JP2018119077A - Curable 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 curable composition from which a film having suppressed surface roughness can be produced, a film, an optical filter, a laminate, a solid-state image sensor, an image display device and an infrared sensor.SOLUTION: The curable composition comprises a compound represented by formula (1) below and a curable compound. In the formula, Rand Reach independently represent an aryl group or the like; Rto Reach independently represent a hydrogen atom or a substituent; Xand Xeach independently represent a hydrogen atom or a substituent; and an atom in X, bonded to a N atom on a pyrrolopyrrole ring in formula (1) is different from an atom in X, bonded to a N atom on the pyrrolopyrrole ring in formula (1).SELECTED DRAWING: None

Description

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

  Video cameras, digital still cameras, mobile phones with camera functions, and the like use CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state imaging devices for color images. These solid-state imaging devices use silicon photodiodes having sensitivity to infrared rays in the light receiving portion. For this reason, visual sensitivity correction may be performed using a near-infrared cut filter. As the near-infrared absorbing compound, a pyrrolopyrrole compound or the like is known (for example, see Patent Document 1).

  Patent Document 2 describes an invention relating to a resin composition containing a near-infrared fluorescent dye and a resin, and pyrrolopyrrole boron complex and the like are described as the near-infrared fluorescent dye.

International Publication WO2009 / 123056 International Publication WO2015 / 056779

According to the study of the present inventors, it has been found that a film obtained using a curable composition containing a pyrrolopyrrole compound tends to cause surface roughness.
Therefore, the objective of this invention is providing the curable composition which can manufacture the film | membrane with which the surface roughness was suppressed. Another object of the present invention is to provide a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor in which surface roughness is suppressed.

式中、Ｒ¹およびＲ²は、各々独立にアルキル基、アリール基またはヘテロアリール基を表す；
Ｒ³〜Ｒ⁶は、各々独立に水素原子または置換基を表し、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶は、それぞれ結合して環を形成していてもよい；
Ｘ¹およびＸ²は、各々独立に水素原子または置換基を表し、かつ、Ｘ¹の式（１）におけるピロロピロール環上のＮ原子と結合する原子と、Ｘ²の式（１）におけるピロロピロール環上のＮ原子と結合する原子とが互いに異なる。
＜２＞ 式（１）において、Ｘ¹およびＸ²は、各々独立に、水素原子、アルキル基、アルコキシ基、アシル基、アシルオキシ基、アリール基、ヘテロアリール基、（Ｒ^7A）₂Ｂ−、（Ｒ^7B）₂Ｐ−、（Ｒ^7C）₃Ｓｉ−、（Ｒ^7D）_nＭ¹−またはＭ²−を表し、Ｒ^7A〜Ｒ^7Dは、各々独立に水素原子または置換基を表し、ｎは２〜４の整数を表し、Ｍ¹は、ｎ＋１価の金属原子を表し、Ｍ²は１価の金属原子を表し、
Ｘ¹が（Ｒ^7A）₂Ｂ−、（Ｒ^7B）₂Ｐ−、（Ｒ^7C）₃Ｓｉ−、（Ｒ^7D）_nＭ¹−またはＭ²−を表す場合、Ｘ¹はＲ²、Ｒ³およびＲ⁴の少なくとも１つと共有結合または配位結合していてもよく、
Ｘ²が（Ｒ^7A）₂Ｂ−、（Ｒ^7B）₂Ｐ−、（Ｒ^7C）₃Ｓｉ−、（Ｒ^7D）_nＭ¹−またはＭ²−を表す場合、Ｘ²はＲ¹、Ｒ⁵およびＲ⁶の少なくとも１つと共有結合または配位結合していてもよい、
＜１＞に記載の硬化性組成物。
＜３＞ 式（１）において、Ｘ¹およびＸ²のいずれか一方は、（Ｒ^7A）₂Ｂ−を表す、＜２＞に記載の硬化性組成物。
＜４＞ 式（１）において、Ｘ¹およびＸ²のいずれか一方は、水素原子、アルキル基、アルコキシ基、アシル基、アシルオキシ基、アリール基またはヘテロアリール基を表す、＜２＞または＜３＞に記載の硬化性組成物。
＜５＞ 更に、下記式（１０）で表される化合物を含む、＜１＞〜＜４＞のいずれか１つに記載の硬化性組成物；

式中、Ｒ¹¹およびＲ¹²は、各々独立にアルキル基、アリール基またはヘテロアリール基を表す；
Ｒ¹³〜Ｒ¹⁶は、各々独立に水素原子または置換基を表し、Ｒ¹³とＲ¹⁴、Ｒ¹⁵とＲ¹⁶は、それぞれ結合して環を形成していてもよい；
Ｘ¹¹およびＸ¹²は、各々独立に水素原子または置換基を表し、かつ、Ｘ¹¹の式（１０）におけるピロロピロール環上のＮ原子と結合する原子と、Ｘ¹²の式（１０）におけるピロロピロール環上のＮ原子と結合する原子とが同一である。
＜６＞ 式（１０）において、Ｘ¹¹およびＸ¹²が水素原子であるか、または、同一の置換基である、＜５＞に記載の硬化性組成物。
＜７＞ 式（１０）において、Ｘ¹¹およびＸ¹²は同一の置換基であって、（Ｒ^17A）₂Ｂ−を表し、Ｒ^17Aは水素原子または置換基を表す、＜５＞に記載の硬化性組成物。
＜８＞ 更に、有彩色着色剤を含む、＜１＞〜＜７＞のいずれか１つに記載の硬化性組成物。
＜９＞ 更に、赤外線を透過させて可視光を遮光する色材を含む、＜１＞〜＜７＞のいずれか１つに記載の硬化性組成物。
＜１０＞ ＜１＞〜＜９＞のいずれか１つに記載の硬化性組成物から得られる膜。
＜１１＞ ＜１０＞に記載の膜を有する光学フィルタ。
＜１２＞ 光学フィルタが、近赤外線カットフィルタまたは赤外線透過フィルタである、＜１１＞に記載の光学フィルタ。
＜１３＞ ＜１０＞に記載の膜を有する積層体。
＜１４＞ ＜１０＞に記載の膜を有する固体撮像素子。
＜１５＞ ＜１０＞に記載の膜を有する画像表示装置。
＜１６＞ ＜１０＞に記載の膜を有する赤外線センサ。 Under such circumstances, as a result of intensive studies by the present inventors, it was found that a film with suppressed surface roughness can be produced by using a compound represented by the formula (1) described below, and the present invention was completed. I came to let you. The present invention provides the following.
<1> A curable composition comprising a compound represented by the following formula (1) and a curable compound;

In the formula, R ¹ and R ² each independently represents an alkyl group, an aryl group or a heteroaryl group;
R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring;
X ¹ and X ² each independently represent a hydrogen atom or a substituent, and an atom bonded to the N atom on the pyrrolopyrrole ring in formula (1) of X ¹ and pyrrolo in formula (1) of X ² The N atom on the pyrrole ring is different from the atom bonded to it.
<2> In the formula (1), X ¹ and X ² are each independently a hydrogen atom, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, heteroaryl group, (R ^7A ) ₂ B—, (R ^7B ) ₂ P—, (R ^7C ) ₃ Si—, (R ^7D ) _n M ¹ — or M ² —, R ^{7A to} R ^7D each independently represents a hydrogen atom or a substituent, n Represents an integer of 2 to 4, M ¹ represents an n + 1 valent metal atom, M ² represents a monovalent metal atom,
X ¹ is _{^{(R 7A) 2 B -,}} (R 7B) 2 P -, (R 7C) 3 Si -, (R 7D) n M 1 - or M ² - may represent, X ¹ is R ^2, R ³ and R ⁴ may be bonded at least one covalent or coordinate,
X ² is _{^{(R 7A) 2 B -,}} (R 7B) 2 P -, (R 7C) 3 Si -, (R 7D) n M 1 - or M ² - may represent, X ² is R ^1, R ⁵ and at least one covalent bond or may be coordinated with the binding of R ^6,
The curable composition as described in <1>.
<3> In the formula (1), any one of X ¹ and X ² represents (R ^7A ) ₂ B—, and the curable composition according to <2>.
<4> In Formula (1), any one of X ¹ and X ² represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, or a heteroaryl group, <2> or <3 > Curable composition.
<5> Furthermore, the curable composition as described in any one of <1>-<4> containing the compound represented by following formula (10);

In the formula, R ¹¹ and R ¹² each independently represents an alkyl group, an aryl group or a heteroaryl group;
R ^{13 to} R ¹⁶ each independently represents a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ , and R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring;
X ¹¹ and X ¹² each independently represent a hydrogen atom or a substituent, and an atom bonded to an N atom on the pyrrolopyrrole ring in the formula (10) of X ¹¹ and a pyrrolo in the formula (10) of X ¹² The atom bonded to the N atom on the pyrrole ring is the same.
<6> The curable composition according to <5>, wherein in formula (10), X ¹¹ and X ¹² are hydrogen atoms or the same substituent.
<7> In the formula (10), X ¹¹ and X ¹² are the same substituent, and represent (R ^17A ) ₂ B—, R ^17A represents a hydrogen atom or a substituent, described in <5> Curable composition.
<8> The curable composition according to any one of <1> to <7>, further including a chromatic colorant.
<9> Furthermore, the curable composition as described in any one of <1>-<7> containing the coloring material which permeate | transmits infrared rays and shields visible light.
<10> A film obtained from the curable composition according to any one of <1> to <9>.
<11> An optical filter having the film according to <10>.
<12> The optical filter according to <11>, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter.
<13> A laminate having the film according to <10>.
<14> A solid-state imaging device having the film according to <10>.
<15> An image display device having the film according to <10>.
<16> An infrared sensor having the film according to <10>.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which can manufacture the film | membrane with which the surface roughness was suppressed can be provided. In addition, it is possible to provide a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor in which surface roughness is suppressed.

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 group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes group (atomic group) which has a substituent with the group (atomic group) which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include an emission line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, and electron beams.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement.
In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, near-infrared light refers to light (electromagnetic wave) having a maximum absorption wavelength range of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

<Curable composition>
The curable composition of this invention is characterized by containing the compound (henceforth a compound (1)) represented by Formula (1) mentioned later, and a curable compound.

By using the curable composition of the present invention, a film with suppressed surface roughness can be produced. It is estimated that the reason why such an effect is obtained is as follows. In the compound (1), the atom bonded to the N atom on the pyrrolopyrrole ring in the formula (1) of X ¹ is different from the atom bonded to the N atom on the pyrrolopyrrole ring in the formula (1) of X ^2. . That is, in the compound (1), the structures on the two N atoms on the pyrrolopyrrole ring are asymmetric. By setting it as such a structure, it is estimated that the ease of overlapping of molecules fell and the crystallinity of compound (1) fell. As a result, it is presumed that the film in which the precipitation of the compound (1) during film formation was suppressed and the surface roughness was suppressed could be manufactured.
Further, the compound (1) is excellent in visible transparency while being excellent in infrared shielding properties. For this reason, the curable composition of this invention containing a compound (1) can manufacture the film | membrane excellent in the spectral characteristics. For example, by using the curable composition of the present invention, a near-infrared cut filter having excellent visible transparency and excellent infrared shielding properties can be produced. Further, in the curable composition of the present invention, in addition to the compound (1), a colorant that transmits infrared rays and shields visible light is further contained, so that the spectral characteristics are excellent and specific infrared rays are selectively used. It is also possible to manufacture an infrared transmission filter that transmits through the light. In the infrared transmission filter, the compound (1) has a role of limiting the transmitted light (near infrared) to the longer wavelength side. And since compound (1) is excellent in visible transparency and infrared shielding property, it is easy to control the spectrum in the visible region to be shielded and the spectrum in the infrared region to be transmitted within an appropriate range.
Hereinafter, each component of the curable composition of this invention is demonstrated.

式中、Ｒ¹およびＲ²は、各々独立にアルキル基、アリール基またはヘテロアリール基を表す；
Ｒ³〜Ｒ⁶は、各々独立に水素原子または置換基を表し、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶は、それぞれ結合して環を形成していてもよい；
Ｘ¹およびＸ²は、各々独立に水素原子または置換基を表し、かつ、Ｘ¹の式（１）におけるピロロピロール環上のＮ原子と結合する原子と、Ｘ²の式（１）におけるピロロピロール環上のＮ原子と結合する原子とがそれぞれ異なる。 << Compound Represented by Formula (1) (Compound (1)) >>
The curable composition of this invention contains the compound (compound (1)) represented by following formula (1). Since the compound (1) has a maximum absorption wavelength in the near infrared region, it is also a near infrared absorbing compound.

In the formula, R ¹ and R ² each independently represents an alkyl group, an aryl group or a heteroaryl group;
R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring;
X ¹ and X ² each independently represent a hydrogen atom or a substituent, and an atom bonded to the N atom on the pyrrolopyrrole ring in formula (1) of X ¹ and pyrrolo in formula (1) of X ² The atom bonded to the N atom on the pyrrole ring is different.

In Formula (1), R ¹ and R ² each independently represents an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
R ¹ and the carbon number of the alkyl group represented by R ² is preferably 1 to 30, more preferably from 1 to 20, 1 to 10 is more preferred.
R ¹ and the carbon number of the aryl group represented by R ² is preferably 6 to 30, more preferably 6 to 20, 6 to 12 are particularly preferred.
The number of carbon atoms constituting the heteroaryl group represented by R ¹ and R ² is preferably 1 to 30, 1 to 12 is more preferable. As a kind of hetero atom which comprises a heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned, for example. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 is preferable, and 1 to 2 is more preferable. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further preferably a single ring or a condensed ring having 2 to 4 condensations.
The alkyl group, aryl group, and heteroaryl group described above may have a substituent or may be unsubstituted. It preferably has a substituent. Examples of the substituent include 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, alkylsulfino Group, arylsulfino group, hydrazino group, imino group, silyl group, hydroxy group, halogen atom, cyano group, etc., hydrocarbon group which may contain oxygen atom, hydroxy group or halogen Atom is preferable.

Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group as a substituent 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 —, and more preferably —O—. L is also preferably -OCO-.
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. When L is —OCO—, R ^x1 is preferably an aryl 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.

R ¹ and R ² are preferably each independently an aryl group having a substituent. When R ¹ and R ² contain a group having a long-chain alkyl group (preferably an alkyl group having 7 to 30 carbon atoms) as a substituent, the compound (1) has good solvent solubility, and such a compound Can be preferably used as a dye. The long-chain alkyl group may be either linear or branched, but is preferably a branched alkyl group. Examples of the group having a long-chain alkyl group (preferably an alkyl group having 7 to 30 carbon atoms) include an alkoxy group having 7 to 30 carbon atoms, a hydrocarbon group having an alkoxy group having 7 to 30 carbon atoms, and 7 to 30 carbon atoms. And a heteroaryl group having an alkoxy group.
When R ¹ and R ² have a hydrocarbon group having a small carbon number (preferably a hydrocarbon group having 1 to 6 carbon atoms), a heteroaryl group, a hydroxy group, or the like as a substituent, the compound (1) is Such a compound can be preferably used as a pigment because of low solvent solubility.

Specific examples of R ¹ and R ² include the following. In the following, Me represents a methyl group and Bu represents a butyl group. * Represents a bonding position in the formula (1).

In Formula (1), R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. Examples of the substituent include the following substituent T.
(Substituent T)
Alkyl group (preferably 1-30 carbon atoms), alkenyl group (preferably 2-30 carbon atoms), alkynyl group (preferably 2-30 carbon atoms), aryl group (preferably 6-30 carbon atoms), amino group (Preferably 0-30 carbon atoms), alkoxy group (preferably 1-30 carbon atoms), aryloxy group (preferably 6-30 carbon atoms), heteroaryloxy group (preferably 1-30 carbon atoms), acyl A group (preferably having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), an acyloxy group (preferably having 2 to 30 carbon atoms), Acylamino group (preferably having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms), aryloxycarbonylamino group Preferably 7-30 carbon atoms, sulfamoyl group (preferably 0-30 carbon atoms), carbamoyl group (preferably 1-30 carbon atoms), alkylthio group (preferably 1-30 carbon atoms), arylthio group (preferably 6-30 carbon atoms), heteroarylthio group (preferably 1-30 carbon atoms), alkylsulfonyl group (preferably 1-30 carbon atoms), arylsulfonyl group (preferably 6-30 carbon atoms), heteroarylsulfonyl Group (preferably having 1 to 30 carbon atoms), alkylsulfinyl group (preferably having 1 to 30 carbon atoms), arylsulfinyl group (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably having 1 to 30 carbon atoms) Ureido group (preferably having 1 to 30 carbon atoms), phosphoramide group (preferably having 1 to 30 carbon atoms), hydro Shi group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a heteroaryl group (preferably having 1 to 30 carbon atoms). When these groups are further substitutable groups, they may further have a substituent. Examples of the further substituent include the groups described for the substituent T described above.

In Formula (1), it is preferable that one of R ³ and R ⁴ and one of R ⁵ and R ⁶ are an electron withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-attracting group. Here, the substituent constant obtained by Hammett's rule includes a σp value and a σm value. These values can be found in many common books. In the present invention, substituents having Hammett's substituent constant σ value of 0.2 or more can be exemplified as electron-attracting groups. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and still more 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 (σp value = 0.66), a carboxyl group (—COOH: σp value = 0.45), and an alkoxycarbonyl group (for example, —COOMe: σp value = 0. 45), an aryloxycarbonyl group (for example, —COOPh: σp value = 0.44), a carbamoyl group (for example, —CONH ₂ : σp value = 0.36), an alkylcarbonyl group (for example, —COMe: σp value = 0.50), an arylcarbonyl group (for example, —COPh: σp value = 0.43), an alkylsulfonyl group (for example, —SO ₂ Me: σp value = 0.72), an arylsulfonyl group (for example, —SO ₂ Ph: σp value = 0.68). Here, Me represents a methyl group, and Ph represents a phenyl group. Regarding the Hammett's substituent constant σ value, for example, paragraph numbers 0017 to 0018 of JP 2011-68731 A can be referred to, and the contents thereof are incorporated herein.

In formula (1), one of R ³ and R ⁴ preferably represents an electron withdrawing group (preferably a cyano group), and the other represents a heteroaryl group. One of R ⁵ and R ⁶ preferably represents an electron withdrawing group (preferably a cyano group), and the other represents a heteroaryl group. The heteroaryl group is preferably a group represented by the following formula (A-1) or a group represented by (A-2).

In the formula (A-1), X ¹ 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 ^a1 and R ^a2 represent Each independently represents a hydrogen atom or a substituent, and R ^a1 and R ^a2 may be bonded to each other to form a ring. * Represents a bonding position in the formula (1).
Examples of the substituent represented by R ^a1 , R ^a2 and R ^{X1 to} R ^X3 include a substituent T, and an alkyl group, an aryl group, and a halogen atom are preferable.

式中、Ｘ¹は、Ｏ、Ｓ、ＮＲ^X1またはＣＲ^X2Ｒ^X3を表し、Ｒ^X1〜Ｒ^X3は、各々独立に水素原子または置換基を表し、Ｒ^101a〜Ｒ^109aは、各々独立に水素原子または置換基を表す。＊は、式（１）における結合位置を表す。Ｒ^101a〜Ｒ^109aが表す置換基としては、置換基Ｔが挙げられる。 The ring formed by combining R ^a1 and R ^a2 is preferably an aromatic ring. When R ^a1 and R ^a2 form a ring, ^{examples of} (A-1) include a group represented by the following (A-1-1) and a group represented by (A-1-2). Can be mentioned.

In the formula, X ¹ 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 ^{101a to} R ^109a each independently represent hydrogen Represents an atom or substituent. * Represents a bonding position in the formula (1). ^Examples of the substituent represented by R ^{101a to} R ^109a include the substituent T.

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 in the formula (1). Examples of the substituent represented by R ^Y1 include a substituent T, and an alkyl group, an aryl group, and a halogen atom are preferable.

式中、Ｒ^201a〜Ｒ^227aは、各々独立して、水素原子または置換基を表し、＊は、式（１）における結合位置を表す。Ｒ^201a〜Ｒ^227aが表す置換基としては、置換基Ｔが挙げられる。 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 (A-2) include a group represented by the following (A-2-1) and a group represented by (A-2-2). It is done.

In the formula, R ^{201a to} R ^227a each independently represent a hydrogen atom or a substituent, and * represents a bonding position in the formula (1). ^Examples of the substituent represented by R ^{201a to} R ^227a include the substituent T.

Specific examples of the heteroaryl group represented by R ^{3 to} R ⁶ include the following groups. In the following, Bu represents a butyl group. * Represents a bonding position in the formula (1).

In the formula (1), R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. When R ³ and R ⁴ are bonded to form a ring, it is preferable to form a 5- to 7-membered ring (preferably a 5- or 6-membered ring). Also, if R ⁵ and R ⁶ are bound to form a ring, it is preferable to form a 5-7 membered ring (preferably 5 or 6 membered ring). As specific examples of the ring formed, for example, paragraphs 0019 to 0021 of JP 2011-68731 A can be referred to, and the contents thereof are incorporated in the present specification.

In formula (1), X ¹ and X ² are, each independently, represent a hydrogen atom or a substituent, and the atom bonded to the N atom on the pyrrolo pyrrole ring in the formula X ¹ (1), X ² In the formula (1), the N atom on the pyrrolopyrrole ring is different from the atom bonded thereto.

X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a heteroaryl group, (R ^7A ) ₂ B-, (R ^7B ) ₂ P-, It preferably represents (R ^7C ) ₃ Si-, (R ^7D ) _n M ¹ -or M ^2- . R ^{7A to} R ^7D each independently represents a hydrogen atom or a substituent, n represents an integer of 2 to 4, M ¹ represents an n + 1 valent metal atom, and M ² represents a monovalent metal atom. .

X ¹ and X ² carbon atoms in the alkyl group and alkoxy group represented by is preferably 1 to 30, more preferably from 1 to 20, 1 to 10 is more preferred.
X ¹ and the number of carbon atoms of the aryl group X ² represents preferably 6 to 30, more preferably 6 to 20, 6 to 12 are particularly preferred.
The number of carbon atoms constituting the heteroaryl group in which X ¹ and X ² represents preferably 1 to 30, 1 to 12 is more preferable. As a kind of hetero atom which comprises a heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned, for example. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 is preferable, and 1 to 2 is more preferable. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further preferably a single ring or a condensed ring having 2 to 4 condensations.
Examples of the acyl group represented by X ¹ and X ² include a group represented by —C (═O) —R ^X100 . Further, examples of the acyloxy group represented by X ¹ and X ² include a group represented by —O—C (═O) —R ^X100 . R ^X100 represents an alkyl group, an aryl group, or a heteroaryl group. Examples of the alkyl group, aryl group or heteroaryl group include the groups described above as represented by X ¹ and X ² .
The alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, and heteroaryl group described above may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T.

Examples of the substituent represented by R ^{7A to} R ^7D include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group, and a halogen atom, an alkyl group, and an aryl group. Group or heteroaryl group is preferable, a halogen atom, an alkyl group or an aryl group is more preferable, and an aryl group is more preferable. A plurality of R ^7A , R ^7B , R ^7C and R ^7D may be the same or different. Moreover, several R ^<7A >, R ^<7B >, R ^<7C >, and R ^<7D > may mutually couple ^| bond together and may form the ring.

As the halogen atom represented by R ^{7A to} R ^7D , 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 the alkyl group and alkoxy group which R ^{< 7A} > -R <^7D> represents, 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 and alkoxy group may be linear, branched or cyclic, but are preferably linear or branched.
As for carbon number of the alkenyl group which R ^{< 7A} > -R <^7D> represents, 2-40 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.
6-20 are preferable and, as for carbon number of the aryl group and aryloxy group which R ^{< 7A} > -R <^7D> represents, 6-12 are more preferable. The aryl group and aryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T, and an alkyl group, an alkoxy group, a halogen atom, and the like are preferable.
The heteroaryl group and heteroaryloxy group represented by R ^{7A to} R ^7D may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3. The hetero atom constituting the heteroaryl ring 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 ring, 3-18 are more preferable, 3-12 are more preferable, and 3-5 are especially preferable. The heteroaryl ring is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group and heteroaryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T, and an alkyl group, an alkoxy group, a halogen atom, and the like are preferable.

Examples of the n + 1 valent metal atom represented by M ¹ include magnesium, aluminum, calcium, barium, zinc, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, and platinum.

Examples of the monovalent metal atom represented by M ² include lithium, sodium, potassium, silver, cesium and the like.

In the formula (1), when X ¹ represents (R ^7A ) ₂ B—, (R ^7B ) ₂ P—, (R ^7C ) ₃ Si—, (R ^7D ) _n M ¹ — or M ² — ¹ may be covalently or coordinately bonded to at least one of R ² , R ³ and R ⁴ . When X ² represents (R ^7A ) ₂ B-, (R ^7B ) ₂ P-, (R ^7C ) ₃ Si-, (R ^7D ) _n M ¹ -or M ^2- , X ² represents R ¹ , R ⁵ and R ⁶ may be covalently bonded or coordinately bonded.

Specific examples of the group represented by (R ^7A ) ₂ B— include the following groups. In the following, Bu represents a butyl group. * Represents a bonding position in the formula (1).

In Formula (1), any one of X ¹ and X ² represents (R ^7A ) ₂ B—, or represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, or heteroaryl. It is preferable that ^one of X ¹ and X ² represents (R ^7A ) ₂ B-, and the other represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, or heteroaryl. It is more preferable that ^one of X ¹ and X ² represents (R ^7A ) ₂ B—, and the other represents a hydrogen atom, an alkyl group, an acyloxy group, or an aryl group. It is particularly preferred that either ¹ or X ² represents (R ^7A ) ₂ B— and the other represents a hydrogen atom. By using such a compound, precipitation at the time of film formation can be more effectively suppressed, and it is easy to produce a film with more suppressed surface roughness. Further, if either one of X ¹ and X ² are (R ^7A) ₂ B- is heat resistance and visible transparency is improved. And one of X ¹ and X ² is (R ^7A ) ₂ B— and the other is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group or a heteroaryl group, While maintaining excellent visible transparency, the crystallinity of the compound can be greatly reduced, and the precipitation of crystals during film formation can be more effectively suppressed.

Specific examples of the compound (1) include the following compounds. In the following, Bu represents a butyl group and Ph represents a phenyl group. In addition, symbols such as C-1, A-2, and B-1 added to the following table are groups shown in the above specific examples.

  The compound (1) may be a pigment or a dye. In the present invention, the pigment means a compound that is difficult to dissolve in a solvent. For example, the pigment preferably has a solubility in 100 g of water at 23 ° C. and a solubility in 100 g of cyclohexanone at 23 ° C. of less than 0.1 g, and more preferably less than 0.01 g. Moreover, in this invention, a dye means the compound which is easy to melt | dissolve with respect to a solvent. For example, the solubility of the dye in 100 g of water at 23 ° C. or the solubility in 100 g of cyclohexanone at 23 ° C. is preferably 0.1 g or more, and more preferably 1 g or more.

  The maximum absorption wavelength of the compound (1) is preferably in the wavelength range of 700 to 1000 nm. In this specification, “having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm” means a wavelength exhibiting the maximum absorbance in the wavelength range of 700 to 1000 nm in the absorption spectrum of the compound (1) in the solution. It means having. Examples of the measurement solvent used for measuring the absorption spectrum of compound (1) include chloroform, ethyl acetate, and tetrahydrofuran. When the compound (1) is a compound that dissolves in chloroform, chloroform is used as a measurement solvent.

  In the curable composition of the present invention, the content of the compound (1) is preferably 0.01 to 50% by mass with respect to the total solid content of the curable composition of the present invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.

式中、Ｒ¹¹およびＲ¹²は、各々独立にアルキル基、アリール基またはヘテロアリール基を表す；
Ｒ¹³〜Ｒ¹⁶は、各々独立に水素原子または置換基を表し、Ｒ¹³とＲ¹⁴、Ｒ¹⁵とＲ¹⁶は、それぞれ結合して環を形成していてもよい；
Ｘ¹¹およびＸ¹²は、各々独立に水素原子または置換基を表し、かつ、Ｘ¹¹の式（１０）におけるピロロピロール環上のＮ原子と結合する原子と、Ｘ¹²の式（１０）におけるピロロピロール環上のＮ原子と結合する原子とが同一である。 << Other pyrrolopyrrole compounds >>
The curable composition of the present invention can contain a pyrrolopyrrole compound (hereinafter, also referred to as other pyrrolopyrrole compound) other than the compound (1) described above. The other pyrrolopyrrole compound is preferably a compound represented by the following formula (10).

In the formula, R ¹¹ and R ¹² each independently represents an alkyl group, an aryl group or a heteroaryl group;
R ^{13 to} R ¹⁶ each independently represents a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ , and R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring;
X ¹¹ and X ¹² each independently represent a hydrogen atom or a substituent, and an atom bonded to an N atom on the pyrrolopyrrole ring in the formula (10) of X ¹¹ and a pyrrolo in the formula (10) of X ¹² The atom bonded to the N atom on the pyrrole ring is the same.

R < ¹¹ > -R < ¹⁶ > in Formula (10) is synonymous with R < ¹ > -R < ⁶ > demonstrated by Formula (1), and its preferable range is also the same.

Examples of the substituent represented by X ¹¹ and X ¹² in the formula (10) include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a heteroaryl group, (R ^17A ) ₂ B-, (R ^17B ) ₂ P _{^{-, (R 17C) 3 Si}} -, (R 17D) n M 1 -, M 2 - and the like. R ^{17A to} R ^17D each independently represents a hydrogen atom or a substituent, n represents an integer of 2 to 4, M ¹ represents an n + 1 valent metal atom, and M ² represents a monovalent metal atom. . Preferred ranges of the alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, and heteroaryl group represented by X ¹¹ and X ¹² are the same as those described for X ¹ and X ² in the above formula (1). The preferable range is also the same. Also, monovalent metal atom n + 1 valent metal atom represented by M ^1, the M ² represents, as the substituent represented by R ^17A to R ^17D, M ¹ of formula (1) described above, M ^2, R ^7A ~ It is the same as R ^7D and the preferred range is also the same.

In the formula (10), X ¹¹ and X ¹² are preferably hydrogen atoms or the same substituent. More preferably X ¹¹ and X ¹² are the same substituents, more preferably, X ¹¹ and X ¹² may be the same substituent, a ₂ B- (R ^17A).

  Such a compound is easier to synthesize than the compound (1) in which the structures on the two N atoms on the pyrrolopyrrole ring are asymmetric. In particular, a compound having the same substituent on two N atoms on the pyrrolopyrrole ring is easier to synthesize than compound (1). On the other hand, compounds having the same substituent on two N atoms on the pyrrolopyrrole ring tend to have high crystallinity, but by using together with compound (1), precipitation of crystals during film formation can be suppressed, It is easy to produce a film with suppressed surface roughness.

Specific examples of other pyrrolopyrrole compounds include the following compounds. Further, compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037 to 0052 of JP-A-2011-68731, paragraph numbers 0010 to of international publication WO2015 / 166873 And the like, the contents of which are incorporated herein.

  When the curable composition of the present invention contains another pyrrolopyrrole compound, the content of the other pyrrolopyrrole compound is 0.01 to 50% by mass with respect to the total solid content of the curable composition of the present invention. preferable. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less. Moreover, it is preferable that content of the compound (1) in the total mass of a compound (1) and another pyrrolopyrrole compound is 0.1-99 mass%. The lower limit is preferably 1% by mass, and more preferably 3% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 97% by mass or less. If content of a compound (1) is the said range, it will be easy to manufacture the film | membrane with which surface roughening was suppressed. In addition, the upper limit of the content of the compound (1) in the total mass of the compound (1) and other pyrrolopyrrole compounds can be 60% by mass or less from the viewpoint of cost, and should be 50% by mass or less. It can also be 30 mass% or less.

<< Other near-infrared absorbing compounds >>
The curable composition of the present invention may further include the above-described compound (1) and a near infrared absorbing compound other than the other pyrrolopyrrole compound (also referred to as other near infrared absorbing compound).
Other near infrared absorbing compounds include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, rylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, Examples thereof include azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, copper compounds, and the like. Examples of the squarylium compound include the compounds described in paragraph numbers 0044 to 0049 of JP2011-208101A, the contents of which are incorporated herein. Examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267 and compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040. Incorporated herein. Examples of the diimonium compound include compounds described in JP-T-2008-528706, and the contents thereof are incorporated herein. Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, oxytitanium phthalocyanine described in JP2006-343631A, paragraphs 0013 to 0029 of JP2013-195480A. And the contents of which are incorporated herein. As a naphthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-77153 is mentioned, for example, The content is integrated in this specification. Further, as the cyanine compound, phthalocyanine compound, naphthalocyanine compound, diimonium compound, and squarylium compound, the compounds described in paragraph numbers 0010 to 0081 of JP 2010-1111750 A may be used, and the contents thereof are described in this specification. Incorporated. In addition, as for the cyanine compound, for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. . Examples of the copper complex include a copper complex described in paragraphs 0009 to 0049 of International Publication WO2016 / 068037, a phosphate ester copper complex described in paragraphs 0022 to 0042 of JP2014-41318A, and JP2015. Examples include sulfonic acid copper complexes described in paragraph Nos. 0021 to 0039 of JP-A-430663, and the contents thereof are incorporated herein.

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

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

When the curable composition of the present invention contains another near infrared absorbing compound, the content of the other near infrared absorbing compound is 0.01 to 50 based on the total solid content of the curable composition of the present invention. Mass% is preferred. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.
Moreover, content of the sum total of a compound (1), another pyrrolopyrrole compound, and another near-infrared absorption compound is 0.01-50 mass with respect to the total solid of the curable composition of this invention. % Is preferred. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.

<< Curable compound >>
The curable composition of the present invention contains a curable compound. Examples of the curable compound include a crosslinkable compound and a resin. The resin may be a non-crosslinkable resin (a resin having no crosslinkable group) or a crosslinkable resin (a resin having a crosslinkable group). Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxymethyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The crosslinkable resin (resin having a crosslinkable group) is also a crosslinkable compound.

  In the present invention, it is preferable to use a curable compound containing at least a resin, more preferably a resin and a monomer type crosslinkable compound, and a resin and a group having an ethylenically unsaturated bond. It is more preferable to use a monomer type crosslinkable compound.

  In the curable composition of this invention, it is preferable that content of a curable compound is 0.1-80 mass% with respect to the total solid of a curable composition. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and further preferably 5% by mass or more. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less. Only one type of curable compound 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.

(Crosslinkable compound)
Examples of the crosslinkable compound include a compound having a group having an ethylenically unsaturated bond, a compound having an epoxy group, a compound having a methylol group, and a compound having an alkoxymethyl group. The crosslinkable compound may be a monomer or a resin. A monomer type crosslinkable compound having a group having an ethylenically unsaturated bond can be preferably used as a radical polymerizable compound. Moreover, the compound which has an epoxy group, the compound which has a methylol group, and the compound which has an alkoxymethyl group can be used preferably as a cationically polymerizable compound.

  The molecular weight of the monomer type crosslinkable compound is preferably less than 2000, more preferably 100 or more and less than 2000, and even more preferably 200 or more and less than 2000. The upper limit is preferably 1500 or less, for example. The weight average molecular weight (Mw) of the resin type crosslinkable compound 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.

Examples of the resin type crosslinkable compound include an epoxy resin and a resin containing a repeating unit having a crosslinkable group. Examples of the repeating unit having a crosslinkable group include the following (A2-1) to (A2-4).

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

L ⁵¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or Represents an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof. 1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic. 6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable.

P ¹ represents a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxymethyl group.

  The compound having a group having an ethylenically unsaturated bond is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. As examples of the compound containing a group having an ethylenically unsaturated bond, description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Specific examples 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.) Company-made), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.) ), Dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene group Structure attached via a call residue or propylene glycol residue are preferable. These oligomer types can also be used. Further, refer to the descriptions of paragraph numbers 0034 to 0038 of JP2013-253224A, paragraph number 0477 of JP2012-208494A (paragraph number 0585 of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein. Specific examples of the compound having a group having an ethylenically unsaturated bond include diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available product: M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin Nakamura) Chemical Industry Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA) can also be used. These oligomer types can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

  The compound containing a group having an ethylenically unsaturated bond may further have an acid group such as a carboxyl group, a sulfo group, or a phosphate group. As a commercial item, Toagosei Co., Ltd. Aronix series (for example, M-305, M-510, M-520) etc. are mentioned, for example.

  A compound containing a group having an ethylenically unsaturated bond is also a preferred embodiment of a compound having a caprolactone structure. As the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein. Examples of commercially available products include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd. And TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

  When this invention contains the compound containing the group which has an ethylenically unsaturated bond, content of the compound containing the group which has an ethylenically unsaturated bond is 0.1 with respect to the total solid of a curable composition. % By mass or more is preferable, 0.5% by mass or more is more preferable, 1% by mass or more is further preferable, and 5% by mass or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.

  Examples of the compound having an epoxy group (hereinafter also referred to as an epoxy compound) include a monofunctional or polyfunctional glycidyl ether compound and a polyfunctional aliphatic glycidyl ether compound. Moreover, as an epoxy compound, the compound which has an alicyclic epoxy group can also be used.

  Examples of the epoxy compound include compounds having one or more epoxy groups per molecule. The epoxy compound is preferably a compound having 1 to 100 epoxy groups per 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 epoxy compound may be 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 weight average molecular weight of the epoxy compound is preferably 2000 to 100,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

  Commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Adekaglycilol ED-505 (manufactured by ADEKA Corporation, epoxy group-containing monomer), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, containing epoxy group) Polymer). Moreover, as an epoxy compound, Paragraph Nos. 0034 to 0036 of JP 2013-011869 A, Paragraph Nos. 0147 to 0156 of JP 2014-043556 A, Paragraph Nos. 0085 to 0092 of JP 2014-089408 A are described. The prepared compounds can also be used. These contents are incorporated herein.

When the curable composition of this invention contains an epoxy compound, 0.1 mass% or more is preferable with respect to the total solid of a curable composition, and, as for content of an epoxy compound, 0.5 mass% or more is preferable. More preferably, it is more preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
Moreover, when the curable composition of this invention contains a radically polymerizable compound and an epoxy compound, as for mass ratio of both, radically polymerizable compound: epoxy compound = 100: 1-100: 400 is preferable, and 100: 1 ~ 100: 100 is more preferred.

  Examples of the compound having a methylol group (hereinafter also referred to as a methylol compound) include a compound in which a methylol group is bonded to a carbon atom that forms a nitrogen atom or an aromatic ring. Examples of the compound having an alkoxymethyl group (hereinafter also referred to as an alkoxymethyl compound) include compounds in which an alkoxymethyl group is bonded to a carbon atom that forms a nitrogen atom or an aromatic ring. Compounds having an alkoxymethyl group or a methylol group bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethyl Urea urea, methylolated urea and the like are preferable. In addition, descriptions of paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 0095 to 0126 of JP-A-2014-089408 can be referred to, and the contents thereof are incorporated in this specification.

  When the curable composition of the present invention contains a methylol compound, the content of the methylol compound is preferably 0.1% by mass or more, and 0.5% by mass or more with respect to the total solid content of the curable composition. More preferably, it is more preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.

  When the curable composition of the present invention contains an alkoxymethyl compound, the content of the alkoxymethyl compound is preferably 0.1% by mass or more, based on the total solid content of the curable composition, and 0.5% by mass. The above is more preferable, 1% by mass or more is further preferable, and 5% by mass or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.

(resin)
In the curable composition of the present invention, a resin can be used as the curable compound. It is preferable to use a curable compound containing at least a resin. The resin can also be used as a dispersant. A resin used for dispersing pigments 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 resin having a crosslinkable group also corresponds to a crosslinkable compound.

  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.

  As the resin, (meth) acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin. One of these resins may be used alone, or two or more thereof may be mixed and used. As an epoxy resin, a polymer type compound is mentioned among the compounds illustrated as an epoxy compound demonstrated in the column of the crosslinkable compound mentioned above. Further, as the resin, a resin described in an example of International Publication WO2016 / 086645 and a resin described in an example of JP-A-2006-146619 can also be used.

  The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group. These acid groups may be used alone or in combination of two or more. A resin having an acid group can be preferably used as an alkali-soluble resin. When the curable composition of the present invention contains an alkali-soluble resin, a desired pattern can be formed by alkali development.

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

  The resin having an acid group may further contain a repeating unit having a crosslinkable group. When the resin having an acid group further contains a repeating unit having a crosslinkable group, the content of the repeating unit having a crosslinkable group in all the repeating units is preferably from 10 to 90 mol%. More preferably, it is 90 mol%, and it is further more preferable that it is 20-85 mol%. The content of the repeating unit having an acid group in all repeating units is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and 5 to 30 mol%. Further preferred.

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

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

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

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

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

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

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

  Examples of the resin having an acid group include those described in paragraphs 0558 to 0571 of JP2012-208494A (paragraph numbers 0687 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408. The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification.

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

Examples of the resin having an acid group include resins having the following structure. In the following structural formulas, Me represents a methyl group.

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

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

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

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

The alkyl group represented by R ^{10 to} R ¹³ may be linear, branched or cyclic, and is preferably cyclic. The alkyl group may have a substituent or may be unsubstituted. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. R ¹⁰ to R ¹³ the number of carbon atoms of the aryl group represented by preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹⁰ is preferably a cyclic alkyl group or an aryl group. R ¹¹ and R ¹² are preferably a linear or branched alkyl group. R ¹³ is preferably a linear alkyl group, a branched alkyl group, or an aryl group.

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

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

  The curable composition of this invention can contain a dispersing agent as resin. In particular, when a pigment is used, it is preferable to include a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). The dispersant preferably includes at least an acidic dispersant, and more preferably only an acidic dispersant. When the dispersant contains at least an acidic dispersant, the dispersibility of the pigment is improved, and excellent developability is obtained. For this reason, a pattern can be suitably formed by a photolithography method. In addition, it is preferable that content of an acidic dispersing agent is 99 mass% or more in the total mass of a dispersing agent, for example that a dispersing agent is only an acidic dispersing agent, and shall be 99.9 mass% or more. You can also.

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 carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
The basic 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 exceeds 50 mol% 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.

  The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, a residue generated on the base of the pixel can be further reduced when a pattern is formed by a photolithography method.

The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for the solvent by the graft chain, it is excellent in pigment dispersibility and dispersion stability after aging. Details of the graft copolymer can be referred to the description of paragraph numbers 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein. Specific examples of the graft copolymer include the following resins. The following resins are also resins having acid groups (alkali-soluble resins). Examples of the graft copolymer include resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.

  In the present invention, as the resin (dispersant), it is also preferable to use an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain. A resin having at least one basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

Regarding the oligoimine-based dispersant, the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein. Specific examples of the oligoimine dispersant include the following. The following resins are also resins having acid groups (alkali-soluble resins). Further, as the oligoimine dispersant, resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can also be used.

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

  In the curable composition of the present invention, the resin content is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on the total solid content of the curable composition. 20 mass% or more is especially preferable. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

  When the curable composition of the present invention includes a resin having an acid group, the content of the resin having an acid group is preferably 1% by mass or more and more preferably 5% by mass or more with respect to the total solid content of the composition. Preferably, 10% by mass or more is more preferable, and 20% by mass or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

Further, when the curable composition of the present invention contains a monomer type crosslinkable compound having a group having an ethylenically unsaturated bond and a resin, the monomer type crosslinkable having a group having an ethylenically unsaturated bond is used. The mass ratio of the compound and the resin is preferably a monomer type crosslinkable compound / resin having a group having an ethylenically unsaturated bond = 0.4 to 1.4. The lower limit of the mass ratio is preferably 0.5 or more, and more preferably 0.6 or more. The upper limit of the mass ratio is preferably 1.3 or less, and more preferably 1.2 or less. If the said mass ratio is the said range, it will be easy to form the pattern excellent in the rectangularity.
Further, the mass ratio of the monomer type crosslinkable compound having a group having an ethylenically unsaturated bond and the resin having an acid group is such that the monomer type crosslinkable compound having a group having an ethylenically unsaturated bond / acid group. It is preferable that it is resin = 0.4-1.4. The lower limit of the mass ratio is preferably 0.5 or more, and more preferably 0.6 or more. The upper limit of the mass ratio is preferably 1.3 or less, and more preferably 1.2 or less. If the said mass ratio is the said range, it will be easy to form the pattern excellent in the rectangularity.

<< Photoinitiator >>
The curable composition of the present invention can contain a photoinitiator. Examples of the photoinitiator include a photoradical polymerization initiator and a photocationic polymerization initiator. It is preferable to select and use according to the kind of curable compound. When a radical polymerizable compound is used as the curable compound, it is preferable to use a photo radical polymerization initiator as the photo initiator. When a cationic polymerizable compound is used as the curable compound, it is preferable to use a cationic photopolymerization initiator as the photoinitiator. 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.

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

(Photo radical polymerization initiator)
Examples of the photo radical polymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides. Thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, and the like. Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryls from the viewpoint of exposure sensitivity. Preferred are imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl substituted coumarin compound, oxime compound, α-hydroxyketone compound, α -Compounds selected from aminoketone compounds and acylphosphine compounds are more preferred, and oxime compounds are even more preferred. As a photoinitiator, description of Paragraphs 0065-0111 of Unexamined-Japanese-Patent No. 2014-130173 can be referred, This content is integrated in this specification.

  Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF). Examples of commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819, DAROCUR-TPO (above, manufactured by BASF).

  Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2006-21012. Etc. 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-propionyloxyimibutan-2-one, 2- Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In addition, J.H. C. S. Perkin II (1979, pp. 1653-1660), J. MoI. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP 2000-66385 A, JP 2000-80068 A, Special Table 2004 Examples thereof include compounds described in JP-A-534797 and JP-A-2006-342166. As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF) are also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 (manufactured by ADEKA Corporation), Adeka Arcles NCI-930 (manufactured by ADEKA Corporation), Adeka Optomer N -1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP2012-14052A) can also be used.

  In the present invention, an oxime compound having a fluorene ring can also be used as a radical 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 radical 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. These contents are incorporated herein.

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

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

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

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

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

(Photocationic polymerization initiator)
A photoacid generator is mentioned as a photocationic polymerization initiator. Examples of photoacid generators include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyls that generate acids upon decomposition by light irradiation. Examples thereof include sulfonate compounds such as sulfonate. Regarding the details of the cationic photopolymerization initiator, the description of paragraph numbers 0139 to 0214 of JP-A-2009-258603 can be referred to, and the contents thereof are incorporated herein.

  A commercial item can also be used for a photocationic polymerization initiator. As a commercial item of a photocationic polymerization initiator, Adeka Arkles SP series (for example, Adeka Arkles SP-606 etc.) made from ADEKA Corporation, IRGACURE250, IRGACURE270, IRGACURE290 made from BASF Corporation etc. are mentioned.

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

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

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

  The polyvalent carboxylic acid is a compound having at least two carboxyl groups. In addition, when a geometric isomer or an optical isomer exists in the following compound, it is not particularly limited. As the polyvalent carboxylic acid, a bifunctional to hexafunctional carboxylic acid is preferable, for example, 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid. Alkyltricarboxylic acids such as acid and citric acid; aliphatic cyclic polyvalents such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid Carboxylic acids; Dimers that are multimers of unsaturated fatty acids such as linolenic acid and oleic acid and their reduction products; butanedioic acid, malic acid, hexanedioic acid, pentanedioic acid, heptanedioic acid, octanedioic acid, nonane Linear alkyl diacids such as diacid and decanedioic acid are preferred, butane diacid, hexa Acid, pentanedioic acid, heptanoic acid, octanoic acid, nonanoic acid, decane diacid preferably, particularly butane diacid, heat resistance, and more preferable from the viewpoint of transparency of the film.

  The content of the acid anhydride and polycarboxylic acid is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the epoxy compound. Part is more preferred.

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

  In the curable composition of the present invention, the content of the ultraviolet absorber is preferably 0.01 to 10% by mass, and 0.01 to 5% by mass with respect to the total solid content of the curable composition of the present invention. More preferred. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Chromatic colorant >>
The curable 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 the wavelength range of 400 nm or more and less than 650 nm.

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

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

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

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

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

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

  When the curable composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 60% by mass or less based on the total solid content of the curable composition. 50 mass% or less is more preferable, 30 mass% or less is still more preferable, 20 mass% or less is still more preferable, and 15 mass% or less is especially preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.

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

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

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

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

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

  In formula (B1), X represents an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group, and an acid group or a basic group is preferable. Examples of the acid group include a carboxyl group and a sulfo group. An amino group is mentioned as a basic group.

  Examples of the pigment derivative include, for example, JP-A-56-118462, JP-A-63-264664, JP-A-1-217077, JP-A-3-9961, JP-A-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-10 -30063, JP-A-10-195326, paragraphs 0086 to 0098 of international publication WO2011 / 024896, paragraphs 0063 to 0094 of international publication WO2012 / 102399, etc. can also be used. The contents of which are incorporated herein.

  When the curable composition of this invention contains a pigment derivative, 1-50 mass parts is preferable with respect to 100 mass parts of pigments. 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 may be used, or two or more pigment derivatives may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Solvent >>
The curable composition of the present invention can contain a solvent. Examples of the solvent include organic solvents. The type of the solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons and the like. Regarding these details, paragraph number 0223 of International Publication No. WO2015 / 1666779 can be referred to, the contents of which are incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. In this invention, the organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents may be better reduced for environmental reasons (for example, 50 mass ppm (parts per to the total amount of organic solvent)). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).

  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 10 mass ppb (parts per billion) or less, for example. 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 but 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 curable composition.

<< Polymerization inhibitor >>
The curable composition of the present invention can contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) can be mentioned. Of these, p-methoxyphenol is preferred. As for content of a polymerization inhibitor, 0.001-5 mass% is preferable with respect to the total solid of a curable composition.

<< Silane coupling agent >>
The curable composition of the present invention can contain a silane coupling agent. 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. Examples of functional groups other than hydrolyzable groups include vinyl groups, styryl groups, (meth) acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. (Meth) acryloyl group and epoxy group are preferable. Examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. Incorporated herein.

  0.01-15.0 mass% is preferable with respect to the total solid of a curable composition, and, as for content of a silane coupling agent, 0.05-10.0 mass% is more preferable. Only one type of silane coupling agent 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.

<< Surfactant >>
The curable composition of the present invention may contain a surfactant. 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. As for the surfactant, paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, and the contents thereof are incorporated herein.

  In the present invention, the surfactant is preferably a fluorosurfactant. By including a fluorinated surfactant in the curable composition of the present invention, liquid properties (particularly fluidity) can be further improved, and liquid-saving properties can be further improved. In addition, a film with small thickness unevenness can be formed.

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

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

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

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

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

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

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

  0.001 mass%-5.0 mass% are preferable with respect to the total solid of the curable composition of this invention, and, as for content of surfactant, 0.005-3.0 mass% is more preferable. Only one type of surfactant 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 curable 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, if necessary). Agents, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, and the like. Properties such as film properties can be adjusted by appropriately containing these components. 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. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP 2011-90147 A), a thioether compound, or the like can be used. Examples of commercially available products include ADEKA Corporation's ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330). The content of the antioxidant is preferably 0.01 to 20% by mass and more preferably 0.3 to 15% by mass with respect to the total solid content of the curable composition of the present invention. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

  The viscosity (23 ° C.) of the curable composition of the present invention is preferably 1 to 100 mPa · s, for example, when a film is formed by coating. 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.

  The solid content concentration of the curable composition of the present invention is changed depending on the coating method or the like, but is preferably 1 to 50% by 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.

  There is no limitation in particular as a storage container of the curable composition of this invention, A well-known storage container can be used. In addition, as a storage container, in order to suppress impurities from being mixed into raw materials and compositions, the inner wall of the container is made into a seven-layer structure using a multilayer bottle composed of six types and six layers of resin and six types of resin. It is also preferred to use bottles. An example of such a container is a container described in JP-A-2015-123351.

  The use of the curable composition of the present invention is not particularly limited. For example, it can be preferably used to form a near infrared cut filter. Moreover, in the curable composition of this invention, the infrared rays transmission filter which can permeate | transmit only the near infrared rays more than a specific wavelength can also be formed by containing the coloring material which shields visible light further.

<Method for preparing curable composition>
The curable composition of the present invention can be prepared by mixing the aforementioned components. In preparing the curable composition, all components may be simultaneously dissolved or dispersed in a solvent to prepare a curable composition. If necessary, two or more solutions or appropriate combinations of each component may be prepared. A curable composition may be prepared by preparing a dispersion in advance and mixing these at the time of use (at the time of application).

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

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

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

<Membranes and laminates>
Next, the film of the present invention will be described. The film of the present invention is obtained from the curable composition of the present invention described above. The film of the present invention can be preferably used as a near-infrared cut filter or an infrared transmission filter. It can also be used as a heat ray shielding filter. The film of the present invention may have a pattern, or may be a film without a pattern (flat film). The film of the present invention may be used by being laminated on a support, or the film of the present invention may be peeled off from a support. When the film of the present invention is used as an infrared transmission filter, examples of the infrared transmission filter include a filter that blocks visible light and transmits light having a wavelength of 900 nm or more. When the film of the present invention is used as an infrared transmission filter, the above-described compound (1) and a colorant that shields visible light (preferably a colorant containing two or more chromatic colorants, or Or a filter using a composition containing an organic black colorant) or a layer of a colorant that blocks visible light in addition to the layer containing the compound (1) It is preferable that When the film of the present invention is used as an infrared transmission filter, the compound (1) has a role of limiting transmitted light (near infrared rays) 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.

  Moreover, the laminated body of this invention has the film | membrane and color filter of this invention. In the laminated body, the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction. When the film of the present invention and the color filter are not adjacent 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. A color filter can be manufactured using the coloring composition containing a chromatic colorant. As a chromatic colorant, the chromatic colorant demonstrated as what is contained in the curable composition of this invention is mentioned. The coloring composition can further contain a curable compound (resin, radical polymerizable compound, etc.), a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber and the like. About these details, the material demonstrated as what is contained in the curable composition of this invention is mentioned, These can be used similarly.

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

  When the film of the present invention is used as a near-infrared cut filter, the film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 700 to 1000 nm. The average transmittance at a wavelength of 400 to 550 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more. Moreover, it is preferable that the transmittance | permeability in the full range of wavelength 400-550 nm is 70% or more, It is more preferable that it is 80% or more, It is still more preferable that it is 90% or more. Moreover, although the preferable range of the infrared shielding property of a near-infrared cut filter changes with uses, it is preferable that the transmittance | permeability in at least 1 point of the range of wavelength 700-1000 nm is 20% or less, and 15% or less is more preferable, 10% or less is more preferable.

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

  The 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.

<Method for producing membrane>
Next, the manufacturing method of the film | membrane of this invention is demonstrated. The film | membrane of this invention can be manufactured through the process of apply | coating the curable composition of this invention.

  In the method for producing a film of the present invention, the curable composition is preferably applied on a support. Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, or quartz glass. These substrates may be formed with an organic film, an inorganic film, or the like. Examples of the material for the organic film include the resins described in the column of the curable composition described above. Further, as the support, a substrate made of a resin can be used. The support may be formed with a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like. The support may be formed with a black matrix that isolates each pixel. In addition, 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, if necessary. In the case where a glass substrate is used as the support, it is preferable to use an inorganic film formed on the glass substrate or dealkalized on the glass substrate.

  As a method for applying the curable composition, 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 “Spreading and usable ink jet-unlimited possibilities in patents, published in February 2005, Sumibe Techno Research” (particularly from page 115) 133), JP2003-262716A, JP2003-185831A, JP2003-261627A, JP2012-126830A, JP2006-169325A, and the like. Can be mentioned.

The composition layer formed by applying the curable composition may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. By performing the pre-baking temperature at 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, the characteristics of the organic material can be more effectively maintained.
The pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.

  The film manufacturing method of the present invention may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method. Note that in the case where the film of the present invention is used as a flat film, a step of forming a pattern may not be performed. Hereinafter, the process of forming a pattern will be described in detail.

(When forming a pattern by photolithography)
The pattern formation method by the photolithography method includes a step of exposing the composition layer formed by applying the curable composition of the present invention (exposure step), and developing and removing the composition layer in the unexposed area. And a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-bake step) may be provided. Hereinafter, each step will be described.

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

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

  Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate And inorganic alkaline compounds such as. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Further, a surfactant may be used for the developer. Examples of the surfactant include the surfactant described as being contained in the curable composition described above, and a nonionic surfactant is preferable. The developer may be once manufactured as a concentrated solution and diluted to a necessary concentration at the time of use from the viewpoint of convenience of transportation and storage. Although a dilution rate is not specifically limited, For example, it can set to the range of 1.5-100 times. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) with a pure water after image development.

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

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

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

  When the film of the present invention is used as a near-infrared cut filter, in addition to the film of the present invention, it may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. When the near-infrared cut filter further has a copper-containing layer and / or a dielectric multilayer film, a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be easily obtained. Moreover, it can be set as the near-infrared cut filter excellent in ultraviolet-shielding property because a near-infrared cut filter has an ultraviolet absorption layer further. As the ultraviolet absorbing layer, for example, the absorbing layer described in Paragraph Nos. 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 090960 can be referred to, and the contents thereof are incorporated herein. As the dielectric multilayer film, the description of paragraph numbers 0255 to 0259 of JP 2014-41318 A can be referred to, and the contents thereof are incorporated in the present specification. As a layer containing copper, the glass base material (copper containing glass base material) comprised with the glass containing copper and the layer (copper complex containing layer) containing a copper complex can also be used. Examples of the copper-containing glass substrate include a phosphate glass containing copper and a fluorophosphate glass containing copper. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott Co., Ltd.), CD5000 (manufactured by HOYA Corporation), and the like. Examples of the copper complex include the compounds described in paragraph numbers 0009 to 0049 of International Publication No. WO2016 / 068037, the contents of which are incorporated herein.

  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 curable composition of the present invention, and only one of the filters is used as the curable composition of the present invention. It can also be formed.

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

  On the support, there are a plurality of photodiodes that constitute the light receiving area of the solid-state imaging device, and transfer electrodes made of polysilicon, etc., and light shielding made of tungsten or the like that opens only the light receiving part of the photodiodes on the photodiodes and transfer electrodes. A device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light shielding film and the photodiode light receiving portion on the light shielding film, and the film in the present invention on the device protective film. is there. Furthermore, it is on the device protective film and has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) under the film in the present invention (on the side close to the support), or on the film in the present invention. The structure etc. which have a means may be sufficient. In addition, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. In this case, the partition wall preferably has a lower refractive index than each 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 image display device of the present invention includes the film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For the definition and details of image display devices, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute, 1990)”, “Display Device (written by Junaki Ibuki, published in 1989 by Sangyo Tosho) ) "Etc. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”. The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. The spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.

<Infrared sensor>
The infrared sensor of the present invention includes the above-described film of the present invention. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of an infrared sensor of the present invention will be described with reference to the drawings.

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

  The near-infrared cut filter 111 can be formed using the curable composition of the present invention. The spectral characteristic of the near-infrared cut filter 111 is selected according to the emission wavelength of the infrared light-emitting diode (infrared LED) to be used.

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

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

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

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

  In the infrared sensor shown in FIG. 1, a near-infrared cut filter (another near-infrared cut filter) different from the near-infrared cut filter 111 may be further disposed on the planarizing layer 116. Other near infrared cut filters include those having a layer containing copper and / or a dielectric multilayer film. About these details, what was mentioned above is mentioned. Further, as another near infrared cut filter, a dual band pass filter may be used.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis example>
(Synthesis Example of Compound P-19)
Compound P-19 was synthesized according to the following scheme. 10 parts by mass of Compound A shown in the following scheme and 4.8 parts by mass of 2- (2-benzothiazolyl) acetonitrile are heated and stirred in 200 parts by mass of toluene, and then 10.5 parts by mass of phosphorus oxychloride. And heated to reflux for 4 hours. After the reaction, the mixture was cooled to room temperature, 200 parts by mass of methanol was added, and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were separated by filtration and washed with 400 parts by mass of methanol. The obtained crystal was blown and dried at 50 ° C. for 12 hours to obtain 8.1 parts by mass of Compound B.
To 70 parts by mass of toluene containing 0.9 part by mass of 2-aminoethyl diphenylborinate, 1.3 parts by mass of titanium chloride was added and stirred at 35 ° C. for 30 minutes. Next, 5 parts by mass of Compound B was added, and the mixture was further stirred under heating under reflux conditions for 3 hours. The mixture was cooled to room temperature, 140 parts by mass of methanol was added, and the mixture was further stirred for 30 minutes. The precipitated crystals were collected by filtration and purified by silica column chromatography (chloroform solvent) to obtain 1.3 parts by mass of Compound P-19.
The mass spectrum of the obtained compound was as follows.
Mass spectrum: M + = 1357.9

<Test Example 1>
The solubility of the compounds shown in the following table in cyclohexanone was observed and evaluated.
A: The solubility of the compound with respect to 100 g of cyclohexanone at 23 ° C. is 1 g or more.
B: The solubility of the compound with respect to 100 g of cyclohexanone at 23 ° C. is 0.1 g or more and less than 1 g.
C: The solubility of the compound in 100 g of cyclohexanone at 23 ° C. is less than 0.1 g.

  As shown in Table 2, Examples 1 to 3 using compounds P-1, P-8, and P-9, which are compounds with asymmetric structures on two N atoms on the pyrrolopyrrole ring, were dissolved. The property was good.

In addition, the compounds P-1, P-8, and P-9 in the above table are the compounds listed in Table 1 as specific examples of the compound (1). Compounds R-1 and R-2 are compounds having the following structures.

<Test Example 2>
The following raw materials were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to produce a curable composition. In Example 129, a mixture of P-19 and P-56 (P-19 / P-56 = 50/50 (mass ratio)) was used as the compound. In Example 130, a mixture of P-47 and P-56 (P-47 / P-56 = 80/20 (mass ratio)) was used as the compound. In Example 131, a mixture of P-10 and P-42 (P-10 / P-42 = 60/40 (mass ratio)) was used as a compound. In Example 132, a mixture of P-10 and S-1 (P-10 / S-1 = 10/90 (mass ratio)) was used as the compound. In Example 133, a mixture of P-19 and S-2 (P-19 / S-2 = 5/95 (mass ratio)) was used as the compound. In Example 134, a mixture of P-42 and S-3 (P-42 / S-3 = 20/80 (mass ratio)) was used as a compound. In Example 135, a mixture of P-47 and S-4 (P-47 / S-4 = 15/85 (mass ratio)) was used as a compound. In Example 136, a mixture of P-56 and S-5 (P-56 / S-5 = 10/90 (mass ratio)) was used as the compound.

架橋性モノマー１（ジペンタエリスリトールヘキサアクリレート（日本化薬社製、ＫＡＹＡＲＡＤ ＤＰＨＡ））・・・・・１．２８質量部
光重合開始剤（下記構造の化合物）・・・・１．４０質量部

界面活性剤１（メガファックＲＳ−７２−Ｋ（ＤＩＣ製、３０％プロピレングリコールモノメチルエーテルアセテート溶液））
・・・・・１．５９質量部
シクロペンタノン・・・・・８６．３質量部 (Curable composition)
Compounds shown in the following table: 1.92 parts by mass Resin 1 (resin having the following structure, Mw = 40,000): 7.51 parts by mass

Crosslinkable monomer 1 (dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA)) ... 1.28 parts by weight Photopolymerization initiator (compound having the following structure) ... 1.40 parts by weight

Surfactant 1 (Megafac RS-72-K (manufactured by DIC, 30% propylene glycol monomethyl ether acetate solution))
・ ・ ・ ・ ・ 1.59 parts by mass Cyclopentanone 86.3 parts by mass

(Evaluation of surface roughness)
Each curable composition was spin-coated on a glass substrate so that the film thickness after film formation was 1.0 μm to form a coating film. Then, after heating at 100 ° C. for 2 minutes using a hot plate, the entire surface was exposed at an exposure amount of 1000 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Subsequently, it heated for 5 minutes (post-baking) at 200 degreeC using the hotplate, and the film | membrane was manufactured. The manufactured film was subjected to heat treatment at 230 ° C. for 30 minutes, and the heat-treated film was subjected to heat treatment at 200 times bright field using an optical microscope (Olympus MX-61L). It was observed for unevenness and crystal precipitation. When unevenness and crystal precipitation are not confirmed by an optical microscope and the film is a uniform film, it is determined that the resistance to thermal stress during the heat treatment is excellent.
A: Unevenness and crystal precipitation are not observed.
B: Slight unevenness or crystal precipitation is observed C: Strong unevenness is observed or crystals are vigorously precipitated.

  As shown in the above table, surface roughness of the films using the curable compositions of the examples was suppressed. In addition, as described in Examples 129 to 131, even when two types of compounds having asymmetric structures on two N atoms on the pyrrolopyrrole ring are used in combination, surface roughness can be effectively suppressed. I was able to. In addition, as shown in Examples 132 to 136, a compound having an asymmetric structure on two N atoms on the pyrrolopyrrole ring and a compound having a symmetrical structure on two N atoms on the pyrrolopyrrole ring were used in combination. Even in this case, surface roughness could be effectively suppressed. On the other hand, Comparative Examples 101 and 102 using only compounds having symmetrical structures on two N atoms on the pyrrolopyrrole ring were inferior in surface roughness.

An infrared transmission filter that selectively transmits predetermined infrared rays can be produced by further blending a coloring material that blocks visible light into the curable composition. The same effect can be obtained by further blending a pigment derivative.
In the above curable composition, the same effect can be obtained by replacing the types of the resin, the crosslinkable monomer, the photopolymerization initiator, the surfactant and the solvent with the compounds described in the present specification.

In the above table, compounds P-1, P-6, P-9, P-10, P-11, P-19, P-20, P-22, P-24, P-26, P-27, P-29, P-37, P-40, P-42, P-45, P-46, P-47, P-48, P-50, P-51, P-54, P-55, P- 56, P-57, P-59, P-60, P-63, and P-75 are the compounds listed in Table 1 as specific examples of the compound (1). Compounds R-1 and R-2 are compounds having the structure described above. Compounds S-1 to S-5 are compounds having the following structures.

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

Claims (16)

A curable composition comprising a compound represented by the following formula (1) and a curable compound;

In the formula, R ¹ and R ² each independently represents an alkyl group, an aryl group or a heteroaryl group;
R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring;
X ¹ and X ² each independently represent a hydrogen atom or a substituent, and an atom bonded to the N atom on the pyrrolopyrrole ring in formula (1) of X ¹ and pyrrolo in formula (1) of X ² The N atom on the pyrrole ring is different from the atom bonded to it. In the formula (1), X ¹ and X ² are each independently a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a heteroaryl group, (R ^7A ) ₂ B—, (R ^7B ) ₂ P—, (R ^7C ) ₃ Si—, (R ^7D ) _n M ¹ — or M ² —, R ^{7A to} R ^7D each independently represents a hydrogen atom or a substituent, 4 represents an integer of 4, M ¹ represents an n + 1 valent metal atom, M ² represents a monovalent metal atom,
X ¹ is _{^{(R 7A) 2 B -,}} (R 7B) 2 P -, (R 7C) 3 Si -, (R 7D) n M 1 - or M ² - may represent, X ¹ is R ^2, R ³ and R ⁴ may be bonded at least one covalent or coordinate,
X ² is _{^{(R 7A) 2 B -,}} (R 7B) 2 P -, (R 7C) 3 Si -, (R 7D) n M 1 - or M ² - may represent, X ² is R ^1, R ⁵ and at least one covalent bond or may be coordinated with the binding of R ^6,
The curable composition according to claim 1. In the formula (1), either one of X ¹ and X ^2, (R ^7A) ₂ represents a B-, curable composition according to claim 2. The curing according to claim 2 or 3, wherein in formula (1), any one of X ¹ and X ² represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group or a heteroaryl group. Sex composition. Furthermore, the curable composition of any one of Claims 1-4 containing the compound represented by following formula (10);

In the formula, R ¹¹ and R ¹² each independently represents an alkyl group, an aryl group or a heteroaryl group;
R ^{13 to} R ¹⁶ each independently represents a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ , and R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring;
X ¹¹ and X ¹² each independently represent a hydrogen atom or a substituent, and an atom bonded to an N atom on the pyrrolopyrrole ring in the formula (10) of X ¹¹ and a pyrrolo in the formula (10) of X ¹² The atom bonded to the N atom on the pyrrole ring is the same. The curable composition according to claim 5, wherein in the formula (10), X ¹¹ and X ¹² are hydrogen atoms or the same substituent. In the formula (10), X ¹¹ and X ¹² are the same substituents, (R ^17A) ₂ B- represents, R ^17A represents a hydrogen atom or a substituent, curability of claim 5 Composition.   Furthermore, the curable composition of any one of Claims 1-7 containing a chromatic colorant.   Furthermore, the curable composition of any one of Claims 1-7 containing the coloring material which permeate | transmits infrared rays and shields visible light.   The film | membrane obtained from the curable composition of any one of Claims 1-9.   An optical filter having the film according to claim 10.   The optical filter according to claim 11, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter.   A laminate comprising the film according to claim 10 and a color filter.   A solid-state imaging device having the film according to claim 10.   An image display device comprising the film according to claim 10.   An infrared sensor having the film according to claim 10.

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