JP2017181705A - Composition, film, optical filter, laminate, solid state image sensor, image display device, and infrared sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which allows manufacturing a film excellent in spectral characteristics in a visible range and a near-infrared region, such a film, an optical filter, a laminate, a solid state image sensor, an image display device, and an infrared sensor.SOLUTION: A composition includes a compound with an absorption resulting from inter-band transition in the range of wavelengths of 700-2000 nm, and resin. The compound preferably has a band-gap energy of 0.62-1.80 eV in the range of wavelengths of 700-2000 nm at 25°C. The compound is preferably of a III-V family chemical compound.SELECTED DRAWING: None

Description

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

  Solid-state imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since the solid-state imaging device uses a silicon photodiode having sensitivity to infrared rays in the light receiving portion, visual sensitivity correction may be performed using a near-infrared cut filter.

The near-infrared cut filter is manufactured using a composition containing a near-infrared absorber. Known near infrared absorbers include CsWO ₄ particles (see Patent Document 1), YbPO ₄ particles (see Patent Document 2), and the like.

  On the other hand, Patent Document 3 describes an invention relating to a light receiving device using a semiconductor stacked body having a GaInAs light receiving layer.

JP 2009-114326 A JP-A-9-156234 JP 2012-199554 A

It is described in Patent Documents 1 and 2, and CSWO ₄ particles, YbPO ₄ particles are near-infrared absorbing agent using a near-infrared reflectivity caused by plasma oscillation of free electrons. However, near-infrared cut filters using CsWO ₄ particles or YbPO ₄ particles have insufficient light transmittance in the visible region.

  Patent Document 3 is an invention relating to a light receiving device using a semiconductor laminate, and there is no description or suggestion regarding spectroscopy in the visible region and near infrared region.

  Accordingly, an object of the present invention is to provide a film having excellent spectral characteristics in the visible region and the near infrared region (for example, good light transmittance in the visible region and shielding of light in the near infrared region (near infrared)). Composition, film, optical filter, laminate, solid-state imaging device, and image display device capable of producing a film with excellent properties and a film that can selectively transmit part of light in the near infrared region (near infrared) And providing an infrared sensor.

As a result of intensive studies on CsWO ₄ and YbPO ₄ , the present inventors have found that these compounds have absorption derived from interband transition in the ultraviolet region. These compounds are affected by absorption due to interband transitions in the ultraviolet region, resulting in disturbances in the visible region, resulting in absorption in the visible region and light in the visible region. It was thought that the permeability to was reduced. Therefore, the present inventor examined a compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm. Surprisingly, the present inventors have studied the light transmittance in the visible region and the light in the near infrared region (near infrared light). ) Was found to have good shielding properties. And it discovered that the film | membrane excellent in the spectral characteristic of a visible region and a near-infrared area | region could be manufactured by using this compound, and came to complete this invention. The present invention provides the following.
<1> A composition comprising a compound having an absorption derived from interband transition in a wavelength range of 700 to 2000 nm and a resin.
<2> The compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm has a band gap energy at 25 ° C. in the wavelength range of 700 to 2000 nm of 0.62 to 1.80 eV, <1 The composition according to>.
<3> The composition according to <1> or <2>, wherein the compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm is a III-V group compound.
<4> The composition according to any one of <1> to <3>, wherein the compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm is InGaAs.
<5> The composition according to any one of <1> to <4>, wherein the compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm is a particle.
<6> The composition according to <5>, wherein the resin contains a dispersant.
<7> The composition according to any one of <1> to <6>, further including a polymerizable compound.
<8> The composition according to <7>, further comprising a photopolymerization initiator.
<9> The composition according to any one of <1> to <8>, further comprising an antioxidant.
<10> The composition according to any one of <1> to <9>, further comprising a near-infrared absorber different from a compound having absorption derived from interband transition in a wavelength range of 700 to 2000 nm.
<11> The composition according to <10>, wherein the near-infrared absorber is an organic dye.
<12> The composition according to any one of <1> to <11>, further comprising a colorant that transmits at least part of light in the near infrared region and shields light in the visible region. .
<13> A film using the composition according to any one of <1> to <12>.
<14> An optical filter having the film according to <13>.
<15> The optical filter according to <14>, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter.
<16> A pixel of the film according to <13>,
The optical filter according to <14> or <15>, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.
<17> A laminate having the film according to <13> and a color filter containing a chromatic colorant.
<18> A solid-state imaging device having the film according to <13>.
<19> An image display device having the film according to <13>.
<20> An infrared sensor having the film according to <13>.

  According to the present invention, it is possible to provide a composition, a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor capable of producing a film having excellent spectral characteristics in the visible region and the near infrared region. Became.

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

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the notation of a group (atomic group) in the present specification, the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value measured by gel permeation chromatography (GPC).
In this specification, near-infrared light refers to light (electromagnetic wave) having a maximum absorption wavelength range of 700 to 2500 nm.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

<Composition>
The composition of the present invention comprises a compound having an absorption derived from interband transition in a wavelength range of 700 to 2000 nm and a resin.
A compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm has good transparency to light in the visible region and shielding property to light in the near infrared region (near infrared). And the film | membrane excellent in the spectral characteristic of a visible region and a near-infrared area | region can be manufactured by using the composition of this invention containing this compound.
Hereinafter, each component of the composition of the present invention will be described.

<< Compound having absorption derived from interband transition in wavelength range of 700 to 2000 nm >>
The composition of the present invention contains a compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm (hereinafter also referred to as compound A).
Compound A preferably has absorption derived from interband transition in the wavelength range of 750 to 2000 nm, and more preferably has absorption derived from interband transition in the wavelength range of 800 to 1800 nm. By using a compound having absorption derived from interband transition in the above-mentioned range, it is easy to produce a film having excellent spectral characteristics in the visible region and near infrared region. Moreover, it is preferable that the compound A does not have absorption derived from interband transition in an ultraviolet region. Compound A is preferably an inorganic compound, and more preferably an inorganic compound having a metal bond.

Here, the compound having absorption derived from interband transition is a compound having an electronic band structure. Specific examples include compounds having a valence band, a forbidden band, and a conduction band. Examples of such a compound include a compound having an infinitely connected structure such as a metal bond or a covalent bond, and a wave function of a valence level uniformly spreading. Such compounds have various wave number spaces.
In the above-mentioned compound, electrons do not stop at one atom but spread over several atoms due to metal bonds and covalent bonds. For this reason, the electron orbit is overlapped by the number of atoms. However, due to Pauli's exclusion law, only two electrons can enter the same electron orbit, so the energy level must be adjusted so that the overlapping electron orbits do not enter the same orbit. Therefore, there is a range in possible energy. This width is defined as a band, and the forbidden band between the conduction band and the valence band is defined as a band gap.

  One of the near-infrared absorbers is an organic dye, but generally, an organic dye does not have an infinitely connected bond unlike the above compound. An organic dye is a compound in which interactions between molecules are relatively loosely bonded by van der Waals force. When such a compound is viewed as a whole molecule, there is an energy barrier between the molecules, so that the energy level of the molecular orbital is discrete and cannot have a wave number space. For this reason, organic dyes generally do not have a band structure. That is, it can be said that there is no interband transition in the organic dye.

  The band gap energy of a compound can be observed by measuring the absorbance of the compound with a spectrophotometer and measuring the band gap energy of the compound. The band gap energy of the compound can be measured by the following method.

The absorbance of the compound is measured with a UV-Vis near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) to measure the transmission spectrum in the wavelength range of 400 to 2000 nm.
About the transmission spectrum measured by said method, it plots on the graph which makes a vertical axis | shaft (ahv) ^0.5 and a horizontal axis | shaft energy value (eV), and converts into a (ahv) ^0.5- eV curve. Here, the (ahv) ^0.5 -eV curve is a graph in which the vertical axis is (ahv) ^0.5 and the horizontal axis is the energy value (eV). a is absorbance, h is Planck's constant, and v is frequency.

The energy value E ^{1 at} a certain wavelength λ ¹ has the following relationship. The wavelength can be converted into an energy value from the following relational expression.
E ¹ = 1240 / λ ¹
The unit of E ¹ is eV, and the unit of λ ¹ is nm.

In the above (AHV) ^0.5 -eV curve, calculates the tangent of a portion rising value of (AHV) ^0.5, the energy value at the intersection of the tangent line in the portion before the rise of the value of (AHV) ^0.5, the intersection of the aforementioned Let the energy value at be the band gap energy.

  The band gap energy at 25 ° C. in the wavelength range of 700 to 2000 nm of compound A is preferably 0.62 to 1.80 eV. The lower limit is more preferably 0.70 eV or more. The upper limit is more preferably 1.50 eV or less. When the bandgap energy is in the above range, the shielding property and visible transparency in the near infrared region are more excellent.

In the present invention, the compound A is preferably a III-V group compound. The group III-V compound has good transparency to light in the visible region and shielding property to light in the near infrared region (near infrared).
Here, the III-V compound includes a group III material such as aluminum (Al), gallium (Ga), and indium (In), nitrogen (N), phosphorus (P), arsenic (As), and antimony (Sb). These are compounds in which Group V materials are combined. The group III-V compound may be a compound in which one type of group III material and one type of group V material are combined, two or more types of group III material, and one type of group V material. The compound which the above combined may be sufficient, and the compound which 1 or more types of III group material and 2 or more types of V group material combined may be sufficient. By changing the composition, it is possible to change the band gap energy and the wavelength band of absorption derived from interband transition.

  Specific examples of the compound A include InGaAs.

  In the present invention, the compound A is preferably a particle. Examples of the shape of the particles include isotropic shapes (for example, spherical, polyhedral shapes, etc.), anisotropic shapes (for example, needle shapes, rod shapes, plate shapes, etc.), and irregular shapes.

  When compound A is a particle, the average primary particle size of compound A is preferably 100 to 1000 nm. The upper limit is more preferably 800 nm or less, and even more preferably 600 nm or less. The lower limit is more preferably 150 nm or more, and further preferably 200 nm or more. The average primary particle diameter of Compound A can be determined by measuring 100 particle diameters of a portion where Compound A particles are not aggregated with a transmission electron microscope (TEM) and calculating the average value. Further, the average secondary particle diameter of Compound A is preferably 200 to 2000 nm. The upper limit is preferably 1500 nm or less. The lower limit is preferably 300 nm or more. In the present specification, the average secondary particle size of Compound A means the average particle size of secondary particles in which the primary particles of Compound A are aggregated. The average secondary particle size of compound A can be determined by observing the particle size of secondary particles of compound A with a transmission electron microscope, measuring 100 particles, and calculating the average value.

  When compound A is a particle, the average major axis length of the primary particles of compound A is preferably 100 to 1000 nm. The upper limit is more preferably 800 nm or less, and even more preferably 600 nm or less. The lower limit is more preferably 150 nm or more, and further preferably 200 nm or more. The major axis of the primary particles refers to the longest diameter of the particles in a transmission electron microscope photograph of the compound A particles. The average major axis length of the primary particles is obtained by observing the particles of Compound A with a transmission electron microscope (TEM), observing the major axis length of the portion where the particles are not aggregated, measuring 100 particles, and calculating the average value. Can be determined by

When compound A is a particle, at least a part of the particle surface of compound A may be coated with a resin. That at least a part of the particle surface of the compound A is coated with the resin means that the resin may be adsorbed on the particle surface of the compound A, and the resin is not adsorbed on the particle surface of the compound A, and the predetermined space The particles of Compound A may be covered. Examples of the form of adsorption include chemical adsorption and physical adsorption.
Resin used for surface treatment may be single 1 type, and may combine 2 or more types of resin.

  In the composition of this invention, it is preferable that content of the compound A is 1-60 mass% with respect to the total solid of the composition of this invention. The upper limit is preferably 55% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more. By setting it within this range, a film having excellent spectral characteristics in the visible region and near infrared region can be produced. Compound A may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that the sum total is the said range.

<< Other near-infrared absorbers >>
The composition of this invention can contain the near-infrared absorber different from the compound A mentioned above (henceforth other near-infrared absorbers). In the present invention, the near-infrared absorber means a material having absorption in the near-infrared region (preferably in the wavelength range of 700 to 1300 nm, more preferably in the wavelength range of 700 to 1000 nm).

  Other near infrared absorbers are preferably organic dyes. In the present invention, the organic dye means a dye compound composed of an organic compound. The organic dye is preferably a compound having a maximum absorption wavelength in a wavelength range of 700 to 1300 nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm. Other near infrared absorbers may be dyes or pigments.

Specific examples of other near infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, rylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethanes Examples include compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, and dibenzofuranone compounds. Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A No. 2009-263614. Examples of the phthalocyanine compound include oxytitanium phthalocyanine pigments. As the phthalocyanine compound, naphthalocyanine compound, imonium compound, cyanine compound, squarylium compound and croconium compound, the compounds described in paragraph Nos. 0010 to 0081 of JP-A No. 2010-1111750 may be used. Incorporated into. In addition, as for the cyanine compound, for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. .
Other near infrared absorbers are preferably pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, and rylene compounds, more preferably pyrrolopyrrole compounds, cyanine compounds, and squarylium compounds, and even more preferably pyrrolopyrrole compounds.
Other near-infrared absorbers are IRA828, IRA842, IRA848, IRA850, IRA851, IRA866, IRA870, IRA884 (manufactured by Exiton), SDO-C33 (manufactured by Arimoto Chemical Co., Ltd.), e-color IR-14, E-ex color IR-10A, e-ex color TX-EX-801B, e-ex color TX-EX-805K, e-ex color TX-EX-815K (manufactured by Nippon Shokubai Co., Ltd.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by Hakko Chemical), Epolight V-63, Epolight 3801, Epolight 3036 (EPOLIN Manufactured), PRO-JET825LDI (manufactured by FUJIFILM Corporation), NK-3027, NKX-113, NKX-1199, SMP-363, SMP-387, SMP-388, SMP-389 (manufactured by Hayashibara), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) can also be used.

式（Ｉ）中、Ａ¹およびＡ²は、それぞれ独立にヘテロアリール基を表し、
Ｂ¹およびＢ²はそれぞれ独立に−ＢＲ¹Ｒ²基を表し、Ｒ¹およびＲ²は、それぞれ独立に置換基を表し、Ｒ¹とＲ²は互いに結合して環を形成してよく、
Ｃ¹およびＣ²は、それぞれ独立に、アルキル基、アリール基、またはヘテロアリール基を表し、
Ｄ¹およびＤ²は、それぞれ独立に置換基を表す。 (Pyrrolopyrrole compound)
The pyrrolopyrrole compound used as another near infrared absorber is preferably a compound represented by the following formula (I).

In formula (I), A ¹ and A ² each independently represent a heteroaryl group,
B ¹ and B ² each independently represent a —BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, and R ¹ and R ² may be bonded to each other to form a ring;
C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group,
D ¹ and D ² each independently represent a substituent.

In formula (I), A ¹ and A ² each independently represents a heteroaryl group. A ¹ and A ² may be the same group or different groups. A ¹ and A ² are preferably the same group.
The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and even more preferably a single ring or a condensed ring having 2 to 4 condensations. . The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, 3-12 are still more preferable, and 3-10 are especially preferable. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring.

The heteroaryl group is preferably a group represented by the following formula (A-1) and a group represented by the following formula (A-2).

In formula (A-1), X ¹ each independently represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^{X1 to} R ^X3 each independently represent a hydrogen atom or a substituent, ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ may combine with each other to form a ring. * Represents a bonding position with the formula (I).
The substituents represented by R ³ , R ⁴ and R ^{X1 to} R ^X3 are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryls. Oxycarbonyl group, heteroaryloxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, Arylthio group, heteroarylthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, Examples include acid amide group, mercapto group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, silyl group, hydroxy group, halogen atom, cyano group, alkyl group, aryl group Groups and halogen atoms are preferred.
1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-8 are still more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above, and examples thereof include a halogen atom and an aryl group.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above, and examples include a halogen atom and an alkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

式中、Ｘ¹は、それぞれ独立に、Ｏ、Ｓ、ＮＲ^X1またはＣＲ^X2Ｒ^X3を表し、Ｒ^X1〜Ｒ^X3は、それぞれ独立して水素原子または置換基を表し、Ｒ¹⁰¹〜Ｒ¹⁰⁹は、それぞれ独立して水素原子または置換基を表す。＊は、式（Ｉ）との結合位置を表す。 The ring formed by combining R ³ and R ⁴ is preferably an aromatic ring. When R ³ and R ⁴ form a ring, the group represented by the formula (A-1), the group represented by the formula (A-1-1), and the group represented by the formula (A-1-2) And the like.

In the formula, each X ¹ independently represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^{X1 to} R ^X3 each independently represents a hydrogen atom or a substituent, and R ^{101 to} R ^{109 each} represents Each independently represents a hydrogen atom or a substituent. * Represents a bonding position with the formula (I).

In formula (A-2), Y ^{1 to} Y ⁴ each independently represent N or CR ^Y1 , at least two of Y ^{1 to} Y ⁴ are CR ^Y1 , and R ^Y1 represents a hydrogen atom or a substituent. And adjacent R ^Y1 may be bonded to each other to form a ring. * Represents a bonding position with the formula (I).
Examples of the substituent represented by R ^Y1 include the substituents described above, and an alkyl group, an aryl group, and a halogen atom are preferable. 1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-8 are still more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described above, and examples thereof include a halogen atom and an aryl group.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents, and examples thereof include a halogen atom and an alkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

式中、Ｒ²⁰¹〜Ｒ²²⁷は、それぞれ独立に、水素原子または置換基を表し、＊は、式（Ｉ）との結合位置を表す。 At least two of Y ^{1 to} Y ⁴ are CR ^Y1 , and adjacent R ^Y1 may be bonded to each other to form a ring. The ring formed by bonding adjacent R ^Y1 is preferably an aromatic ring. When adjacent R ^Y1 forms a ring, examples of the group represented by the formula (A-2) include groups represented by the formulas (A-2-1) to (A-2-5). .

In the formula, R ^{201 to} R ²²⁷ each independently represents a hydrogen atom or a substituent, and * represents a bonding position with the formula (I).

In formula (I), B ¹ and B ² each independently represent a —BR ¹ R ² group, and R ¹ and R ² each independently represent a substituent. R ¹ and R ² may be bonded to each other to form a ring. Examples of the substituent include the groups described above for A ¹ and A ^2. A halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a heteroaryl group is preferable, and a halogen atom, an aryl group or a heteroaryl group is preferable. Are more preferable, and an aryl group or a heteroaryl group is still more preferable. R ¹ and R ² may be the same group or different groups. R ¹ and R ² are preferably the same group. B ¹ and B ² may be the same group or different groups. B ¹ and B ² are preferably the same group.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom is particularly preferable.
As for carbon number of an alkyl group, 1-40 are preferable. For example, the lower limit is more preferably 3 or more. For example, the upper limit is more preferably 30 or less, and further preferably 25 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
As for carbon number of an alkenyl group, 2-40 are preferable. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenyl group may be linear, branched or cyclic.
As for carbon number of an alkoxy group, 1-40 are preferable. For example, the lower limit is more preferably 3 or more. For example, the upper limit is more preferably 30 or less, and further preferably 25 or less. The alkoxy group may be linear, branched or cyclic.
6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. About these details, what was mentioned above is mentioned.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, 3-12 are still more preferable, and 3-5 are especially preferable. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. About these details, what was mentioned above is mentioned.

R ¹ and R ² of the —BR ¹ R ² group may be bonded to each other to form a ring. For example, the structures shown in the following (B-1) to (B-4) are exemplified. In the following, R represents a substituent, R ^{a1 to} R ^a4 each independently represents a hydrogen atom or a substituent, m1 to m3 each independently represents an integer of 0 to 4, and * represents a formula ( Represents the binding position to I). Examples of the substituent represented by R and R ^{a1 to} R ^a4 include the substituents described for R ¹ and R ² , and a halogen atom and an alkyl group are preferable.

In formula (I), C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group. C ¹ and C ² may be the same group or different groups. C ¹ and C ² are preferably the same group. C ¹ and C ² are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group.
1-40 are preferable, as for carbon number of an alkyl group, 1-30 are more preferable, and 1-25 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. A phenyl group or a naphthyl group is particularly preferred.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, and 3-12 are still more preferable.

The alkyl group, aryl group, and heteroaryl group described above may have a substituent or may be unsubstituted. It preferably has a substituent.
Examples of the substituent include a hydrocarbon group which may contain an oxygen atom, an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a heteroaryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group. Group, arylthio group, heteroarylthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoric acid amide group, mercapto group, sulfo group, Examples thereof include a carboxy group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxy group, a halogen atom, and a cyano group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
As for carbon number of an alkyl group, 1-40 are preferable. The lower limit is more preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. As for carbon number of a branched alkyl group, 3-40 are preferable. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkyl group is preferably 2 to 10, for example, and more preferably 2 to 8.
As for carbon number of an alkenyl group, 2-40 are preferable. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. As for carbon number of a branched alkenyl group, 3-40 are preferable. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkenyl group is preferably 2 to 10, and more preferably 2 to 8.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.
Examples of the hydrocarbon group containing an oxygen atom include a group represented by ^-LRx1 .
L represents —O—, —CO—, —COO—, —OCO—, — (OR ^x2 ) _m — or — (R ^x2 O) _m —. R ^x1 represents an alkyl group, an alkenyl group or an aryl group. R ^x2 represents an alkylene group or an arylene group. m represents an integer of 2 or more, and m R ^x2 may be the same or different.
L is preferably -O-,-(OR ^x2 ) _m- ^or- (R ^x2 O) _m- , more preferably -O-.
The alkyl group, alkenyl group and aryl group represented by R ^x1 have the same ^{meanings as} described above, and the preferred ranges are also the same. R ^x1 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
1-20 are preferable, as for carbon number of the alkylene group which ^Rx2 represents, 1-10 are more preferable, and 1-5 are still more preferable. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched. 6-20 are preferable and, as for carbon number of the arylene group which ^Rx2 represents, 6-12 are more preferable. R ^x2 is preferably an alkylene group.
m represents an integer greater than or equal to 2, 2-20 are preferable and 2-10 are more preferable.

The substituent which the alkyl group, aryl group and heteroaryl group may have is preferably a group having a branched alkyl structure. The substituent is preferably a hydrocarbon group that may contain an oxygen atom, and more preferably a hydrocarbon group containing an oxygen atom. The hydrocarbon group containing an oxygen atom is preferably a group represented by —O—R ^x1 . R ^x1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and particularly preferably a branched alkyl group. That is, the substituent is more preferably an alkoxy group, and particularly preferably a branched alkoxy group. When the substituent is an alkoxy group, a film having excellent heat resistance and light resistance can be easily obtained. As for carbon number of an alkoxy group, 1-40 are preferable. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. As for carbon number of a branched alkoxy group, 3-40 are preferable. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkoxy group is preferably 2 to 10, and more preferably 2 to 8.

In formula (I), D ¹ and D ² each independently represents a substituent. D ¹ and D ² may be the same group or different groups. D ¹ and D ² are preferably the same group.
Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, Acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl Group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoric acid amide group, Mercapto group, a sulfo group, a carboxy group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, hydroxy group, a halogen atom, and a cyano group. D ¹ and D ² are preferably electron withdrawing groups.

A substituent having a positive Hammett substituent constant σ _p value (sigma para value) acts as an electron withdrawing group. In the present invention, a substituent having a Hammett's σ _p value of 0.2 or more can be exemplified as an electron withdrawing group. The σ _p value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (0.66), a carboxy group (—COOH: 0.45), an alkoxycarbonyl group (for example, —COOMe: 0.45), an aryloxycarbonyl group (for example, , -COOPh: 0.44), a carbamoyl group (e.g., -CONH _2: 0.36), an alkylcarbonyl group (e.g., -COMe: 0.50), an arylcarbonyl group (e.g., -COPh: 0.43) , Alkylsulfonyl groups (for example, —SO ₂ Me: 0.72), arylsulfonyl groups (for example, —SO ₂ Ph: 0.68), and the like. A cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group are preferred, and a cyano group is more preferred. Here, Me represents a methyl group, Ph represents a phenyl group, and the numerical values in parentheses are σ _p values. As for Hammett's σ _p value, paragraph numbers 0024 to 0025 of JP-A-2009-263614 can be referred to, the contents of which are incorporated herein.

The pyrrolopyrrole compound is preferably a compound represented by the following formula (II) or a compound represented by the following formula (III). According to this aspect, it is easy to form a pattern having excellent infrared shielding properties and light resistance.

In Formula (II), X ¹ and X ² each independently represent O, S, NR ^X1 or CR ^X2 R ^X3 , R ^{X1 to} R ^X3 each independently represent a hydrogen atom or a substituent,
R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent,
R ³ and R ⁴ , or R ⁵ and R ⁶ may be bonded to each other to form a ring,
B ¹ and B ² each independently represent a —BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, and R ¹ and R ² may be bonded to each other to form a ring;
C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group,
D ¹ and D ² each independently represent a substituent.

^{B 1, B 2, C 1} , C 2, D 1 and D ² of formula (II) has the same meaning as ^{B 1, B 2, C 1} , C 2, D 1 and D ² of formula (I) The preferable range is also the same. X ¹ , X ² and R ^{3 to} R ^{6 in} formula (II) have the same meanings as X ¹ , R ³ and R ^{4 in} formula (A-1) described above, and preferred ranges are also the same.

In formula (III), Y ^{1 to} Y ⁸ each independently represent N or CR ^Y1 , at least two of Y ^{1 to} Y ⁴ are CR ^Y1 , and at least two of Y ^{5 to} Y ⁸ are CR ^{Y 1} , R ^Y1 represents a hydrogen atom or a substituent, and adjacent R ^Y1 may be bonded to each other to form a ring;
B ¹ and B ² each independently represent a —BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, and R ¹ and R ² may be bonded to each other to form a ring;
C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group,
D ¹ and D ² each independently represent a substituent.

^{B 1, B 2, C 1} , C 2, D 1 and D ² of formula (III) has the same meaning as ^{B 1, B 2, C 1} , C 2, D 1 and D ² of formula (I) The preferable range is also the same. Y < ¹ > -Y < ⁸ > of Formula (III) is synonymous with Y < ¹ > -Y < ⁴ > of Formula (A-2) mentioned above, and its preferable range is also the same.

  Specific examples of the pyrrolopyrrole compound include the following compounds. In the following structural formulas, Ph represents a phenyl group, Me represents a methyl group, and Bu represents a butyl group. Further, specific examples of the pyrrolopyrrole compound include compounds described in paragraph numbers 0049 to 0058 of JP-A-2009-263614, and the contents thereof are incorporated in the present specification.

式（１）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下記式（２）で表される基を表す；

式（２）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、波線は式（１）との連結手を表す。 (Squarylium compound)
The squarylium compound used as another near infrared absorber is preferably a compound represented by the following formula (1).

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

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

A ¹ and A ² in Formula (1) each independently represent an aryl group, a heteroaryl group, or a group represented by Formula (2), and a group represented by Formula (2) is preferable.
The number of carbon atoms of the aryl group represented by A ¹ and A ² is preferably 6-48, more preferably 6 to 24, 6 to 12 are particularly preferred. Specific examples include a phenyl group and a naphthyl group.
The heteroaryl group represented by A ¹ and A ² is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations, a single ring or a condensed ring. More preferred are fused rings having 2 or 3 numbers. As a hetero atom contained in a heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, and a nitrogen atom and a sulfur atom are preferable. 1-3 are preferable and, as for the number of heteroatoms, 1-2 are more preferable. Specific examples include a heteroaryl group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered or 6-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.

  The aryl group and heteroaryl group may have a substituent. When the aryl group and heteroaryl group have two or more substituents, the plurality of substituents may be the same or different.

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

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

1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-8 are still more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
2-40 are preferable, as for carbon number of an alkynyl group, 2-30 are more preferable, and 2-25 are especially preferable. The alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. 7-40 are preferable, as for carbon number of an aralkyl group, 7-30 are more preferable, and 7-25 are still more preferable.
The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and still more preferably a single ring or a condensed ring having 2 to 4 condensations. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heteroaryl group, 3-18 are more preferable, and 3-12 are still more preferable.
The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents.

Next, the group represented by the formula (2) represented by A ¹ and A ² will be described.

In the formula (2), R ² represents an alkyl group, an alkenyl group or an aralkyl group, and an alkyl group is preferable.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-12 are still more preferable, and 2-8 are especially preferable.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-12 are still more preferable.
The alkyl group and the alkenyl group may be linear, branched or cyclic, and are preferably linear or branched.
7-30 are preferable and, as for carbon number of an aralkyl group, 7-20 are more preferable.

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

In the formula (1), cations are delocalized and exist as follows.

環Ａおよび環Ｂは、それぞれ独立に、芳香族環または複素芳香族環を表し、
Ｘ^AおよびＸ^Bはそれぞれ独立に置換基を表し、
Ｇ^AおよびＧ^Bはそれぞれ独立に置換基を表し、
ｋＡは０〜ｎ_A、ｋＢは０〜ｎ_Bの整数を表し、
ｎ_Aおよびｎ_Bはそれぞれ環Ａまたは環Ｂに置換可能な最大の整数を表し、
Ｘ^AとＧ^A、Ｘ^BとＧ^Bは互いに結合して環を形成しても良く、Ｇ^AおよびＧ^Bがそれぞれ複数存在する場合は、互いに結合して環構造を形成していても良い。 The squarylium compound is preferably a compound represented by the following formula (5).

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

G ^A and G ^B each independently represent a substituent. Examples of the substituent include the substituent described in the above formula (1).

X ^A and X ^B each independently represent a substituent. Examples of the substituent include the substituent described in the above formula (1), and a group having active hydrogen is preferable. —OH, —SH, —COOH, —SO ₃ H, —NR ^X1 R ^X2 , —NHCOR ^X1 , —CONR ^X1 R ^X2 , —NHCONR ^X1 R ^X2 , —NHCOOR ^X1 , —NHSO ₂ R ^X1 , —B (OH) ₂ and —PO (OH) ₂ are more preferable, —OH, —SH and —NR ^X1 R ^X2 is more preferred.
R ^X1 and R ^X1 each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group, and an alkyl group is preferable. The alkyl group is preferably linear or branched. The details of the alkyl group, the alkenyl group, the alkynyl group, the aryl group, and the heteroaryl group are synonymous with the ranges described in the above-described substituent column.

Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring.
The aromatic ring and heteroaromatic ring may be a single ring or a condensed ring.
Specific examples of the aromatic ring and heteroaromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole Ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phena Tororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring or a naphthalene ring is preferable.
The aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include the substituent described in the above formula (1).

X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural may be bonded to each other to form a ring.
The ring is preferably a 5-membered ring or a 6-membered ring. The ring may be monocyclic or multicyclic.
X ^A and G ^A, X ^B and G ^B, when forming a G ^A or between G ^B are bonded to each other rings, may be they are attached directly to form a ring, an alkylene group, -CO-, A ring may be formed by bonding via a divalent linking group selected from the group consisting of —O—, —NH—, —BR— and combinations thereof. X ^A and G ^A, X ^B and G ^B, G ^A or between G ^B each other, it is preferable to form a ring via -BR-.
R represents a hydrogen atom or a substituent. Examples of the substituent include the substituent described in the above formula (1), and an alkyl group or an aryl group is preferable.

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

Specific examples of the squarylium compound include the following compounds. Moreover, the compound of Unexamined-Japanese-Patent No. 2011-208101, Paragraph Nos. 0044-0049 is mentioned, The content shall be integrated in this specification.

式（Ｃ）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。 (Cyanine compound)
The cyanine compound used as another near infrared absorber is preferably a compound represented by the following formula (C).
Formula (C)

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

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

In the formula (C), R ¹⁰¹ and R ¹⁰² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group.
1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-8 are especially preferable. The alkyl group may be linear, branched or cyclic.
2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic.
2-20 are preferable, as for carbon number of an alkynyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkynyl group may be linear, branched or cyclic.
6-25 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are the most preferable. The aryl group may be unsubstituted or may have a substituent.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. 7-40 are preferable, as for carbon number of an aralkyl group, 7-30 are more preferable, and 7-25 are still more preferable.
The alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group. A carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may have a hydrogen atom dissociated or in a salt state.

式（ａ）中、＊は、メチン鎖との連結手を表し、Ａ¹は、−Ｏ−を表す。 In the formula (C), L ¹ represents a methine chain having an odd number of methine groups. L ¹ is preferably a methine chain having 3, 5 or 7 methine groups.
The methine group may have a substituent. The methine group having a substituent is preferably a central (meso-position) methine group. Specific examples of the substituent include a substituent that the nitrogen-containing heterocycle of Z ¹ and Z ² may have, a group represented by the following formula (a), and the like. Further, two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.

In formula (a), * represents a bond with a methine chain, and A ¹ represents —O—.

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

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

Specific examples of the cyanine compound include the following compounds. Moreover, the compound as described in Unexamined-Japanese-Patent No. 2015-172004 and Unexamined-Japanese-Patent No. 2015-172102 is mentioned.

  In the present invention, inorganic particles may be used as the other near infrared absorber. Examples of the inorganic particles include metal oxide particles and metal particles. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped zinc oxide) particles, and fluorine-doped dioxide dioxide. Examples include tin (tin dioxide doped with fluorine) particles, niobium doped titanium dioxide (titanium dioxide doped with niobium) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. The shape of the inorganic particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.

Moreover, a tungsten oxide type compound can also be used for an inorganic particle. Specifically, a tungsten oxide compound represented by the following formula (W-1) is preferable.
M _x W _y O _z (W-1)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
As the metal represented by M, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al , Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, alkali metals are preferable, Rb or Cs is more preferable, and Cs is particularly preferable. . The metal of M may be one type or two or more types.

Specific examples of the tungsten oxide compound include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like, and Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable. Cs _0.33 WO ₃ is more preferable.
The tungsten oxide compound is available as a dispersion of tungsten fine particles such as YMF-02 and YMS-01A-2 manufactured by Sumitomo Metal Mining Co., Ltd., for example.

  The average particle size of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average particle diameter of the inorganic particles is within such a range, the transparency in the visible region can be further ensured. From the viewpoint of avoiding light scattering, the average particle size is preferably as small as possible, but for reasons such as ease of handling during production, the lower limit of the average particle size of the inorganic particles is 1 nm or more.

When the composition of this invention contains other near-infrared absorbers, 0.1-80 mass parts is preferable with respect to 100 mass parts of compound A, and, as for content of another near-infrared absorber, 5-60 A mass part is more preferable, and 10-40 mass parts is still more preferable. If it is the said range, the shielding property of the light of a near-infrared area | region can be improved more.
Moreover, it is also preferable that other near-infrared absorbers are substantially comprised only of the organic pigment | dye. According to this aspect, the light shielding property in the near infrared region can be further improved while maintaining the light transmittance in the visible region. It is preferable that the content of the organic dye in the other near infrared absorber is 99% by mass or more, and that the other near infrared absorber is substantially composed only of the organic dye, and 99.5% by mass. % Or more is more preferable, and it is more preferable that the composition is composed only of organic dyes.

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

The pigment is preferably an organic pigment, and examples thereof include the following. However, the pigment that can be used in the present invention is not limited to these.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange pigment)
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment),
These organic pigments can be used alone or in various combinations.

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

When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the composition, 15 A mass% or less is more preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, the composition of this invention can also be made into the aspect which does not contain a chromatic color agent substantially. When the chromatic colorant is not substantially contained, the content of the chromatic colorant is preferably 0.005% by mass or less and more preferably 0.001% by mass or less in the total solid content of the composition of the present invention. More preferably, it does not contain a chromatic colorant.

<< Coloring material that transmits at least part of light in the near infrared region and shields light in the visible region (coloring material that blocks visible light) >>
The composition of the present invention may contain a colorant that transmits at least part of light in the near infrared region and shields light in the visible region (hereinafter also referred to as colorant that shields visible light). it can.

The color material that blocks visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).
(1): An embodiment containing two or more chromatic colorants.
(2): An embodiment containing an organic black colorant.

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

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

When two or more kinds of chromatic colorants are included as a colorant that blocks visible light, the chromatic colorants are red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. It is preferable that it is a coloring agent chosen from these. Examples of combinations of chromatic colorants include the following.
(1) Embodiment containing yellow colorant, blue colorant, purple colorant and red colorant (2) Embodiment containing yellow colorant, blue colorant and red colorant (3) Yellow colorant, purple colorant And (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) a purple colorant And an embodiment containing an orange colorant (7) an embodiment containing a green colorant, a purple colorant and a red colorant (8) an embodiment containing a green colorant and a red colorant.

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

When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 30% by mass or less, and 20% by mass with respect to the total solid content of the composition. The following is more preferable, and 15% by mass or less is still more preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, the composition of this invention can also be made into the aspect which does not contain the coloring material which shields visible light substantially. When the coloring material that blocks visible light is substantially not contained, the content of the coloring material that blocks visible light is preferably 0.005% by mass or less in the total solid content of the composition of the present invention, and 0.001. It is more preferable that the content is less than or equal to mass%, and it is even more preferable not to contain a colorant that blocks visible light.

<< Pigment derivative >>
When the composition of the present invention contains a pigment, it can further contain a pigment derivative. As the pigment derivative, a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group is preferable.

  As the pigment skeleton of the pigment constituting the pigment derivative, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, thiazine indigo dye skeleton, azo Choose from dye skeleton, quinophthalone dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzoimidazole dye skeleton and benzoxazole dye skeleton At least one selected from the above is preferred.

  Specific examples of the pigment derivative include JP-A No. 56-118462, JP-A No. 63-264664, JP-A No. 1-217077, JP-A No. 3-9961, JP-A No. 3-26767, JP-A-3-153780, JP-A-3-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158, JP-A Nos. 10-30063, 10-195326, paragraphs 0086 to 0098 of International Publication WO2011 / 024896, paragraphs 0063 to 0094 of International Publication WO2012 / 102399, etc. These contents are incorporated herein.

  When the composition of this invention contains a pigment derivative, as for content of a pigment derivative, 1-50 mass parts is preferable with respect to 100 mass parts of pigments contained in a composition. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. If content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only one pigment derivative or two or more pigment derivatives may be used, and in the case of two or more pigment derivatives, the total amount is preferably within the above range.

<< Resin >>
The composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particulate compound A, various particles such as pigments in the composition, and the use of a binder. Note that a resin mainly used for dispersing particles and the like is also referred to as a dispersant. However, such use of the resin is an example, and the resin can be used for purposes other than such use.

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

  The glass transition temperature of the resin is preferably 0 to 100 ° C. The lower limit is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and still more preferably 23 ° C. or higher. The upper limit is preferably 95 ° C. or lower, and more preferably 90 ° C. or lower. In the present invention, the glass transition temperature of the resin is 10 ° C./200° C. from −20 ° C. to 200 ° C. in a nitrogen stream using a differential scanning calorimeter (Seiko Instruments, DSC1000), weighing 5 mg of sample in a sample pan. It is the value measured by raising the temperature at a temperature elevation rate of minutes. The average value of the temperature at which the baseline begins to deviate and the temperature at which the baseline returns to the base line was taken as the glass transition temperature of the resin.

  Types of resin include (meth) acrylic resin, epoxy resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, Examples thereof include a polyimide resin, a polyamideimide resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, and a polysiloxane resin. One of these resins may be used alone, or two or more thereof may be mixed and used. Here, the compound A tends to generate heat with the absorption of near infrared rays. For this reason, the resin is preferably a resin that has high heat resistance and is not easily discolored by heat. For example, a resin having a glass transition temperature of 23 ° C. or higher is preferable.

  The resin may have an acid group. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxy group. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins. Hereinafter, the resin having an acid group is also referred to as an alkali-soluble resin.

  As the alkali-soluble resin, a polymer having a carboxy group in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification. Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxy group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. , Vinyl compounds include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used. Only one kind of these other monomers copolymerizable with (meth) acrylic acid may be used, or two or more kinds may be used.

  Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-component copolymer comprising / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

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

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

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

In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n- Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl and the like An alkyl group substituted with an aryl group of Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  As a specific example of the ether dimer, for example, paragraph 0317 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

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

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

In the formula (X), the number of carbon atoms of the alkylene group R ₂ is preferably 2-3. Although the carbon number of the alkyl group of R ₃ is 1 to 20, more preferably 1 to 10, alkyl group of R ₃ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Examples of the alkali-soluble resin include paragraphs 0558 to 0571 of JP2012-208494A (paragraph Nos. 0805 to 0700 of US 2012/0235099 corresponding), JP2012-198408A. Paragraphs 0076 to 0099, which are incorporated herein by reference. Specific examples of the alkali-soluble resin include the following resins. In the following structural formulas, Me represents a methyl group.

  The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

  The resin (including the alkali-soluble resin) may have a curable group. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

  Examples of the resin containing a curable group and an acid group (an alkali-soluble resin having a curable group) include NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Phototomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.). Ltd.), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 ( Daicel USB Co., Ltd.), Acryl Cure RD-F8 (Nippon Shokubai Co., Ltd.), and the like.

  In the present invention, the resin is Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (day Oil Co., Ltd., epoxy group-containing polymer), ARTON F4520 (manufactured by JSR Co., Ltd.), Acrybase FF-187 (Fujikura Kasei Co., Ltd.) and the like can also be used.

(Dispersant)
It is preferable that the composition of this invention contains a dispersing agent as resin. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 5 to 105 mgKOH / g. The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amine.

  In the present invention, a graft copolymer may be used as the dispersant. The graft copolymer is preferably a resin having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. Moreover, 40-10000 are preferable, as for the number of atoms except the hydrogen atom per graft chain, 50-2000 are more preferable, and 60-500 are still more preferable.

  Examples of the main chain structure of the graft copolymer include a (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a polyether structure. Of these, a (meth) acrylic structure is preferable. The graft chain of the graft copolymer is a graft chain having a poly (meth) acrylic structure, a polyester structure, or a polyether structure in order to improve the interaction between the graft site and the solvent, thereby increasing the dispersibility. A graft chain having a polyester structure or a polyether structure is more preferable.

  As the dispersant, a graft copolymer containing a repeating unit represented by any of the following formulas (111) to (114) can also be used.

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

W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, A methyl group is particularly preferred. Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group. Examples of the divalent linking group include —CO—, —O—, —NH—, an alkylene group, an arylene group, and a combination thereof. The structure of the monovalent group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ is not particularly limited. Examples thereof include an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.

  In Formula (111) to Formula (114), n, m, p, and q are each independently an integer of 1 to 500. Moreover, in Formula (111) and Formula (112), j and k each independently represent an integer of 2 to 8. J and k in Formula (111) and Formula (112) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.

In Formula (113), R ³ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same as or different from each other.

In formula (114), R ⁴ represents a hydrogen atom or a monovalent group. The monovalent group is not particularly limited in terms of structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. In the formula (114), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

Regarding the details of the above formula, the description of paragraph numbers 0025 to 0069 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. Specific examples of the graft copolymer include the following resins.

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

  The oligoimine resin includes, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and a repeating unit represented by the formula (I-2a). Examples thereof include a resin containing at least one.

Ｒ¹およびＲ²は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１〜６が好ましい）を表す。ａは、各々独立に、１〜５の整数を表す。＊は繰り返し単位間の連結部を表す。
Ｒ⁸および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および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であることが好ましい。より好ましくは、ＣＲ⁸ＣＲ⁹の炭素原子およびＮ（窒素原子）を合わせて５〜７員の非芳香族複素環を形成する構造であり、更に好ましくは５員の非芳香族複素環を形成する構造であり、特に好ましくはピロリジンを形成する構造である。この構造は更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部分構造を有する基を表す。
Ｙは原子数４０〜１０，０００の側鎖を表す。
上記樹脂（オリゴイミン系樹脂）は、更に式（Ｉ−３）、式（Ｉ−４）、および、式（Ｉ−５）で表される繰り返し単位から選ばれる１種以上を含有していてもよい。上記樹脂が、このような繰り返し単位を含むことで、粒子の分散性能を更に向上させることができる。

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units.
R ⁸ and R ⁹ are the same groups as R ¹ .
L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms). Are preferred), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, or a linking group thereof. Among these, a single bond or —CR ⁵ R ⁶ —NR ⁷ — (imino group is X or Y) is preferable. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
L ^a is a CR ⁸ CR ^9, a structure forming a ring structure together with N, be combined with the carbon atoms of CR ⁸ CR ⁹ is a structure that forms a non-aromatic heterocyclic ring having 3 to 7 carbon atoms preferable. More preferably, it is a structure in which the carbon atom of CR ⁸ CR ⁹ and N (nitrogen atom) are combined to form a 5- to 7-membered non-aromatic heterocyclic ring, and more preferably a 5-membered non-aromatic heterocyclic ring is formed. Particularly preferred is a structure forming pyrrolidine. This structure may further have a substituent such as an alkyl group.
X represents a group having a partial structure having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.
The resin (oligoimine-based resin) may further contain one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5). Good. When the resin contains such a repeating unit, the dispersion performance of the particles can be further improved.

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

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

  In the present invention, a resin represented by the following formula (100) can also be used as the resin (dispersant).

In the above formula (100), R ¹ represents an (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, an imide group, a complex Monovalent substitution having at least one group selected from the group consisting of a cyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxy group Represents a group. The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. P ¹ represents a monovalent polymer chain. The m P ¹ may be the same or different.

In the above formula (100), A ¹ represents an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, or an alkyleneoxy chain. A group selected from the group consisting of a group having an imide group, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxy group Represents a monovalent substituent having at least one kind). As long as at least one adsorption site is included in one A ¹ , two or more adsorption sites may be included. In one of A ^1, as an embodiment that includes two or more adsorption sites, may be branched in chain saturated hydrocarbon group (linear, it is preferably 1 to 10 carbon atoms ), A saturated cyclic hydrocarbon group (preferably having 3 to 10 carbon atoms), an aromatic group (preferably having 5 to 10 carbon atoms, for example, a phenylene group), etc. Are bonded to form a monovalent substituent, and a mode in which two or more adsorption sites are bonded through a chain saturated hydrocarbon group to form a monovalent substituent is preferable. In the case where the adsorption site itself constitutes a monovalent substituent, the adsorption site itself may be a monovalent substituent represented by A ¹ . First, the adsorption site constituting A ¹ will be described below.

Examples of the acid group in A ¹ include a carboxy group, a sulfo group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and a boric acid group, and a carboxy group and a sulfo group. A monosulfate group, a phosphate group, a monophosphate group, a phosphonic acid group and a phosphinic acid group are preferred, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and a phosphinic acid group are more preferred, and a carboxy group is further preferable.

As the urea group in A ¹ , for example, —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms). Represents the above aryl group or an aralkyl group having 7 or more carbon atoms.), —NR ¹⁵ CONHR ¹⁷ is preferable, and —NHCONHR ¹⁷ is more preferable.

Examples of the urethane group in A ¹ include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and -NHCOOR ¹⁸ and -OCONHR ²¹ are preferred, -NHCOOR ¹⁸ , -OCONHR ² is more preferred.

Examples of the group having a coordinating oxygen atom in A ¹ include an acetylacetonato group and a crown ether.

Examples of the group having a basic nitrogen atom in A ¹ include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), and the following formula (a2). And an amidinyl group represented by:

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

The group having a basic nitrogen atom includes an amino group (—NH ₂ ), a substituted imino group, and a guanidyl group represented by the above formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently carbon. It represents an alkyl group, a phenyl group, or a benzyl group from 1 to 10. ], In amidinyl group represented by Formula (a2) [Formula (a2), each independently R ¹³ and R ¹⁴ represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group. ] Is preferable. In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, A phenyl group and a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group, a benzyl group; Represents a group. ], In amidinyl group represented by Formula (a2) [Formula (a2), each independently R ¹³ and R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, a benzyl group. ] Is preferable.

The alkyl group for A ¹ may be linear or branched, and is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms. And more preferably an alkyl group having 10 to 18 carbon atoms.
The aryl group for A ¹ is preferably an aryl group having 6 to 10 carbon atoms.

The group having an alkyleneoxy chain in A ¹ is preferably a group whose terminal forms an alkyloxy group, and more preferably a group forming an alkyloxy group having 1 to 20 carbon atoms. The alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, but is preferably composed of 1 to 6 alkyleneoxy groups. Examples of the alkyleneoxy group include —CH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ O—, and the like.

The alkyl group moiety in the alkyloxycarbonyl group of A ^1, is preferably an alkyl group having 1 to 20 carbon atoms.
The alkyl group moiety in the alkylaminocarbonyl group in A ¹ is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the carboxylate group in A ¹ include a group composed of an ammonium salt of a carboxylic acid.
As the sulfonamide group in A ^1, the hydrogen atom bonded to the nitrogen atom of the sulfonamide group may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).

Examples of the heterocyclic group in A ¹ include a thiophene ring group, a furan ring group, a xanthene ring group, a pyrrole ring group, a pyrroline ring group, a pyrrolidine ring group, a dioxolane ring group, a pyrazole ring group, a pyrazoline ring group, and a pyrazolidine ring group. Imidazole ring group, oxazole ring group, thiazole ring group, oxadiazole ring group, triazole ring group, thiadiazole ring group, pyran ring group, pyridine ring group, piperidine ring group, dioxane ring group, morpholine ring group, pyridazine ring group , Pyrimidine ring group, piperazine ring group, triazine ring group, trithiane ring group, isoindoline ring group, isoindolinone ring group, benzimidazolone ring group, benzothiazole ring group, hydantoin ring group, indole ring group, quinoline ring group Carbazole ring group, acridine ring group, acridone ring group, anthraquinone ring group It is below.

Examples of the imide group in A ¹ include a succinimide group, a phthalimide group, and a naphthalimide group.

  The above heterocyclic group and imide group may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxy group, an amino group, a carboxy group, and a sulfonamide. Groups, N-sulfonylamide groups, acetoxy groups and other C1-C6 acyloxy groups, methoxy groups, ethoxy groups and other C1-C20 alkoxy groups, chlorine, bromine and other halogen atoms, methoxycarbonyl groups, ethoxy Examples thereof include C2-C7 alkoxycarbonyl groups such as carbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate.

The alkoxysilyl group in A ¹ may be any of monoalkoxysilyl group, dialkoxysilyl group and trialkoxysilyl group, but is preferably trialkoxysilyl group, for example, trimethoxysilyl group, triethoxysilyl group Etc.
Examples of the epoxy group in A ¹ include a substituted or unsubstituted oxirane group (ethylene oxide group).

In Formula (100), R ¹ represents a (m + n) -valent linking group. The (m + n) -valent linking group includes 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. The group which consists of is mentioned.

Ｌ₃は３価の基を表す。Ｔ₃は単結合又は２価の連結基を表し、３個存在するＴ₃は互いに同一であっても異なっていてもよい。
Ｌ₄は４価の基を表す。Ｔ₄は単結合又は２価の連結基を表し、４個存在するＴ₄は互いに同一であっても異なっていてもよい。
Ｌ₅は５価の基を表す。Ｔ₅は単結合又は２価の連結基を表し、５個存在するＴ₅は互いに同一であっても異なっていてもよい。
Ｌ₆は６価の基を表す。Ｔ₆は単結合又は２価の連結基を表し、６個存在するＴ₆は互いに同一であっても異なっていてもよい。 The (m + n) -valent linking group is preferably a group represented by any of the following formulas.

L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and three T _{3 s} may be the same or different from each other.
L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent linking group, and four T _{4 s} may be the same or different from each other.
L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent linking group, and five T _{5 s} may be the same or different from each other.
L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent linking group, and six T _{6 s} may be the same as or different from each other.

  Specific examples of the (m + n) -valent linking group include a group composed of a combination of two or more of the following structural units or the following structural units (which may form a ring structure). For details of the (m + n) -valent linking group, paragraph numbers 0043 to 0055 of JP-A-2014-177613 can be referred to, and the contents thereof are incorporated in the present specification.

In the formula (100), P ¹ represents a monovalent polymer chain. The monovalent polymer chain is a vinyl polymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and a modified or copolymer thereof (for example, polyether / Polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer and graft copolymer may be used). And at least one selected from the group consisting of vinyl polymers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof is more preferable. .

式中、Ｘ¹は水素原子または１価の有機基を表す。Ｘ¹は水素原子または炭素数１〜１２のアルキル基が好ましく、水素原子またはメチル基がより好ましく、メチル基が特に好ましい。
Ｒ¹⁰は水素原子又は１価の有機基を表し、水素原子、アルキル基、アリール基またはヘテロアリール基が好ましく、水素原子またはアルキル基がより好ましい。Ｒ¹⁰がアルキル基である場合、アルキル基としては、炭素数１〜２０の直鎖状アルキル基、炭素数３〜２０の分岐状アルキル基、又は炭素数５〜２０の環状アルキル基が好ましく、炭素数１〜２０の直鎖状アルキル基がより好ましく、炭素数１〜６の直鎖状アルキル基が特に好ましい。式（Ｌ）中に構造の異なるＲ¹⁰を２種以上有していても良い。
Ｒ¹¹及びＲ¹²は、分岐若しくは直鎖のアルキレン基（炭素数は１〜１０が好ましく、２〜８であることがより好ましく、３〜６であることが更に好ましい。）を表す。各一般式中に構造の異なるＲ¹¹又はＲ¹²を２種以上有していても良い。
ｋ１、ｋ２、ｋ３は、それぞれ独立に、５〜１４０の数を表す。 The monovalent polymer chain represented by P ¹ is preferably a polymer chain having a structure represented by the formulas (L), (M), and (N).

In the formula, X ¹ represents a hydrogen atom or a monovalent organic group. X ¹ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
R ¹⁰ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ¹⁰ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. It may have the formula (L) with different R ¹⁰ structurally more in.
R ¹¹ and R ¹² represent a branched or straight chain alkylene group (the number of carbon atoms is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 6). Each general formula may have two or more types of R ¹¹ or R ¹² having different structures.
k1, k2, and k3 each independently represents a number of 5 to 140.

P ¹ preferably contains at least one repeating unit. The number k of repeating units in P ¹ is preferably 3 or more, and more preferably 5 or more, from the viewpoint of exhibiting steric repulsion and improving dispersibility. Further, from the viewpoint of causing particles to be densely present in the film, the number of repeating units k described above is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.

The monovalent polymer chain represented by P ¹ is preferably soluble in an organic solvent. If it is soluble in the organic solvent, the affinity with the organic solvent is good, and the dispersion stabilization of the particles can be improved.

In the formula (100), R ² represents a single bond or a divalent linking group. The divalent linking group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Groups. The above-mentioned group may be unsubstituted or may further have a substituent. Specific examples of the divalent linking group include a group constituted by combining two or more of the following structural units or the following structural units. For details of the divalent linking group, paragraph numbers 0071 to 0075 of JP-A-2007-277514 can be referred to, and the contents thereof are incorporated in the present specification.

In formula (100), m represents a positive number of 8 or less. m is preferably 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.
In formula (100), n represents 1-9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

The resin represented by the formula (100) is preferably a resin represented by the formula (100a).

In the formula (100a), A ² has an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, or an alkyleneoxy chain. At least one group selected from the group consisting of a group, an imide group, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxy group The monovalent substituent which has a seed is represented. R ³ represents a (m + n) -valent linking group. R ⁴ and R ⁵ represent a single bond or a divalent linking group. P ² represents a monovalent polymer chain. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. The n A ² and R ⁴ may be the same, or the m P ² and R ⁵ may be the same or different.

A ^{2 in the} formula (100a) has the same meaning as A ^{1 in} the formula (100), and preferred embodiments thereof are also the same.

In the formula (100a), as the divalent linking group represented by R ⁴ or R ⁵ , the same divalent linking groups as those represented by R ² in the formula (100) are used. The preferred embodiments are also the same.

In the formula (100a), the (m + n) -valent linking group represented by R ³ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. And groups consisting of atoms and 0-20 sulfur atoms. The details of the (m + n) -valent linking group include the (m + n) -valent linking group described in R ¹ of the formula (100), and the preferred embodiments are also the same.

  In formula (100a), m and n have the same meanings as m and n in formula (100), respectively, and the preferred embodiments are also the same.

In formula (100), the monovalent polymer chain represented by P ² has the same meaning as P ^{1 in} (100), and the preferred embodiment is also the same.

The resin represented by the formula (100) is also preferably a resin represented by the formula (100b).

In the formula (100b), R ⁶ represents a (m + n1 + n2) -valent linking group. R ^{7 to} R ⁹ each independently represents a single bond or a divalent linking group. A ³ represents a monovalent substituent having at least one acid group. A ⁴ represents a monovalent substituent different from A ³ . P ¹ represents a monovalent polymer chain. m represents a positive number of 8 or less, n1 represents 1 to 8, n2 represents 1 to 8, and m + n1 + n2 satisfies 3 to 10. n1 pieces of A ³ and R ⁷ may be the same or different from each other. n2 A ⁴ and R ⁸ may be the same or different from each other.

M in the formula (100b) has the same meaning as m in the formula (100), and the preferred embodiment is also the same.
P ³ in the formula (100b) has the same meaning as P ¹ in the formula (100), and the preferred embodiment is also the same.
The (m + n1 + n2) -valent linking group represented by R ⁶ in the formula (100b) is 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And groups consisting of 0 to 20 sulfur atoms. The details of the (m + n) -valent linking group include the (m + n) -valent linking group described in R ¹ of the formula (100), and the preferred embodiments are also the same.

As the divalent linking group represented by R ^{7 to} R ⁹ in formula (100b), the same divalent linking groups as those represented by R ² in formula (100) can be used, which is preferable. The aspect is also the same.

Preferred examples of the acid group A ³ in the formula (100b) include a carboxy group, a sulfo group, a monosulfate group, a phosphate group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and a boric acid group. Carboxy group, sulfo group, monosulfate group, phosphoric acid group, monophosphate group, phosphonic acid group, and phosphinic acid group are preferred, and carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, and phosphinic acid group are more preferred. Preferably, a carboxy group is more preferable.

Examples of the monovalent substituent represented by A ⁴ in Formula (100b) include the monovalent substituents described for A ¹ in Formula (100) (excluding an acid group). Among these, a monovalent substituent having at least one functional group having a pKa of 5 or more is preferable, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, At least a group selected from the group consisting of an alkyl group, an aryl group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a group having an alkyleneoxy chain, an imide group, a carboxylate group, a sulfonamide group, a hydroxy group and a heterocyclic group A monovalent substituent having one kind is more preferable, and an alkyl group, an aryl group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a urea group or a urethane group is still more preferable.

As a combination of A ³ and A ⁴ , A ³ is a monovalent substituent having at least one functional group having a pKa of less than 5, and A ⁴ is a monovalent substituent having at least one functional group having a pKa of 5 or more. Combinations that are substituents are preferred.

A ³ is a monovalent substituent having at least one group selected from the group consisting of a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and a phosphinic acid group, and A ⁴ is a coordinating oxygen Group having an atom, group having a basic nitrogen atom, phenol group, urea group, urethane group, alkyl group, aryl group, alkyloxycarbonyl group, alkylaminocarbonyl group, group having an alkyleneoxy chain, imide group, carboxylic acid More preferably, it is a monovalent substituent having at least one group selected from the group consisting of a base, a sulfonamide group, a hydroxy group and a heterocyclic group. A ³ is a monovalent substituent having a carboxy group, and A ⁴ is an alkyl group, an aryl group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a urea group or a urethane group. More preferably.

  1000-50000 is preferable, as for the weight average molecular weight of resin represented by Formula (100), 3000-30000 is more preferable, 3000-20000 is still more preferable. If it is the said range, the dispersibility of particle | grains is favorable.

The resin represented by the formula (100) is described in paragraph No. 0039 of Japanese Patent Application Laid-Open No. 2007-277514 (corresponding to [0053] of US Patent Application Publication No. 2010/0233595) and Japanese Patent Application Laid-Open No. 2015-2015. The description of Paragraph Nos. 0081 to 0117 of Japanese Patent No. 34961 can be referred to, and the contents thereof are incorporated in the present specification. Specific examples of the resin represented by the formula (100) include the following resins. In addition, the resins described in paragraph numbers 0223 to 0291 of JP-A-2014-177613, paragraph numbers 0229 to 0295 of JP-A-2014-062211, and paragraph numbers 0251 to 0337 of JP-A-2014-177614 are listed. This content is incorporated into the present invention.

  The method for synthesizing the resin represented by the formula (100) is not particularly limited, and examples thereof include a method in which a vinyl monomer is radically polymerized in the presence of a mercaptan compound having a plurality of adsorption sites. For details of the method for synthesizing the resin represented by the formula (100), refer to paragraphs 0114 to 0140, 0266 to 0348, and paragraphs 0077 to 0108 of JP 2014-177614 A. This content is incorporated herein by reference.

  The dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid). Ester), 110 (copolymer containing an acid group), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”, BYK-Chemie “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)”, EFKA “EFKA 4047, 4050-4165 (polyurethane)”, EFKA 4330-4340 (block copolymer), 4400-4402 (modified poly) Acrylate), 5010 (polyesteramide), 5765 (high molecular weight polymer) Carboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co.," Floren TG-710 manufactured by Kyoeisha Chemical Co., Ltd. (Urethane oligomer) ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) ”manufactured by Enomoto Kasei Co., Ltd., # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), Kao, MS, C, SN-B (aromatic) Sulfonic acid formalin polycondensate) ”,“ Homogenol L- ”manufactured by Kao Corporation 8 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”manufactured by Kao Corporation,“ Acetamine 86 (stearylamine acetate) ”manufactured by Kao Corporation, Nippon Lubrizol Corporation ) "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals,“ Hinoact T ”manufactured by Kawaken Fine Chemicals Co., Ltd. -8000E ", Shin-Etsu Chemical Co., Ltd." organosiloxane polymer KP341 ", Morishita Sangyo" EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA " "Polymer 450", Sannopco "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100", ADEKA "Adeka Pluronic L31, F38, L42, L44, L61, L64" F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", Sanyo Chemical Co., Ltd." Ionette S-20 ", and the like.

  In addition, resin demonstrated with the said dispersing agent can also be used for uses other than a dispersing agent. For example, it can be used as a binder. Moreover, resin (dispersant) which has an acid group can also be used as alkali-soluble resin.

  In the composition of the present invention, the resin content is preferably 0.1 to 80% by mass relative to the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less. The resin may contain only 1 type, and may contain 2 or more types of resin. When 2 or more types are included, the total amount is preferably within the above range.

  In the composition of the present invention, the content of the alkali-soluble resin is preferably 0.1 to 40% by mass with respect to the total solid content of the composition. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Alkali-soluble resin may contain only 1 type and may contain 2 or more types. When 2 or more types of alkali-soluble resins are included, the total amount is preferably within the above range.

  In the composition of the present invention, 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 30% by mass or less, and more preferably 25% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Further, the content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the metal compound A particles. 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. The dispersing agent may contain only 1 type and may contain 2 or more types. When two or more kinds of dispersants are included, the total amount is preferably within the above range.

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

  The polymerizable compound may be in the form of either a monomer or a polymer, but is preferably a monomer. The monomer type polymerizable compound preferably has a molecular weight of 200 to 3,000. The upper limit of the molecular weight is preferably 2500 or less, and more preferably 2000 or less. The lower limit of the molecular weight is preferably 250 or more, and more preferably 300 or more.

As examples of the polymerizable compound, the description in paragraph numbers 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound include ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercial product, NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310 ; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) And these (meth) acryloyl groups are ethylene Recall, structures linked via a propylene glycol residue are preferable. These oligomer types can also be used. Moreover, description of the polymeric compound of Paragraph Nos. 0034-0038 of Unexamined-Japanese-Patent No. 2013-253224 can be referred, This content is integrated in this specification. In addition, polymerizable monomers described in paragraph No. 0477 of JP 2012-208494 A (paragraph No. 0585 of the corresponding US Patent Application Publication No. 2012/0235099), and the like are described in the present specification. Incorporated into.
Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (as a commercial product, M-460; manufactured by Toagosei Co., Ltd.) is preferable. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomer types can also be used. For example, RP-1040 (Nippon Kayaku Co., Ltd. product) etc. are mentioned.

  The polymerizable compound may have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group. The polymerizable compound having an acid group can be obtained by a method in which a part of the hydroxy group of the polyfunctional alcohol is (meth) acrylated, and an acid anhydride is added to the remaining hydroxy group to form a carboxy group. Further, an acid group may be introduced by reacting the above-mentioned hydroxy group with a non-aromatic carboxylic acid anhydride or the like. Specific examples of the non-aromatic carboxylic acid anhydride include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. Is more preferable, and in the above-mentioned ester, a compound in which the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol is more preferable. Examples of commercially available products include Aronix M-510, M-520 (manufactured by Toagosei Co., Ltd.), CBX-0, CBX-1 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

  A preferable example of the polymerizable compound is a polymerizable compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. The polymerizable compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

  In the formula (Z-1), all six Rs are groups represented by the formula (Z-2), or 1 to 5 of the six Rs are represented by the formula (Z-2). And the remainder is a group represented by the formula (Z-3).

式（Ｚ−２）中、Ｒ¹は水素原子又はメチル基を示し、ｍは１又は２の数を示し、「＊」は結合手であることを示す。

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

式（Ｚ−３）中、Ｒ¹は水素原子又はメチル基を示し、「＊」は結合手であることを示す。

In formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

The polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

  As the polymerizable compound, a compound represented by the formula (Z-4) or (Z-5) can also be used.

In formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —. , Each y independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group.
In formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In Formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
Further, the formula (Z-4) or formula (Z-5) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side A form in which the terminal of X is bonded to X is preferred.

  The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), among which exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Co., Ltd. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

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

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

  In the composition of the present invention, the content of the polymerizable compound is preferably 0.01 to 50% by mass in the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 15% by mass or less. When the curable composition of this invention contains 2 or more types of polymeric compounds, it is preferable that the total amount exists in the said range.

<< photopolymerization initiator >>
The composition of the present invention preferably contains a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, a US patent Examples thereof include compounds described in the specification of No. 42122976.

  Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyls from the viewpoint of exposure sensitivity. Compounds selected from the group consisting of imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred. Examples of α-aminoketone compounds include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopropane-1- ON, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- And (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. Examples of commercially available α-aminoketone compounds include IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF). Examples of commercially available α-hydroxyketone compounds include IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE 819 and IRGACURE TPO (trade names: both manufactured by BASF).

  It is also preferable to use an oxime compound as the photopolymerization initiator. Specific examples of the oxime compound include a compound described in JP-A No. 2001-233842, a compound described in JP-A No. 2000-80068, a compound described in JP-A No. 2006-342166, and JP-A No. 2006-21012. The compounds described in the publication can be used.

  Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2 -One, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660, J. MoI. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like. . IRGACURE OXE01, IRGACURE OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF) are also suitably used as commercial products. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-930 (manufactured by ADEKA), Adeka Optomer N-1919 (manufactured by ADEKA, Japanese Patent Laid-Open No. 2012) The photopolymerization initiator 2) described in Japanese Patent No. 14052 can be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Publication WO2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No. 7,556,910, a compound described in Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, and Japanese Patent Application Laid-Open No. 2014-137466 As described in paragraph numbers 0076 to 0079 of the publication Or the like may be used compounds.
Preferably, for example, paragraph numbers 0274 to 0275 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime compound may be an oxime compound in which the oxime N—O bond is an (E) isomer, or the oxime N—O bond may be a (Z) oxime compound. Z) It may be a mixture with the body.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

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

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

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

  In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication WO2015 / 036910.

  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 a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm.

  The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and more preferably 5,000 to 200,000 from the viewpoint of sensitivity. 000 is particularly preferred. A known method can be used to measure the molar extinction coefficient of the compound. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L.

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

  As for content of a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid of the composition of this invention, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass. %. Within this range, better sensitivity and pattern formability can be obtained. The composition of this invention may contain only 1 type and 2 or more types of photoinitiators. When 2 or more types are included, the total amount is preferably within the above range.

<< Chain transfer agent >>
The composition of the present invention preferably contains a chain transfer agent. According to this aspect, in exposure at the time of pattern formation, curing of the film surface (pattern surface) can be promoted by exposure. For this reason, it is possible to suppress a decrease in film thickness during exposure and to easily form a pattern having excellent rectangularity.

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

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

<< Compound having epoxy group >>
The composition of this invention can also contain the compound which has an epoxy group. As for the compound which has an epoxy group, the compound which has 1 or more of epoxy groups in 1 molecule is mentioned, The compound which has 2 or more is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is preferably 2 or more.

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

  The compound having an epoxy group may be either a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). . The molecular weight of the compound having an epoxy group (in the case of a polymer, the weight average molecular weight) is preferably from 200 to 100,000, more preferably from 500 to 50,000.

  Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein. As commercial products, for example, as bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation) and the like. As bisphenol F type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S (Nippon Kayaku Co., Ltd.) and the like. Examples of the phenol novolac type epoxy resin include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. Is mentioned. Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), OXT-221 (manufactured by Toagosei Co., Ltd.), and the like.

  As the compound having an epoxy group, a compound described in paragraph No. 0045 of JP2009-265518A can also be used.

  When the compound having an epoxy group is contained, the content of the compound having an epoxy group is preferably 0.5 to 20% by mass in the total solid content of the composition. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.

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

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

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

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

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

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

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

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

<< Silane coupling agent >>
The composition of the present invention can further contain a silane coupling agent. In the present invention, the silane coupling agent is a component different from the polymerizable compound described above. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, the functional group other than the hydrolyzable group is preferably a group that interacts with the resin or forms a bond and exhibits affinity. Examples thereof include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, and an isocyanate group, and a (meth) acryloyl group and an epoxy group are preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group and at least one of a (meth) acryloyl group and an epoxy group.

Specific examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, parastyryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldi Toxisilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl- Butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate , 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like. . In addition to the above, alkoxy oligomers can be used. Also, the following compounds can be used.

  Commercially available products include Shin-Etsu Silicone's KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM- 403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, K M-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X- 41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40- 9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238, and the like. Examples of the silane coupling agent include compounds described in JP-A 2009-288703, paragraphs 0018 to 0036, and compounds described in JP-A 2009-242604, paragraphs 0056 to 0066. Are incorporated herein.

  0.01-15.0 mass% is preferable with respect to the total solid of a composition, and, as for content of a silane coupling agent, 0.05-10.0 mass% is more preferable. The silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

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

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

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

  Specific examples of the fluorosurfactant include surfactants described in paragraph numbers 0060 to 0064 of JP-A-2014-41318 (paragraph numbers 0060 to 0064 of the corresponding international publication WO 2014/17669 pamphlet) and the like. Examples include surfactants described in paragraph numbers 0117 to 0132 of Kokai 2011-132503, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, the product made by OMNOVA) etc. are mentioned.

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

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

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

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

  Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene 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) ), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd.), Orphine E1010, Surfynol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd.) and the like.

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

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

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

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

<< UV absorber >>
It is preferable that the composition of this invention contains a ultraviolet absorber.
Examples of the ultraviolet absorber include conjugated diene compounds and diketone compounds, and conjugated diene compounds are preferable. The conjugated diene compound is more preferably a compound represented by the following formula (UV-1).

In Formula (UV-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but do not represent a hydrogen atom at the same time.
R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.
R ¹ and R ² are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.
R ³ and R ⁴ represent an electron withdrawing group. R ³ and R ⁴ are preferably acyl, carbamoyl, alkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfamoyl, acyl, carbamoyl Group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group are preferred. R ³ and R ⁴ may be bonded to each other to form a cyclic electron withdrawing group. Examples of the cyclic electron-attracting group formed by combining R ³ and R ⁴ with each other include a 6-membered ring containing two carbonyl groups.
At least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.

Specific examples of the ultraviolet absorber represented by the formula (UV-1) include the following compounds. The description of the substituent of the ultraviolet absorber represented by the formula (UV-1) is given in paragraphs 0024 to 0033 of WO2009 / 123109 (paragraph numbers 0040 to 0059 of the corresponding US Patent Application Publication No. 2011/0039195). ), The contents of which are incorporated herein. Preferable specific examples of the compound represented by the formula (UV-1) are exemplified compounds of paragraph Nos. 0034 to 0037 of WO 2009/123109 (paragraph No. 0060 of the corresponding US Patent Application Publication No. 2011/0039195). The descriptions of (1) to (14) can be referred to, and the contents thereof are incorporated in the present specification. As a commercial item of the ultraviolet absorber shown by a formula (UV-1), UV503 (made by Daito Chemical Co., Inc.) etc. are mentioned, for example.

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

In the formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0 to 4. Substituents are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, acyloxy groups, Amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl group, aryl Sulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfinyl, ureido, phosphate amide, mercapto, E group, a carboxy group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, hydroxy group, a halogen atom, or a cyano group, an alkyl group and alkoxy group are preferred.
As for carbon number of an alkyl group, 1-20 are preferable. Examples of the alkyl group include linear, branched, and cyclic, and linear or branched is preferable, and branched is more preferable.
As for carbon number of an alkoxy group, 1-20 are preferable. Examples of the alkoxy group include straight chain, branched, and cyclic, and straight chain or branched is preferable, and branched is more preferable.
A combination in which one of R ¹⁰¹ and R ¹⁰² is an alkyl group and the other is an alkoxy group is preferable.
m1 and m2 each independently represent 0-4. m1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.

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

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

0.01-10 mass% is preferable with respect to the total solid of the composition of this invention, and, as for content of a ultraviolet absorber, 0.01-5 mass% is more preferable.
It is preferable to contain 5-100 mass parts of ultraviolet absorbers with respect to 100 mass parts of a polymeric compound. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.

<< 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 phenolic hydroxy group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds , Cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, phosphorus compounds, lactone compounds, transition metal compounds (FeCl ₃ , CuCl _2, etc.). In addition, these compounds may be composite compounds in which a plurality of structures that exhibit a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton are present in the same molecule. For example, compounds described in JP-A-10-46035 are also preferably used. Specific examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) can be mentioned. Of these, paramethoxyphenol is preferred.
As for content of a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a composition.
It is preferable that a polymerization inhibitor contains 0.001-1 mass part with respect to 100 mass parts of a polymeric compound. The upper limit is preferably 0.5 parts by mass or less, and more preferably 0.2 parts by mass or less. The lower limit is preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more.

<< Antioxidant >>
The composition of the present invention preferably contains an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite compound, a thioether compound, a hindered amine compound, and the like, and a phenol compound and a hindered amine compound are preferable. The molecular weight of the antioxidant is preferably 500 or more.

  As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. In particular, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, methyl group, ethyl group, propionyl group, isopropionyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl. Group, t-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable. A compound having a phenol group and a phosphite group in the same molecule is also preferred.

式（Ａ）〜（Ｃ）において、Ｒは、水素原子または置換基を表す。置換基としては、ハロゲン原子、アミノ基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルアミノ基、アリールアミノ基、アルキルスルホニル基、アリールスルホニル基などが挙げられる。アミノ基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルアミノ基、アリールアミノ基、アルキルスルホニル基、アリールスルホニル基は、更に置換基を有していてもよい。 The phenol compound is preferably a polysubstituted phenol compound. Polysubstituted phenolic compounds can be broadly classified into three types ((A) hindered type, (B) semi-hindered type, and (C) less hindered type) having different substitution positions and structures.

In formulas (A) to (C), R represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsulfonyl group, and arylsulfonyl group. The amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsulfonyl group, and arylsulfonyl group may further have a substituent.

  The phenol compound is preferably a compound in which a plurality of structures represented by the above formulas (A) to (C) are present in the same molecule, and the structure represented by the above formulas (A) to (C) is 2 in the same molecule. More preferably, there are -4 compounds.

Examples of the phenol compound include p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, 4,4-thiobis (3-methyl-6-tert-butylphenol), 2,2′- Examples thereof include compounds selected from the group consisting of methylene bis (4-methyl-6-tert-butylphenol), phenol resins, and cresol resins.
Representative examples available as commercial products include (A) Sumilizer BHT (manufactured by Sumitomo Chemical), Irganox 1010, 1222 (manufactured by BASF), Adekastab AO-20, AO-50, AO-50F, AO-60, AO-60G, AO-330 (manufactured by ADEKA Co., Ltd.), etc., and (B) include Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 245 (manufactured by BASF), Adeka Stub AO-80 (( (Cade) includes ADK STAB AO-30 and AO-40 (made by ADEKA).

式（ＨＡ）において、波線は、ヒンダードアミン化合物を構成する他の原子または原子団との連結手を表す。Ｒ¹〜Ｒ⁴はそれぞれ独立して水素原子またはアルキル基を表し、Ｒ⁵は、水素原子、アルキル基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基を表す。
ヒンダードアミン化合物は、上記式（ＨＡ）で表される部分構造を一分子中に２個以上有する化合物が好ましい。上限は、１００個以下が好ましく、５０個以下がより好ましく、２０個以下が更に好ましく、１０個以下が特に好ましい。
ヒンダードアミン化合物としては、アデカスタブＬＡ−５２、ＬＡ−５７、ＬＡ−６３Ｐ、ＬＡ−６８、ＬＡ−７２、ＬＡ−７７Ｙ、ＬＡ−７７Ｇ、ＬＡ−８１、ＬＡ−８２、ＬＡ−８７（（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the hindered amine compound include compounds having one or more partial structures represented by the following formula (HA) in one molecule.
Formula (HA)

In the formula (HA), a wavy line represents a bond with another atom or atomic group constituting the hindered amine compound. R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.
The hindered amine compound is preferably a compound having two or more partial structures represented by the above formula (HA) in one molecule. The upper limit is preferably 100 or less, more preferably 50 or less, still more preferably 20 or less, and particularly preferably 10 or less.
Examples of hindered amine compounds include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, and LA-87 (ADEKA Corporation). Manufactured).

  As the phosphite compound, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine and at least one compound selected from the group consisting of ethyl bis (2,4-ditert-butyl-6-methylphenyl) phosphite.

  As the antioxidant, in addition to those described above, ADK STAB PEP-36A, ADK STAB AO-412S (manufactured by ADEKA Corporation), and the like can also be used.

  0.01-20 mass% is preferable with respect to the total solid of a composition, and, as for content of antioxidant, 0.3-15 mass% is more preferable. Only one type of antioxidant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<< Other ingredients >>
The composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a thermal polymerization inhibitor, a plasticizer, and other auxiliary agents (for example, conductive particles, fillers, An antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, a surface tension adjusting agent, a chain transfer agent, and the like). By appropriately containing these components, it is possible to adjust the properties such as the stability and film properties of the target optical filter such as a near-infrared cut filter. These components are described in, for example, paragraph No. 0183 of JP2012-003225A (corresponding to paragraph No. 0237 of US Patent Application Publication No. 2013/0034812), paragraph No. of JP2008-250074. Descriptions such as 0101-0104, 0107-0109, and the like can be referred to, and the contents thereof are incorporated in the present specification.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the aforementioned components.
In preparing the composition, the respective components may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, each component is suitably used as two or more solutions or dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
It is also preferable to include a process for dispersing the particles. In the process of dispersing the particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the pulverization efficiency by increasing the filling rate of beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, the process and disperser for dispersing particles are described in “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion technology and industrial application centering on suspension (solid / liquid dispersion system)”. The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, published in General Materials, Management Development Center Publishing Department, October 10, 1978 ”can be suitably used. In the process of dispersing the particles, the particles may be refined in the salt milling process. As materials, equipment, processing conditions and the like used in the salt milling process, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.

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

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

The viscosity (at 23 ° C.) of the composition of the present invention is preferably 1 to 100 mPa · s. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
Although the total solid content of the composition of this invention is changed by the application method, it is preferable that it is 1-50 mass%, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.

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

<Membrane>
The film of the present invention is formed using the above-described composition of the present invention. The film of the present invention can be preferably used as a near-infrared cut filter or an infrared transmission filter. The film of the present invention may have a pattern, or may be a film without a pattern (flat film). Moreover, the film of the present invention may be used in a state of being laminated on a support, or the film of the present invention may be used after being peeled from the support.

  When the film of the present invention is used as an infrared transmission filter, it is a filter using a composition containing the above-described metal compound A and a colorant that blocks visible light, or other than the above-described layer containing the metal compound A. In addition, it is preferable that the filter includes a layer containing a coloring material that blocks visible light. When using the film | membrane of this invention as an infrared rays permeable filter, the metal compound A mentioned above has a role which limits the light (near-infrared ray) which permeate | transmits to a longer wavelength side.

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

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

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

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

  The film of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device. Further, the film of the present invention includes a lens having a function of absorbing or cutting near infrared rays (a lens for a camera such as a digital camera, a mobile phone, and an in-vehicle camera, an optical lens such as an f-θ lens and a pickup lens) and a semiconductor light receiving element. Optical filters, agricultural coatings for selective use of sunlight, recording media using near infrared absorption heat, near infrared filters for electronic devices and photographs, protective glasses, sunglasses, heat ray blocking filters Used for optical character reading and recording, confidential document copy prevention, electrophotographic photosensitive member, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

<Pattern formation method>
Next, the pattern forming method will be described. The pattern forming method includes a step of forming a composition layer on a support using the composition, and a pattern is formed on the composition layer by a photolithography method or a dry etching method. Forming.

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

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

Examples of the support include a support made of a material such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Further, a support for a solid-state imaging element in which a solid-state imaging element (light receiving element) such as a CCD or CMOS is provided on the support can be used.
The pattern may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface). If necessary, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

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

  The composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.

(When forming a pattern by photolithography)
<< Exposure process >>
Next, the composition layer is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 0.03~2.5J / cm ^2, more preferably 0.05~1.0J / cm ^2, and most preferably 0.08~0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (preferably 15% by volume or less, more preferably 5% by volume or less, More preferably, it may be exposed in a substantially oxygen-free manner, and in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (preferably 22% by volume or more, more preferably 30% by volume or more, further preferably 50% by volume). The above may be used for exposure. The exposure illuminance can be appropriately set. For example, 1000 W / m ^{2 to} 100,000 W / m ² (preferably 5000 W / m ² or more, more preferably 15000 W / m ² or more, and further preferably 35000 W / m ^2. The above range can be selected. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.

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

  Examples of the alkali agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene Compounds. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Moreover, you may use an inorganic alkaline compound for the alkali agent of a developing solution. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metaoxalate and the like. Further, a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described composition, and a nonionic surfactant is preferable. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) with a pure water after image development.

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

(When pattern is formed by dry etching method)
The pattern formation by the dry etching method is performed by curing the composition layer formed on the support to form a cured product layer, and then using the patterned photoresist layer as a mask to etch the obtained cured product layer. Can be used. In forming the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable. Regarding the pattern formation by the dry etching method, the description of paragraph numbers 0010 to 0067 of JP 2013-064993 A can be referred to, and the contents thereof are incorporated in the present specification.

<Optical filter>
Next, the optical filter of the present invention will be described. The optical filter of the present invention has the film of the present invention. The optical filter can be preferably used as a near-infrared cut filter or an infrared transmission filter.

In addition to the film of the present invention, the optical filter of the present invention may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, and the like.
For example, when the optical filter of the present invention is used as a near-infrared cut filter, in addition to the film of the present invention, a copper-containing layer or a dielectric multilayer film further provides a wide viewing angle and an infrared shielding property. An excellent near-infrared cut filter can be obtained. Further, in addition to the film of the present invention, a near-infrared cut filter having excellent ultraviolet shielding properties can be obtained by further comprising an ultraviolet absorbing layer. As an ultraviolet absorber contained in an ultraviolet absorption layer, the ultraviolet absorber demonstrated with the composition of this invention is mentioned. Moreover, as an ultraviolet absorption layer, description of the paragraph numbers 0040-0070 and 0119-0145 of WO2015 / 099060 can be referred, for example, The content is integrated in this specification. As the dielectric multilayer film, the description of paragraph numbers 0255 to 0259 of JP 2014-41318 A can be referred to, and the contents thereof are incorporated in the present specification. As a layer containing copper, the glass substrate (copper containing glass substrate) comprised with the glass containing copper and the layer (copper complex containing layer) containing a copper complex are mentioned. Examples of the copper-containing glass substrate include a phosphate glass containing copper and a fluorophosphate glass containing copper. Commercially available products of copper-containing glass include NF-50 (trade name, manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (trade name, manufactured by Schott Corp.), CD5000 (trade name, manufactured by HOYA Corporation). ) And the like. As a copper complex containing layer, the layer formed using the copper complex containing composition containing a copper complex is mentioned. The copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1200 nm. The maximum absorption wavelength of the copper complex is more preferably in the wavelength region of 720 to 1200 nm, and still more preferably in the wavelength region of 800 to 1100 nm.

  In addition, an embodiment in which the optical filter of the present invention has pixels of the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferable embodiment.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The infrared transmission filter 114 having the above-described spectral characteristics can be formed using a composition containing a color material that blocks visible light. The details of the colorant that blocks visible light are the same as those described in the above-described composition of the present invention.

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

  The infrared transmission filter 114 having the spectral characteristics described above can be formed using a composition containing a colorant that blocks visible light and a near-infrared absorber. The details of the colorant that blocks visible light are the same as those described in the above-described composition of the present invention. As a near-infrared absorber, the metal compound A etc. which were demonstrated with the composition of this invention mentioned above are mentioned.

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

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by using HPC-8220GPC (manufactured by Tosoh Corp.) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ2000 column, The column temperature was set to 40 ° C., 10 μL of a tetrahydrofuran solution having a sample concentration of 0.1% by mass was injected into the column, and tetrahydrofuran was eluted as an elution solvent at a flow rate of 0.35 mL / min. The sample peak was detected and calculated using a calibration curve prepared using standard polystyrene.

<Manufacture of InGaAs particles>
As the InGaAs particles, InGaAs particles produced as follows were used. First, In particles (particle size of 45 μm or less, manufactured by High Purity Chemical Laboratory Co., Ltd.), Ga particles (particle size of 850 μm or less, manufactured by High Purity Chemical Laboratory Co., Ltd.) and As particles (particle size of 300 μm or less, high purity) Chemical Research Laboratory Co., Ltd.) was subjected to plasma treatment in Ar gas to form various nanoparticles. The nanoparticles after the plasma treatment were allowed to stand for 24 hours in an Ar gas atmosphere under the conditions of an O ₂ concentration of 50 volume ppm or less and 30 ° C. Subsequently, it was allowed to stand at 30 ° C. for 24 hours in a state where O ₂ gas was introduced into the Ar atmosphere so that the O ₂ concentration was 100 ppm.
Thereafter, the obtained particles were classified using a TTSP separator manufactured by Hosokawa Micron under the conditions of a yield of 10% to obtain powders of various nanoparticles. About the obtained powder, when the average particle diameter of 100 particles was obtained by arithmetic mean by observation with a transmission electron microscope, the average primary particle diameter of In particles was 200 nm, the average primary particle diameter of Ga particles was 1000 nm, The average primary particle diameter of As particles was 500 nm.
Using the powder described above, InGaAs particles were produced using an apparatus according to the composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098. Specifically, in the composite fine particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to a high frequency oscillation coil of a plasma torch, and an argon gas of 50 L / min is used as a plasma gas from a plasma gas supply source. An argon-thermal plasma flame was generated in the plasma torch. Moreover, 10 L / min carrier gas was supplied from the spray gas supply source of the material supply apparatus. Then, the In particles, Ga particles, and As particles obtained as described above were added at a ratio of 26.5% by mass, 23.5% by mass, and 50.0% by mass, respectively, and an argon gas as a carrier gas At the same time, it was supplied into a thermal plasma flame in the plasma torch, evaporated in the thermal plasma flame, and highly dispersed in a gas phase state. Moreover, argon was used as the gas supplied into the chamber by the gas supply device. The flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1000 L / min. The pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value). In this way, InGaAs particles were obtained.

  About the obtained InGaAs particles, the contents of indium (In) atoms, gallium (Ga) atoms, and arsenic (As) atoms were measured by ICP (inductively coupled plasma) emission spectroscopy. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used. As a result, the In content was 26.5 mass%, the Ga content was 23.5 mass%, and the As content was 50.0 mass%.

  Moreover, the average primary particle diameter of the obtained InGaAs particles was 600 nm. The average primary particle diameter of the InGaAs particles was obtained by measuring 100 particle diameters of a portion where the InGaAs particles were not aggregated with a transmission electron microscope and calculating the average value.

(Preparation of dispersion)
A raw material having the following composition was dispersed using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) for 2 hours. 1 and 2 were prepared.

・プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ） ・・・７７．７７部 -Composition of dispersion 1-
InGaAs particles (average primary particle diameter: 600 nm) 15.1 parts Dispersant 1 (resin with the following structure, weight average molecular weight 32700, the numerical values attached to the repeating units of the main chain are molar ratios, side chains The numerical value written together with the repeating part of (2) indicates the number of repetitions of the repeating part.)... 7.2 parts

・ Propylene glycol monomethyl ether acetate (PGMEA) ... 77.77 parts

・ＰＧＭＥＡ ・・・７７．７７部 -Composition of dispersion 2-
InGaAs particles (average primary particle diameter: 600 nm) 15.1 parts Dispersant 2 (Resin having the following structure, weight average molecular weight 22900, the numerical value attached to the repeating unit of the main chain is the molar ratio, and the side chain The numerical value written together with the repeating part of (2) indicates the number of repetitions of the repeating part.)... 7.2 parts

・ PGMEA ... 77.77 parts

・ＰＧＭＥＡ ・・・７７．７７部 -Composition of dispersion 3-
InGaAs particles (average primary particle diameter 600 nm) 15.1 parts Dispersant 3 (resin having the following structure, weight average molecular weight 20000, l / m = 3.5 / 2.5 (molar ratio), n1 / n2 = 90/10 (mass ratio))... 7.2 parts

・ PGMEA ... 77.77 parts

・ＰＧＭＥＡ ・・・７７．７７部 -Composition of dispersion 4-
InGaAs particles (average primary particle diameter 600 nm) 15.1 parts Dispersant 4 (resin with the following structure, weight average molecular weight 24000, the numerical values attached to the repeating units of the main chain are molar ratios, side chains The numerical value written together with the repeating part of (2) indicates the number of repetitions of the repeating part.)... 7.2 parts

・ PGMEA ... 77.77 parts

・顔料誘導体（下記化合物） ・・・３．０部

・分散剤２・・・７．２部
・ＰＧＭＥＡ ・・・７７．７７部
なお、ピロロピロール顔料の平均一次粒子径は、ピロロピロール顔料の粒子が凝集していない部分の粒子径を、透過型電子顕微鏡で１００個計測し、平均値を算出して求めた。 -Composition of dispersion 5-
Pyrrolopyrrole pigment (the following compound, average primary particle size 100 nm) ... 12.2 parts

・ Pigment derivative (the following compound) ・ ・ ・ 3.0 parts

-Dispersant 2 ... 7.2 parts-PGMEA ... 77.77 parts The average primary particle diameter of the pyrrolopyrrole pigment is the transmission diameter of the part where the particles of the pyrrolopyrrole pigment are not aggregated. 100 pieces were measured with an electron microscope, and the average value was calculated.

-Composition of dispersion 6-
CsWO ₄ particles (average primary particle diameter 20 nm) 15.1 parts Dispersant 1 7.2 parts PGMEA 77.77 parts The average primary particle diameter of CsWO ₄ particles is: The particle diameter of the portion where CsWO ₄ particles are not aggregated was measured with a transmission electron microscope, and the average value was calculated.

(Preparation of composition)
The raw materials shown in the following table were mixed and stirred at the ratio (parts by mass) shown in the following table, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.60 μm to prepare a composition.

樹脂１：下記構造の樹脂（重量平均分子量１００００、ガラス転移温度４６℃、主鎖の繰り返し単位に付記した数値はモル比である。）のシクロヘキサノン４０質量％溶液

樹脂２：下記構造の樹脂（重量平均分子量４１４００、ガラス転移温度５３℃、主鎖の繰り返し単位に付記した数値はモル比である。）のシクロヘキサノン４０質量％溶液

樹脂３：下記構造の樹脂（重量平均分子量１１０００、ガラス転移温度不明、主鎖の繰り返し単位に付記した数値はモル比である。）のシクロヘキサノン４０質量％溶液

樹脂４：下記構造の樹脂（重量平均分子量１４０００、ガラス転移温度７９℃、主鎖の繰り返し単位に付記した数値はモル比である。）のシクロヘキサノン４０質量％溶液

樹脂５：下記構造の樹脂（重量平均分子量１００００、ガラス転移温度５６℃、主鎖の繰り返し単位に付記した数値はモル比である。）のシクロヘキサノン４０質量％溶液

有機溶剤１：シクロヘキサノン
有機溶剤２：シクロペンタノン
重合性化合物１：下記化合物の混合物（左側化合物と右側化合物とのモル比が７：３の混合物）

重合性化合物２：下記化合物

重合性化合物３：下記化合物

重合性化合物４：下記化合物

光重合開始剤１：ＩＲＧＡＣＵＲＥ ＯＸＥ０１（ＢＡＳＦ社製）
光重合開始剤２：下記化合物

光重合開始剤３：アデカアークルズＮＣＩ−８３１（（株）ＡＤＥＫＡ製）
光重合開始剤４：下記化合物

酸化防止剤１：アデカスタブＡＯ−８０（フェノール化合物、（株）ＡＤＥＫＡ製）
酸化防止剤２：アデカスタブＬＡ−５２（ヒンダードアミン化合物、（株）ＡＤＥＫＡ製）
重合禁止剤：ｐ−メトキシフェノール
界面活性剤：下記混合物（重量平均分子量１４０００、下記の式中、繰り返し単位の割合を示す％は質量％である。）の１質量％シクロヘキサノン溶液

The raw materials described in the above table are as follows.
(Dispersion)
Dispersions 1-6: Dispersions 1-6 described above
(Organic dye)
pp-1, pp-2, sq-1, cy-1: The following compounds. The following compounds are near infrared absorbers.

Resin 1: A cyclohexanone 40 mass% solution of a resin having the following structure (weight average molecular weight 10,000, glass transition temperature 46 ° C., the numerical value attached to the repeating unit of the main chain is a molar ratio)

Resin 2: Cyclohexanone 40% by mass solution of resin having the following structure (weight average molecular weight 41400, glass transition temperature 53 ° C., the numerical value attached to the repeating unit of the main chain is a molar ratio)

Resin 3: A cyclohexanone 40 mass% solution of a resin having the following structure (weight average molecular weight 11000, unknown glass transition temperature, the numerical value added to the repeating unit of the main chain is a molar ratio)

Resin 4: A cyclohexanone 40 mass% solution of a resin having the following structure (weight average molecular weight 14000, glass transition temperature 79 ° C., the numerical value added to the repeating unit of the main chain is a molar ratio)

Resin 5: A cyclohexanone 40 mass% solution of a resin having the following structure (weight average molecular weight 10,000, glass transition temperature 56 ° C., the numerical value added to the repeating unit of the main chain is a molar ratio)

Organic solvent 1: Cyclohexanone Organic solvent 2: Cyclopentanone Polymerizable compound 1: Mixture of the following compounds (Mix ratio of left compound to right compound is 7: 3)

Polymerizable compound 2: the following compound

Polymerizable compound 3: the following compound

Polymerizable compound 4: the following compound

Photopolymerization initiator 1: IRGACURE OXE01 (manufactured by BASF)
Photopolymerization initiator 2: the following compound

Photopolymerization initiator 3: Adeka Arcles NCI-831 (manufactured by ADEKA)
Photopolymerization initiator 4: the following compound

Antioxidant 1: ADK STAB AO-80 (phenol compound, manufactured by ADEKA Corporation)
Antioxidant 2: ADK STAB LA-52 (hindered amine compound, manufactured by ADEKA Corporation)
Polymerization inhibitor: p-methoxyphenol Surfactant: 1% by mass cyclohexanone solution of the following mixture (weight average molecular weight 14,000,% in the following formula,% representing the proportion of repeating units is mass%)

<Manufacture of membrane>
Each composition was spin-coated on a glass substrate so that the film thickness after film formation was 1.0 μm, and 1000 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). The whole surface was exposed. Subsequently, it heated at 220 degreeC for 5 minute (s) using the hotplate, and the film | membrane was manufactured.

<Spectroscopic evaluation>
About said film | membrane, the transmittance | permeability was measured in the range of wavelength 400-1300nm using the ultraviolet visible near-infrared spectrophotometer U-4100 (made by Hitachi High-Technologies Corporation). The light shielding property in the near-infrared region was determined based on the following criteria for the minimum value (T1) of the transmittance in the wavelength range of 700 to 1000 nm. Regarding the light transmittance in the visible region, the minimum transmittance (T2) in the wavelength range of 400 nm or more and less than 700 nm was determined according to the following criteria.
-Criteria for light shielding in the near infrared region (near infrared shielding)-
3: T1 <5%
2: 5% ≦ T1 <20%
1: 20% ≦ T1
-Criteria for light transmittance (visible transparency) in the visible region-
3: 90% ≦ T2
2: 70% ≦ T2 <90%
1: 70%> T2

From the above results, the films of the examples had good light transmittance (visible transparency) in the visible region and excellent light shielding properties (near infrared shielding properties) in the near infrared region. The film | membrane of the Example was able to be used suitably as a near-infrared cut off filter. Moreover, Examples 2-5 which further mix | blended the organic pigment | dye were able to shield the near infrared rays of a wide wavelength range compared with the other Examples.
On the other hand, the film of the comparative example was inferior in light transmittance in the visible region.

  In an Example, the infrared rays transmission filter excellent in spectral variability is obtained by mix | blending the coloring material which light-shields visible light further.

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

Claims (20)

  A composition comprising a compound having an absorption derived from interband transition in a wavelength range of 700 to 2000 nm and a resin.   The compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm has a band gap energy at 25 ° C. in the wavelength range of 700 to 2000 nm of 0.62 to 1.80 eV. The composition as described.   The composition according to claim 1 or 2, wherein the compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm is a III-V group compound.   The composition according to any one of claims 1 to 3, wherein the compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm is InGaAs.   The composition according to any one of claims 1 to 4, wherein the compound having absorption derived from interband transition in the wavelength range of 700 to 2000 nm is a particle.   The composition of claim 5, wherein the resin comprises a dispersant.   Furthermore, the composition of any one of Claims 1-6 containing a polymeric compound.   Furthermore, the composition of Claim 7 containing a photoinitiator.   Furthermore, the composition of any one of Claims 1-8 containing antioxidant.   Furthermore, the composition of any one of Claims 1-9 containing the near-infrared absorber different from the compound which has the absorption derived from the transition between bands in the range of the said wavelength 700-2000 nm.   The composition according to claim 10, wherein the near-infrared absorber is an organic dye.   Furthermore, the composition of any one of Claims 1-11 containing the coloring material which permeate | transmits at least one part of the light of a near infrared region, and light-shields the light of a visible region.   The film | membrane using the composition of any one of Claims 1-12.   An optical filter having the film according to claim 13.   The optical filter according to claim 14, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter. A membrane pixel according to claim 13;
The optical filter according to claim 14 or 15, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.   A laminate comprising the film according to claim 13 and a color filter containing a chromatic colorant.   A solid-state imaging device having the film according to claim 13.   An image display device comprising the film according to claim 13.   An infrared sensor having the film according to claim 13.

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