JP2018045011A - Infrared absorbent, composition, film, optical filter, laminate, solid state imaging device, image display apparatus, and infrared sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared absorbent that has a good infrared shielding property and can manufacture a film excellent in heat resistance and light resistance; and to provide a composition, film, optical filter, laminate, solid state imaging device, image display apparatus, and infrared sensor.SOLUTION: The present infrared absorbent contains a near-infrared absorption pigment including, in a molecule, at least one selected from an anion site and a cation site, and a metal component including a metal atom selected from Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn, Si, and Al. The total amount of the metal atom included in the metal component is 0.00001 to 1 parts by mass based on 100 parts by mass of the near-infrared absorption pigment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an infrared absorbent, a composition, a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor.

  Video cameras, digital still cameras, mobile phones with camera functions, and the like use CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state imaging devices for color images. These solid-state imaging devices use silicon photodiodes having sensitivity to infrared rays in the light receiving portion. For this reason, in a solid-state image sensor, visual sensitivity correction may be performed using a near-infrared cut filter. The near-infrared cut filter is manufactured using, for example, a composition containing an infrared absorber.

  As the infrared absorber, diimonium dyes, cyanine dyes, squarylium dyes, porphyrin dyes and the like are known (for example, Patent Documents 1 to 4).

  On the other hand, Patent Document 5 includes (A) a dye multimer, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) an organic solvent, and (X) an inorganic metal containing no dye skeleton. It describes that a chromatic color filter is produced using a colored radiation-sensitive composition having a salt content of 0.1% by mass or less based on the solid content of the salt.

JP 2007-92060 A JP 2008-88426 A JP 2015-172102 A Japanese Patent Laid-Open No. 2006-102862 JP 2012-181502 A

  In recent years, there has been a demand for further improvement of the infrared shielding property in a film containing an infrared absorbent such as a near infrared cut filter. In addition, films containing infrared absorbers such as near-infrared cut filters are required to further improve heat resistance and light resistance, and are not easily colored by heating or light irradiation. What has a property and infrared shielding property is desired.

  Patent Document 5 is a chromatic color filter, and there is no description about a film containing an infrared absorber.

  Therefore, an object of the present invention is to provide an infrared absorber capable of producing a film having good infrared shielding properties and excellent heat resistance and light resistance. Another object of the present invention is to provide a composition, a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared ray that can produce a film having good infrared shielding properties and excellent heat resistance and light resistance. It is to provide a sensor.

Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the above-described object can be achieved by using an infrared absorbent described later. The present invention provides the following.
<1> A near-infrared absorbing dye containing at least one selected from an anion portion and a cation portion in the molecule, and Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn And a metal component containing a metal atom selected from Si and Al, and the total amount of metal atoms contained in the metal component is 0.00001 to 1 part by mass with respect to 100 parts by mass of the near-infrared absorbing dye. Absorbent.
<2> The infrared absorbing agent according to <1>, wherein the near infrared absorbing dye has a maximum absorption wavelength in a range of 650 to 1500 nm.
<3> The near-infrared absorbing dye is selected from a pyrrolopyrrole dye skeleton, a polymethine dye skeleton, a diimonium dye skeleton, a dithiolene dye skeleton, a phthalocyanine dye skeleton, a porphyrin dye skeleton, an azo dye skeleton, a triarylmethane dye skeleton, and a perylene dye skeleton. The infrared absorber according to <1> or <2>, which has a dye skeleton.
<4> A composition comprising the infrared absorbent according to any one of <1> to <3> and a solvent.
<5> The composition according to <4>, further comprising a resin.
<6> The composition according to <4> or <5>, further comprising a pigment derivative.
<7> The composition according to any one of <4> to <6>, further comprising a polymerizable compound and a photopolymerization initiator.
<8> A film using the composition according to any one of <4> to <7>.
<9> An optical filter having the film according to <8>.
<10> The optical filter according to <9>, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter.
<11> A pixel of the film according to <8>,
The optical filter according to <9> or <10>, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.
<12> A laminate having the film according to <8> and a color filter containing a chromatic colorant.
<13> A solid-state imaging device having the film according to <8>.
<14> An image display device having the film according to <8>.
<15> An infrared sensor having the film according to <8>.

  ADVANTAGE OF THE INVENTION According to this invention, the infrared absorber which can manufacture the film | membrane etc. with favorable infrared shielding property and excellent in heat resistance and light resistance can be provided. Moreover, a composition, a film | membrane, an optical filter, a laminated body, a solid-state image sensor, an image display apparatus, and an infrared sensor can be provided.

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

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

<Infrared absorber>
The infrared absorber of the present invention includes a near-infrared absorbing dye containing at least one selected from an anion site and a cation site in the molecule, Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, And a metal component containing a metal atom selected from Pd, Cu, Zn, Si and Al, and the total amount of metal atoms contained in the metal component is 0.00001 to 1 mass per 100 parts by mass of the near-infrared absorbing dye. It is a part.

  By using the infrared absorbent of the present invention, a film having good infrared shielding properties and excellent heat resistance and light resistance can be produced. It is assumed that the mechanism for obtaining such an effect is as follows. That is, the near-infrared absorbing dye contained in the infrared absorbent of the present invention contains at least one kind selected from an anion portion and a cation portion (hereinafter, the anion portion and the cation portion are also referred to as an ionic portion) in the molecule. In addition, ion exchange is likely to occur between the near-infrared absorbing dye and the metal atom of the metal component, and metal ions are easily taken into the dye skeleton. As a result, it is presumed that the crystallinity of the near-infrared absorbing dye is improved, coloring due to heating or light irradiation is less likely to occur, and the heat resistance and light resistance of the film are improved. On the other hand, if the near-infrared absorbing dye takes in too much metal ions, the near-infrared absorbing dye component is lowered, so that the infrared shielding ability is considered to be lowered. However, the metal component is contained in 100 parts by mass of the near-infrared absorbing dye. When the total amount of metal atoms is 0.00001 to 1 part by mass, the amount of metal ions taken into the dye skeleton can be moderately suppressed, and as a result, excellent infrared shielding ability can be maintained. It is thought that it was made.

  In the present invention, the case where a salt is formed with an anion of a near-infrared absorbing dye and a counter cation is included in the case where the molecule has an anion site. Further, the case where a salt is formed with a cation of a near-infrared absorbing dye and a counter anion is also included in the case where the molecule has a cation moiety. Moreover, when it has an anion site | part and a cation site | part in the molecule | numerator of a near-infrared absorption pigment | dye, it is a near-infrared absorption pigment | dye which has an anion site | part and a cation site | part in a molecule | numerator. In the present invention, as the near infrared absorbing dye, a near infrared absorbing dye having an anion portion and a cation portion in the molecule is particularly preferable.

In the infrared absorber of this invention, the total amount of the metal atom contained in a metal component is 0.00001-1 mass part with respect to 100 mass parts of the above-mentioned near-infrared absorption pigment | dye. If the total amount of metal atoms is 0.00001 part by mass or more, ion exchange is likely to occur between the ion site in the near-infrared absorbing dye and the metal atom of the metal component, and a film having excellent infrared shielding properties is formed. be able to. Moreover, if the total amount of metal atoms is 1 part by mass or less, the crystallinity of the near-infrared absorbing dye can be maintained well, and a film excellent in heat resistance and light resistance can be formed. The upper limit of the total amount of metal atoms contained in the metal component is preferably 0.9 parts by mass or less, more preferably 0.8 parts by mass or less, and further preferably 0.7 parts by mass or less. Preferably, it is 0.6 parts by mass or less. The lower limit of the total amount of metal atoms contained in the metal component is preferably 0.00005 parts by mass or more, and more preferably 0.0001 parts by mass or more. According to this aspect, the above-described effects tend to be obtained more remarkably.
In the present invention, the content of the metal atom in the metal component is a value measured by inductively coupled plasma optical emission spectrometry (ICP-OES). Details of the measurement conditions are described in the examples described later.

In the infrared absorbent of the present invention, the content of the near infrared absorbing dye is preferably 90% by mass or more, and more preferably 95% by mass or more based on the total solid content of the infrared absorbent. An upper limit can be made into 99.99999 mass% or less, for example.
In the infrared absorber of the present invention, the content of the metal component is preferably 0.99% by mass or less, more preferably 0.1% by mass or less, based on the total solid content of the infrared absorber. . A lower limit can be 0.00001 mass% or more, for example. Moreover, it is preferable that it is 1.0 mass part or less with respect to 100 mass parts of a near-infrared absorption pigment | dye, and, as for content of a metal component, it is more preferable that it is 0.1 mass part or less. A lower limit can be 0.00001 mass part or more, for example.

  In the infrared absorbent of the present invention, the near infrared absorbing dye preferably has a maximum absorption wavelength in the range of 650 to 1500 nm. The lower limit is preferably 670 nm or more, and more preferably 700 nm or more. The upper limit is preferably 1300 nm or less, more preferably 1200 nm or less, still more preferably 1100 nm or less, and particularly preferably 1000 nm or less.

  In the present invention, the infrared absorber may have an ionic site of a near-infrared absorbing dye in the dye skeleton, or may be in a substituent bonded to the dye skeleton. The type of the near-infrared absorbing dye is not particularly limited as long as it is a dye containing at least one kind (ionic site) selected from an anion site and a cation site in the molecule. Examples include compounds having a dye skeleton selected from a pyrrolopyrrole dye skeleton, a polymethine dye skeleton, a diimonium dye skeleton, a dithiolene dye skeleton, a phthalocyanine dye skeleton, a porphyrin dye skeleton, an azo dye skeleton, a triarylmethane dye skeleton, and a perylene dye skeleton. It is done. Here, the polymethine dye skeleton includes a cyanine dye skeleton, a merocyanine dye skeleton, a squarylium dye skeleton, a croconium dye skeleton, an oxonol dye skeleton, and the like depending on the type of bonded atomic groups. Among these, as the polymethine dye skeleton, a cyanine dye skeleton, a squarylium dye skeleton and a croconium dye skeleton are preferable, and a cyanine dye skeleton and a squarylium dye skeleton are more preferable.

式中、Ｒ^1aおよびＲ^1bは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²およびＲ³は、各々独立に水素原子または置換基を表し、Ｒ²およびＲ³は、互いに結合して環を形成してもよく、Ｒ⁴は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、−ＢＲ^4AＲ^4B、または金属原子を表し、Ｒ⁴は、Ｒ^1a、Ｒ^1bおよびＲ³から選ばれる少なくとも一つと共有結合もしくは配位結合していてもよく、Ｒ^4AおよびＲ^4Bは、各々独立に置換基を表す。Ｒ^1a、Ｒ^1b、Ｒ²〜Ｒ⁴の少なくとも一つが、カチオン部位を有する基（以下、カチオン性基ともいう）およびアニオン部位を有する基（以下、アニオン性基ともいう）から選ばれる少なくとも１種を有する。 The compound having a pyrrolopyrrole dye skeleton is preferably a compound represented by the formula (PP). According to this aspect, it is easy to obtain a film having excellent heat resistance and light resistance.

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ are They may be bonded to each other to form a ring, and each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^4A R ^4B , or a metal atom, and R ⁴ represents R ^At least one selected from ^1a , R ^1b and R ³ may be covalently or coordinately bonded, and R ^4A and R ^4B each independently represent a substituent. At least one of R ^1a , R ^1b and R ^{2 to} R ⁴ is selected from a group having a cation moiety (hereinafter also referred to as a cationic group) and a group having an anion moiety (hereinafter also referred to as an anionic group). Has a seed.

Examples of the anionic group include —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , and —PO ₄ H ^— . Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, phosphonium and the like), and ammonium cations are particularly preferable. The ammonium cation, -N (R) ₃ ⁺ and the like. R each independently represents a hydrogen atom or an alkyl group, and at least one of R represents an alkyl group. 1-10 are preferable and, as for carbon number of an alkyl group, 1-5 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear.

  As for the details of the formula (PP), paragraph numbers 0017 to 0047 of JP 2009-263614 A, paragraph numbers 0011 to 0036 of JP 2011-68731 A, paragraph numbers 0010 to 0024 of international publication WO 2015/166873. The contents of which are incorporated herein by reference.

R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Further, the alkyl group, aryl group and heteroaryl group represented by R ^1a and R ^1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in paragraph Nos. 0020 to 0022 of JP-A-2009-263614, the above-described cationic group, and the above-described anionic group. Of these, an alkoxy group having a cationic group and / or an anionic group as a substituent is preferable.

At least one of R ² and R ³ is preferably an electron withdrawing group, R ² represents an electron withdrawing group (preferably a cyano group), and R ³ more preferably represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations. 1-3 are preferable and, as for the number of the hetero atoms which comprise a heteroaryl group, 1-2 are more preferable. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms.

R ⁴ is preferably a hydrogen atom or a group represented by —BR ^4A R ^4B . The substituent represented by R ^4A and R ^4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and an aryl group. Particularly preferred. Specific examples of the group represented by —BR ^4A R ^4B include a difluoroboron group, a diphenylboron group, a dibutylboron group, a dinaphthylboron group, and a catecholboron group. Of these, a diphenylboron group is particularly preferred.

Specific examples of the compound having a pyrrolopyrrole dye skeleton include the following compounds. In the following structural formulas, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

式（ＳＱ）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロアリール基または式（Ａ−１）で表される基を表す；

式（Ａ−１）中、Ｚ¹は、含窒素複素環を形成する非金属原子団を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は連結手を表す。
式（ＳＱ）の詳細については、特開２０１１−２０８１０１号公報の段落番号００２０〜００４９の記載を参酌でき、この内容は本明細書に組み込まれる。 The compound having a squarylium dye skeleton is preferably a compound represented by the following formula (SQ).

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

In formula (A-1), Z ¹ represents a nonmetallic atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, A wavy line represents a connecting hand.
Regarding the details of the formula (SQ), the description of paragraph numbers 0020 to 0049 of JP2011-208101A can be referred to, and the contents thereof are incorporated in the present specification.

In the formula (SQ), cations are delocalized as follows.

Specific examples of the compound having a squarylium dye skeleton include the following compounds. Further, compounds described in paragraph numbers 0044 to 0049 of JP2011-208101A can be mentioned, the contents of which are incorporated herein.

式中、Ｚ¹およびＺ²は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子団であり、
Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
Ｌ¹は、奇数個のメチン基を有するメチン鎖を表し、
ａおよびｂは、それぞれ独立に、０または１であり、
ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹は対アニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹は対カチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 As the compound having a cyanine dye skeleton, a compound represented by the formula (C) is preferable.
Formula (C)

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

Examples of counter cations include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ etc.), transitions Metal ions (Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ etc.), other metal ions (Al ³⁺ etc.), ammonium ions, triethylammonium ions, tributylammonium ions, Pyridinium ion, tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium ion and the like can be mentioned.

Ｍ¹は遷移金属を表し、ｎは１〜２の整数を表し、Ｒ^A1〜Ｒ^A8は、それぞれ独立して、水素原子または置換基を表す。式Ａの詳細については、特開２０１５−４０８９５号公報の段落００３０〜００５０を参酌でき、この内容は本明細書に組み込まれる。 Examples of counter anions include halogen ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ions, ethyl sulfate ions, SO ₄ ²⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , B ( C ₆ F ₅ ) ₄ ⁻ , ClO ₄ ⁻ , tris (halogenoalkylsulfonyl) methide anion (eg (CF ₃ SO ₂ ) ₃ C ⁻ ), di (halogenoalkylsulfonyl) imide anion (eg (CF ₃ SO ₂ ) ₂ N ^-), etc. tetracyanoborate anions. Moreover, as a counter anion, the counter anion represented by Formula A can also be used.
Formula A

M ¹ represents a transition metal, n represents an integer of 1 to 2, and R ^{A1 to} R ^A8 each independently represent a hydrogen atom or a substituent. Regarding the details of Formula A, paragraphs 0030 to 0050 of JP-A-2015-40895 can be referred to, and the contents thereof are incorporated in the present specification.

Specific examples of the compound having a cyanine dye skeleton include the following compounds. In the following structural formulas, Me represents a methyl group. Further, compounds described in JP-A-2016-75720, JP-A-2008-88426, JP-A-2015-172102, and JP-A-2015-40895 are exemplified, and the contents thereof are incorporated in the present specification. It is.

式（Ｃｒ）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロアリール基または式（Ａ−１）で表される基を表す；

式（Ａ−１）中、Ｚ¹は、含窒素複素環を形成する非金属原子団を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は連結手を表す。 The compound having a croconium dye skeleton is preferably a compound represented by the following formula (Cr).

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

In formula (A-1), Z ¹ represents a nonmetallic atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, A wavy line represents a connecting hand.

Regarding the details of the formula (Cr), the descriptions of paragraph numbers 0007 to 0016 of JP-A-5-155145 and paragraph numbers 0011 to 0038 of JP-A-2007-31644 can be referred to, and the contents thereof are described in this specification. Incorporated. Specific examples of the compound having a croconium dye skeleton include the following compounds. Moreover, the compound described in Unexamined-Japanese-Patent No. 5-155145 and Unexamined-Japanese-Patent No. 2007-31644 is also mentioned, The content of these is integrated in this specification.

式中、Ｒ¹¹〜Ｒ¹⁸は、それぞれ独立して、アルキル基またはアリール基を表し、Ｖ¹¹〜Ｖ¹⁵は、それぞれ独立して、アルキル基、アリール基、ハロゲン原子、アルコキシ基またはシアノ基を表し、Ｘは対アニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、ｎ１〜ｎ５は、それぞれ独立して、０〜４である。対アニオンの具体例としては、上述した対アニオンが挙げられる。 As the compound having a diimonium dye skeleton, a compound represented by the following formula (Im) is preferable.
Formula (Im)

In the formula, each of R ^{11 to} R ¹⁸ independently represents an alkyl group or an aryl group, and each of V ^{11 to} V ¹⁵ independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a cyano group. X represents a counter anion, c represents a number necessary for balancing the electric charge, and n1 to n5 are each independently 0 to 4. Specific examples of the counter anion include the counter anions described above.

Specific examples of the compound having a diimonium dye skeleton include the following compounds. Moreover, the compound described in Unexamined-Japanese-Patent No. 2012-012399 and Unexamined-Japanese-Patent No. 2007-92060 is also mentioned, The content of these is integrated in this specification. In the following structural formulas, Me represents a methyl group, Pr represents a propyl group, and Cy represents a cyclohexyl group.

Ｒ¹〜Ｒ¹²はそれぞれ独立に、水素原子、ハロゲン原子、ＯＲ（Ｒ＝Ｈまたは炭素数１〜２０の炭化水素基）、ＣＯＯＲ（Ｒ＝Ｈまたは炭素数１〜２０の炭化水素基）、ＣＮ、ＮＯ₂、ＣＯＮＨ₂、炭化水素基、または、炭化水素基の少なくとも一部が、ハロゲン原子、酸素原子、窒素原子および硫黄原子からなる群より選ばれる少なくとも１つの原子で置換された基を表し、Ｒ^A〜Ｒ^Fはそれぞれ独立に、電子対、Ｈ、アルキル基、アリール基、または、アルキル基の少なくとも一部が、ハロゲン原子、酸素原子、窒素原子、硫黄原子およびリン原子からなる群より選ばれる少なくとも１つの原子で置換された基を表し、ｐおよびｑはそれぞれ独立に１〜３の整数を表し、Ｘは対アニオンを表し、ｃは電荷のバランスを取るために必要な数を表す。式（Ｐｏｒ）の詳細については、特開２０１６−１０２８６２号公報の段落番号００２４〜００４９の記載を参酌でき、この内容は本明細書に組み込まれる。ポルフィリン化合物の具体例としては下記化合物が挙げられる。また、特開２０１６−１０２８６２号公報に記載された化合物も挙げられ、この内容は本明細書に組み込まれる。以下の構造式中、Ｐｈはフェニル基を表す。

As the porphyrin compound, a compound represented by the following formula (Por) is preferable.
Formula (Por)

R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, OR (R = H or a hydrocarbon group having 1 to 20 carbon atoms), COOR (R = H or a hydrocarbon group having 1 to 20 carbon atoms), CN, NO ₂ , CONH ₂ , a hydrocarbon group, or a group in which at least a part of the hydrocarbon group is substituted with at least one atom selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom and a sulfur atom R ^{A to} R ^F each independently represents an electron pair, H, an alkyl group, an aryl group, or a group in which at least a part of the alkyl group is composed of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. A group substituted with at least one atom selected from the above, p and q each independently represent an integer of 1 to 3, X represents a counter anion, and c is a number necessary for balancing the charge. Represent. For details of the formula (Por), the description of paragraph numbers 0024 to 0049 of JP-A-2006-102862 can be referred to, and the contents thereof are incorporated in the present specification. Specific examples of the porphyrin compound include the following compounds. Moreover, the compound described in Unexamined-Japanese-Patent No. 2006-102862 is also mentioned, The content is integrated in this specification. In the following structural formulas, Ph represents a phenyl group.

  In the infrared absorber of the present invention, the metal component may be any metal component as long as it contains the above-described metal atom. It may be a single metal or a free metal ion. Metal components include metal oxides, metal nitrides, metal carbonates, metal salts (inorganic acid salts, organic acid salts, ammonium salts, etc.), intermetallic compounds, metal complexes, organometallic compounds, (hetero) polyacids And a compound such as a salt thereof. In the present invention, the metal component is preferably a compound having no dye skeleton. In the case where the near-infrared absorbing dye in the present invention is a dye containing a metal atom, the metal component is preferably a metal component containing a metal atom different from the metal atom contained in the near-infrared absorbing dye. For example, when the near-infrared absorbing dye contains Ni atoms, the metal component does not contain Ni atoms, and Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Pd, Cu, Zn, Si and It is preferable that it contains a metal atom selected from Al. Moreover, the metal component in this invention may have infrared absorptivity and does not need to have infrared absorptivity.

The following are mentioned as a preferable aspect of the infrared absorber of this invention.
(1) The near-infrared absorbing dye is a compound having a pyrrolopyrrole dye skeleton (hereinafter also referred to as a pyrrolopyrrole compound), and the metal component is a metal atom M1 selected from Na, K, Cs, Ti, Fe, Ca, and Al. The aspect whose total amount of the said metal atom M1 is 0.00001-1 mass part with respect to 100 mass parts of a pyrrolopyrrole compound.
(2) The near-infrared absorbing dye is a compound having a squarylium dye skeleton (hereinafter also referred to as a squarylium compound), and the metal component includes a metal atom M2 selected from Li, Na, K, Mg, Ca, Fe and Al, The aspect whose total amount of the said metal atom M2 is 0.00001-1 mass part with respect to 100 mass parts of a squarylium compound.
(3) The near-infrared absorbing dye is a compound having a cyanine dye skeleton (hereinafter also referred to as a cyanine compound), and the metal component is a metal atom M3 selected from Na, K, Cs, Li, Mg, Fe, Ca and Al. The aspect whose total amount of the said metal atom M3 is 0.00001-1 mass part with respect to 100 mass parts of a cyanine compound.
(4) The near-infrared absorbing dye is a compound having a diimonium dye skeleton (hereinafter also referred to as a diimonium compound), and the metal component is a metal atom M4 selected from Na, K, Cs, Li, Mg, Fe, Ca, and Al. The aspect whose total amount of the said metal atom M4 is 0.00001-1 mass part with respect to 100 mass parts of a diimonium compound.
(5) A metal atom in which the near-infrared absorbing dye is a compound having a dithiolene dye skeleton (hereinafter also referred to as a dithiolene compound) and the metal component is selected from Na, K, Cs, Li, Mg, Fe, Ca, Al, and Ni The aspect whose total amount of the said metal atom M5 is 0.00001-1 mass part with respect to 100 mass parts of a dithiolene compound including M5.
(6) The near-infrared absorbing dye is a compound having a phthalocyanine dye skeleton (hereinafter also referred to as a phthalocyanine compound), and the metal components are Na, K, Mg, Ca, Fe, Al, Cu, Co, Pd, Zn, Ti and An embodiment in which the metal atom M6 selected from Ni is included and the total amount of the metal atom M6 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the phthalocyanine compound.
(7) The near-infrared absorbing dye is a compound having a porphyrin dye skeleton (hereinafter also referred to as porphyrin compound), and the metal components are Na, K, Ca, Mg, Fe, Al, Cu, Co, Pd, Zn, Ti and An embodiment in which the metal atom M7 selected from Ni is included and the total amount of the metal atom M7 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the porphyrin compound.
(8) The near-infrared absorbing dye is a compound having a triarylmethane dye skeleton (hereinafter also referred to as a triarylmethane compound), and the metal components are Pd, Li, Na, K, Mg, Ca, Mg, Al, and Fe. The aspect which contains the metal atom M8 chosen and the total amount of the said metal atom M8 is 0.00001-1 mass part with respect to 100 mass parts of a triarylmethane compound.
(9) The near-infrared absorbing dye is a compound having a perylene dye skeleton (hereinafter also referred to as a perylene compound), and the metal component includes a metal atom M9 selected from Na, K, Cs, Ca, Mg, Al, and Fe, The aspect whose total amount of the said metal atom M9 is 0.00001-1 mass part with respect to 100 mass parts of a perylene compound.

<Composition>
Next, the composition of the present invention will be described. The composition of the present invention contains the above-described infrared absorber of the present invention and a solvent.

<< Infrared absorber >>
In the composition of the present invention, the content of the infrared absorber is preferably 0.01 to 50% by mass with respect to the total solid content of the composition. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.

<< Solvent >>
The composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition, but is preferably selected in consideration of the applicability and safety of the composition.

  Examples of the organic solvent include the following organic solvents. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyloxyacetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Til, ethyl 3-ethoxypropionate, etc.), alkyl esters of 2-alkyloxypropionic acid (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.) Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Acetoacetate Le, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol Examples thereof include monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons (for example, 50 ppm by weight per part of organic solvent). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).

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

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

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

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

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

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

<< Other near-infrared absorbing compounds >>
The composition of the present invention may further contain a near-infrared absorbing compound (also referred to as other near-infrared absorbing compound) other than the above-described infrared absorber. As other near infrared ray absorbing compounds, for example, inorganic particles can be used. The inorganic particles are preferably metal oxide particles or metal particles in terms of better infrared shielding properties. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. Moreover, a tungsten oxide compound can be used as the inorganic fine particles. The tungsten oxide compound is preferably cesium tungsten oxide. Regarding the details of the tungsten oxide compound, paragraph number 0080 of JP-A-2006-006476 can be referred to, and the contents thereof are incorporated in the present specification. The shape of the inorganic particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.

  The average particle size of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average particle diameter of the inorganic particles is within such a range, the visible transparency is good. From the viewpoint of avoiding light scattering, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the inorganic particles is usually 1 nm or more.

When the composition of the present invention contains other near-infrared absorbing compound, the content of the other near-infrared absorbing compound is preferably 0.01 to 50% by mass with respect to 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 30% by mass or less, and more preferably 15% by mass or less.
Moreover, 0.01-50 mass% is preferable with respect to the total solid of the composition of this invention as content of the sum total of an infrared absorber and another near-infrared absorption compound. 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.

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

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

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

When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less.
10-1000 mass parts is preferable with respect to 100 mass parts of an infrared absorber, and, as for content of a chromatic colorant, 50-800 mass parts is more preferable.
Moreover, it is preferable that the total amount of a chromatic colorant and an infrared absorber shall be 1-80 mass% with respect to the total solid of the composition of this invention. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
When the composition of this invention contains 2 or more types of chromatic colorants, it is preferable that the total amount is in the said range.

<< Coloring material that transmits infrared rays and blocks visible light >>
The composition of the present invention can also contain a colorant that transmits infrared rays and blocks visible light (hereinafter also referred to as a colorant that blocks visible light).
In the present invention, the color material that blocks visible light is preferably a color material that absorbs light in the wavelength range from purple to red. In the present invention, the color material that blocks visible light is preferably a color material that blocks light in the wavelength region of 450 to 650 nm. The color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm.
In the present invention, the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2).
(1): Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants.
(2): Contains an organic black colorant. In the aspect (2), it is also preferable to further contain a chromatic colorant.

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

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

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

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

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

When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 30% by mass or less, and 20% by mass with respect to the total solid content of the composition. The following is more preferable, and 15% by mass or less is still more preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, the composition of this invention can also be made into the aspect which does not contain the coloring material which shields visible light substantially. The phrase “substantially free of a colorant that blocks visible light” means that the content of the colorant that blocks visible light is preferably 0.005% by mass or less in the total solid content of the composition of the present invention. The content is more preferably 001% by mass or less, and even more preferably no colorant that blocks visible light.

<< Pigment derivative >>
When the composition of the present invention contains a pigment, it can further contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a group having a salt structure, or a phthalimidomethyl group, and the pigment derivative represented by the formula (B1) is preferable. .

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

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

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

  In formula (B1), L represents a single bond or a linking group. The linking group is preferably a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. , May be unsubstituted or may further have a substituent.

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

Specific examples of the pigment derivative include the following compounds. Ph in the following structural formulas is a phenyl group.

  When the composition of this invention contains a pigment derivative, as for content of a pigment derivative, 1-50 mass parts is preferable with respect to 100 mass parts of pigments contained in a 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 content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only one type of pigment derivative may be used, or two or more types may be used, and in the case of two or more types, the total amount is preferably within the above range.

<< Resin >>
The composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition and the purpose of a binder. A resin used mainly for dispersing pigments is also called a dispersant. However, such use of the resin is an example, and the resin can be used for purposes other than such use.

  The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more. In the case of an epoxy resin, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 or more, and more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 100 or more, and more preferably 200 or more.

  Resins include (meth) acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin , Polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used.

  Examples of the (meth) acrylic resin include a polymer containing a repeating unit derived from (meth) acrylic acid and / or an ester thereof. Specific examples include polymers obtained by polymerizing at least one selected from (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide and (meth) acrylonitrile.

  Polyester resins include polyols (eg, ethylene glycol, propylene glycol, glycerin, trimethylol propane), polybasic acids (eg, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and aromatic rings thereof. A dicarboxylic acid having 2 to 20 carbon atoms such as an aromatic dicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, etc., wherein the hydrogen atom is substituted with a methyl group, an ethyl group, a phenyl group, or the like, and cyclohexanedicarboxylic acid, etc. Polymers obtained by reaction with alicyclic dicarboxylic acids and the like, and polymers obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone monomers (for example, polycaprolactone).

  Examples of the epoxy resin include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type. Epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group and others Examples thereof include copolymers with other polymerizable unsaturated compounds.

  Examples of the epoxy resin that is a glycidyl etherified product of a phenol compound include 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- (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, diisopropyl Examples thereof include phenols having a redene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

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

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

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

  The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq.

  The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins. Moreover, the resin which has an acid group can also be used as a dispersing agent.

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

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

  The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing the components.

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

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

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

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

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

  The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. Commercially available products include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS resist 106 (all of which are Osaka Organic Chemical Industries). Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UC Corporation), Acryl-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) Is mentioned.

  Examples of the resin having an acid group include those described in paragraphs 0558 to 0571 of JP2012-208494A (paragraph numbers 0687 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408. The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification. As a commercial item, Acrybase FF-426 (Fujikura Kasei Co., Ltd.) is mentioned, for example.

  The acid value of the resin having an acid group 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.

式中、Ｒ⁵は水素原子またはアルキル基を表し、Ｌ⁴〜Ｌ⁷はそれぞれ独立に、単結合または２価の連結基を表し、Ｒ¹⁰〜Ｒ¹³はそれぞれ独立にアルキル基またはアリール基を表す。Ｒ¹⁴およびＲ¹⁵は、それぞれ独立に、水素原子または置換基を表す。 In the composition of the present invention, a resin having a repeating unit represented by formulas (A3-1) to (A3-7) is also preferably used as the resin.

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

R ⁵ represents a hydrogen atom or an alkyl group. 1-5 are preferable, as for carbon number of an alkyl group, 1-3 are more preferable, and 1 is especially preferable. R ⁵ is preferably a hydrogen atom or a methyl group.

L ^{4 to} L ⁷ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or An alkyl group, preferably a hydrogen atom), or a group composed of a combination thereof, and a group composed of a combination of at least one of an alkylene group, an arylene group, and an alkylene group and -O-. 1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic. 6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable.

The alkyl group represented by R ¹⁰ may be linear, branched or cyclic, and is preferably cyclic. The alkyl group may have the above-described substituent and may be unsubstituted. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The number of carbon atoms of the aryl group R ¹⁰ represents preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹⁰ is preferably a cyclic alkyl group or an aryl group.

The alkyl group represented by R ¹¹ and R ¹² may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. 1-12 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are still more preferable. R ^11, R ¹² the number of carbon atoms of the aryl group represented by preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹¹ and R ¹² are preferably a linear or branched alkyl group.

The alkyl group represented by R ¹³ may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. 1-12 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are still more preferable. The number of carbon atoms of the aryl group R ¹³ represents preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹³ is preferably a linear or branched alkyl group or an aryl group.

The substituents represented by R ¹⁴ and R ¹⁵ are halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, Alkylthio group, arylthio group, heteroarylthio group, —NR ^a1 R ^a2 , —COR ^a3 , —COOR ^a4 , —OCOR ^a5 , —NHCOR ^a6 , —CONR ^a7 R ^a8 , —NHCONR ^a9 R ^a10 , —NHCOOR ^a11 , — SO ₂ R ^a12 , —SO ₂ OR ^a13 , —NHSO ₂ R ^a14, or —SO ₂ NR ^a15 R ^a16 may be mentioned. R ^{a1 to} R ^a16 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Among these, it is preferable that at least one of R ¹⁴ and R ¹⁵ represents a cyano group or —COOR ^a4 . R ^a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.

  ARTON F4520 (made by JSR Corporation) etc. are mentioned as a commercial item of resin which has a repeating unit represented by a formula (A3-7). The details of the resin having a repeating unit represented by the formula (A3-7) can be referred to the descriptions in paragraph numbers 0053 to 0075 and 0127 to 0130 of JP2011-100084A, the contents of which are described in this specification. Embedded in the book.

When the composition of the present invention contains a pigment, it preferably contains a resin as a dispersant.
The resin acting as a dispersant is preferably an acid type resin and / or a basic type resin.
Here, the acidic resin represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acid type resin is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and basic groups in the resin is 100 mol%. A resin consisting only of groups is more preferred. The acid group possessed by the acidic resin is preferably a carboxyl group. The acid value of the acid type resin is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
The basic type resin is a resin in which the amount of basic groups is larger than the amount of acid groups. The basic type resin is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups in the resin is 100 mol%. The basic group possessed by the basic type resin is preferably an amine.

  Examples of the dispersant include polymer dispersants [for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate] and the like. The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, etc., and JP-A-2002-273191. Examples thereof include a polymer having a sulfo group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the block polymer include block polymers described in JP-A Nos. 2003-49110 and 2009-52010.

  Examples of the graft polymer include reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. Reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, macromonomers described in JP-A-10-339949, JP-A-2004-37986 and the like, monomers having a nitrogen atom-containing group, A copolymer of the organic dye described in JP 2003-238837 A, JP 2008-9426 A, JP 2008-81732 A, etc. And a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-106268.

  In the present invention, it is preferable to use a graft copolymer containing a repeating unit represented by any of the following formulas (111) to (114) as the resin (dispersant).

In Formula (111) to Formula (114), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represents a hydrogen atom or a monovalent group, Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a monovalent group, R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a monovalent group, and n, m, p, and q are each independently an integer of 1 to 500. J and k each independently represent an integer of 2 to 8, and in formula (113), when p is 2 to 500, a plurality of R ³ may be the same or different from each other; in the formula (114), when q is 2 to 500, even X ⁵ and R ⁴ there are plural different be the same as each other There.

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

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

Ｒ¹及びＲ²は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１〜６が好ましい）を表す。ａは、各々独立に、１〜５の整数を表す。＊は構造単位間の連結部を表す。
Ｒ⁸及びＲ⁹はＲ¹と同義の基である。
Ｌは単結合、アルキレン基（炭素数１〜６が好ましい）、アルケニレン基（炭素数２〜６が好ましい）、アリーレン基（炭素数６〜２４が好ましい）、ヘテロアリーレン基（炭素数１〜６が好ましい）、イミノ基（炭素数０〜６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは−ＣＲ⁵Ｒ⁶−ＮＲ⁷−（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ⁵、Ｒ⁶は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１〜６が好ましい）を表す。Ｒ⁷は水素原子または炭素数１〜６のアルキル基である。
Ｌ^aはＣＲ⁸ＣＲ⁹とＮとともに環構造を形成する構造部位であり、ＣＲ⁸ＣＲ⁹の炭素原子と合わせて炭素数３〜７の非芳香族複素環を形成する構造部位であることが好ましい。さらに好ましくは、ＣＲ⁸ＣＲ⁹の炭素原子及びＮ（窒素原子）とを合わせて５〜７員の非芳香族複素環を形成する構造部位であり、より好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。この構造部位はさらにアルキル基等の置換基を有していてもよい。
ＸはｐＫａ１４以下の官能基を有する基を表す。
Ｙは原子数４０〜１０，０００の側鎖を表す。

R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a represents the integer of 1-5 each independently. * Represents a connecting part between structural units.
R ⁸ and R ⁹ are the same groups as R ¹ .
L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms). Are preferred), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, or a linking group thereof. Among these, a single bond or —CR ⁵ R ⁶ —NR ⁷ — (imino group is X or Y) is preferable. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
L ^a is a structural site to form a ring structure together with CR ⁸ CR ⁹ and N, be combined with the carbon atoms of CR ⁸ CR ⁹ is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms preferable. More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR ⁸ CR ⁹ and N (nitrogen atom), more preferably a 5-membered non-aromatic heterocyclic ring. It is particularly preferable that it is a structural site that forms pyrrolidine. This structural part may further have a substituent such as an alkyl group.
X represents a group having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.

  The oligoimine dispersant further contains at least one selected from structural units represented by formula (I-3), formula (I-4), and formula (I-5) as a copolymerization component. Also good. When the oligoimine-based dispersant contains such a structural unit, the dispersibility of the infrared absorbing compound or the like can be further improved.

^{R 1, R 2, R 8} , R 9, L, La, a and * have the formula (I-1), (I -2), R 1 in ^{(I-2a), R 2} , R 8, R ⁹ Synonymous with L, La, a and *.
Ya represents a side chain having 40 to 10,000 atoms having an anionic group. The structural unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.

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

  The dispersant is also available as a commercial product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie). In addition, pigment dispersants described in paragraph numbers 0041 to 0130 of JP 2014-130338 A can also be used, the contents of which are incorporated herein. Moreover, the resin etc. which have the acid group mentioned above can also be used as a dispersing agent.

In the composition of the present invention, the content of the resin is preferably 1 to 80% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 30% by mass or less.
Moreover, when containing a dispersing agent as resin, 0.1-40 mass% is preferable with respect to the total solid of a composition. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Further, the content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

<< polymerizable compound >>
The composition of the present invention preferably contains a polymerizable compound. The polymerizable compound is preferably a compound that can be polymerized by the action of radicals. That is, the polymerizable compound is preferably a radical polymerizable compound. The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and 3 groups having an ethylenically unsaturated bond. More preferred are compounds having one or more. The upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound.

  The polymerizable compound may be in the form of either a monomer or a polymer, but is preferably a monomer. The monomer type polymerizable compound preferably has a molecular weight of 100 to 3,000. 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. Moreover, it is also preferable that a polymeric compound is a compound which does not have molecular weight distribution substantially. Here, having substantially no molecular weight distribution means that the dispersity of the compound (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 1.5. 0.0 to 1.3 is more preferable.

  As examples of the polymerizable compound, the description in paragraph numbers 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. As a polymerizable compound, ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercial product, NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330). Manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D) -310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) And these (meth) acryloyl groups are A structure bonded via an ethylene glycol residue and / or a propylene glycol residue is preferable. These oligomer types can also be used. In addition, the description of paragraph numbers 0034 to 0038 in JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Moreover, the polymerizable monomer etc. which are described in Unexamined-Japanese-Patent No. 2012-208494 Paragraph No. 0477 (corresponding Paragraph No. 0585 of US Patent Application Publication No. 2012/0235099) and the like are described in the present specification. Incorporated into. Diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6- Hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferable. These oligomer types can also be used. For example, RP-1040 (Nippon Kayaku Co., Ltd. product) etc. are mentioned.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Examples of the polymerizable compound having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. A polymerizable compound in which an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is Pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

  It is also a preferred embodiment that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. As the polymerizable compound having a caprolactone structure, the description of paragraph numbers 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein. The compound having a caprolactone structure is, for example, commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, such as DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. SR-494, which is a tetrafunctional acrylate having four, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

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

When the composition of this invention contains a polymeric compound, 0.1-40 mass% is preferable with respect to the total solid of a composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types of polymeric compounds together, it is preferable that a total amount becomes the said range.
When the composition contains an epoxy resin and a polymerizable compound, the mass ratio of the polymerizable compound and the epoxy resin is preferably polymerizable compound: epoxy resin = 100: 1 to 100: 400, and 100: 1 to 100: 1. 100: 100 is more preferable.

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

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

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

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

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

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

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

  In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. Regarding the details of the formula (OX-1), the description of paragraph numbers 0276 to 0304 in JP 2013-029760 A can be referred to, and the contents thereof are incorporated in the present specification.

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

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

  In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP2013-114249A, paragraph numbers 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

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

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

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

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

<< Compound having alkoxysilyl group >>
The composition of the present invention preferably contains a compound having an alkoxysilyl group. 1-5 are preferable, as for carbon number of the alkoxy group in an alkoxy silyl group, 1-3 are more preferable, and 1 or 2 is especially preferable. The number of alkoxysilyl groups is preferably 2 or more, more preferably 2 to 3 in a molecule. Examples of the compound having an alkoxysilyl group include compounds described in paragraph numbers 0044 to 0047 of JP-A-2015-125710, the contents of which are incorporated herein.

  When the composition of the present invention contains a compound having an alkoxysilyl group, the content of the compound having an alkoxysilyl group is preferably 0.1 to 40% by mass relative to the total solid content of the composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One type of compound having an alkoxysilyl group may be used alone, or two or more types may be used in combination. When two or more compounds having an alkoxysilyl group are used in combination, the total amount is preferably within the above range.

<< Catalyst >>
The composition of the present invention may further contain a catalyst. In particular, when a compound having an alkoxysilyl group is contained, the sol-gel reaction is accelerated by containing a catalyst, and a firm cured film is obtained. Examples of the catalyst include an acid catalyst and a base catalyst. Acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and R in the structural formula represented by RCOOH substituted with other elements or substituents. And substituted carboxylic acids, sulfonic acids such as benzenesulfonic acid, phosphoric acid and the like. Further, Lewis acids such as aluminum chloride, aluminum acetylacetonate, zinc chloride, tin chloride, boron trifluoride diethyl ether complex, iodotrimethylsilane, etc. may be used. Examples of the base catalyst include ammoniacal basic compounds such as aqueous ammonia and organic amines such as ethylamine and aniline. Moreover, the catalyst of Unexamined-Japanese-Patent No. 2013-201007 paragraph number 0070-0076 can also be used for a catalyst.
The content of the catalyst is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and further preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the compound having an alkoxysilyl group. Part. The composition of the present invention may contain only one type of catalyst or two or more types of catalysts. When two or more types of catalysts are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
The composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) can be mentioned. Of these, p-methoxyphenol is preferred. As for content of a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a composition.

<<< surfactant >>>
The composition of the present invention may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

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

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

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

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

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

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

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

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

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

  Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

  Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

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

<< UV absorber >>
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like can be used. Regarding these details, the description of paragraph numbers 0052 to 0072 of JP2012-208374A and paragraph numbers 0317 to 0334 of JP2013-68814A can be referred to, and the contents thereof are incorporated in this specification. As a commercial item of a conjugated diene compound, UV-503 (Daito Chemical Co., Ltd. product) etc. are mentioned, for example. Moreover, as a benzotriazole compound, you may use the MYUA series (Chemical Industry Daily, February 1, 2016) made from Miyoshi oil and fat.
0.01-10 mass% is preferable with respect to the total solid of the composition of this invention, and, as for content of a ultraviolet absorber, 0.01-5 mass% is more preferable.

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

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

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

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the aforementioned components.
In preparing the composition, the respective components may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time. If necessary, two or more solutions or dispersions containing each component appropriately prepared in advance may be used. You may mix these at the time of application | coating, and you may prepare as a composition.

  Moreover, when the composition of this invention contains particles, such as a pigment, it is preferable to include the process of disperse | distributing particles. In the process of dispersing the particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the pulverization efficiency by increasing the filling rate of beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, the process and disperser for dispersing particles are described in “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion technology and industrial application centering on suspension (solid / liquid dispersion system)”. The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, published in General Materials, Management Development Center Publishing Department, October 10, 1978 ”can be suitably used. In the process of dispersing the particles, the particles may be refined in the salt milling process. For materials, equipment, processing conditions, etc. used in the salt milling process, for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.

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

When using the filters, different filters (for example, a first filter and a second filter) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
Moreover, you may combine the filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as the first filter can be used.
Moreover, filtration with a 1st filter may be performed only with respect to a dispersion liquid, and after mixing other components, it may filter with a 2nd filter.

<Membrane>
Next, the film of the present invention will be described. The film of the present invention is formed using the above-described composition of the present invention. Since the film | membrane of this invention is excellent in infrared shielding property and visible transparency, it can be preferably used as a near-infrared cut filter. The film of the present invention can also be used as an infrared transmission filter or a heat ray shielding filter. The film of the present invention may have a pattern, or may be a film without a pattern (flat film). Further, the film of the present invention may be used by being laminated on a support, or may be used after being peeled off from the support.

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

  The film of the present invention can also be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using the coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the composition of the present invention. The coloring composition can further contain a resin, a radical polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. About these details, the material demonstrated by the composition of this invention is mentioned, These can be used. Moreover, it is good also as a filter provided with the function as a near-infrared cut filter and a color filter by making the film | membrane of this invention contain a chromatic colorant.

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

When the film of the present invention is used as a near infrared cut filter, the film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 650 to 1500 nm. The average transmittance at a wavelength of 400 to 550 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more. Moreover, it is preferable that the transmittance | permeability in the full range of wavelength 400-550 nm is 70% or more, It is more preferable that it is 80% or more, It is still more preferable that it is 90% or more.
Moreover, although the preferable range of the infrared shielding property of a near-infrared cut filter changes with uses, it is preferable that the transmittance | permeability in at least 1 point of the range of wavelength 650-1500 nm is 20% or less, 15% or less is more preferable, 10% or less is more preferable.

  When the film of the present invention is used as an infrared transmission filter, it preferably has the following spectral characteristics (1). According to this aspect, it is possible to form a film that can transmit infrared rays with less visible light-derived noise.

  (1) The maximum value of the light transmittance in the thickness direction of the film is 20% or less in the wavelength range of 400 to 830 nm, and the minimum value of the light transmittance in the thickness direction of the film is in the range of wavelength 1000 to 1300 nm. Is 80% or more. A film having such spectral characteristics can be preferably used as an infrared transmission filter that blocks light in the wavelength range of 400 to 750 nm and transmits light having a wavelength of 900 nm or more.

  The spectral characteristic of the film is a value obtained by measuring the transmittance in a wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

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

  When the film of the present invention is used as a near infrared cut filter or an infrared transmission filter, a near infrared cut filter and an infrared transmission filter can be used in combination. By using a combination of a near-infrared cut filter and an infrared transmission filter, it can be preferably used for an infrared sensor that detects infrared rays having a specific wavelength. When both filters are used in combination, both the near-infrared cut filter and the infrared transmission filter can be formed using the composition of the present invention, and only one of them is formed using the composition of the present invention. You can also.

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

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

<Laminate>
The laminate of the present invention has the film of the present invention and a color filter containing a chromatic colorant. In the laminate of the present invention, the film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention may be formed on a substrate different from the substrate on which the color filter is formed. Another member (for example, a microlens, a flattening layer, or the like) constituting the solid-state imaging device may be interposed between the film and the color filter.

<Pattern formation method>
Next, the pattern formation method using the composition of this invention is demonstrated. The pattern forming method includes a step of forming a composition layer on a support using the composition of the present invention, and a step of forming a pattern on the composition layer by a photolithography method or a dry etching method. It is preferable.

  When manufacturing the laminated body which the film | membrane of this invention and the color filter laminated | stacked, you may perform the pattern formation of the film | membrane of this invention, and the pattern formation of a color filter separately. Further, pattern formation may be performed on the laminate of the film of the present invention and the color filter (that is, pattern formation of the film of the present invention and the color filter may be performed simultaneously).

  The case where the pattern formation of the film of the present invention and the color filter is performed separately means the following aspect. A pattern is formed on one of the film and the color filter of the present invention. Next, the other filter layer is formed on the patterned filter layer. Subsequently, pattern formation is performed with respect to the filter layer which has not performed pattern formation.

  The pattern forming method may be a pattern forming method by a photolithography method or a pattern forming method by a dry etching method.

  When the pattern formation of the film of the present invention and the pattern formation of the color filter are separately performed, the pattern formation method of each filter layer may be performed only by a photolithography method or only by a dry etching method. Alternatively, one filter layer may be patterned by photolithography, and the other filter layer may be patterned by dry etching. When pattern formation is performed using both dry etching and photolithography, pattern formation may be performed by dry etching for the first layer, and pattern formation may be performed by photolithography for the second and subsequent layers. preferable.

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

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

  As the support, for example, a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used. The pattern may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface). If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

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

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

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

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

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

  After the development, after drying, a heat treatment (post-bake) can be performed. Post-baking is a heat treatment after development for complete film curing. When performing post-baking, the post-baking temperature is preferably 100 to 240 ° C, for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. In addition, when an organic electroluminescence (organic EL) element is used as the light source, or when the photoelectric conversion film of the image sensor is made of an organic material, the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable. The lower limit can be, for example, 50 ° C. or higher. Post-bake is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to satisfy the above conditions for the developed film. Can do. Further, when a pattern is formed by a low temperature process, post baking is not necessary.

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

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

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

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

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

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

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

Hereinafter, an embodiment of an infrared sensor of the present invention will be described with reference to the drawings.
In FIG. 1, reference numeral 110 denotes a solid-state image sensor. The imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114. A color filter 112 is laminated on the near infrared cut filter 111. A micro lens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlens 115.

  The near-infrared cut filter 111 is a filter that transmits light in the visible region and shields light in the near-infrared region. The spectral characteristics of the near-infrared cut filter 111 are selected according to the emission wavelength of the infrared light-emitting diode (infrared LED) to be used. The near-infrared cut filter 111 can be formed using the composition of the present invention.

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

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

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

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

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

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

<Manufacture of infrared absorber 1>
According to the following scheme, a near-infrared absorbing dye (A-1) was synthesized to produce an infrared absorbent 1.

Compound (A-1-a) was synthesized according to the method described in US Pat. No. 5,969,154 using 4- (1-methylheptoxy) benzonitrile as a starting material.
¹ H-NMR (DMSO (dimethyl sulfoxide): 28% by mass methanol solution of sodium methoxide = 95: 5 (mass ratio) mixed solution): δ 0.82 (t, 6H), 1.15-1.70 ( m, 26H), 4.40 (m, 2H), 6.78 (d, 4H), 8.48 (d, 2H)

2. 20.0 parts by mass of compound (A-1-a) and 15.4 parts by mass of 2- (2-benzothiazolyl) acetonitrile are stirred in 230 parts by mass of toluene, and 45.0 parts by mass of phosphorus oxychloride is added dropwise. The mixture was heated to reflux for 5 hours. After completion of the reaction, the mixture was cooled to an internal temperature of 25 ° C., and 200 parts by mass of methanol was added dropwise over 60 minutes while maintaining the internal temperature at 30 ° C. or lower. After completion of dropping, the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were separated by filtration and washed with 100 parts by mass of methanol. To the obtained crystal, 200 parts by mass of methanol was added, heated under reflux for 30 minutes, allowed to cool to 30 ° C., and the crystal was filtered off. The obtained crystal was blown and dried at 40 ° C. for 12 hours to obtain 8.8 parts by mass of the compound (A-1-b).
¹ H-NMR (CDCl ₃ ): δ 0.90-1.90 (m, 32H), 4.54 (m, 2H), 7.12 (d, 4H), 7.20-7.40 (m, 2H), 7.43 (t, 2H), 7.75 (d, 4H), 7.81 (t, 4H)

3.9 parts by weight of diphenylborinic acid 2-aminoethyl ester and 6.0 parts by weight of compound (A-1-b) were stirred in 60 parts by weight of toluene, and at an external temperature of 40 ° C., titanium tetrachloride 10.6 A part by mass was added dropwise over 10 minutes and stirred for 30 minutes. The temperature was raised to an external temperature of 130 ° C. and heated to reflux for 3 hours. The mixture was allowed to cool to an internal temperature of 30 ° C, and 40 parts by mass of methanol was added dropwise while maintaining the internal temperature at 30 ° C or lower. After dropping, the mixture was stirred for 30 minutes, and the precipitated crystals were collected by filtration and washed with 35 parts by mass of methanol. To the obtained crystals, 50 parts by mass of methanol was added, heated under reflux for 30 minutes, allowed to cool to 30 ° C., and the crystals were filtered off twice. The obtained crystal was blown and dried at 40 ° C. for 12 hours to obtain 4.6 parts by mass of the compound (A-1-c).
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)
A peak with a molecular weight of 1090.9 was observed by MALDI-MS, and it was identified as a compound (A-1-c). The maximum absorption wavelength of the compound (A-1-c) was 782 nm in DMSO (dimethyl sulfoxide).

4.6 parts by mass of compound (A-1-C), 10 parts by mass of 4-[(diethylamino) methyl] -benzoic acid chloride, 87 parts by mass of dimethylacetamide (DMAc), and 16.7 parts of triethylamine Part by mass was added and stirred for 5 minutes. The external temperature was raised to 110 ° C. and heated for 4 hours. The mixture was allowed to cool to an internal temperature of 30 ° C., and the precipitated crystals were separated by filtration. Subsequently, the filtered crystal was washed with 100 parts by mass of methanol and 100 parts by mass of water. 200 parts by mass of distilled water was added to the washed crystal, heated to reflux for 30 minutes, allowed to cool to 30 ° C., and the crystal was filtered off. 200 parts by mass of dimethyl sulfoxide was added to the filtered crystals and heated at 80 ° C. for 30 minutes. After heating, the mixture was allowed to cool to 30 ° C. and the crystals were filtered off. Next, 200 parts by mass of methanol was added to the filtered crystals, heated to reflux for 30 minutes, allowed to cool to 30 ° C., and the crystals were filtered. The filtered crystals were blown and dried at 50 ° C. for 24 hours to obtain 5.5 parts by mass of the compound (A-1-d).
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)

  1.0 part by mass of compound (A-1-d) and 0.96 part by mass of sodium 2-bromoacetate were added to 7.89 parts by mass of absolute ethanol and heated to reflux. After completion of the reaction, the solvent was removed, and the residue was washed with hexane and filtered. The obtained crystal was blown and dried at 50 ° C. for 24 hours to obtain 0.5 parts by mass of an infrared absorbent 1 containing a near-infrared absorbing dye (A-1).

<Manufacture of infrared absorber 2>
A near-infrared absorbing dye (A-2) was synthesized according to the following scheme to produce an infrared absorbing agent 2.

To the reaction vessel, 413 mg (1.1 mmol) of compound (A-2-a) was added, and the atmosphere was replaced with nitrogen. 30 mL of tetrahydrofuran (THF) was added to protect from light, 213 mg (5.6 mmol) of LiAlH ₄ was added, and the mixture was heated to reflux overnight. After returning to room temperature, it is quenched with saturated aqueous sodium tartrate solution, extracted with ethyl acetate, washed once with water, dried over Na ₂ SO ₄ and concentrated under reduced pressure to obtain compound (A-2-b). (Yield 356 mg, 1.1 mmol).
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 7.72 (brs, 1H), 7.60 (d, J = 1.2 Hz, 1H), 7.52 (m, 2H), 7.50 ( m, 1H), 6.85 (d, J = 2.3 Hz, 1H), 2.54 (s, 3H), 1.45 (s, 9H), 1.43 (s, 9H)
To the reaction vessel, 62.4 mg (0.547 mmol) of squaric acid and 0.356 g (1.13 mmol) of compound (A-2-b) were added and the atmosphere was replaced with nitrogen. 20 mL of n-butanol and toluene were added at a ratio of 1: 1, and the mixture was heated to reflux. After completion of the reaction, the mixture was allowed to cool and concentrated under reduced pressure. By washing with methanol, an infrared absorbent 2 containing a near-infrared absorbing dye (A-2) was obtained (yield of near-infrared absorbing dye (A-2) 0.2744 g, 0.383 mmol, 70% yield).
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 10.19 (brs, 1H, minor), 9.97 (brs, 1H, major), 9.42 (s, 1H, major), 9.24 ( s, 1H, minor), 7.80-7.78 (m, 2H), 7.73-7.68 (m, 4H), 2.76 (s, 3H, minor), 2.64 (s, 3H, major), 1.63-1.48 (m, 36H)

特許第４９５１２９５号明細書に記載された方法を参考に、化合物（Ａ−３−ａ）を合成した。
３口スラスコ中で化合物（Ａ−３−ａ）９．２１ｇを酢酸エチル１２０ｍｌに溶解し、アセトニトリル４０ｍｌを添加して室温にて攪拌した。ここへデュポン社製オキソン（ＯＸＯＮＥ；商品名、シグマ・アルドリッチ・ジャパンより購入、２ＫＨＳＯ₅・ＫＨＳＯ₄・Ｋ₂ＳＯ₄の組成よりなる）１２．３ｇと過塩素酸ナトリウム２．４４ｇを水４０ｍｌに溶解した水溶液を３０分かけて滴下した後、そのまま３時間攪拌した。このものを分液し、水６０ｍｌと飽和食塩水１０ｍｌの混合液で１回洗浄した後、ロータリーエバポレーターで濃縮して得られた残留物に酢酸エチルを添加して、得られた結晶を濾過、乾燥して近赤外線吸収色素（Ａ−３）を含む赤外線吸収剤３を１０．４ｇを得た（近赤外線吸収色素（Ａ−３）の収率９３％） <Manufacture of infrared absorber 3>
A near-infrared absorbing dye (A-3) was synthesized according to the following scheme to produce an infrared absorbing agent 3.

The compound (A-3-a) was synthesized with reference to the method described in Japanese Patent No. 4951295.
In a three-necked flask, 9.21 g of compound (A-3-a) was dissolved in 120 ml of ethyl acetate, 40 ml of acetonitrile was added, and the mixture was stirred at room temperature. Here, DuPont's Oxone (trade name, purchased from Sigma-Aldrich Japan, 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ composition) 12.3g and sodium perchlorate 2.44g in 40ml water The dissolved aqueous solution was added dropwise over 30 minutes and then stirred for 3 hours. This was separated, washed once with a mixture of 60 ml of water and 10 ml of saturated brine, and then concentrated with a rotary evaporator. Ethyl acetate was added to the resulting residue, and the resulting crystals were filtered. 10.4 g of infrared absorber 3 containing a near infrared absorbing dye (A-3) was obtained by drying (yield of near infrared absorbing dye (A-3) 93%).

<Manufacture of infrared absorber 4>
An infrared absorber 4 containing a near-infrared absorbing dye (A-4) was produced with reference to the method described in JP-A-2008-88426 (Comparative Example 2).

<Manufacture of infrared absorber 5>
An infrared absorbent 5 containing a near-infrared absorbing dye (A-5) was produced with reference to a method described in JP-A-2006-102862.

特開２０１５−１７２１０２号公報に記載された方法を参考に化合物（Ａ−６−ａ）を合成した。
化合物（Ａ−６−ａ）をアセトンに溶解させ、対応する金属ホウ素塩を加え、室温で塩交換を行った。次いで、１．０ｍｏｌ／Ｌの希硫酸水溶液で洗浄することで近赤外線吸収色素（Ａ−６）を含む赤外線吸収剤６を得た（近赤外線吸収色素（Ａ−６）の収率６７％）。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ６）：ｄ１．４８（ｔ，Ｊ＝７．４Ｈｚ，６Ｈ），２．０１（ｍ，２Ｈ），２．０４（ｓ，１２Ｈ），２．７７（ｔ，Ｊ＝６．０Ｈｚ，４Ｈ），４．４４（ｑ，Ｊ＝７．２Ｈｚ，４Ｈ），６．４３（ｄ，Ｊ＝１４．４Ｈｚ，２Ｈ），７．５２（ｍ，２Ｈ），７．６３（ｍ，２Ｈ），７．７０（ｄ，Ｊ＝９．０Ｈｚ，２Ｈ），８．０５（ｍ，４Ｈ），８．３０（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．５２（ｄ，Ｊ＝１４．４Ｈｚ，２Ｈ）。 <Production of infrared absorber 6>
A near-infrared absorbing dye (A-6) was synthesized according to the following scheme to produce an infrared absorbing agent 6.

The compound (A-6-a) was synthesized with reference to the method described in JP-A-2015-172102.
The compound (A-6-a) was dissolved in acetone, the corresponding metal boron salt was added, and salt exchange was performed at room temperature. Subsequently, it was washed with a 1.0 mol / L dilute sulfuric acid aqueous solution to obtain an infrared absorbent 6 containing a near infrared absorbing dye (A-6) (near infrared absorbing dye (A-6) yield 67%). .
¹ H-NMR (DMSO-d6): d1.48 (t, J = 7.4 Hz, 6H), 2.01 (m, 2H), 2.04 (s, 12H), 2.77 (t, J = 6.0 Hz, 4H), 4.44 (q, J = 7.2 Hz, 4H), 6.43 (d, J = 14.4 Hz, 2H), 7.52 (m, 2H), 7.63 (M, 2H), 7.70 (d, J = 9.0 Hz, 2H), 8.05 (m, 4H), 8.30 (d, J = 8.5 Hz, 2H), 8.52 (d , J = 14.4 Hz, 2H).

<Manufacture of infrared absorber 7>
In the synthesis step of the near infrared absorbing dye (A-6), the near infrared absorbing dye (A-6) is obtained in the same manner except that deionized water is used instead of the 1.0 mol / L dilute sulfuric acid aqueous solution. Infrared absorber 7 containing was produced.

<Manufacture of infrared absorber 8>
In the synthesis process of the near-infrared absorbing dye (A-2), it is the same except that a process of washing the near-infrared absorbing dye (A-2) with a 4 mol / L hydrochloric acid aqueous solution after washing with methanol and then washing with methanol is added. By the method, the infrared absorber 8 containing a near-infrared absorption pigment | dye (A-2) was manufactured.

<Measurement of the amount of metal atoms contained in the infrared absorber>
By the following method, the amount of metal atoms contained in the infrared absorber (total amount of Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn, Si and Al) It was measured. The infrared absorbent 1 contained at least Ti as a metal atom. Infrared absorbers 2 and 8 contained at least Li as a metal atom. The infrared absorber 3 contained at least Na as a metal atom. The infrared absorbent 4 contained at least K as a metal atom. The infrared absorber 5 contained at least Na as a metal atom. Infrared absorbers 6 and 7 contained at least Li as a metal atom.
1) Precision weighing 20 mg of sample (infrared absorber) (n = 3)
2) Add 5 ml of 16 mol / L nitric acid 3) Ashing using microwave (Teflon (registered trademark) container, 240 ° C.)
4) Add H ₂ O to prepare a sample to 40 mL 5) Inductively coupled plasma optical emission spectrometry (ICP-OES), using Optims7300DV manufactured by PerkinElmer as a measuring device, the amount of metal atoms contained in the infrared absorber Is quantified by the calibration curve method

<Preparation of coloring material composition>
10 parts by mass of the infrared absorber 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 of the organic solvent shown in the following table, 0. After 520 parts by mass of 5 mm diameter zirconia beads were dispersed with a paint shaker for 30 minutes, filtration was performed using DFA4201NXEY (0.45 μm nylon filter) manufactured by Nippon Pole, and the beads were separated by filtration. 2, 4-10 were produced. The coloring material composition 3 used the absorbent 3 as it was. In addition, the color material composition 7 was used by mixing the infrared absorbent 1 and the infrared absorbent 2 in a mass ratio as an infrared absorbent at a ratio of infrared absorbent 1 / infrared absorbent 2 = 50/50. . Moreover, the color material composition 7 was used as an infrared absorber by mixing the infrared absorber 1 and the infrared absorber 3 at a mass ratio of infrared absorber 1 / infrared absorber 3 = 50/50. .

（樹脂）
Ｄ−１：下記構造の樹脂（Ｍｗ＝２２９００、主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である）
Ｄ−２：下記構造の樹脂（Ｍｗ＝３８９００、主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である）

（溶剤）
ＰＧＭＥＡ（プロピレングリコールメチルエーテルアセテート）
シクロヘキサノン (Pigment derivative)
C-1 to C-3: Compounds having the following structures

(resin)
D-1: Resin having the following structure (Mw = 22900, the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units)
D-2: Resin having the following structure (Mw = 38900, the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units)

(solvent)
PGMEA (propylene glycol methyl ether acetate)
Cyclohexanone

<Preparation of the curable composition of Examples 1-2, 4-9, and Comparative Examples 1-2>
The following components were mixed to prepare a curable composition. In Example 9, 0.5 parts by mass of additive I-2 was further added.
-Color material composition obtained above: 55 parts by mass-Polymerizable compound: 4.5 parts by mass-Resin: 7.0 parts by mass-Photopolymerization initiator: 0.8 parts by mass-Polymerization inhibitor: 0. 001 parts by mass, surfactant: 0.03 parts by mass, UV absorber: 1.3 parts by mass, solvent: 31 parts by mass

<Preparation of the curable composition of Example 3>
50.0 parts by mass of resin D-5 and 100 parts by mass of methyl ethyl ketone were added and dissolved by stirring at 20 to 35 ° C. for 2 hours. Next, 0.75 part by mass of the color material composition 3 was added and stirred at 20 to 35 ° C. until uniform. Further, 0.500 parts by mass of Additive I-1 and 1.3 parts by mass of UV absorber H-1 were added, and the mixture was stirred at 20 to 35 ° C. for 1 hour to obtain the curable composition of Example 3. Prepared.

<Preparation of the curable composition of Example 10>
A curable composition of Example 10 was prepared by using the same method as above except that the color material composition 3 was changed to the color material composition 2.

（紫外線吸収剤）
・Ｈ−１：ＵＶ−５０３、大東化学（株）製
（添加剤）
・Ｉ−１：ブタン二酸
・Ｉ−２：アルコキシシリル基を有する化合物（ＫＢＭ−９６５９、信越シリコーン社製）
（溶剤）
ＰＧＭＥＡ（プロピレングリコールメチルエーテルアセテート）
ＰＧＭＥ（プロピレングリコールメチルエーテル）
シクロヘキサノン
メチルエチルケトン The raw materials described in the above table are as follows.
(Polymerizable compound)
M-1: Aronix M-305, manufactured by Toagosei Co., Ltd. M-2: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd. (resin)
D-3: Acrybase FF-426, manufactured by Fujikura Kasei Co., Ltd. D-4: ARTON F4520, manufactured by JSR Co., Ltd. D-5: Marproof G-0150M, manufactured by NOF Corporation (photopolymerization) Initiator)
E-1: IRGACURE OXE02, manufactured by BASF (polymerization inhibitor)
F-1: Paramethoxyphenol (surfactant)
G-1: the following mixture (Mw = 14000). In the following formula,% indicating the ratio of repeating units is mass%.

(UV absorber)
・ H-1: UV-503, manufactured by Daito Chemical Co., Ltd. (additive)
I-1: Butanedioic acid I-2: Compound having an alkoxysilyl group (KBM-9659, manufactured by Shin-Etsu Silicone)
(solvent)
PGMEA (propylene glycol methyl ether acetate)
PGME (propylene glycol methyl ether)
Cyclohexanone methyl ethyl ketone

<Production of near-infrared cut filter>
Each curable composition prepared above was applied to a glass substrate using a spin coater (Mikasa Co., Ltd.) to form a coating film, and after preheating (prebaking) at 100 ° C. for 120 seconds, The exposure was performed using an i-line stepper or aligner at an exposure amount of 500 mJ / cm ² . Subsequently, post heating (post-baking) was performed at 220 ° C. for 300 seconds to form a film having a thickness of 0.8 μm, and a near infrared cut filter was obtained.

<Evaluation of infrared shielding properties>
The transmittance of the maximum absorption wavelength (> 650 nm) in the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Infrared shielding was evaluated according to the following criteria.
A: Transmittance ≦ 5%
B: 5% <transmittance ≦ 15%
C: 15% <transmittance ≦ 25%
D: 25% <transmittance

<Heat resistance evaluation>
The near infrared cut filter was heated on a hot plate at 260 ° C. for 300 seconds. The transmittance of the near-infrared cut filter before and after heating with respect to light having a wavelength of 400 to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). In the range of 400 nm to 1200 nm, the change in transmittance at the wavelength where the change in transmittance before and after heating was the largest was calculated from the following formula and evaluated according to the following criteria.
Transmittance change = | (transmittance after heating−transmittance before heating) |
A: Change in transmittance is less than 3% B: Change in transmittance is 3% or more and less than 5% C: Change in transmittance is 5% or more

<Light resistance evaluation>
The near-infrared cut filter was set in a fading test machine equipped with a super xenon lamp (100,000 lux), and light irradiation was performed for 50 hours under the condition that no ultraviolet cut filter was used. Next, the transmission spectrum of the near-infrared cut filter after light irradiation is measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), and the residual ratio is calculated from the following formula for the absorbance at the maximum absorption wavelength. The light resistance was evaluated according to the following criteria.
Residual rate (%) = {(absorbance of near infrared cut filter after light irradiation) / (absorbance of near infrared cut filter before light irradiation)} × 100
A: Residual rate exceeds 95% and 100%
B: Residual rate exceeds 80% and 95% or less C: Residual rate 80% or less

  As shown in the above table, in the examples, a film excellent in infrared shielding property, heat resistance and light resistance could be produced.

[Test Example 1]
The composition of Example 2 was applied on a silicon wafer by spin coating so that the film thickness after film formation was 1.0 μm. Then, it heated at 100 degreeC for 2 minute (s) using the hotplate. Subsequently, it heated at 200 degreeC for 5 minute (s) using the hotplate. Next, a 2 μm square Bayer pattern (near infrared cut filter) was formed by dry etching.
Next, the Red composition was applied onto the Bayer pattern of the near-infrared cut filter by spin coating so that the film thickness after film formation was 1.0 μm. Subsequently, it heated at 100 degreeC for 2 minute (s) using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a 2 μm square dot pattern mask at 1000 mJ / cm ² . Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with the spin shower and further washed with pure water. Next, the Red composition was patterned on the Bayer pattern of the near-infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form red, green, and blue coloring patterns.
Next, the infrared transmission filter forming composition was applied onto the patterned film by spin coating so that the film thickness after film formation was 2.0 μm. Subsequently, it heated at 100 degreeC for 2 minute (s) using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a 2 μm square Bayer pattern mask at 1000 mJ / cm ² . Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with the spin shower and further washed with pure water. Subsequently, the infrared transmission filter was patterned in the portion where the Bayer pattern of the near infrared cut filter was removed by heating at 200 ° C. for 5 minutes using a hot plate. This was incorporated into a solid-state imaging device according to a known method.
The obtained solid-state imaging device was irradiated with an infrared light emitting diode (infrared LED) light source in a low illuminance (0.001 Lux) environment to capture an image, and the image performance was evaluated. The subject was clearly recognized on the image. Moreover, the incident angle dependency was good.

  The Red composition, Green composition, Blue composition and infrared transmission filter forming composition used in Test Example 1 are as follows.

(Red composition)
The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Red composition.
Red pigment dispersion-51.7 parts by mass Resin 4 (40 mass% PGMEA solution) ... 0.6 parts by mass Polymerizable compound 4 ... 0.6 parts by mass Photopolymerization initiator 1 ... 0. 3 parts by mass Surfactant 1 ... 4.2 parts by mass PGMEA ... 42.6 parts by mass

(Green composition)
The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Green composition.
Green pigment dispersion ... 73.7 parts by weight Resin 4 (40% by weight PGMEA solution) ... 0.3 parts by weight Polymerizable compound 1 ... 1.2 parts by weight Photopolymerization initiator 1 ... 0 .6 parts by mass Surfactant 1 ... 4.2 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Chemical Co., Ltd.) ... 0.5 parts by mass PGMEA ... 19.5 parts by mass

(Blue composition)
The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion 44.9 parts by mass Resin 4 (40% by mass PGMEA solution) ... 2.1 parts by mass Polymerizable compound 1 ... 1.5 parts by mass Polymerizable compound 4 ... 0.7 parts by mass Photopolymerization initiator 1 ... 0.8 parts by mass Surfactant 1 ... 4.2 parts by mass PGMEA ... 45.8 parts by mass

(Infrared transmission filter forming composition)
The components in the following composition were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare an infrared transmission filter forming composition.
Pigment dispersion 1-1 ... 46.5 parts by mass Pigment dispersion 1-2 ... 37.1 parts by mass Polymerizable compound 5 ... 1.8 parts by mass Resin 4 ... 1.1 parts by mass Photopolymerization initiator 2 ... 0.9 parts by mass Surfactant 1 ... 4.2 parts by mass Polymerization inhibitor (p-methoxyphenol) ... 0.001 parts by mass Silane coupling agent ... 0 .6 parts by mass PGMEA ... 7.8 parts by mass

  The raw materials used in the Red composition, Green composition, Blue composition, and infrared transmission filter forming composition are as follows.

Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment Yellow 139 (4.3 parts by mass), a dispersant (Disperbyk-161, manufactured by BYK Chemie) (6.8 parts by mass), and PGMEA (79.3 parts by mass) were mixed with a bead mill (zirconia beads 0. 3 mm diameter) and mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

Green pigment dispersion C.I. I. 6.4 parts by mass of Pigment Green 36, C.I. I. Pigment Yellow 150 (5.3 parts by mass), a dispersant (Disperbyk-161, manufactured by BYK Chemie) (5.2 parts by mass), and PGMEA (83.1 parts by mass) were mixed with a bead mill (zirconia beads 0.3 mm). The pigment dispersion was prepared by mixing and dispersing for 3 hours. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

Blue pigment dispersion C.I. I. Pigment Blue 15: 6 is 9.7 parts by mass, C.I. I. Pigment Violet 23, 2.4 parts by mass, a dispersant (Disperbyk-161, manufactured by BYK Chemie) 5.5 parts by mass, and PGMEA 82.4 parts by mass were mixed with a bead mill (zirconia beads 0.3 mm). The pigment dispersion was prepared by mixing and dispersing for 3 hours. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.

-Pigment dispersion 1-1
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion 1-1 was prepared.
-Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139) ... 11.8 parts by mass-Resin (Disperbyk-111, manufactured by BYKChemie) ... 9.1 parts by mass / PGMEA 79.1 parts by mass

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

・重合性化合物５：下記構造（左側化合物と右側化合物とのモル比が７：３の混合物）

Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 4: the following structure

Polymerizable compound 5: The following structure (a mixture in which the molar ratio of the left compound to the right compound is 7: 3)

Resin 4: The following structure (acid value: 70 mg KOH / g, Mw = 11000, ratio in the structural unit is a molar ratio)

Photopolymerization initiator 1: IRGACURE-OXE01 (manufactured by BASF)
-Photopolymerization initiator 2: The following structure

-Surfactant 1: 1 mass% PGMEA solution of the following mixture (Mw = 14000). In the following formula,% indicating the ratio of repeating units is mass%.

Silane coupling agent: A compound having the following structure. In the following structural formulas, Et represents an ethyl group.

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

Claims (15)

  A near-infrared absorbing dye containing at least one selected from an anion site and a cation site in the molecule; Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn, Si and And a metal component containing a metal atom selected from Al, and the total amount of the metal atoms contained in the metal component is 0.00001 to 1 part by mass with respect to 100 parts by mass of the near-infrared absorbing dye. Absorbent.   The infrared absorbing agent according to claim 1, wherein the near infrared absorbing dye has a maximum absorption wavelength in a range of 650 to 1500 nm.   The near-infrared absorbing dye is a dye skeleton selected from a pyrrolopyrrole dye skeleton, a polymethine dye skeleton, a diimonium dye skeleton, a dithiolene dye skeleton, a phthalocyanine dye skeleton, a porphyrin dye skeleton, an azo dye skeleton, a triarylmethane dye skeleton, and a perylene dye skeleton. The infrared absorber according to claim 1, comprising:   The composition containing the infrared absorber of any one of Claims 1-3, and a solvent.   Furthermore, the composition of Claim 4 containing resin.   The composition according to claim 4 or 5, further comprising a pigment derivative.   Furthermore, the composition of any one of Claims 4-6 containing a polymeric compound and a photoinitiator.   The film | membrane using the composition of any one of Claims 4-7.   An optical filter having the film according to claim 8.   The optical filter according to claim 9, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter. A film pixel according to claim 8;
The optical filter according to claim 9 or 10, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.   A laminate comprising the film according to claim 8 and a color filter containing a chromatic colorant.   A solid-state imaging device having the film according to claim 8.   An image display device comprising the film according to claim 8.   An infrared sensor having the film according to claim 8.

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