² and R ³ may be bonded to each other to form a ring, R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, R ⁴ may be covalently bonded to at least one selected from R ^1a , R ^1b and R ^{3 or} Coordination bonding, R ^4A and R ^4B each independently represent a substituent. The material according to any one of items 1 to 6 of the scope of patent application, wherein the pigment structure represented by P of the formula (B1) is selected from the group consisting of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, Quinacridone pigment structure, anthraquinone pigment structure, bianthraquinone pigment structure, benzisoindole pigment structure, thiazide indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthalenephthalein At least one of cyanine pigment structure, dioxazine pigment structure, perylene pigment structure, percyclic ketone pigment structure, benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure, and benzoxazole pigment structure. A composition comprising the material described in any one of items 1 to 7 of the scope of the patent application. The composition described in item 8 of the scope of the patent application further contains one or more selected from organic solvents, resins, and pigment derivatives. A curable composition comprising the composition described in item 8 or 9 of the scope of patent application and a curable compound. A cured film using the curable composition described in item 10 of the scope of the patent application. An optical filter having a cured film as described in item 11 of the scope of patent application. The optical filter described in item 12 of the scope of patent application is at least one selected from a color filter, an infrared cut filter, and an infrared transmission filter. The optical filter described in item 12 or 13 of the scope of patent application, which has: the pixels of the cured film described in item 11 of the scope of patent application; and selected from red, green, blue, magenta, yellow, and cyan , Black and colorless pixels. A solid-state imaging element having a cured film as described in item 11 of the scope of patent application. An infrared sensor with a hardened film as described in item 11 of the scope of patent application. A camera module having a solid-state imaging element and a hardened film as described in item 11 of the scope of patent application. A method for manufacturing a material, the material includes pigment A and a compound B having an adsorbent structure to resin, wherein the compound B is a pigment derivative represented by formula (B1), and in the presence of an adsorbent to resin In the case of the compound B of the structure, the raw material compound of the pigment A is reacted to synthesize the pigment A, and the pigment A is selected from a phthalocyanine compound, a naphthalocyanine compound, a perylene compound, and a pyrrolopyrrole compound , Cyanine compounds, dithiol metal complexes, naphthoquinone compounds, iminium compounds, azo compounds, and squaraine ylide compounds,

In the formula, P represents a pigment structure, L represents a single bond or a linking group, X represents an acidic group, a basic group, a group with a salt structure or a phthalimide group, m represents an integer of 1 or more, and n represents An integer of 1 or more, when m is 2 or more, the plural L and X may be different from each other, and when n is 2 or more, the plural X may be different from each other. The pigment structure is selected from pyrrolopyrrole pigment structure, diketone Pyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, dianthraquinone pigment structure, benzisoindole pigment structure, thiazide indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalein Cyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, peruranone pigment structure, benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure and benzoxazole pigment At least one structure. The method for manufacturing the material described in item 18 of the scope of patent application, wherein when the pigment A is synthesized, in the presence of the compound B, the raw material compound of the pigment A is reacted to synthesize the pigment A, And a material in which the compound B is attracted to the inside of the particles of the pigment A is produced.

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