JP6760805B2 - Infrared absorbers, compositions, films, optical filters, laminates, solid-state image sensors, image displays and infrared sensors - Google Patents

Description

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

CCD (charge coupling element) and CMOS (complementary metal oxide semiconductor), which are solid-state image sensors for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state image sensors use silicon photodiodes that are sensitive to infrared rays in their light-receiving parts. Therefore, in the solid-state image sensor, the near-infrared cut filter may be used to correct the luminosity factor. The near-infrared cut filter is manufactured, for example, using a composition containing an infrared absorber.

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

On the other hand, Patent Document 5 contains (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 is described that a chromatic color filter is produced by using a colored sensational radiation composition in which the content of the salt with respect to the dye solid content is 0.1% by mass or less.

JP-A-2007-92060 Japanese Unexamined Patent Publication No. 2008-88426 JP-A-2015-172102 Japanese Unexamined Patent Publication No. 2016-102862 Japanese Unexamined Patent Publication No. 2012-181502

In recent years, there has been a demand for further improvement in infrared shielding properties in films containing infrared absorbers such as near-infrared cut filters. Further, a film containing an infrared absorber such as a near-infrared cut filter is required to have further improvement in heat resistance and light resistance, is less likely to be colored by heating or light irradiation, and is excellent in visible transparency even after heating or light irradiation. Those having properties and infrared shielding properties are desired.

Note that Patent Document 5 is a chromatic color filter and does not describe a film containing an infrared absorber.

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

Under such circumstances, as a result of diligent studies by the present inventors, it has been found that the above object can be achieved by using an infrared absorber described later. The present invention provides:
<1> A near-infrared absorbing dye containing at least one selected from an anion moiety and a cation moiety in the molecule, and Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn. Infrared rays, which include 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 absorber according to <1>, wherein the near-infrared absorbing dye has a maximum absorption wavelength in the range of 650 to 1500 nm.
<3> The near-infrared absorbing pigment is selected from the pyrolopyrrole pigment skeleton, the polymethine pigment skeleton, the diimonium pigment skeleton, the dithiolene pigment skeleton, the phthalocyanine pigment skeleton, the porphyrin pigment skeleton, the azo pigment skeleton, the triarylmethane pigment skeleton and the perylene pigment skeleton. The infrared absorber according to <1> or <2>, which has a pigment skeleton.
<4> A composition containing the infrared absorber 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> The film pixels according to <8> and
The optical filter according to <9> or <10>, which has 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 image sensor 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>.

According to the present invention, it is possible to provide an infrared absorber capable of producing a film or the like having good infrared shielding property and excellent heat resistance and light resistance. In addition, a composition, a film, an optical filter, a laminate, a solid-state image sensor, an image display device, and an infrared sensor can be provided.

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

The contents of the present invention will be described in detail below.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excima laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl "represents both acryloyl and / or methacryloyl.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) is used as a column. It can be determined by using a 0.0 mm ID (inner diameter) x 15.0 cm) and using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
In the present 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 the present specification, the near infrared ray means light (electromagnetic wave) having a maximum absorption wavelength region of 700 to 2500 nm.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if 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 moiety and a cation moiety in the molecule, and Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, It contains a metal component containing a metal atom selected from Pd, Cu, Zn, Si and Al, and the total amount of the metal atom contained in the metal component is 0.00001 to 1 mass with respect to 100 parts by mass of the near-infrared absorbing dye. It is characterized by being a part.

By using the infrared absorber of the present invention, it is possible to produce a film or the like having good infrared shielding property and excellent heat resistance and light resistance. It is presumed that the mechanism for obtaining such an effect is as follows. That is, since the near-infrared absorbing dye contained in the infrared absorber of the present invention contains at least one selected from an anionic moiety and a cation moiety (hereinafter, the anionic moiety and the cation moiety are collectively referred to as an ion moiety) in the molecule. , 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. By setting the total amount of metal atoms to be 0.00001 to 1 part by mass, the amount of metal ions taken into the dye skeleton can be appropriately suppressed, and as a result, excellent infrared shielding ability can be maintained. It is thought that it was possible.

In the present invention, the case where the salt is formed by the anion of the near-infrared absorbing dye and the counter cation is also included when the molecule has an anion moiety. Further, the case where a salt is formed by the cation of the near-infrared absorbing dye and the counter anion is also included when the molecule has a cation site. When the molecule of the near-infrared absorbing dye has an anion moiety and a cation moiety, the near-infrared absorbing dye has an anion moiety and a cation moiety in the molecule. In the present invention, as the near-infrared absorbing dye, a near-infrared absorbing dye having an anion moiety and a cation moiety in the molecule is particularly preferable.

In the infrared absorber of the present invention, 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 above-mentioned near infrared absorbing dye. When the total amount of metal atoms is 0.00001 parts 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, forming a film having excellent infrared shielding properties. be able to. Further, when 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 having excellent 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. It is preferably 0.6 parts by mass or less, particularly preferably. 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-mentioned 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 emission spectrometry (ICP-OES). Details of the measurement conditions will be described in Examples described later.

In the infrared absorber of the present invention, the content of the near-infrared absorbing dye is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total solid content of the infrared absorber. The upper limit can be, for example, 99.999999% by mass or less.
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. .. The lower limit can be, for example, 0.00001 mass% or more. The content of the metal component is preferably 1.0 part by mass or less, and more preferably 0.1 part by mass or less, with respect to 100 parts by mass of the near-infrared absorbing dye. The lower limit can be, for example, 0.00001 parts by mass or more.

In the infrared absorber 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, more preferably 700 nm or more. The upper limit is preferably 1300 nm or less, more preferably 1200 nm or less, further preferably 1100 nm or less, and particularly preferably 1000 nm or less.

In the present invention, the infrared absorber may have an ion site of the near-infrared absorbing dye in the dye skeleton, or may have a substituent bonded to the dye skeleton. The type of the near-infrared absorbing dye may be any dye containing at least one type (ion site) selected from an anionic site and a cation site in the molecule, and is not particularly limited. For example, a compound having a pigment skeleton selected from a pyrolopyrrole pigment skeleton, a polymethine pigment skeleton, a diimonium pigment skeleton, a dithiolene pigment skeleton, a phthalocyanine pigment skeleton, a porphyrin pigment skeleton, an azo pigment skeleton, a triarylmethane pigment skeleton and a perillene pigment skeleton can be mentioned. Be done. Here, the polymethine pigment skeleton includes a cyanine pigment skeleton, a merocyanine pigment skeleton, a squarylium pigment skeleton, a croconium pigment skeleton, an oxonol pigment skeleton, and the like, depending on the type of atomic group to which they are bound. Among them, as the polymethine pigment skeleton, a cyanine pigment skeleton, a squarylium pigment skeleton and a croconium pigment skeleton are preferable, and a cyanine pigment skeleton and a squarylium pigment 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 pigment 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 respectively} . They may be bonded to each other to form a ring, where R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, where R ⁴ is R. ^It may be covalently or coordinated with at least one selected from ^1a , R ^1b and R ³ , where 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 cationic moiety (hereinafter, also referred to as a cationic group) and a group having an anionic moiety (hereinafter, also referred to as an anionic group). Has a seed.

Examples of the anionic _{^{group, -SO 3 -, -COO -,}} -PO 4 -, -PO 4 H - , and the like. Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium and phosphonium), 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. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The alkyl group may be linear, branched or cyclic, but a linear group is preferable.

For details of the formula (PP), paragraph numbers 0017 to 0047 of JP2009-263614, paragraphs 0011 to 0036 of JP2011-68831, and paragraphs 0010 to 0024 of International Publication WO2015 / 166873. The description of the above can be taken into consideration, and these contents are incorporated in the present specification.

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 substituent described in paragraphs 0020 to 0022 of JP-A-2009-263614, the above-mentioned cationic group, and the above-mentioned 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-attracting group, R ² is more preferably an electron-attracting group (preferably a cyano group), and R ³ is more preferably a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms.

R ⁴ is preferably a hydrogen atom or a group represented by −BR ^4A R ^4B . As the substituent represented by R ^4A and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, an alkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is preferable. Especially preferable. -BR ^4A Specific examples of the group represented by R ^4B include a difluoroboron group, a diphenylboron group, a dibutylboron group, a dinaphthylboron group, and a catechol boron group. Of these, the diphenylboron group is particularly preferable.

Specific examples of the compound having a pyrrolopyrrole pigment skeleton include the following compounds. In the following structural formula, 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。 As the compound having a squarylium pigment skeleton, a compound represented by the following formula (SQ) is preferable.

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

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

In the formula (SQ), the cation is delocalized and exists as follows.

Specific examples of the compound having a squarylium pigment skeleton include the compounds shown below. In addition, the compounds described in paragraphs 0044 to 0049 of JP2011-208101A can be mentioned, and the contents thereof are incorporated in the present specification.

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 pigment skeleton, the compound represented by the formula (C) is preferable.
Equation (C)

In the formula, Z ¹ and Z ² are non-metal atomic groups each independently forming a 5- or 6-membered nitrogen-containing heterocycle which may be fused.
R ¹⁰¹ and R ¹⁰² independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, respectively.
L ¹ represents a methine chain having an odd number of methine groups.
a and b are independently 0 or 1, respectively.
When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond.
When the site represented by Cy in the formula is a cation part, X ¹ represents a counter anion, c represents the number required to balance the charges, and the site represented by Cy in the formula is an anion. When it is a part, X ¹ represents a counter cation, c represents the number required to balance 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, Examples thereof include pyridinium ion, tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, and diazabicycloundecenium ion.

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- toluenesulfonate ion, ethyl sulfate _{^{ion, SO 4 2-, SbF 6 -}} , PF 6 -, BF 4 -, B ( ^{_{C 6 F 5) 4 -,}} ClO 4 -, tris (halogenoalkyl alkylsulfonyl) methide anion _{(e.g., (CF 3 SO 2) 3} C -), di (halogenoalkyl) imide anion (e.g. (CF ₃ SO _{2) 2} N ^-), etc. tetracyanoborate anions. Further, as the counter anion, a counter anion represented by the formula A can also be used.
Formula A

M ¹ represents a transition metal, n represents an integer of 1 to 2, R ^A1 to R ^A8 each independently represent a hydrogen atom or a substituent. For details of the formula A, paragraphs 0030 to 0050 of JP2015-40895 can be referred to, and the contents thereof are incorporated in the present specification.

Specific examples of the compound having a cyanine pigment skeleton include the following compounds. In the following structural formula, Me represents a methyl group. In addition, the compounds described in JP-A-2016-75720, JP-A-2008-88426, JP-A-2015-172102, and JP-A-2015-40895 are mentioned, and the contents thereof are incorporated in the present specification. Is done.

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。 As the compound having a croconium pigment skeleton, a compound represented by the following formula (Cr) is preferable.

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

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

For details of the formula (Cr), the description of paragraphs 0007 to 0016 of JP-A-5-155145 and paragraph numbers 0011 to 0038 of JP2007-31644 can be referred to, and the contents thereof are described in the present specification. Be incorporated. Specific examples of the compound having a croconium pigment skeleton include the following compounds. In addition, the compounds described in JP-A-5-155145 and JP-A-2007-31644 are also mentioned, and their contents are incorporated in the present 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 pigment skeleton, a compound represented by the following formula (Im) is preferable.
Equation (Im)

In the formula, R ^{11 to} R ¹⁸ each independently represent an alkyl group or an aryl group, and V ^{11 to} V ¹⁵ each independently represent an alkyl group, an aryl group, a halogen atom, an alkoxy group or a cyano group. Represented, X represents the counter anion, c represents the number required to balance the charges, and n1 to n5 are 0 to 4 independently of each other. Specific examples of the counter anion include the above-mentioned counter anion.

Specific examples of the compound having a diimonium pigment skeleton include the following compounds. In addition, the compounds described in JP-A-2012-012399 and JP-A-2007-92060 are also mentioned, and their contents are incorporated in the present specification. In the following structural formula, 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.
Expression (Por)

R ^{1 to} R ¹² are independently hydrogen atom, halogen atom, OR (R = H or hydrocarbon group having 1 to 20 carbon atoms), COOR (R = H or hydrocarbon group having 1 to 20 carbon atoms), A group in which at least a part of CN, NO ₂ , CONH ₂ , a hydrocarbon group, or a 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. represent, each R ^a to R ^F are independently an electron pair, H, an alkyl group, an aryl group, or at least a part of the alkyl group, a halogen atom, an oxygen atom, a nitrogen atom, the group consisting of sulfur and phosphorus atoms Represents a group substituted with at least one atom selected from, p and q each independently represent an integer of 1-3, X represents a counter anion, and c represents the number required to balance the charges. Represent. For details of the formula (Por), the description in paragraphs 0024 to 0049 of JP2016-102862A can be referred to, and the contents thereof are incorporated in the present specification. Specific examples of the porphyrin compound include the following compounds. In addition, the compounds described in JP-A-2016-102862 are also mentioned, and the contents thereof are incorporated in the present specification. In the following structural formula, Ph represents a phenyl group.

In the infrared absorber of the present invention, the metal component may be any as long as it contains the above-mentioned metal atom. It may be a simple substance of a metal or a free metal ion. The metal components include metal oxides, metal nitrides, metal carbon oxides, metal salts (inorganic acid salts, organic acid salts, ammonium salts, etc.), intermetallic compounds, metal complexes, organic metal compounds, and (hetero) polyacids. And a compound such as a salt thereof. In the present invention, the metal component is preferably a compound having no pigment skeleton. Further, when 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 a Ni atom, the metal component does not contain a Ni atom, and Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Pd, Cu, Zn, Si and It preferably contains a metal atom selected from Al. Further, the metal component in the present invention may or may not have infrared absorption.

Preferred embodiments of the infrared absorber of the present invention include the following.
(1) The near-infrared absorbing dye is a compound having a pyrolopyrrolop pigment skeleton (hereinafter, also referred to as a pyrolopyrrolop compound), and a metal atom M1 whose metal component is selected from Na, K, Cs, Ti, Fe, Ca and Al. An embodiment in which the total amount of the metal atom M1 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the 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 contains a metal atom M2 selected from Li, Na, K, Mg, Ca, Fe and Al. An embodiment in which the total amount of the metal atom M2 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the squarylium compound.
(3) The near-infrared absorbing dye is a compound having a cyanine pigment skeleton (hereinafter, also referred to as a cyanine compound), and a metal atom M3 whose metal component is selected from Na, K, Cs, Li, Mg, Fe, Ca and Al. An embodiment in which the total amount of the metal atom M3 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the 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 a metal atom M4 whose metal component is selected from Na, K, Cs, Li, Mg, Fe, Ca and Al. An embodiment in which the total amount of the metal atom M4 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the diimonium compound.
(5) 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 a metal atom selected from Na, K, Cs, Li, Mg, Fe, Ca, Al and Ni. An embodiment in which the total amount of the metal atom M5 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the dithiolene compound containing M5.
(6) The near-infrared absorbing dye is a compound having a phthalocyanine pigment 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 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 containing the metal atom M6 selected from Ni.
(7) The near-infrared absorbing dye is a compound having a porphyrin dye skeleton (hereinafter, also referred to as a porphyrin compound), and the metal components are Na, K, Ca, Mg, Fe, Al, Cu, Co, Pd, Zn, Ti and An embodiment in which 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 containing the metal atom M7 selected from Ni.
(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 component is from Pd, Li, Na, K, Mg, Ca, Mg, Al and Fe. An embodiment in which the total amount of the metal atom M8 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the triarylmethane compound containing the selected metal atom M8.
(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 contains a metal atom M9 selected from Na, K, Cs, Ca, Mg, Al and Fe. An embodiment in which the total amount of the metal atom M9 is 0.00001 to 1 part by mass with respect to 100 parts by mass of the perylene compound.

<Composition>
Next, the composition of the present invention will be described. The composition of the present invention contains the above-mentioned 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, more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, 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 coatability of the composition, but it is preferably selected in consideration of the coatability 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, alkyloxyoxyacetate. (For example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate) (Ethyl, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate)) , 2-Methyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2- Ethyl methyl propionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , 2-oxobutanoate methyl, 2-oxobutanoate ethyl 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, and 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 the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. Examples of aromatic hydrocarbons include toluene, xylene and the like. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. It can be milion) or less, can be 10 mass ppm or less, or can be 1 mass ppm or less).

The organic solvent may be used alone or in combination of two or more. 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 , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and a mixed solution composed of two or more selected from propylene glycol methyl ether acetate are 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 parts) or less. If necessary, a solvent at the mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical 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 diameter of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and even 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 but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.

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 further 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 another near-infrared absorbing compound) other than the above-mentioned infrared absorber. As the other near-infrared absorbing compound, for example, inorganic particles can also be used. The inorganic particles are preferably metal oxide particles or metal particles in that they have more excellent infrared shielding properties. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimonthine oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). Examples thereof include SnO ₂ ) particles and niob-doped titanium dioxide (Nb-doped TiO ₂ ) particles. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles and the like. Further, as the inorganic fine particles, a tungsten oxide compound can be used. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, paragraph number 0080 of JP2016-006476A can be referred to, and the content thereof is 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 whether it is spherical or non-spherical.

The average particle size of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, still more preferably 200 nm or less. When the average particle size of the inorganic particles is in such a range, the visible transparency is good. From the viewpoint of avoiding light scattering, it is preferable that the average particle size is small, but the average particle size of the inorganic particles is usually 1 nm or more for reasons such as ease of handling during production.

When the composition of the present invention contains another 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, more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 15% by mass or less.
The total content of the infrared absorber and 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, more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 15% by mass or less.

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

The dye is not particularly limited, and a known dye can be used. The chemical structures include pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapylidene, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene can be used. Moreover, you may use the multimer of these dyes. Further, 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.
The content of the chromatic colorant is preferably 10 to 1000 parts by mass, more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the infrared absorber.
The total amount of the chromatic colorant and the infrared absorber 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 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 the present invention contains two or more kinds of chromatic colorants, the total amount thereof is preferably within the above range.

<< Color material that transmits infrared rays and blocks visible light >>
The composition of the present invention may also contain a coloring material that transmits infrared rays to block visible light (hereinafter, also referred to as a coloring material that blocks visible light).
In the present invention, the coloring material that blocks visible light is preferably a coloring material that absorbs light in the purple to red wavelength range. Further, 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. Further, 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 coloring material that blocks visible light preferably satisfies at least one of the following requirements (1) and (2).
(1): Contains two or more kinds of chromatic colorants, and forms black with a combination of two or more kinds of chromatic colorants.
(2): Contains an organic black colorant. In the aspect of (2), it is also preferable to further contain a chromatic colorant.

Further, in the present invention, the organic black colorant as a coloring material that blocks visible light is a material that absorbs visible light but transmits at least a part of infrared rays. Therefore, in the present invention, the organic black colorant as a coloring material 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, perillene compounds, and azo compounds, and bisbenzofuranone compounds and perillene compounds are preferable. Examples of the bisbenzofuranone compound include the compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234. For example, as "Irgaphor Black" manufactured by BASF. It is available. Examples of the perillene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned. Examples of the azomethine compound include compounds described in JP-A-1-170601 and JP-A-2-34664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.

In the present invention, the coloring material that blocks visible light has, for example, A / B which is the 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 preferably 4.5 or more.
The above characteristics may be satisfied by one kind of material or a combination of a plurality of materials. For example, in the case of the above aspect (1), it is preferable to combine a plurality of chromatic colorants to satisfy the above spectral characteristics. Further, in the case of the above aspect (2), the organic black colorant may satisfy the above spectral characteristics. Further, the above spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.

Examples of the combination of chromatic colorants when black is formed by the combination of two or more kinds of 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 coloring material that blocks visible light, the content of the coloring material that blocks visible light is preferably 30% by mass or less, preferably 20% by mass, based on the total solid content of the composition. The following is more preferable, and 15% by mass or less is further preferable. The lower limit can be, for example, 0.01% by mass or more, and can also be 0.5% by mass or more.
Further, the composition of the present invention may be in an embodiment that does not substantially contain a coloring material that blocks visible light. The fact that the color material that blocks visible light is not substantially contained means that the content of the color material that blocks visible light is preferably 0.005% by mass or less based on the total solid content of the composition of the present invention. It is more preferably 001% by mass or less, and further preferably it does not contain a coloring material 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 replaced with an acidic group, a basic group, a group having a salt structure or a phthalimide methyl group, and a 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 phthalimide methyl group, and m is an integer of 1 or more. , N represents an integer of 1 or more, and when m is 2 or more, the plurality of Ls and Xs may be different from each other, and when n is 2 or more, the plurality of Xs may be different from each other.

In formula (B1), P represents a pigment structure, pyrrolopyrrolop pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, dianthraquinone pigment structure, benzoisoindole pigment structure, thiazine indigo pigment structure. , Azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, perinone pigment structure, benzoimidazolone pigment structure, benzothiazole pigment structure, benzoimidazole pigment structure and benzoxazole pigment structure At least one selected from the above is preferable, at least one selected from the pyrolopyrrolop pigment structure, the diketopyrrolopyrrole pigment structure, the quinacridone pigment structure and the benzoimidazolone pigment structure is more preferable, and the pyrolopyrrolop pigment structure is particularly preferable.

In formula (B1), L represents a single bond or 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. , It may be unsubstituted or may have an additional substituent.

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

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

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment contained in the composition. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be enhanced and the aggregation of the pigment can be efficiently suppressed. The pigment derivative may be of only one type or of two or more types, and in the case of two or more types, the total amount is preferably in 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 a composition or for a binder. The resin mainly used for dispersing pigments and the like is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for a purpose other than such an application.

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, 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, more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 100 or more, more preferably 200 or more.

Examples of the resin include (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and 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 polymers containing repeating units derived from (meth) acrylic acid and / or an ester thereof. Specific examples thereof include polymers obtained by polymerizing at least one selected from (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide and (meth) acrylonitrile.

Examples of the polyester resin include polyols (for example, ethylene glycol, propylene glycol, glycerin, and trimethylolpropane), polybasic acids (for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids thereof, and aromatic rings thereof. Aromatic dicarboxylic acid in which the hydrogen atom is substituted with a methyl group, an ethyl group, a phenyl group, etc., an aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as adipic acid, sebacic acid, dodecanedicarboxylic acid, and cyclohexanedicarboxylic acid. Examples thereof include a polymer obtained by reacting with an alicyclic dicarboxylic acid) and a polymer obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer (for example, polycaprolactone).

Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which 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 resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidylizing halogenated phenols, condensate of silicon compound having an epoxy group and other silicon compounds, polymerizable unsaturated compound having an epoxy group and other Examples thereof include a copolymer with another polymerizable unsaturated compound.

Examples of the epoxy resin which 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, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) Phenyl] Propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol , Hydroquinone, pyrogallol, fluoroglucinol, phenols having a diisopropyridene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene. Some epoxy resins and the like can be mentioned.

As the epoxy resin which is a glycidyl etherified product of novolak resin, for example, various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F and bisphenol S, and naphthols are used as raw materials. Examples thereof include glycidyl etherified products of various novolak resins such as novolak resin, xylylene skeleton-containing phenol novolac resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, and fluorene skeleton-containing phenol novolac resin.

Examples of the alicyclic epoxy resin include an alicyclic skeleton having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. Epoxy resin can be 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 a heterocyclic epoxy resin having a heterocycle such as an isocyanul ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins made 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 the epoxy resin obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol A. Epoxy resins obtained by glycidylating halogenated phenols can be mentioned.

As a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound, the commercially available products include Marproof G-0150M, G-0105SA, G-0130SP, and others. Examples thereof include G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by Nichiyu Co., Ltd., epoxy group-containing polymer). Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of copolymers of other polymerizable unsaturated compounds include methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane, etc., and in particular, methyl (meth) acrylate, Benzyl (meth) acrylate and styrene are preferable.

The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even 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 only one type or two or more types. The resin having an acid group can also be used as an alkali-soluble resin. Further, the resin having an acid group can also be used as a dispersant.

As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferable. Specific examples include alkali-soluble methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins. Examples thereof include a phenol resin, an acidic cellulose derivative having a carboxyl group in the side chain, and a resin in which an acid anhydride is added 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, vinyl compounds and the like. Examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples thereof include α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like. As the other monomer, N-substituted maleimide monomers described in JP-A-10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used. The other monomer copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

Resins having an acid group are benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth). A multi-element copolymer composed of acrylate / (meth) acrylic acid / other monomer 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 / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylate copolymer, 2-hydroxyethylmethacrylate / polystyrene macromonomer / methylmethacrylate / methacrylate copolymer, 2-hydroxyethylmethacrylate / polystyrene Macromonomers / benzyl methacrylate / methacrylic acid copolymers and the like 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 dimer"). 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 the formula (ED1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or 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-A-2010-168539 can be referred to.

As a specific example of the ether dimer, for example, paragraph No. 0317 of JP2013-29760A can be referred to, and the content thereof is incorporated in the present specification. The ether dimer may be of only one type or of two or more types.

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 the compound represented by the following formula (X).

In 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 and may contain 1 to 20 carbon atoms. Represents the alkyl group of. 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 Daicel NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic acidomer. Diamond Shamlock Co., Ltd.), Viscort R-264, and KS resist 106 (all from Osaka Organic Chemical Industry). Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Acrylic-RD-F8 (manufactured by Nippon Catalyst Co., Ltd.), etc. Can be mentioned.

Examples of the resin having an acid group include paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685-0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408. The description of paragraphs 0076 to 09999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Examples of commercially available products include Acribase FF-426 (Fujikura Kasei Co., Ltd.).

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, it is also preferable to use as the resin a resin having a repeating unit represented by the formulas (A3-1) to (A3-7).

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

R ⁵ represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R ⁵ is preferably a hydrogen atom or a methyl group.

L ^{4 to} L ⁷ each independently represent a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , -NR ^10- (R ¹⁰ is a hydrogen atom or (Representing an alkyl group, a hydrogen atom is preferable), or a group consisting of a combination thereof is mentioned, and a group consisting of at least one of an alkylene group, an arylene group and an alkylene group and -O- is preferable. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. 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 either monocyclic or polycyclic. The number of carbon atoms in the arylene group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

The alkyl group represented by R ¹⁰ may be linear, branched or cyclic, and cyclic is preferable. The alkyl group may have the above-mentioned substituents or may be unsubstituted. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group represented by R ¹⁰ preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6. R ¹⁰ is preferably a cyclic alkyl group or 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. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The aryl group represented by R ¹¹ and R ¹² preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6. R ¹¹ and R ¹² are preferably linear or branched alkyl groups.

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. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The aryl group represented by R ¹³ preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6. 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 atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, allyloxy group, heteroaryloxy group, 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 ,- ^Examples thereof include SO ₂ R ^a12 , -SO ₂ OR ^a13 , -NHSO ₂ R ^a14 or -SO ₂ NR ^a15 R ^a16 . R ^{a1 to} R ^a16 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Among them, at least one of R ¹⁴ and R ¹⁵ preferably represents a cyano group or −COOR ^a4 . R ^a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.

Examples of commercially available resins having a repeating unit represented by the formula (A3-7) include ARTON F4520 (manufactured by JSR Corporation). Further, for details of the resin having a repeating unit represented by the formula (A3-7), the description of paragraphs 0053 to 0075 and 0127 to 0130 of JP2011-100084A can be referred to, and the contents thereof are described in the present specification. Incorporated into the book.

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

Dispersants include polymer dispersants [for example, resins having an amine group (polyamide amines and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, etc. Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formarin condensate] and the like. Polymer dispersants can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.

Examples of the terminal-modified polymer include the polymers having a phosphoric acid group at the terminal described in JP-A-3-112992, JP-A-2003-533455, etc., and those described in JP-A-2002-273191. Examples thereof include polymers having a sulfo group at the end, and polymers having a partial skeleton of an organic dye or a heterocycle described in JP-A-9-77994. Further, a polymer in which two or more anchor sites (acid groups, basic groups, partial skeletons of organic dyes, heterocycles, etc.) on the pigment surface are introduced into the polymer terminals described in JP-A-2007-277514 is also available. It has excellent dispersion stability and is preferable.

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

Examples of the graft-type 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, etc., macromolecules described in JP-A-10-339949, JP-A-2004-37986, etc., and monomers having a nitrogen atom-containing group. , JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc., a graft-type polymer having a partial skeleton or heterocycle of an organic dye, JP-A-2010 Examples thereof include a copolymer of a macromolecule 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 formulas (111) to (114), W ¹ , W ² , W ³ , and W ⁴ independently represent an oxygen atom or NH, and represent X ¹ , X ² , X ³ , X ⁴ , and X, respectively. 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, Z ¹ , Z ² , Z ³ and Z. ⁴ 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 independently integers of 1 to 500. the stands, j and k independently denote an integer of 2-8, in the formula (113), when p is 2 to 500, R ³ existing in plural numbers may be different, even the same as each other, In formula (114), when q is 2 to 500, a plurality of X ⁵ and R ⁴ existing may be the same or different from each other.

For details of the graft copolymer, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the above contents are incorporated in the present specification. Specific examples of the graft copolymer include the following resins. In addition, the resins described in paragraphs 0072 to 0094 of JP2012-255128A are mentioned, and the contents thereof are incorporated in the present specification.

Further, in the present invention, as the resin (dispersant), 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. The oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. A resin having a basic nitrogen atom on at least one of them is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. The oligoimine-based 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 a structural unit represented by the formula (I-2a). Dispersants containing structural units and the like can be mentioned.

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 represent a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a represents an integer of 1 to 5 independently of each other. * Represents the connection between structural units.
R ⁸ and R ⁹ are synonymous with 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), and a heteroarylene group (preferably having 1 to 6 carbon atoms). (Preferably), imino group (preferably having 0 to 6 carbon atoms), ether group, thioether group, carbonyl group, or a linking group according to a combination thereof. Among them, a single bond or −CR ⁵ R ⁶ −NR ⁷ − (the imino group is X or Y) is preferable. Here, R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom, and 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 site that forms a 5- to 7-membered non-aromatic heterocycle by combining the carbon atom and N (nitrogen atom) of CR ⁸ CR ⁹ , and more preferably a 5-membered non-aromatic heterocycle. It is a structural site that forms pyrrolidine, and is particularly preferable. This structural site may further have a substituent such as an alkyl group.
X represents a group having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.

The oligoimine-based dispersant further contains at least one selected from the structural units represented by the formulas (I-3), (I-4), and (I-5) as a copolymerization component. May be good. When the oligoimine-based dispersant contains such a structural unit, the dispersibility of the infrared absorbing compound and 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 It is synonymous with ⁹ , L, La, a and *.
Ya represents a side chain having an anionic group and having 40 to 10,000 atoms. The structural unit represented by the formula (I-3) is obtained by adding an oligomer or a polymer having a group 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 to react. It is possible to form by.

Regarding the oligoimine-based dispersant, the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and this content is incorporated in the present specification. Specific examples of the oligoimine-based dispersant include the following. Further, the resin described in paragraph numbers 0168 to 0174 of JP2012-255128A can be used.

The dispersant is also available as a commercially available product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie). Further, the pigment dispersant described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification. Further, the above-mentioned resin having an acid group or the like can also be used as a dispersant.

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, more preferably 7% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less.
When the dispersant is contained as the resin, the content of the dispersant is preferably 0.1 to 40% by mass with respect to the total solid content of the 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. 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 radically 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. Compounds having more than one are more preferable. 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, a (meth) acryloyl group and the like, and a (meth) acryloyl group is preferable. The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.

The polymerizable compound may be in the form of a monomer or a polymer, but a monomer is preferable. The monomer-type polymerizable compound preferably has a molecular weight of 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. Further, it is also preferable that the polymerizable compound is a compound having substantially no molecular weight distribution. Here, the fact that the compound has substantially no molecular weight distribution means that the degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the compound is preferably 1.0 to 1.5. .0 to 1.3 are more preferred.

As an example of the polymerizable compound, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification. Examples of the polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol triacrylate (commercially available KAYARAD D-330). ; Nippon Kayaku Co., Ltd.), Dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D) -310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available, KAYARAD DPHA; Nihon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Industry Co., Ltd. , And these (meth) acryloyl groups are bonded via an ethylene glycol residue and / or a propylene glycol residue. Also, these oligomer types can be used. Further, the description of paragraphs 0034 to 0038 of JP2013-253224A can be referred to, and this content is incorporated in the present specification. In addition, the polymerizable monomers described in paragraph No. 0477 of JP2012-208494A (paragraph No. 0585 of the corresponding US Patent Application Publication No. 2012/0235099) are mentioned, and the contents thereof are described in the present specification. Is incorporated into. In addition, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., A-TMMT), 1,6- Hexanediol diacrylate (KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.) is also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be 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 an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A polymerizable compound obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group is preferable, and particularly preferably, the aliphatic polyhydroxy compound is used in this ester. It is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-305, M-510, and M-520 of the Aronix series as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. The acid value of the polymerizable compound having an acid group is preferably 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 preferable 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, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, dimethylolpropane, pentaerythritol, and dipenta. Ε-Caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyvalent alcohols such as erythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Can be mentioned. As the polymerizable compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. The compound having a caprolactone structure is, for example, an ethyleneoxy chain manufactured by Sartmer, such as DPCA-20, DPCA-30, DPCA-60, DPCA-120, which is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. Examples thereof include 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 Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. 2-16765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. In addition, 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 should be used. Can be done. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and UA. -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, further preferably 20% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used in combination, the total amount is preferably in the above range.
When the composition contains an epoxy resin and a polymerizable compound, the mass ratio of the polymerizable compound to the epoxy resin is preferably polymerizable compound: epoxy resin = 100: 1 to 100: 400, and 100: 1 to 100. 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. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays 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, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like can be mentioned. Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japanese Patent No. 42, 2924 (1969), British Patent No. 1388492, Compound described in JP-A-53-133428, German Patent No. 3337024, F.I. C. J. by Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-58241, compound described in JP-A-5-281728, compound described in JP-A-5-341920, US Pat. Examples include the compounds described in No. 4212976.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. A compound selected from the group consisting of an imidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound is preferable.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound can also be preferably used. For example, the α-aminoketone compound described in JP-A-10-291969 and the 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, and IRGACURE-127 (all manufactured by BASF) can be used. As the α-aminoketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF) can be used. As the α-aminoketone compound, the compound described in JP-A-2009-191179 can be used. As the acylphosphine compound, commercially available products IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF) can be used.

It is preferable to use an oxime compound as the photopolymerization initiator. Specific examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, the compound described in JP-A-2006-342166, and JP-A-2016-21012. Described in the publication. Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, and 2-one. Acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- On, 2-ethoxycarbonyloxyimine-1-phenylpropane-1-one and the like can be mentioned. In addition, J. C. S. Perkin II (1979, pp. 1653-1660), J. Mol. C. S. Perkin II (1979, pp. 156-162), Journal of Photologicr Science and Technology (1995, pp. 202-232), JP-A-2000-66385, JP-A-2000-80068, JP-A-2004. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 534977 and Japanese Patent Application Laid-Open No. 2006-342166.
As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 (manufactured by ADEKA Corporation), ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation), ADEKA PTOMER N -1919 (Photopolymerization initiator 2) manufactured by ADEKA Corporation and described in JP2012-14052A can also be used.

Further, as an oxime compound other than the above, the compound described in JP-A-2009-5199004, in which an oxime is linked to the N-position of the carbazole ring, and US Pat. No. 6,626,957 in which a hetero-substituent is introduced at the benzophenone moiety are described. Compounds, compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety, ketooxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton. In the same molecule, the compound described in US Pat. No. 7,556,910, the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, and the like are used. May be 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 NO bond of the oxime is the (E) form, or the oxime compound in which the NO bond of the oxime is the (Z) form. Z) It may be a mixture with a 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. For the details of the formula (OX-1), the description in paragraphs 0276 to 0304 of JP2013-209760A 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 the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein by reference.

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

In the present invention, an oxime compound having a nitro group can be used as the 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 the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS 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 the wavelength region of 350 nm to 500 nm, and more preferably a compound having an absorption maximum in the wavelength region of 360 nm to 480 nm. Further, 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 of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, It is particularly preferably 000.
The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

The photopolymerization initiator also preferably contains an oxime compound and an α-aminoketone compound. By using both in combination, the developability is improved and it is easy to form a pattern having excellent rectangularity. 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, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is in the above range, better sensitivity and pattern forming property can be obtained. The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<< Compound having an alkoxysilyl group >>
The composition of the present invention also preferably contains a compound having an alkoxysilyl group. The number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2. It is preferable to have two or more alkoxysilyl groups in one molecule, and it is more preferable to have two or three alkoxysilyl groups. Examples of the compound having an alkoxysilyl group include the compounds described in paragraphs 0044 to 0047 of JP-A-2015-125710, the contents of which are incorporated in the present specification.

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 with respect to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, further preferably 20% by mass or less. The compound having an alkoxysilyl group may be used alone or in combination of two or more. When two or more compounds having an alkoxysilyl group are used in combination, the total amount is preferably in the above range.

<< Catalyst >>
The composition of the present invention can further contain a catalyst. In particular, when a compound having an alkoxysilyl group is contained, the sol-gel reaction is promoted by containing the catalyst, and a strong cured film can be obtained. Examples of the catalyst include an acid catalyst and a base catalyst. As the acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, sulfite, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and R having a structural formula represented by RCOOH are replaced with other elements or substituents. Examples thereof include substituted carboxylic acid, sulfonic acid such as benzenesulfonic acid, and phosphoric acid. Further, Lewis acids such as aluminum chloride, aluminum acetylacetonate, zinc chloride, tin chloride, boron trifluoride diethyl ether complex, and imidazole trimethylsilane may be used. Examples of the base catalyst include ammoniacal base compounds such as aqueous ammonia and organic amines such as ethylamine and aniline. Further, as the catalyst, the catalyst described in paragraphs 0070 to 0076 of JP2013-201007A can also be used.
The content of the catalyst is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the compound having an alkoxysilyl group. It is a department. The composition of the present invention may contain only one type of catalyst, or may contain two or more types of catalysts. When two or more types of catalysts are contained, the total amount thereof is preferably in 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. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferable. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition.

<<< Surfactant >>>
The composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. 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 containing a fluorine-based surfactant in the composition of the present invention, the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. be able to. When a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

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

Specific examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-41318 (paragraphs 0060 to 0064 of the corresponding international publication 2014/17669) and the like. The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503 are mentioned, and their contents are incorporated in the present specification. Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (or more, DIC). (Manufactured by Sumitomo 3M Ltd.), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC- Examples thereof include 381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like.

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied is also suitable. Can be used. Examples of such a fluorine-based surfactant include the Mega Fvck DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Mega Fvck DS. -21 can be mentioned 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。 A block polymer can also be used as the fluorine-based surfactant. For example, the compounds described in JP-A-2011-89090 can be 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 groups and propyleneoxy groups) (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 fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, for example 14,000. In the above compounds,% indicating the ratio of the repeating unit is mass%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylates, glycerol ethoxylates, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl 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), Solsparse 20000 (Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

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

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

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

<< 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 and the like can be used. For details thereof, the description of paragraphs 0052 to 0072 of JP2012-208374A and paragraphs 0317 to 0334 of JP2013-68814 can be referred to, and these contents are incorporated in the present specification. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Further, as the benzotriazole compound, the MYUA series (The Chemical Daily, February 1, 2016) manufactured by Miyoshi Oil & Fat may be used.
The content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition of the present invention.

<< Other ingredients >>
The compositions of the present invention, as required, include sensitizers, curing accelerators, fillers, thermosetting accelerators, thermal polymerization inhibitors, plasticizers, adhesion accelerators and other auxiliaries (eg, conductive particles). , Filler, antifoaming agent, flame retardant, leveling agent, peeling accelerator, antioxidant, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained. For these components, the description of paragraph numbers 0101 to 0104, 0107 to 0109, etc. 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 ester compound, and a thioether compound. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite ester compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. These may be used in mixture of 2 or more types. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred 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, and a methyl group, an ethyl group, a propionyl group, an isopropionyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and an isopentyl group. More preferred are groups, t-pentyl groups, hexyl groups, octyl groups, isooctyl groups and 2-ethylhexyl groups. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] Ethyl] amines and ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) include at least one compound selected from the group. These are available as commercial products. For example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 Co., Ltd. ADEKA) and the like. The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. The antioxidant may be of only one type or of two or more types. In the case of two or more types, the total amount is preferably in 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, an infrared transmission filter, and the like.

<Method of preparing composition>
The composition of the present invention can be prepared by mixing the above-mentioned components.
In preparing the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then sequentially blended. In addition, there are no particular restrictions on the order of loading and working conditions when blending. For example, all the components may be dissolved or dispersed in a solvent at the same time to prepare a composition, or if necessary, two or more solutions or dispersions in which each component is appropriately mixed may be prepared in advance and used. These may be mixed (at the time of application) and prepared as a composition.

When the composition of the present invention contains particles such as pigments, it is preferable to include a process of dispersing the particles. In the process of dispersing particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter and to process the particles under conditions in which the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing particles are "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industrial application centered on suspension (solid / liquid dispersion system)". The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Practical Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the particles, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-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 and reducing defects. As the filter, any filter conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). A filter using a material such as (including the polyolefin resin of) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specific examples thereof include filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.

When using filters, different filters (eg, first filter and second filter) may be combined. At that time, the filtration with each filter may be performed only once or twice or more.
Further, filters having different pore diameters may be combined within the above-mentioned range. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd. can do.
As the second filter, one formed of the same material as the first filter can be used.
Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration with the second filter may be performed.

<Membrane>
Next, the film of the present invention will be described. The film of the present invention is made by using the composition of the present invention described above. Since the film of the present 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 having no pattern (flat film). Further, the film of the present invention may be used by being laminated on the support, or may be peeled off from the support.

The film thickness of the film of the present invention can be appropriately adjusted according to the intended 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. The color filter can be produced by using a 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 radically polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber and the like. For these details, the materials described in the compositions of the present invention can be mentioned and these can be used. Further, the film of the present invention may contain a chromatic colorant to form a filter having a function as a near-infrared cut filter and a color filter.

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 blocks 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 the light having a wavelength in the visible region, and among the light having a wavelength in the visible region, it passes the light in a specific wavelength region and blocks the light in the specific wavelength region. It may be something to do. Further, in the present invention, the color filter means a filter that passes light in a specific wavelength region and blocks light in a specific wavelength region among light having a wavelength in the visible region. Further, the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray).

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. Further, the transmittance in the entire range of the wavelength of 400 to 550 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
The preferred range of infrared shielding property of the near-infrared cut filter varies depending on the application, but the transmittance at at least one point in the wavelength range of 650 to 1500 nm is preferably 20% or less, more preferably 15% or less. 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 obtain a film capable of transmitting infrared rays in a state where there is little noise derived from visible light.

(1) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less, and the minimum value of the light transmittance in the film thickness direction in the wavelength range of 1000 to 1300 nm. Is 80% or more. A film having such spectral characteristics can be preferably used as an infrared transmissive 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 characteristics of the film are values obtained by measuring the transmittance in the 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, it may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, or the like, in addition to the film of the present invention.
Since the near-infrared cut filter further has a copper-containing layer and / or a dielectric multilayer film, it is easy to obtain a near-infrared cut filter having a wide viewing angle and excellent infrared shielding property. Further, since the near-infrared cut filter further has an ultraviolet absorbing layer, it can be a near-infrared cut filter having excellent ultraviolet shielding property. As the ultraviolet absorbing layer, for example, the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015 / 09960 can be referred to, and the contents thereof are incorporated in the present specification. As the dielectric multilayer film, the description in paragraphs 025 to 0259 of JP2014-413118A can be referred to, and the contents thereof are incorporated in the present specification. As the copper-containing layer, a glass base material made of copper-containing glass (copper-containing glass base material) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of the copper-containing glass base material include copper-containing phosphate glass and copper-containing fluoride glass. Examples of commercially available copper-containing glass products include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (all manufactured by Schott AG), CD5000 (manufactured by HOYA Corporation), and the like. Examples of the copper complex-containing layer include a layer formed by using a composition containing a copper complex. The copper complex is preferably a compound having a maximum absorption wavelength in the 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 even more 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 near-infrared cut filter and an infrared transmission filter in combination, 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 by using the composition of the present invention, and only one of them is formed by using the composition of the present invention. You can also do it.

The film of the present invention can be used for solid-state imaging devices such as CCD (charge coupling element) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.

<Optical filter>
Next, the optical filter of the present invention will be described. The optical filter of the present invention has the above-mentioned 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. A preferred embodiment of the optical filter of the present invention is also a mode having pixels using the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless.

<Laminated body>
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 to each other in the thickness direction. When the film of the present invention and the color filter are not adjacent to each other 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. Other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state image sensor may be interposed between the film and the color filter.

<Pattern formation method>
Next, a pattern forming method using the composition of the present invention will be described. 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. Is preferable.

When producing a laminate in which the film of the present invention and the color filter are laminated, the pattern formation of the film of the present invention and the pattern formation of the color filter may be performed separately. Further, a pattern may be formed on the laminate of the film of the present invention and the color filter (that is, the pattern of the film of the present invention and the color filter may be formed at the same time).

The case where the film and the color filter of the present invention are separately patterned means the following aspects. Pattern formation is performed on either the film or the color filter of the present invention. Next, the other filter layer is formed on the patterned filter layer. Next, pattern formation is performed on the filter layer that has not been pattern-formed.

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

The pattern forming method in 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 step of developing and removing an unexposed portion to perform a pattern. It is preferable to include a step of forming the above. If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided.
Further, the pattern forming 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 the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the cured product layer using the resist pattern as an etching mask to form a pattern. .. Hereinafter, each step will be described.

<< Step of forming the composition layer >>
In the step of forming the composition layer, each composition is used to form the composition layer on the support.

As the support, for example, a substrate for a solid-state image sensor 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 forming surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-forming surface side (back surface). If necessary, an undercoat layer may be provided on the support in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface of the substrate.

As a method of 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 rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nanoimprint method and the like can be mentioned. The method of application to an inkjet is not particularly limited, and for example, the method described in the patent gazette shown in "Expandable / Usable Inkjet-Infinite Possibilities Seen in Patents-, Issued in February 2005, Sumi Betechno Research". (In particular, pages 115 to 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. The method described in is mentioned.

The composition layer formed on the support may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process.
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. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. By performing the prebaking 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 maintained more effectively.
The prebaking time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.

(When forming a pattern by photolithography)
<< Exposure process >>
Next, the composition layer is exposed in a pattern (exposure step). For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. As a result, the exposed portion can be cured.
As the radiation (light) that can be used for exposure, ultraviolet rays such as g-ray and i-line are preferable, and i-ray 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, and in addition to the operation 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 anoxic). ), Or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, 50% 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. Development and removal of the unexposed portion can be performed using a developing solution. As a result, the composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains on the support.
As the developing solution, an alkaline developing solution that does not damage the underlying solid-state image sensor or circuit is desirable.
The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.

Examples of the alkaline agent used in the developing solution include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrol, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene. Examples thereof include compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the developing solution, 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, more preferably 0.01 to 1% by mass. Moreover, you may use a surfactant as a developer. Examples of the surfactant include the surfactant described in the above-mentioned composition, and a nonionic surfactant is preferable. When a developer composed of such an alkaline aqueous solution is used, it is preferable to wash (rinse) it with pure water after development.

It is also possible to perform heat treatment (post-baking) after developing and drying. Post-baking is a post-development heat treatment to complete the curing of the film. When post-baking is performed, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film hardening, 200 to 230 ° C. is more preferable. Further, when an organic electroluminescence (organic EL) element is used as the light emitting 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. It is preferably 100 ° C. or lower, more preferably 90 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher. Post-baking should be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the above conditions are met. Can be done. Also, when the pattern is formed by a low temperature process, post-baking may not be performed.

(When forming a pattern by dry etching method)
In the pattern formation by the dry etching method, the composition layer formed on the support is cured to form a cured product layer, and then the obtained cured product layer is masked with a patterned photoresist layer. This can be done using an etching gas. In forming the photoresist layer, it is preferable to further perform a prebaking treatment. In particular, as the photoresist forming process, it is desirable to carry out a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and this content is incorporated in the present specification.

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

On the support, a transfer electrode made of a plurality of photodiodes and polysilicon or the like constituting the light receiving area of the solid-state image sensor is provided, and light shielding made of tungsten or the like in which only the light receiving portion of the photodiode is opened on the photodiode and the transfer electrode. It has a film, 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 part on the light-shielding film, and has the film of the present invention on the device protective film. is there. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the film of the present invention (the side closer to the support), or condensing on the film of the present invention. It may be a configuration having means or the like. Further, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the imaging device having such a structure include the devices described in JP-A-2012-227478 and JP-A-2014-179757.

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

For the definition and details of the image display device, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)" ) ”And so on. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

The image display device may 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, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.

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

Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.
In FIG. 1, reference numeral 110 is a solid-state image sensor. The imaging region provided on the solid-state image sensor 110 includes a near-infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the near infrared cut filter 111. A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. The flattening 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) used. The near-infrared cut filter 111 can be formed by using the composition of the present invention.

The color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-043556 can be taken into consideration, and this content is 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 transmittance filter 114 preferably has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 650 nm of 30% or less. It is more preferably% or less, further preferably 10% or less, and particularly preferably 0.1% or less. It is preferable that the transmittance satisfies the above conditions in the entire 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.

The infrared transmittance filter 114 preferably has a 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) of 70% or more, and more preferably 80% or more. , 90% or more is more preferable. The 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 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, the film can be a film satisfying the above-mentioned spectral characteristics.
The method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.
The film thickness was measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.
The spectral characteristics of the film are values obtained by measuring the transmittance in the 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 transmittance filter 114 has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 450 to 650 nm of 20% or less, and the film. It is preferable that the transmittance of light having a wavelength of 835 nm in the thickness direction of the film is 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 70% or more.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. In the following, NMR is an abbreviation for nuclear magnetic resonance. In the following structural formula, Ph represents a phenyl group.

<Manufacturing of infrared absorber 1>
A near-infrared absorbing dye (A-1) was synthesized according to the following scheme to produce an infrared absorbing agent 1.

Using 4- (1-methylheptoxy) benzonitrile as a raw material, compound (A-1-a) was synthesized according to the method described in US Pat. No. 5,969,154.
^{1 1} H-NMR (DMSO (dimethyl sulfoxide): 28% by mass methanol solution of sodium methoxide = 95: 5 (mass ratio) mixed solution): δ0.82 (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 were stirred in 230 parts by mass of toluene, and 45.0 parts by mass of phosphorus oxychloride was added dropwise. The mixture was heated under 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 of 30 ° C. or lower. After completion of the 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. 200 parts by mass of methanol was added to the obtained crystals, the mixture was heated under reflux for 30 minutes, allowed to cool to 30 ° C., and the crystals were filtered off. The obtained crystals were air-dried at 40 ° C. for 12 hours to obtain 8.8 parts by mass of compound (A-1-b).
^{1 1} H-NMR (CDCl ₃ ): δ0.90-1.90 (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 mass of diphenylborinic acid 2-aminoethyl ester and 6.0 parts by mass of compound (A-1-b) were stirred in 60 parts by mass of toluene, and 10.6 parts of titanium tetrachloride was stirred at an external temperature of 40 ° C. The parts by mass were added dropwise over 10 minutes and stirred for 30 minutes. The temperature was raised to an external temperature of 130 ° C., and the mixture was heated under reflux for 3 hours. The mixture was allowed to cool until the internal temperature reached 30 ° C., and 40 parts by mass of methanol was added dropwise while maintaining the internal temperature of 30 ° C. or lower. After the dropping, the mixture was stirred for 30 minutes, the precipitated crystals were filtered off, and washed with 35 parts by mass of methanol. 50 parts by mass of methanol was added to the obtained crystals, the mixture was heated under reflux for 30 minutes, allowed to cool until the temperature reached 30 ° C., and the crystals were separated by filtration twice. The obtained crystals were air-dried at 40 ° C. for 12 hours to obtain 4.6 parts by mass of compound (A-1-c).
^{1 1} H-NMR (DMSO): δ6.20-6.30 (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 compound (A-1-c). The maximum absorption wavelength of 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. Parts by mass were added and stirred for 5 minutes. The circumscribed temperature was raised to 110 ° C. and heated for 4 hours. The crystals were allowed to cool until the internal temperature reached 30 ° C., and the precipitated crystals were filtered off. Then, the filtered crystals were 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 crystals, the mixture was heated under reflux for 30 minutes, allowed to cool to 30 ° C., and the crystals were filtered off. 200 parts by mass of dimethyl sulfoxide was added to the filtered crystals, and the mixture was heated at 80 ° C. for 30 minutes. After the heating was completed, the crystals were 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, the mixture was heated under reflux for 30 minutes, allowed to cool to 30 ° C., and the crystals were filtered off. The separated crystals were air-dried at 50 ° C. for 24 hours to obtain 5.5 parts by mass of compound (A-1-d).
^{1 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 the mixture was heated under reflux. After completion of the reaction, the solvent was removed, and the residue was washed with hexane and filtered off. The obtained crystals were air-dried at 50 ° C. for 24 hours to obtain 0.5 parts by mass of an infrared absorber 1 containing a near-infrared absorbing dye (A-1).

<Manufacturing 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.

413 mg (1.1 mmol) of compound (A-2-a) was added to the reaction vessel, and the mixture was replaced with nitrogen. 30 mL of tetrahydrofuran (THF) was added to shield the light from light, 213 mg (5.6 mmol) of LiAlH ₄ was added, and the mixture was heated under reflux overnight. After returning to room temperature, quenching with saturated aqueous sodium tartrate solution, extraction with ethyl acetate, washing once with water, drying with Na ₂ SO ₄ , and concentration under reduced pressure to obtain compound (A-2-b). (Yield 356 mg, 1.1 mmol).
^{1 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 = 2.3Hz, 1H), 2.54 (s, 3H), 1.45 (s, 9H), 1.43 (s, 9H)
62.4 mg (0.547 mmol) of squaric acid and 0.356 g (1.13 mmol) of compound (A-2-b) were added to the reaction vessel and substituted with nitrogen. 20 mL of n-butanol and toluene was added at a ratio of 1: 1 and the mixture was heated under reflux. After completion of the reaction, the mixture was allowed to cool and concentrated under reduced pressure. The infrared absorber 2 containing the near-infrared absorbing dye (A-2) was obtained by washing with methanol (yield 0.2744 g, 0.383 mmol, yield 70% of the near-infrared absorbing dye (A-2)).
^{1 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％） <Manufacturing 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.

Compound (A-3-a) was synthesized with reference to the method described in Japanese Patent No. 4951295.
9.21 g of compound (A-3-a) was dissolved in 120 ml of ethyl acetate in 3-port sulsco, 40 ml of acetonitrile was added, and the mixture was stirred at room temperature. Here, 12.3 g of DuPont OXONE (trade name, purchased from Sigma-Aldrich Japan, consisting of 2KHSO ₅ , KHSO ₄ , K ₂ SO ₄ ) and 2.44 g of sodium perchlorate in 40 ml of water. The dissolved aqueous solution was added dropwise over 30 minutes, and then the mixture was stirred as it was for 3 hours. This product was separated, washed once with a mixed solution of 60 ml of water and 10 ml of saturated brine, concentrated with a rotary evaporator, ethyl acetate was added to the obtained residue, and the obtained crystals were filtered. Dry to obtain 10.4 g of the infrared absorber 3 containing the near-infrared absorbing dye (A-3) (yield 93% of the near-infrared absorbing dye (A-3)).

<Manufacturing 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).

<Manufacturing of infrared absorber 5>
An infrared absorber 5 containing a near-infrared absorbing dye (A-5) was produced with reference to the method described in JP-A-2016-102862.

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）。 <Manufacturing 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.

A compound (A-6-a) was synthesized with reference to the method described in JP-A-2015-172102.
Compound (A-6-a) was dissolved in acetone, the corresponding metal boron salt was added, and salt exchange was carried out at room temperature. Next, the infrared absorber 6 containing the near-infrared absorbing dye (A-6) was obtained by washing with a 1.0 mol / L dilute sulfuric acid aqueous solution (yield 67% of the near-infrared absorbing dye (A-6)). ..
^{1 1} H-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).

<Manufacturing of infrared absorber 7>
In the process of synthesizing the near-infrared absorbing dye (A-6), the near-infrared absorbing dye (A-6) is used in the same manner except that deion-exchanged water is used instead of the 1.0 mol / L dilute sulfuric acid aqueous solution. An infrared absorber 7 containing the same was produced.

<Manufacturing of infrared absorber 8>
The same applies to the process of synthesizing the near-infrared absorbing dye (A-2), except that a step of washing the near-infrared absorbing dye (A-2) with a 4 mol / L hydrochloric acid aqueous solution and then washing with methanol is added after washing with methanol. By the method, an infrared absorber 8 containing a near-infrared absorbing dye (A-2) was produced.

<Measurement of the amount of metal atoms contained in the infrared absorber>
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) is determined by the following method. It was measured. The infrared absorber 1 contained at least Ti as a metal atom. The 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 absorber 4 contained at least K as a metal atom. The infrared absorber 5 contained at least Na as a metal atom. The infrared absorbers 6 and 7 contained at least Li as a metal atom.
1) Weigh 20 mg of sample (infrared absorber) precisely (n = 3)
2) Add 5 ml of 16 mol / L nitric acid 3) Incinerate using microwave (Teflon® container, 240 ° C)
4) Add H ₂ O to prepare the sample to 40 mL. 5) Inductively coupled plasma emission spectrometry (ICP-OES) using Optims 7300DV manufactured by Parkin Elmer as a measuring device, and the amount of metal atoms contained in the infrared absorber. Quantitative by calibration curve method

<Preparation of color material composition>
10 parts by mass of the infrared absorber shown in the table below, 3.0 parts by mass of the pigment derivative shown in the table below, 7.8 parts by mass of the resin shown in the table below, 109 parts by mass of the organic solvent shown in the table below, 0. After dispersing 520 parts by mass of 5 mm diameter zirconia beads 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 to 10 were manufactured. The color material composition 3 used the absorbent 3 as it was. Further, the color material composition 7 was used as an infrared absorber by mixing the infrared absorber 1 and the infrared absorber 2 in a mass ratio of infrared absorber 1 / infrared absorber 2 = 50/50. .. Further, the color material composition 7 was used as an infrared absorber by mixing the infrared absorber 1 and the infrared absorber 3 in 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 with the following structure

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

(solvent)
PGMEA (Propylene Glycol Methyl Ether Acetate)
Cyclohexanone

<Preparation of curable compositions of Examples 1-2, 4-9, Comparative Examples 1-2>
The following components were mixed to prepare a curable composition. Only in Example 9, 0.5 parts by mass of the additive I-2 was further added.
-Color material composition obtained above: 55 parts by mass-Polymer 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, ultraviolet absorber: 1.3 parts by mass, solvent: 31 parts by mass

<Preparation of 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 the mixture was stirred at 20 to 35 ° C. for 2 hours to dissolve. Next, 0.75 parts by mass of the coloring material composition 3 was added, and the mixture was stirred at 20 to 35 ° C. until uniform. Further, 0.500 parts by mass of the additive I-1 and 1.3 parts by mass of the ultraviolet 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 curable composition of Example 10>
The 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 listed 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: Acribase FF-426, manufactured by Fujikura Kasei Co., Ltd. ・ D-4: ARTON F4520, manufactured by JSR Corporation ・ 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 the repeating unit is mass%.

(UV absorber)
-H-1, UV-503, manufactured by Daito Kagaku Co., Ltd. (additive)
-I-1: Butanedioic acid-I-2: Compound having an alkoxysilyl group (KBM-9569, manufactured by Shinetsu Silicone Co., Ltd.)
(solvent)
PGMEA (Propylene Glycol Methyl Ether Acetate)
PGME (Propylene Glycol Methyl Ether)
Cyclohexanone methyl ethyl ketone

<Making a near-infrared cut filter>
Each curable composition prepared above is applied to a glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film, and is preheated (prebaked) at 100 ° C. for 120 seconds. Exposure was performed with an exposure amount of 500 mJ / cm ² using an i-line stepper or an aligner. Then, after heating (post-baking) at 220 ° C. for 300 seconds, a film having a film thickness of 0.8 μm was formed to obtain a near-infrared cut filter.

<Evaluation of infrared shielding>
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). The infrared shielding property 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.
Change in transmittance = | (Transmittance after heating-Transmittance before heating) |
A: Transmittance change is less than 3% B: Transmittance change is 3% or more and less than 5% C: Transmittance change is 5% or more

<Light resistance evaluation>
A near-infrared cut filter was set in a fading tester equipped with a super xenon lamp (100,000 lux), and light irradiation was performed for 50 hours under the condition that the ultraviolet cut filter was not 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 of the absorbance at the maximum absorption wavelength is calculated from the following formula. Then, 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: Survival rate exceeds 95% and is 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, it was possible to produce a film having excellent infrared shielding property, heat resistance and light resistance.

[Test Example 1]
The composition of Example 2 was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. It was then heated at 200 ° C. for 5 minutes using a hot plate. Next, a 2 μm square Bayer pattern (near infrared cut filter) was formed by a dry etching method.
Next, the Red composition was applied onto the Bayer pattern of the near-infrared cut filter by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1000 mJ / cm ² through a mask with a 2 μm square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. The Red composition was then 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 composition for forming an infrared transmission filter was applied onto the patterned film by a spin coating method so that the film thickness after film formation was 2.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1000 mJ / cm ² through a 2 μm square Bayer pattern mask. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Next, the infrared transmission filter was patterned on the missing portion of the Bayer pattern of the near infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. This was incorporated into a solid-state image sensor according to a known method.
The obtained solid-state image sensor was irradiated with an infrared light emitting diode (infrared LED) light source in an environment of low illuminance (0.001 Lux) to capture an image, and the image performance was evaluated. I was able to clearly recognize the subject on the image. In addition, the incident angle dependence was good.

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

(Red composition)
The following components were mixed, 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% by 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, 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 mass Resin 4 (40% by mass PGMEA solution) ... 0.3 parts by mass Polymerizable compound 1 ... 1.2 parts by mass Photopolymerization initiator 1 ... 0 .6 parts by mass Surface initiator 1 ・ ・ ・ 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・ ・ 0.5 parts by mass PGMEA ・ ・ ・ 19.5 parts by mass

(Blue composition)
The following components were mixed, 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 Polymerized 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

(Composition for forming an infrared transmission filter)
The components having the following composition were mixed, 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 composition for forming an infrared transmission filter.
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 Surface active agent 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 for the Red composition, the Green composition, the Blue composition, and the composition for forming an infrared transmission filter are as follows.

-Red pigment dispersion C. I. Pigment Red 254 at 9.6 parts by mass, C.I. I. A mixed solution consisting of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was used in a bead mill (zirconia beads 0. A pigment dispersion was prepared by mixing and dispersing for 3 hours with a diameter of 3 mm). After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

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

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

・ Pigment dispersion 1-1
The mixed solution having the following composition was mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) using zirconia beads having a diameter of 0.3 mm. To prepare a pigment dispersion liquid 1-1.
-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 BYK Chemie) ... 9.1 parts by mass ・ PGMEA ・ ・ ・ 79.1 parts by mass

-Pigment dispersion 1-2
The mixed solution having the following composition was mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) using zirconia beads having a diameter of 0.3 mm. The pigment dispersion liquid 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 BYK Chemie)-・ ・ 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 the structural unit is the 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 of the left compound and the right compound having a molar ratio of 7: 3)

-Resin 4: The following structure (acid value: 70 mgKOH / g, Mw = 11000, ratio in structural unit is 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 the repeating unit is mass%.

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

110: Solid-state image sensor, 111: Near-infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Microlens, 116: Flattening layer

Claims (15)

Near-infrared absorbing dyes containing at least one selected from anionic and cationic moieties in the molecule, Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn, Si and The near-infrared absorbing dye contains a metal component containing a metal atom selected from Al, and the near-infrared absorbing dye is a pyrolopyrrole dye skeleton, a polymethine dye skeleton, a dithiolene dye skeleton, a phthalocyanine dye skeleton, a porphyrin dye skeleton, an azo dye skeleton, and a triarylmethane dye. It is a compound having a pigment skeleton selected from a skeleton and a perylene dye skeleton, 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. , Infrared absorber,
With solvent
Compositions for near-infrared cut filters or infrared transmission filters, including. Near-infrared absorbing dyes containing at least one selected from anionic and cationic moieties in the molecule, Li, Na, K, Cs, Mg, Ca, Ti, Fe, Co, Ni, Pd, Cu, Zn, Si and The near-infrared absorbing dye is a compound having a pyrolopyrrole dye skeleton, which contains a metal component containing a metal atom selected from Al, and the metal component contains at least Ti as a metal atom of the near-infrared absorbing dye. An infrared absorber having a total amount of the metal atoms contained in the metal component of 0.00001 to 1 part by mass with respect to 100 parts by mass.
With solvent
Compositions for near-infrared cut filters or infrared transmission filters, including. The composition according to claim 1 or 2 , wherein the near-infrared absorbing dye is a near-infrared absorbing dye having an anion moiety and a cation moiety in the molecule. The composition according to any one of claims 1 to 3, wherein the near-infrared absorbing dye has a maximum absorption wavelength in the range of 650 to 1500 nm. The composition according to any one of claims 1 to 4 , further comprising a resin. The composition according to any one of claims 1 to 5 , further comprising a pigment derivative. The composition according to any one of claims 1 to 6, further comprising a polymerizable compound and a photopolymerization initiator. A film using the composition according to any one of claims 1 to 7 . The 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. The pixel of the film according to claim 8 and
The optical filter according to claim 9 or 10 , further comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black and colorless. A laminate having the film according to claim 8 and a color filter containing a chromatic colorant. The solid-state image sensor having the film according to claim 8 . An image display device having the film according to claim 8 . The infrared sensor having the film according to claim 8 .

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