JP2023057054A - Composition and ink composition - Google Patents

Abstract

To suppress increase in viscosity of an ink composition over time.SOLUTION: There is provided a polymer composition which contains two or more polymer compounds each comprising a constituent unit represented by a formula (I). At least one polymer compound among the two or more polymer compounds is a polymer compound having a terminal structure represented by a formula (II), and a ratio of peak intensity derived from the terminal structure represented by a formula (II) to peak intensity derived from main chains is 3.7% or less as measured by infrared spectroscopy. (In formulae (I) and (II), A, B and Y are defined separately.)SELECTED DRAWING: Figure 1

Description

The present invention relates to a composition, and more particularly to an ink composition for forming a functional layer of a photoelectric conversion element.

Photoelectric conversion elements are attracting attention because they are extremely useful devices from the viewpoint of, for example, energy saving and reduction of carbon dioxide emissions.

In the production of a photoelectric conversion element, for example, a photodetector (OPD), a manufacturing method of forming functional layers such as an active layer, an electron transport layer, and a hole transport layer by a coating method of coating an ink composition onto an object to be coated. is applied (see Non-Patent Document 1).

Strobel 2019 Flex. Print. Electron. 4 043001

In the method for producing a photoelectric conversion element as described above, for example, even when the ink composition is applied under the same coating conditions, if the viscosity of the ink composition changes, the thickness of the formed functional layer will not be uniform. In some cases, the characteristics of the manufactured photoelectric conversion element may vary, or the desired characteristics may not be obtained.

（式（Ｉ）中、
Ａは、置換基を有していてもよい２価の有機基を表し、
Ｂは、チアジアゾール骨格、オキサジアゾール骨格、又はトリアゾール骨格を含む環構造を表し、
Ｙは、－ＣＨ－で表される基又は窒素原子を表す。）

（式（ＩＩ）中、
Ｂ及びＹは、前記定義のとおりである。）
［２］ 赤外分光法により測定したときの全ての高分子化合物に含まれる主鎖由来のピーク強度に対する前記式（ＩＩ）で表される末端構造に由来するピーク強度の前記割合が２％以下である、［１］に記載の組成物。
［３］ 前記Ａが、下記式（ＩＶ）で表される２価の有機基である、［１］又は［２］に記載の組成物。

（式（ＩＶ）中、
Ａｒ^２及びＡｒ^３は、それぞれ独立して、置換基を有していてもよい３価の芳香族複素環基を表し、
Ｚは下記式（Ｚ－１）～式（Ｚ－７）のいずれか１つで表される基を表す。）

（式（Ｚ－１）～（Ｚ－７）中、Ｒは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい１価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
－Ｃ（＝Ｏ）－Ｒ^ｃで表される基、又は
－ＳＯ_２－Ｒ^ｄで表される基を表し、
Ｒ^ｃ及びＲ^ｄは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい１価の複素環基を表す。
式（Ｚ－１）～式（Ｚ－７）中、Ｒが２つある場合、２つあるＲは同一であっても異なっていてもよい。）
［４］ 前記Ｂがチアジアゾール骨格を含む、［１］～［３］のいずれか１つに記載の組成物。
［５］ 前記Ａがチオフェン骨格を含む、［１］～［４］のいずれか１つに記載の組成物。
［６］ 有機溶媒をさらに含み、該有機溶媒が芳香族炭化水素を含む、［１］～［５］のいずれか１つに記載の組成物。
［７］ ［１］～［６］のいずれか１つに記載の組成物と、ｎ型半導体材料とを含む、インク組成物。
［８］ ［７］に記載のインク組成物を固化した固化膜。
［９］ ［８］に記載の固化膜を活性層として含む、光電変換素子。
［１０］ アルコール類を含まない溶媒を重合溶媒として用いる重合工程を含む、［１］～［６］のいずれか１つに記載の組成物の製造方法。
［１１］ 前記重合溶媒としてケトン溶媒を用いる、［１０］に記載の組成物の製造方法。 The present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by paying attention to the terminal structure of the polymer compound contained in the ink composition, and completed the present invention. reached.
That is, the present invention provides the following [1] to [11].
[1] contains two or more polymer compounds containing structural units represented by the following formula (I),
At least one of the two or more polymer compounds is a polymer compound having a terminal structure represented by the following formula (II) bonded to a divalent organic group represented by A,
The ratio of the peak intensity derived from the terminal structure represented by the following formula (II) to the peak intensity derived from the main chain contained in all polymer compounds measured by infrared spectroscopy is 3.7% or less. ,Composition.

(In formula (I),
A represents a divalent organic group which may have a substituent,
B represents a ring structure containing a thiadiazole skeleton, an oxadiazole skeleton, or a triazole skeleton,
Y represents a group represented by -CH- or a nitrogen atom. )

(In formula (II),
B and Y are as defined above. )
[2] The ratio of the peak intensity derived from the terminal structure represented by the formula (II) to the peak intensity derived from the main chain contained in all polymer compounds when measured by infrared spectroscopy is 2% or less. The composition according to [1].
[3] The composition according to [1] or [2], wherein A is a divalent organic group represented by the following formula (IV).

(In formula (IV),
Ar ² and Ar ³ each independently represent an optionally substituted trivalent aromatic heterocyclic group,
Z represents a group represented by any one of the following formulas (Z-1) to (Z-7). )

(In the formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^c or a group represented by —SO ₂ —R ^d ,
R ^c and R ^d are each independently
hydrogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
In formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different. )
[4] The composition according to any one of [1] to [3], wherein B contains a thiadiazole skeleton.
[5] The composition according to any one of [1] to [4], wherein A contains a thiophene skeleton.
[6] The composition according to any one of [1] to [5], further comprising an organic solvent, wherein the organic solvent comprises an aromatic hydrocarbon.
[7] An ink composition comprising the composition according to any one of [1] to [6] and an n-type semiconductor material.
[8] A solidified film obtained by solidifying the ink composition according to [7].
[9] A photoelectric conversion device comprising the solidified film according to [8] as an active layer.
[10] A method for producing the composition according to any one of [1] to [6], including a polymerization step using a solvent that does not contain alcohols as a polymerization solvent.
[11] The method for producing a composition according to [10], wherein a ketone solvent is used as the polymerization solvent.

According to the composition of the present invention, it is possible to suppress an increase in viscosity over time in an ink composition for forming a functional layer of a photoelectric conversion element.

FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element. FIG. 2 is a diagram schematically showing a configuration example of an image detection unit. FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit. FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging apparatus. FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device. FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF rangefinder.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that the drawings only schematically show the shape, size and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited by the following description, and each component can be changed as appropriate without departing from the gist of the present invention. In the drawings used for the following description, the same components are denoted by the same reference numerals, and redundant description may be omitted. Also, the configuration according to the embodiment of the present invention is not necessarily used in the illustrated arrangement.

1. Explanation of Common Terms As used herein, the term “polymer compound” means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 ³ or more and 1×10 ⁸ or less. The constituent units contained in the polymer compound are 100 mol % in total.

As used herein, the term "constituent unit" means a unit that exists at least one in a polymer compound and is derived from a monomer compound (monomer).

As used herein, a "hydrogen atom" may be either a protium atom or a deuterium atom.

As used herein, examples of "halogen atoms" include fluorine, chlorine, bromine and iodine atoms.

In the "optionally substituted" aspect, when all hydrogen atoms constituting the compound or group are unsubstituted, and when one or more hydrogen atoms are partially or entirely substituted by a substituent Both aspects are included.

Examples of substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, aryloxy groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, cyano groups, alkylsulfonyl groups, and nitro groups. .

In this specification, the "alkyl group" may have a substituent. An "alkyl group" may be linear, branched, or cyclic, unless otherwise specified. The number of carbon atoms in the linear alkyl group is generally 1-50, preferably 1-30, more preferably 1-20, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, not including the number of carbon atoms in substituents.

Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl, 2-ethylbutyl, n- hexyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, cyclohexylethyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, adamantyl group, n-decyl group, 3,7-dimethyl Unsubstituted alkyl groups such as octyl group, 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group; trifluoromethyl group, pentafluoroethyl group , perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-di-n-hexylphenyl)propyl group, Substituted alkyl groups such as 6-ethyloxyhexyl group are included.

A "cycloalkyl group" may be a monocyclic group or a polycyclic group. A cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituents.

Examples of cycloalkyl groups include unsubstituted alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl groups, and hydrogen atoms in these groups are alkyl groups, alkyloxy groups, and aryl groups. , a group substituted with a substituent such as a fluorine atom.

Specific examples of substituted cycloalkyl groups include a methylcyclohexyl group and an ethylcyclohexyl group.

An "alkenyl group" may be linear or branched. The alkenyl group may have a substituent. The number of carbon atoms in the alkenyl group is usually 2-30, preferably 2-20, not including the number of carbon atoms in the substituents.

Examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, Alkenyl groups having no substituents such as 7-octenyl groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms are included.

A "cycloalkenyl group" may be a monocyclic group or a polycyclic group. A cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituents.

Examples of cycloalkenyl groups include unsubstituted cycloalkenyl groups such as cyclohexenyl groups, and hydrogen atoms in these groups are substituted groups such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. Substituted groups are included.

Examples of substituted cycloalkenyl groups include methylcyclohexenyl and ethylcyclohexenyl groups.

An "alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms in the alkynyl group is usually 2-30, preferably 2-20, not including the number of carbon atoms in the substituents.

Examples of alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl and 5-hexynyl groups. and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms.

A "cycloalkynyl group" may be a monocyclic group or a polycyclic group. A cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group is usually 4-30, preferably 4-20, not including the number of carbon atoms in the substituents.

Examples of cycloalkynyl groups include unsubstituted cycloalkynyl groups such as cyclohexynyl groups, and hydrogen atoms in these groups substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups and fluorine atoms. groups.

Examples of substituted cycloalkynyl groups include methylcyclohexynyl and ethylcyclohexynyl groups.

An "alkyloxy group" may be linear or branched. The alkyloxy group may have a substituent. The number of carbon atoms in the alkyloxy group is generally 1-30, preferably 1-20, not including the number of carbon atoms in the substituent.

Examples of alkyloxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryloxy group, etc. Alkyloxy groups having no substituents, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms are included.

The cycloalkyl group included in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. A cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituent.

Examples of cycloalkyloxy groups include unsubstituted cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy, and hydrogen atoms in these groups are fluorine atoms, alkyl groups, and the like. A group substituted with a substituent can be mentioned.

An "alkylthio group" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms in the alkylthio group is generally 1-30, preferably 1-20, not including the number of carbon atoms in the substituent.

Examples of optionally substituted alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, 3-heptyldodecylthio group, laurylthio group, and a trifluoromethylthio group.

The cycloalkyl group of the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. A cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituent.

A cyclohexylthio group is mentioned as an example of the cycloalkylthio group which may have a substituent.

"P-valent aromatic carbocyclic group" means the remaining atomic group excluding p hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon optionally having a substituent. do. The p-valent aromatic carbocyclic group may further have a substituent.

"Aryl group" means a monovalent aromatic carbocyclic group. The aryl group may have a substituent. The number of carbon atoms in the aryl group is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.

Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, Aryl groups having no substituents such as 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group and 4-phenylphenyl group, and hydrogen atoms in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

The "aryloxy group" may have a substituent. The number of carbon atoms in the aryloxy group is generally 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.

Examples of aryloxy groups include phenoxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, 1-anthracenyloxy groups, 9-anthracenyloxy groups, 1-pyrenyloxy groups, and the like. Examples include aryloxy groups and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups and fluorine atoms.

The "arylthio group" may have a substituent. The number of carbon atoms in the arylthio group is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.

Examples of optionally substituted arylthio groups include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenyl A thio group can be mentioned. "C1-C12" means that the group immediately following it has 1-12 carbon atoms. Furthermore, "Cm-Cn" indicates that the number of carbon atoms in the group immediately following it is from m to n. The same applies hereinafter.

"p-valent heterocyclic group" (p represents an integer of 1 or more.) is a hydrogen directly bonded to a carbon atom or heteroatom constituting a ring from a heterocyclic compound optionally having a substituent It means an atomic group remaining excluding p hydrogen atoms among atoms. A "p-valent heterocyclic group" includes a "p-valent aromatic heterocyclic group". "p-valent aromatic heterocyclic group", from an optionally substituted aromatic heterocyclic compound, p It means the remaining atomic groups excluding hydrogen atoms.

Aromatic heterocyclic compounds include not only compounds in which the heterocycle itself exhibits aromaticity, but also compounds in which an aromatic ring is fused to a heterocycle, even if the heterocycle itself does not exhibit aromaticity. be.

Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocyclic ring itself does not show aromaticity and the aromatic ring is fused to the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyrans.

The p-valent heterocyclic group may have a substituent. The number of carbon atoms in the p-valent heterocyclic group is usually 2 to 60, preferably 2 to 20, not including the number of carbon atoms in the substituents.

Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group), monovalent Examples include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.

A "substituted amino group" means an amino group having a substituent. Alkyl groups, aryl groups, and monovalent heterocyclic groups are preferred as the substituents possessed by the amino group. The number of carbon atoms in the substituted amino group is usually 2-30 not including the number of carbon atoms in the substituent.

Examples of substituted amino groups include dialkylamino groups (eg, dimethylamino group, diethylamino group), diarylamino groups (eg, diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl ) amino group and bis(3,5-di-tert-butylphenyl)amino group).

The "acyl group" may have a substituent. The number of carbon atoms in the acyl group is usually 2-20, preferably 2-18, not including the number of carbon atoms in the substituents. Specific examples of acyl groups include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups.

The term “imine residue” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound. An "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atoms bonded to the nitrogen atoms that constitute the carbon atom-nitrogen double bonds in aldimines are substituted with substituents such as alkyl groups. be done.

The number of carbon atoms in the imine residue is generally 2-20, preferably 2-18. Examples of imine residues include groups represented by the following structural formulas.

An "amide group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an amide. The amide group usually has about 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

The "acid imide group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is generally 4-20. Specific examples of acid imide groups include groups shown below.

"Substituted oxycarbonyl group" means a group represented by R'-O-(C=O)-. Here, R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.
The substituted oxycarbonyl group usually has 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms.

Specific examples of substituted oxycarbonyl groups include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group. group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, tri fluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl, and pyridyloxycarbonyl groups.

An "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group is usually 1-30, not including the number of carbon atoms in the substituents. Specific examples of alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, and dodecylsulfonyl groups.

The "divalent organic group" may be linear, branched or cyclic. Examples of divalent organic groups include divalent linear aliphatic hydrocarbon groups, divalent branched aliphatic hydrocarbon groups, divalent cyclic hydrocarbon groups, divalent aromatic hydrocarbon groups, Divalent heterocyclic groups and divalent aromatic heterocyclic groups are included. When the "divalent organic group" includes a cyclic structure, the "divalent organic group" may include a condensed ring structure and a bridged structure.

"*" attached to the chemical formula represents a bond.

A “π-conjugated system” means a system in which π electrons are delocalized across multiple bonds.

"(Meth)acrylic" includes acrylic, methacrylic, and combinations thereof.

In the present embodiment, the "ink composition" means a liquid composition used in the coating method, and is not limited to colored liquids. Also, the “coating method” means a method of forming a film using a liquid substance represented by an ink composition.

In the present embodiment, the “composition” and “ink composition” may be a solution or a dispersion liquid such as a dispersion liquid, an emulsion (emulsion), or a suspension (suspension).

2. Composition The composition of the present embodiment contains two or more polymer compounds containing structural units represented by the following formula (I),
At least one of the two or more polymer compounds is a polymer compound having a terminal structure represented by the following formula (II) bonded to a divalent organic group represented by A,
The ratio of the peak intensity derived from the terminal structure represented by the following formula (II) to the peak intensity derived from the main chain contained in all polymer compounds measured by infrared spectroscopy is 3.7% or less. , the composition.

In formula (I),
A represents a divalent organic group which may have a substituent,
B represents a ring structure containing a thiadiazole skeleton, an oxadiazole skeleton, or a triazole skeleton,
Y represents a group represented by -CH- or a nitrogen atom.

In formula (II),
B and Y are as defined above.

As described above, the composition of the present embodiment contains two or more polymer compounds. Polymeric compounds that may be included in the composition are typically p-type semiconductor materials. The composition of the present embodiment preferably further contains an organic solvent. Details of the polymer compound and the organic solvent that can be contained in the composition of the present embodiment will be described later.

3. Ink Composition The ink composition of the present embodiment may further contain an n-type semiconductor material in addition to the "composition" already described. That is, the ink composition of the present embodiment preferably contains two or more polymer compounds that are p-type semiconductor materials, an organic solvent, and an n-type semiconductor material.

The ink composition of the present embodiment is assumed to be an ink composition for manufacturing a photoelectric conversion element, preferably an ink composition for forming an active layer, which is a functional layer.

Components that can be included in the “composition” and “ink composition” of the present embodiment are specifically described below.

In this embodiment, the p-type semiconductor material can include two or more electron-donating polymeric compounds, and the n-type semiconductor material can include at least one electron-accepting compound.

Whether the semiconductor material contained in the ink composition functions as a p-type semiconductor material or an n-type semiconductor material is relatively determined from the HOMO energy level value or the LUMO energy level value of the selected compound. I can.

The relationship between the HOMO and LUMO energy level values of the p-type semiconductor material and the HOMO and LUMO energy level values of the n-type semiconductor material indicates that the (solidified) film formed from the ink composition has a photoelectric conversion function, It can be appropriately set within a range in which a predetermined function such as a light detection function is exhibited.

(1) p-type semiconductor material In this embodiment, the p-type semiconductor material is a polymer compound. Specifically, the p-type semiconductor material that the ink composition of the present embodiment may contain is a donor/acceptor containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). It includes a π-conjugated polymer compound having a structure (also referred to as a DA-type conjugated polymer compound).

Here, the donor structural unit is a structural unit with an excess of π electrons, and the acceptor structural unit is a structural unit with a π electron deficiency.

In the present embodiment, the structural unit that can constitute the p-type semiconductor material may be a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, or a donor structural unit and an acceptor structural unit. Structural units linked via spacers (groups or structural units) are also included.

In the present embodiment, the polymer compound that is the p-type semiconductor material includes, for example, polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives. , polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives.

In the present embodiment, the polymer compound that is the p-type semiconductor material preferably contains a structural unit containing a thiadiazole skeleton and/or a structural unit having a thiophene skeleton.

Specifically, the polymer compound that is the p-type semiconductor material contained in the composition of the present embodiment contains two or more polymer compounds containing the structural unit represented by the above formula (I). A polymer having a terminal structure represented by the following formula (II) in which at least one of two or more polymer compounds is bonded to a structural unit that is a divalent organic group represented by A is a compound.

In the present embodiment, the polymer compound having the structural unit represented by formula (I) is, as described above, a structural unit (structure) that is a divalent organic group represented by A, and a structural unit represented by B. and a structural unit (structure) that is a divalent group containing a ring structure.

In this embodiment, A is a donor structural unit (D structural unit), and a structural unit (structure) containing a ring structure represented by B is an acceptor structural unit (A structural unit).

The composition of the present embodiment inevitably contains an impurity polymer compound as an impurity. In the present embodiment, the impurity polymer compound is a polymer compound having a structural unit represented by the above formula (I) and having a terminal structure represented by the above formula (II). be.

As described above, the terminal group represented by formula (II) has a terminal structure containing an amide structure, and is usually derived from a monomer that is a raw material used for synthesizing a polymer compound. The terminal groups represented by formula (II) above include groups generated post-synthetically by, for example, keto tautomerization.

Therefore, the composition of the present embodiment may contain an impurity polymer compound from the beginning, and even if it does not contain an impurity polymer compound at the beginning, for example, keto tautomerization may cause it to In addition, there is a possibility that an impurity polymer compound having a terminal group represented by the above formula (II) is included.

In formula (I), A preferably has a structure (constituent unit) represented by formula (III) below.

In formula (III), Ar ¹ represents a divalent aromatic heterocyclic group or an arylene group.

In formula (III), the number of carbon atoms in the divalent aromatic heterocyclic group (constituent unit) represented by Ar ¹ is usually 2 to 60, preferably 4 to 60, more preferably 4 to is 20. The divalent aromatic heterocyclic group represented by Ar ¹ may have a substituent. Examples of substituents that the divalent aromatic heterocyclic group represented by Ar ¹ may have include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups.

Examples of the divalent aromatic heterocyclic group represented by Ar ¹ include groups represented by the following formulas (101) to (190) (wherein formulas (146), (148), ( 150) and (154) are missing numbers).

In formulas (101) to (190), R has the same meaning as above. When there are multiple R's, the multiple R's may be the same or different.

As the divalent aromatic heterocyclic group (constituent unit) represented by Ar ¹ , divalent groups (constituent units) represented by the following formulas (III-1) to (III-6) are preferred.

In formulas (III-1) to (III-6), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and R has the same meaning as above. When there are multiple R's, the multiple R's may be the same or different.

From the viewpoint of availability of starting compounds (monomers), both X ¹ and X ² in formulas (III-1) to (III-6) are preferably sulfur atoms.

In this embodiment, the polymer compound that is the p-type semiconductor material may contain two or more structural units represented by formula (III).

The arylene group represented by Ar ¹ means an atomic group remaining after removing two hydrogen atoms from an optionally substituted aromatic hydrocarbon. Aromatic hydrocarbons also include compounds having condensed rings, and compounds in which two or more selected from the group consisting of independent benzene rings and condensed rings are bonded directly or via a divalent group such as vinylene.

Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as the above examples of the substituent that the heterocyclic compound may have.

The number of carbon atoms in the arylene group represented by Ar ¹ excluding substituents is usually 6-60, preferably 6-20. The number of carbon atoms in the arylene group including substituents is usually 6-100.

Examples of the arylene group represented by Ar ¹ include a phenylene group (eg, the following formulas 1 to 3), a naphthalene-diyl group (eg, the following formulas 4 to 13), an anthracene-diyl group (eg, the following formulas 14 to formula 19), biphenyl-diyl groups (e.g., formulas 20 to 25 below), terphenyl-diyl groups (e.g., formulas 26 to 28 below), condensed ring compound groups (e.g., formulas 29 to 35 below ), fluorene-diyl groups (eg, formulas 36 to 38 below), and benzofluorene-diyl groups (eg, formulas 39 to 46 below).

In Formulas 1 to 46, R has the same definition as above. When there are multiple R's, the multiple R's may be the same or different.

In formula (I), A is more preferably a structure (constituent unit) represented by formula (IV) below.

In formula (IV),
Ar ² and Ar ³ each independently represent an optionally substituted trivalent aromatic heterocyclic group,
Z represents a group represented by any one of the following formulas (Z-1) to (Z-7).

In formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^c or a group represented by —SO ₂ —R ^d ,
R ^c and R ^d are each independently
hydrogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
In formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different.

R in formulas (Z-1) to (Z-7) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or carbon It is an alkyl group having 1 to 40 atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have a substituent. When there are multiple R's, the multiple R's may be the same or different.

The structure (constituent unit) represented by formula (IV) is preferably a structure (constituent unit) represented by formula (IV-1) below.

In formula (IV-1), Z has the same meaning as above.

Examples of the structure (constitutional unit) represented by formula (IV-1) include structures (constituent units) containing a thiophene skeleton represented by the following formulas (501) to (505).

In formulas (501) to (505) above, R has the same meaning as above. When there are two R's, the two R's may be the same or different.

In the present embodiment, examples of the polymer compound containing the structural unit represented by the above formula (I) include A in the structural unit represented by the formula (I) and at least one end side of the polymer compound. Polymer compounds in which a halogen atom is bonded as a terminal group to A located at .

The polymer compound containing the structural unit represented by the formula (I), which is the p-type semiconductor material of the present embodiment, has the structure represented by the above A (the structure represented by the formula (III) or (IV) (structure unit)), and a structure represented by the following formula (V) (a divalent group (constituent unit) containing a ring structure represented by B).

In the formula (V), B represents a ring structure containing a thiadiazole skeleton, an oxadiazole skeleton or a triazole skeleton, and Y represents a group represented by -CH- or a nitrogen atom.

The number of carbon atoms in the structure (constituent unit) represented by formula (V) is generally 2-20, preferably 4-20, more preferably 4-10.

The structure (structural unit) represented by the following formula (V) may further have a substituent. Examples of substituents include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, Acid imide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups are included.

Examples of the structure (constituent unit) represented by formula (V) include divalent groups represented by formulas (V-1) to (V-3) below.

In formulas (V-1) to (V-3), R has the same meaning as above. When there are multiple R's, the multiple R's may be the same or different.

In the present embodiment, the polymer compound that is the p-type semiconductor material may contain two or more structures represented by A (structures represented by formula (III) or (IV) (structural units)). It may contain two or more structures (constituent units) represented by formula (V).

In the present embodiment, the polymer compound that is the p-type semiconductor material and the impurity polymer compound have a structure represented by A contained in the structural unit represented by the formula (I), and It may be a DA type conjugated polymer compound composed only of a structure containing a ring structure represented by B, and a DA type conjugated polymer compound further containing another structure (constituent unit), good too.

In the polymer compound that is the p-type semiconductor material containing the structural unit represented by the formula (I) already described, the total amount of the structural units represented by the formula (I) is equal to all the structural units contained in the polymer compound. When the amount of is 100 mol%, it is usually 20 to 100 mol%, and from the viewpoint of improving the charge transport property as a p-type semiconductor material, it is preferably 40 to 100 mol%, more preferably 50 to 100 mol %.

A preferred specific example of the polymer compound that is the p-type semiconductor material is a polymer compound represented by the following formula P-1.

In the present embodiment, the polymer compound that is the p-type semiconductor material preferably has a predetermined polystyrene-equivalent weight-average molecular weight.

Here, the polystyrene equivalent weight average molecular weight means the weight average molecular weight calculated using a standard sample of polystyrene using gel permeation chromatography (GPC).

The polystyrene-equivalent weight-average molecular weight of the polymer compound, which is the p-type semiconductor material, is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in a solvent.

In the composition of the present embodiment, from the viewpoint of reducing the viscosity increase rate (%) over time, the main chain-derived main chain containing the structural unit represented by the formula (I) when measured by infrared spectroscopy The ratio of the peak intensity derived from the terminal structure represented by the formula (II) to the peak intensity is preferably 3.7% or less. The ratio is more preferably 3% or less, still more preferably 2% or less, and particularly preferably less than 2%. Here, "3.7% or less" includes the case where the peak intensity is below the detection limit and the ratio of the peak intensity cannot be calculated.

As the numerical value of the ratio of peak intensity increases, the thickening rate tends to increase. Therefore, when an ink composition having a peak intensity ratio within the above range and an ink composition having a peak intensity ratio outside the above range are applied under the same coating conditions, an ink having a peak intensity ratio outside the above range In the composition, the longer the time from the preparation of the ink composition to the formation of the film (solidified film), the longer the time from the preparation of the ink composition to the ink composition immediately before coating compared to the ink composition in which the numerical value of the ratio is within the above range. The viscosity of the material tends to increase. Also, when the film is formed under the same coating conditions, the film thickness increases as the viscosity of the ink increases. Therefore, in an ink composition having a peak intensity ratio value outside the above range, the viscosity increases over time. The thickness of the film will change greatly depending on the time from the preparation to the film formation. As a result, in the photoelectric conversion element including the solidified film formed from the ink composition, the characteristics of the film may vary, or the desired characteristics may not be obtained.

By setting the ratio of the peak intensity derived from the terminal structure represented by the formula (II) measured by infrared spectroscopy as described above, the composition, particularly the functional layer of the photoelectric conversion device is formed. Therefore, it is possible to suppress an increase in the viscosity of the ink composition over time, thereby suppressing variations in the characteristics of the manufactured photoelectric conversion element.

Measurement of the ratio of the terminal structure represented by the formula (II), which is an amide structure, can be carried out, for example, by infrared light according to a conventional method using any suitable conventionally known measuring device (for example, Nicolet iS50 FT-IR manufactured by ThermoFisher) It can be done by spectroscopy.

Specifically, the C═O stretching peak (1700 cm ⁻¹ ) intensity derived from the terminal structure including the amide structure contained in the impurity polymer compound that may be further contained in the polymer compound of the present embodiment is expressed by the formula (1): Divided by the peak (954 cm ⁻¹ ) intensity derived from the main chain containing the structural unit represented by and further multiplied by 100, the ratio (%) of the terminal structure containing the amide structure contained in the impurity polymer compound. do it.

In infrared spectroscopy, absorption in a specific wavelength region derived from a functional group (also referred to as a characteristic absorption band) is observed in a wavelength region of 1500 cm ^-1 or more, and a wavelength region of 1500 cm ^-1 or less (fingerprint region Absorption derived from the functional group and absorption derived from the molecular structure are observed, but the observed absorption peak is affected by the peak shape, peak intensity or baseline shape of the infrared absorption spectrum. may shift in the range of ±10 cm ⁻¹ from the above wavenumbers.

Further, the C=O stretching peak derived from the terminal structure containing the amide structure contained in the impurity polymer compound and the peak derived from the main chain containing the structural unit represented by formula (I) are represented by formula (I) or formula ( Depending on the structure of each of A, B and Y contained in II), the wave number of the absorption peak may shift within the range of ±50 cm ⁻¹ .

In the present embodiment, the C═O stretching peak intensity derived from the terminal structure containing the amide structure contained in the impurity polymer compound and the peak intensity derived from the main chain containing the structural unit represented by formula (I) are each 1700 cm. ⁻¹ and 954 cm ⁻¹ or a peak shifted in the above range, which is a C=O stretching peak derived from a terminal structure including an amide structure contained in the impurity polymer compound and represented by formula (I) The numerical value at the wave number identified as the peak derived from the main chain containing the structural unit is used. If the absorption peak is shifted, the absorption peak may be specified with reference to the shift range and the absorption wavelength region described in the known literature, and the ratio may be calculated.

(Method for producing polymer compound as p-type semiconductor material)
In the present embodiment, the polymer compound, which is the p-type semiconductor material already described, can be produced by any suitable conventionally known production method (e.g., WO 2013/051676, WO 2011/052709, WO 2018/ 220785).

In the present embodiment, the polymer compound, which is the p-type semiconductor material already described, can be produced by a method including a polymerization step (reaction step) using a solvent that does not contain alcohols as a polymerization solvent.

Examples of the "alcohol-free solvent" suitably applicable to the method for producing a polymer compound of the present embodiment include hydrocarbon solvents, ketone solvents, ether solvents, and carboxylic acid ester solvents.

As for the "solvent containing no alcohol", one of the above-exemplified solvents may be used alone, or two or more of them may be used in combination.

In the present embodiment, as the solvent that does not contain an alcohol that is a polymerization solvent, it is preferable to use one or more solvents selected from the group consisting of ether solvents and ketone solvents, and it is more preferable to use a ketone solvent. .

In this embodiment, the polymerization solvent comprises a first solvent that is at least one hydrocarbon solvent, at least one solvent that consists solely of at least one carbon atom, at least one hydrogen atom, and at least one oxygen atom. and water.

The polymerization solvent may include any solvent other than the first solvent, the second solvent, and water. Optional solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, monochlorobenzene, dichlorobenzene, trichlorobenzene. The volume ratio of any solvent is preferably 50% by volume or less, more preferably 25% by volume or less, relative to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water. , more preferably 10% by volume or less. The reaction solvent preferably consists essentially of said first solvent, said second solvent and water.

Hydrocarbon solvents include, for example, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents.

Examples of alicyclic hydrocarbon solvents include cyclohexane and decalin.
Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene (ortho-xylene), trimethylbenzene (eg, mesitylene), tetralin, indane, naphthalene, and methylnaphthalene.

The hydrocarbon solvent is preferably one or more selected from the group consisting of toluene, xylene, trimethylbenzene, decalin, tetralin, indane, naphthalene, and methylnaphthalene, more preferably toluene, mesitylene, xylene, and tetralin. It is one or more selected from the group consisting of, more preferably toluene, mesitylene, xylene or tetralin.

Ether solvents include anisole, cyclopentyl methyl ether, tert-butyl methyl ether, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.

Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of carboxylic acid ester solvents include ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, γ-Butyl lactone can be mentioned.

The first solvent includes, for example, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents.

Aliphatic hydrocarbon solvents include, for example, hexane, heptane, octane, nonane, decane, undecane, and dodecane.

Examples of alicyclic hydrocarbon solvents include cyclohexane and decalin.
Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene (ortho-xylene), trimethylbenzene (eg, mesitylene), tetralin, indane, naphthalene, and methylnaphthalene.

The first solvent may be a single hydrocarbon solvent or a combination of two or more hydrocarbon solvents.

The first solvent is preferably one or more selected from the group consisting of toluene, xylene, trimethylbenzene, decalin, tetralin, indane, naphthalene, and methylnaphthalene, more preferably toluene, mesitylene, xylene, and tetralin. It is one or more selected from the group consisting of, more preferably toluene, mesitylene, xylene or tetralin.

The organic solvent as the second solvent is an oxygen atom such as an oxo group, an oxycarbonyl group (-(C=O)-O- group), an ether bond (-O- group), etc. You may have only one group containing, or may have two or more.

Moreover, the organic solvent as the second solvent may have only one type of group containing an oxygen atom, or may have two or more types thereof.

Second solvents include, for example, ether solvents, ketone solvents, phenol solvents, and carboxylic acid ester solvents.

Ether solvents include anisole, cyclopentyl methyl ether, tert-butyl methyl ether, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.

Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of phenolic solvents include phenol, o-cresol, m-cresol and p-cresol.

Examples of carboxylic acid ester solvents include ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, γ-Butyl lactone can be mentioned.

The second solvent may be used alone or in combination of two or more.

The second solvent is preferably one or more selected from the group consisting of ether solvents and ketone solvents.

The second solvent may be a water immiscible solvent. A solvent "immiscible with water" means a liquid obtained by adding 5% by mass or more of water to the solvent, and a liquid obtained by adding 5% by mass or more of the solvent to water. It means that the liquid obtained by adding to does not form a transparent one-phase solution.

Examples of water-immiscible solvents that can be used as the second solvent include cyclopentyl methyl ether, tert-butyl methyl ether, diisopropyl ether, methyl isobutyl ketone, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, Propyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate.

A solvent "miscible with water" means a liquid obtained by adding 5% by mass or more of water to the solvent, and a liquid obtained by adding 5% by mass or more of the solvent to water. to form a clear one-phase solution in both.

The second solvent may be a water-miscible solvent. Examples of water-miscible solvents that can be used as the second solvent include diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, cyclohexanone, phenol, Ethyl acetate, γ-butyl lactone, preferably one or more selected from the group consisting of ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, cyclohexanone, ethylene glycol dimethyl ether, tetrahydrofuran, More preferably, one or more selected from the group consisting of 2-methyltetrahydrofuran.

Combinations of the first solvent and the second solvent include, for example, all combinations of the above examples of the first solvent and the above examples of the second solvent. The combination of the first solvent and the second solvent is not particularly limited.

The first solvent, second solvent, and water are mixed in a volume ratio of a:b:c. where a+b+c=100 and c is greater than 10 and less than 100. That is, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10% by volume and less than 100% by volume.

The volume ratio of water is determined based on the volume of the first solvent, the volume of the second solvent, and the volume of water used to prepare the reaction solvent.

When the second solvent is miscible with water, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is greater than 10% by volume, preferably 25 vol% or more, more preferably 25 vol% or more, still more preferably 35 vol% or more, still more preferably 35 vol% or more, still more preferably 45 vol% or more, still more preferably 45 vol% %, more preferably 50% by volume or more, and particularly preferably more than 50% by volume.

When the second solvent is miscible with water, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is less than 100% by volume, preferably is 90% by volume or less, more preferably less than 90% by volume, more preferably 80% by volume or less, still more preferably less than 80% by volume, still more preferably 70% by volume or less, and more preferably is less than 70% by volume, more preferably less than 65% by volume, and particularly preferably less than 65% by volume.

When the second solvent is miscible with water, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10% by volume and 100% by volume. less than, preferably 25% by volume or more and 90% by volume or less, more preferably more than 25% by volume and less than 90% by volume, still more preferably 35% by volume or more and 80% by volume or less, still more preferably 35 It is more than 80% by volume, more preferably 45% by volume or more and less than 70% by volume, more preferably more than 45% by volume and less than 70% by volume, still more preferably 50% by volume or more and 65% by volume. or less, and particularly preferably more than 50% by volume and less than 65% by volume.

When the second solvent is immiscible with water, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is greater than 10% by volume, preferably 20 vol% or more, more preferably 20 vol% or more, still more preferably 25 vol% or more, still more preferably 25 vol% or more, still more preferably 35 vol% or more, still more preferably 35 vol% %, more preferably 45% by volume or more, more preferably 45% by volume or more, still more preferably 50% by volume or more, particularly preferably 50% by volume or more.

When the second solvent is immiscible with water, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is less than 100% by volume, preferably is 90% by volume or less, more preferably less than 90% by volume, more preferably 80% by volume or less, still more preferably less than 80% by volume, still more preferably 70% by volume or less, and more preferably is less than 70% by volume, more preferably less than 65% by volume, and particularly preferably less than 65% by volume.

When the second solvent is immiscible with water, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10% by volume and 100% by volume. less than, preferably 20% by volume or more and 90% by volume or less, more preferably more than 20% by volume and less than 90% by volume, still more preferably 25% by volume or more and 90% by volume or less, still more preferably 25 More than 90% by volume, more preferably 35% by volume or more and less than 80% by volume, more preferably more than 35% by volume and less than 80% by volume, still more preferably 45% by volume or more and less than 70% by volume or less, more preferably more than 45% by volume and less than 70% by volume, more preferably more than 50% by volume and less than 65% by volume, and particularly preferably more than 50% by volume and less than 65% by volume.

The mixing volume ratio a:b of the first solvent and the second solvent is preferably in the range of 1:9 to 9:1, more preferably in the range of 3:7 to 7:3.

In the present embodiment, by using a solvent that does not contain alcohols, particularly a ketone solvent, as measured by infrared spectroscopy, the main chain-derived The ratio of the peak intensity derived from the terminal structure represented by the formula (II) to the peak intensity can be 3.7% or less, preferably 2% or less.

(2) n-type semiconductor material The n-type semiconductor material that the ink composition of the present embodiment may contain may be a low-molecular compound or a high-molecular compound.

Examples of n-type semiconductor materials (electron-accepting compounds) that are low molecular weight compounds include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerenes such as _C60 fullerene and fullerene derivatives thereof (hereinafter referred to as fullerene compounds ), and phenanthrene derivatives such as bathocuproin.

Examples of n-type semiconductor materials that are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

As the n-type semiconductor material, one or more selected from fullerenes and fullerene derivatives is preferable, and fullerene derivatives are more preferable.

Examples of fullerenes include _C60 fullerene, _C70 fullerene, _C76 fullerene, _C78 fullerene, and _C84 fullerene. Examples of fullerene derivatives include derivatives of these fullerenes. A fullerene derivative means a compound in which at least a part of fullerene is modified.

Examples of fullerene derivatives include compounds represented by the following formulas.

During the ceremony,
^Ra represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of R ^a may be the same or different.
^Rb represents an alkyl group or an aryl group. A plurality of R ^b may be the same or different.

Examples of groups having an ester structure represented by ^Ra include groups represented by the following formulae.

In formula (19), u1 represents an integer of 1-6. u2 represents an integer from 0 to 6; R ^e represents an alkyl group, an aryl group, or a monovalent heterocyclic group.

Examples of _C60 fullerene derivatives include the following compounds.

Examples of _C70 fullerene derivatives include the following compounds.

Specific examples of fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6]-Phenyl C61 butyric acid methyl ester), [6,6]-phenyl-C71 butyric acid methyl ester ( C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6"-phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester), and [6,6 ]-Thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).

The n-type semiconductor material that can be included in the ink composition of the present embodiment includes compounds that are not fullerene compounds. In this specification, n-type semiconductor materials that are not fullerene compounds are referred to as "non-fullerene compounds." Various compounds are known as non-fullerene compounds, and any suitable conventionally known non-fullerene compound can be used as the n-type semiconductor material in this embodiment.

The ink composition according to the present embodiment may contain only one type of compound that is an n-type semiconductor material, or may contain a plurality of types.

In the present embodiment, the non-fullerene compound, which is the n-type semiconductor material, is preferably a compound containing a perylenetetracarboxylic acid diimide structure. Examples of compounds containing a perylenetetracarboxylic acid diimide structure, which are non-fullerene compounds, include compounds represented by the following formulae.

In the formula, R is as defined above. Multiple R's may be the same or different.

In this embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (VI). The compound represented by the following formula (VI) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.

In the formula (VI), R ¹ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted an alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group show. Multiple R ¹ 's may be the same or different.

Preferably, each of a plurality of R ¹ is independently an optionally substituted alkyl group.

R ² is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, a substituent represents an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group. Multiple R ² may be the same or different.

Preferred examples of the compound represented by formula (VI) include compounds represented by the following formula.

In this embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (VII).

A ¹ -B ¹⁰ -A ² (VII)

In formula (VII),
A ¹ and A ² each independently represent an electron-withdrawing group, and B ¹⁰ represents a group containing a π-conjugated system.

Examples of electron-withdrawing groups A ¹ and A ² include groups represented by —CH═C(—CN) ₂ and groups represented by the following formulas (a-1) to (a-9). and the group to be carried out.

In formulas (a-1) to (a-7),
T represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring. Carbocyclic and heterocyclic rings may be monocyclic or condensed. When these rings have multiple substituents, the multiple substituents may be the same or different.

Examples of optionally substituted carbocyclic rings for T include aromatic carbocyclic rings. The optionally substituted carbocyclic ring for T is preferably an aromatic carbocyclic ring. Specific examples of the optionally substituted carbocyclic ring for T include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring and phenanthrene ring, preferably benzene ring, They are a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.

Examples of the optionally substituted heterocyclic ring for T include aromatic heterocyclic rings, preferably aromatic heterocyclic rings. Specific examples of the optionally substituted heterocyclic ring for T include pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, more preferably a thiophene ring. These rings may have a substituent.

Examples of substituents that the carbocyclic or heterocyclic ring for T may have include halogen atoms, alkyl groups, alkyloxy groups, aryl groups, and monovalent heterocyclic groups, preferably fluorine atoms and/or or an alkyl group having 1 to 6 carbon atoms.

X ⁴ , X ⁵ and X ⁶ each independently represents an oxygen atom, a sulfur atom, an alkylidene group or a group represented by =C(-CN) ₂ , preferably an oxygen atom, a sulfur atom, or =C(-CN) ₂ .

X ⁷ is a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or represents a monovalent heterocyclic group.

R ^a1 , R ^a2 , R ^a3 , R ^a4 , and R ^a5 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyl represents an oxy group, an optionally substituted aryl group or a monovalent heterocyclic group, preferably an optionally substituted alkyl group or an optionally substituted aryl group is.

In formulas (a-8) and (a-9), R ^a6 and R ^a7 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a substituent optionally substituted cycloalkyl group, optionally substituted alkyloxy group, optionally substituted cycloalkyloxy group, optionally substituted monovalent aromatic carbon It represents a cyclic group or an optionally substituted monovalent aromatic heterocyclic group, and a plurality of R ^a6 and R ^a7 may be the same or different.

The electron-withdrawing groups A ¹ and A ² include the following formulas (a-1-1) to (a-1-4), formulas (a-6-1) and formulas (a-7 -1) is preferable, and a group represented by formula (a-1-1) is more preferable. Here, multiple R ^a10 each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group. R ^a3 , R ^a4 and R ^a5 are each independently the same as defined above, preferably each independently an optionally substituted alkyl group or an optionally substituted aryl represents a group.

An example of the group containing a π-conjugated system as B ¹⁰ is a group represented by -(S ¹ ) _n1 -B ¹¹ -(S ² ) _n2 - in the compound represented by formula (VIII) described later. mentioned.

In this embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VIII).

A ¹ -(S ¹ ) _n1 -B ¹¹ -(S ² ) _n2 -A ² (VIII)

In formula (VIII), A ¹ and A ² each independently represent an electron-withdrawing group. Examples and preferred examples of A ¹ and A ² are the same as the examples and preferred examples described for A ¹ and A ² in formula (VII).

S ¹ and S ² each independently represent an optionally substituted divalent carbocyclic group, an optionally substituted divalent heterocyclic group, —C(R ^s1 )= A group represented by C(R ^s2 )- (here, R ^s1 and R ^s2 are each independently a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, or a substituent a good alkyl group or a monovalent heterocyclic group which may have a substituent), or a group represented by -C≡C-.

The divalent carbocyclic group optionally having substituent(s) and the divalent heterocyclic group optionally having substituent(s) represented by S ¹ and S ² may be a condensed ring. . When the divalent carbocyclic group or divalent heterocyclic group has multiple substituents, the multiple substituents may be the same or different.

In formula (VIII), n1 and n2 each independently represent an integer of 0 or greater, preferably each independently represent 0 or 1, more preferably both represent 0 or 1.

Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups.
Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups.
When the divalent aromatic carbocyclic group or divalent aromatic heterocyclic group is a condensed ring, all of the rings constituting the condensed ring may be condensed rings having aromaticity, only a part It may be a condensed ring having aromaticity.

Examples of S ¹ and S ² are groups represented by any of the formulas (101) to (190) given as examples of the divalent aromatic heterocyclic group represented by Ar ³ already explained, and groups in which hydrogen atoms in these groups are substituted with substituents.

S ¹ and S ² preferably each independently represent a group represented by formula (s-1) or (s-2) below.

In formulas (s-1) and (s-2),
^X3 represents an oxygen atom or a sulfur atom.
R ^a10 is as defined above.

S ¹ and S ² are preferably each independently a group represented by formula (142), formula (148), or formula (184), or a group in which a hydrogen atom in these groups is substituted with a substituent and more preferably a group represented by the formula (142) or (184), or a group in which one hydrogen atom in the group represented by the formula (184) is substituted with an alkyloxy group. .

B ¹¹ is a condensed ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic ring structure, a condensed ring group containing no ortho-peri condensed structure, and having a substituent; represents an optional condensed ring group.

The condensed ring group represented by ^B11 may contain a structure in which two or more identical structures are condensed.

When the condensed ring group represented by B ¹¹ has multiple substituents, the multiple substituents may be the same or different.

Examples of the carbocyclic structure that can constitute the condensed ring group represented by B ¹¹ include a ring structure represented by the following formula (Cy1) or (Cy2).

Examples of heterocyclic structures that can constitute the condensed ring group represented by B ¹¹ include ring structures represented by any of the following formulas (Cy3) to (Cy10).

In formula (VIII), B ¹¹ is preferably a condensed ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy10), It is a condensed ring group which does not contain a condensed structure and which may have a substituent. B ¹¹ may include a structure in which two or more identical structures among the structures represented by formulas (Cy1) to (Cy10) are condensed.

B ¹¹ is more preferably a condensed ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy6) and (Cy8), wherein the ortho-pericondensed It is a condensed ring group having no structure and optionally having a substituent.

The substituent that the condensed ring group B ¹¹ may have is preferably an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted and an optionally substituted monovalent heterocyclic group. The aryl group that the condensed ring group represented by B ¹¹ may have may be substituted with, for example, an alkyl group.

Examples of the condensed ring group for B ¹¹ include groups represented by the following formulas (b-1) to (b-14), and hydrogen atoms in these groups are substituents (preferably, substituents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, or an optionally substituted monovalent heterocyclic group ) substituted with. The condensed ring group for B ¹¹ is a group represented by the following formula (b-2) or (b-3), or a hydrogen atom in these groups has a substituent (preferably, a substituent optionally substituted alkyl group, optionally substituted aryl group, optionally substituted alkyloxy group, or optionally substituted monovalent heterocyclic group) is preferred, and a group represented by the following formula (b-2) or (b-3) is more preferred.

In formulas (b-1) to (b-14),
R ^a10 is as defined above.
In formulas (b-1) to (b-14), a plurality of R ^a10 are each independently preferably an optionally substituted alkyl group or optionally substituted It is an aryl group.

Examples of compounds represented by formula (VII) or formula (VIII) include compounds represented by the following formulae.

In the above formula, R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group.
In the above formula, R is preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted alkyloxy group. .

Compounds represented by formula (VII) or (VIII) include compounds represented by the following formulas.

In the ink composition of the present embodiment, the n-type semiconductor material may contain, in addition to the non-fullerene compound, the fullerene and fullerene derivative (fullerene compound) already described in combination.

Preferred specific examples of the n-type semiconductor material in this embodiment include compounds represented by the following formulas.

(3) Organic Solvent The composition and ink composition of the present embodiment may contain an aromatic hydrocarbon as an organic solvent. The aromatic hydrocarbon may have a substituent. The aromatic hydrocarbon is preferably a compound capable of dissolving the polymer compound, which is the p-type semiconductor material already described.

Examples of aromatic hydrocarbons that can be used as organic solvents in the present embodiment include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2, 4-trimethylbenzene (pseudocumene)), butylbenzene (e.g. n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g. 1-methylnaphthalene), 1,2,3,4-tetrahydro Naphthalene (tetralin), indane, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).

In this embodiment, the organic solvent may be composed of only one kind of aromatic hydrocarbon, or may be composed of two or more kinds of aromatic hydrocarbons.

Aromatic hydrocarbons that can constitute the organic solvent are preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, One or more selected from the group consisting of tert-butylbenzene, methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene), more preferably toluene, o-xylene, m -xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene ( o-dichlorobenzene).

The composition and ink composition of this embodiment may contain an alkyl halide as an organic solvent. Alkyl halides that can be used as organic solvents include, for example, chloroform.

In the composition and ink composition of the present embodiment, the organic solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec -butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (1,2-dichlorobenzene) and chloroform.

In the composition and ink composition of the present embodiment, in addition to the organic solvents exemplified above, further organic solvents may be used in combination.

In the present embodiment, further examples of organic solvents include aromatic carbonyl compounds, aromatic ester compounds and nitrogen-containing heterocyclic compounds.

Examples of the aromatic carbonyl compound include acetophenone optionally having substituent(s), propiophenone optionally having substituent(s), butyrophenone optionally having substituent(s), cyclohexylphenone which may be substituted, and benzophenone which may have a substituent.

Examples of the aromatic ester compound include optionally substituted methyl benzoate (methyl benzoate), optionally substituted ethyl benzoate, and optionally substituted benzoic acid. propyl, optionally substituted butyl benzoate, optionally substituted isopropyl benzoate, optionally substituted benzyl benzoate, optionally substituted Cyclohexyl benzoate and phenyl benzoate which may have a substituent may be mentioned.

Examples of nitrogen-containing heterocyclic compounds include optionally substituted pyridine, optionally substituted quinoline, optionally substituted quinoxaline, and optionally substituted optionally substituted pyrimidine, optionally substituted pyrazine, and optionally substituted quinazoline .

The nitrogen-containing heterocyclic compound may have substituents directly attached to the ring structure.
Examples of substituents that the ring structure of the nitrogen-containing heterocyclic compound (e.g., quinoline ring structure, 1,2,3,4-tetrahydroquinoline ring structure, quinoxaline ring structure) may have include: Examples include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen groups, and alkylthio groups.

Examples of nitrogen-containing heterocyclic compounds containing a pyridine ring structure include optionally substituted pyridine, optionally substituted quinoline, and optionally substituted isoquinoline. mentioned.

Examples of the nitrogen-containing cyclic compound containing a pyrazine ring structure include optionally substituted pyrazine and optionally substituted quinoxaline.

Nitrogen-containing cyclic compounds containing a tetrahydropyridine ring structure include, for example, optionally substituted 1,2,3,4-tetrahydroquinoline and optionally substituted 1,2, 3,4-tetrahydroisoquinolines can be mentioned.

Examples of nitrogen-containing cyclic compounds containing a pyrimidine ring structure include optionally substituted pyrimidine and optionally substituted quinazoline.

In the present embodiment, the organic solvent further contains an aromatic carbonyl compound, an aromatic ester compound, or a nitrogen-containing heterocyclic compound as a further organic solvent, or two or more selected from these. It may contain further.

In the present embodiment, it is preferable to use a halogen-free organic solvent, particularly from the viewpoint of environmental conservation.

(Weight ratio of organic solvent and further organic solvent)
When the compositions and ink compositions of the present embodiments contain the organic solvent and the further organic solvent, the weight ratio of the organic solvent to the further organic solvent (organic solvent/further organic solvent) is such that the p-type semiconductor material and the n-type From the viewpoint of further improving the solubility of the semiconductor material, the range is preferably from 80/20 to 99.9/0.1.

(Weight percentage of organic solvent in composition and ink composition)
The total weight of the organic solvent contained in the composition and ink composition of the present embodiment is the solubility of the p-type semiconductor material and the n-type semiconductor material when the total weight of the composition or ink composition is 100% by mass. from the viewpoint of further improving the p-type semiconductor material and n From the viewpoint of making it easier to form a layer having a certain thickness or more by increasing the concentration of the type semiconductor material, the content is preferably 99.9% by mass or less.

The compositions and ink compositions of the present embodiments may further contain any organic solvent in addition to the organic solvent and additional organic solvent already described. When the total weight of all organic solvents contained in the composition or ink composition is 100% by weight, the content of any organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less. Yes, more preferably 3% by weight or less. As the optional organic solvent, it is preferred to use an organic solvent with a higher boiling point than the further organic solvent.

(Concentration of p-type semiconductor material and n-type semiconductor material in ink composition)
The total concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition may be any suitable concentration depending on the thickness of the required functional layer (active layer), desired properties, etc. can. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass or less, more preferably 0.01% by mass or more and 20% by mass or less, particularly preferably 0.01% by mass or more and 10% by mass or less, and even more preferably 0.01% by mass or more and 5 % by mass or less, particularly preferably 0.1% by mass or more and 5% by mass or less.

The p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed in the ink composition. In the ink composition, the p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, more preferably completely dissolved.

(Weight ratio of p-type semiconductor material to n-type semiconductor material (p/n ratio))
The weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material/n-type semiconductor material) in the ink composition is preferably 1/9 or more, more preferably 1/5 or more, and further It is preferably 1/3 or more, preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.

4. Method for Producing Ink Composition In the present embodiment, the ink composition can be produced by any suitable conventionally known method.

The ink composition can be prepared using the previously described "composition" that does not contain an n-type semiconductor material.

In the ink composition, particularly when two or more organic solvents are used, for example, the already described organic solvent and a further organic solvent are mixed to prepare a mixed solvent, and then the mixed solvent is added with the p-type semiconductor material and n A method of manufacturing by adding a type semiconductor material, and furthermore, a (first) composition was prepared by adding a p-type semiconductor material to an organic solvent, and separately from this, an n-type semiconductor material was added to a further organic solvent ( 2) A method of preparing (manufacturing) a composition by mixing two or more compositions obtained, in other words, the step of preparing a composition is the step of preparing two or more compositions and the step of preparing the ink composition can be produced by a production method or the like including the step of mixing two or more compositions.

In preparing the ink composition, the organic solvent (and further organic solvent), the p-type semiconductor material and the n-type semiconductor material may be heated to a temperature below the boiling point of the organic solvent and mixed.

In the present embodiment, the step of preparing the ink composition is preferably carried out under conditions of 0° C. or higher and 200° C. or lower, and preferably carried out under conditions of 0° C. or higher and 100° C. or lower.

In this embodiment, the ink composition prepared as described above may be filtered. Specifically, the filtration of the ink composition is obtained after mixing the organic solvent (and further organic solvent) with the p-type semiconductor material and the n-type semiconductor material in preparing (manufacturing) the ink composition. The mixture (ink composition) may be filtered by a conventional method using a filter having a predetermined pore size.

In this embodiment, filters that can be used for filtration include, for example, filters made of fluororesins such as cellulose acetate, glass fiber, polyvinylidene fluoride (PVdF), and polytetrafluoroethylene (PTFE).

5. Applications of Composition and Ink Composition The composition of the present embodiment can be used for analysis of a component, ie, a polymer compound that is a p-type semiconductor material, and can also be used as a raw material for an ink composition.

The ink composition of the present embodiment is generally used to form a film (solidified film) containing a p-type semiconductor material and an n-type semiconductor material.

The ink composition of the present embodiment is suitably used for forming an active layer, which is a functional layer included in a photoelectric conversion element. In particular, the ink composition of the present embodiment can be used particularly suitably for forming an active layer included in a photodetector, which is a photoelectric conversion element to which a reverse bias voltage is applied during use.

6. Solidified Film of Ink Composition After forming a film (coated coating film) using the ink composition of the present embodiment, the solidified film of the ink composition is formed by removing the solvent from the film and solidifying the film. can be formed. A solidified film of the ink composition can be suitably used to form a functional layer, particularly an active layer, included in a photoelectric conversion element (light detection element). The solidified film of the ink composition can be produced by any suitable conventional production method.

In the present embodiment, the method for producing a solidified film of an ink composition includes a step (i) of applying (coating) the ink composition to an object to be applied to obtain a coating film, and removing a solvent from the obtained coating film. including step (ii). Steps (i) and (ii) are described below.

[Step (i)]
In the step (i), as a method of applying the ink composition to the object to be applied, any conventionally known application method that has already been described can be used. In the present embodiment, the coating method is preferably a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet coating method, a nozzle coating method, or a capillary coating method. A slit coating method, a spin coating method, a capillary coating method, or a bar coating method is more preferable, and a slit coating method or a spin coating method is even more preferable.

In step (i), the ink composition is applied to any desired object. The ink composition can be applied to a functional layer that can be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer, during the manufacturing process of the photoelectric conversion element.

[Step (ii)]
In step (ii), any suitable method can be used as a method for removing the solvent from the coating film of the ink composition formed in step (i). Examples of methods for removing the solvent include drying methods such as hot air drying, infrared heating drying, flash lamp annealing drying, and vacuum drying.

7. Photoelectric conversion element (1) Structure of photoelectric conversion element The photoelectric conversion element according to the present embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode. and wherein the active layer is the solidified film already described.
A configuration example of the photoelectric conversion element of the present embodiment will be specifically described below with reference to the drawings.

FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.

As shown in FIG. 1 , the photoelectric conversion element 10 is provided on a support substrate 11 . The photoelectric conversion element 10 includes a first electrode 12 provided in contact with a support substrate 11 , an electron transport layer 13 provided in contact with the first electrode 12 , and an electron transport layer 13 provided in contact with the electron transport layer 13 . , a hole transport layer 15 provided in contact with the active layer 14, and a second electrode 16 provided in contact with the hole transport layer 15. there is In this configuration example, a sealing member 17 is further provided so as to be in contact with the first electrode 16 .
Constituent elements that can be included in the photoelectric conversion element of this embodiment will be specifically described below.

(substrate)
A photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed with a substrate (sealing substrate). One of a pair of electrodes consisting of a first electrode and a second electrode is usually formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when the layer containing an organic compound is formed.

Materials for the substrate include, for example, glass, plastic, polymer film, and silicon. When an opaque substrate is used, the electrode opposite to the electrode provided on the opaque substrate (in other words, the electrode on the far side from the opaque substrate) is preferably a transparent or translucent electrode. .

(electrode)
A photoelectric conversion element includes a pair of electrodes, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably a transparent or translucent electrode in order to allow light to enter.

Examples of transparent or semi-transparent electrode materials include conductive metal oxide films and semi-transparent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and their composites indium tin oxide (ITO), indium zinc oxide (IZO), conductive materials such as NESA, gold, platinum, silver, copper. ITO, IZO, and tin oxide are preferable as materials for transparent or translucent electrodes. Moreover, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.

If one electrode of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for electrodes with low light transmittance include metals and conductive polymers. Specific examples of low light transmissive electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, Metals such as terbium, ytterbium, and alloys of two or more thereof, or one or more of these metals together with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin alloys with one or more metals selected from the group consisting of graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

(active layer)
The photoelectric conversion element of this embodiment includes the solidified film of the ink composition already described as an active layer. The active layer of this embodiment has a bulk heterojunction structure.

In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness, for example, considering the balance between suppression of dark current and extraction of the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more, particularly from the viewpoint of further reducing dark current. Also, the thickness of the active layer is preferably 5 μm or less, more preferably 1 μm or less, and still more preferably 600 nm or less.

(middle layer)
As shown in FIG. 1, the photoelectric conversion device of the present embodiment includes, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, An intermediate layer (buffer layer) such as a hole injection layer is preferably provided.

Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly( 4-styrenesulfonate)) (PEDOT:PSS).

The intermediate layer can be formed by any suitable conventionally known forming method. The intermediate layer can be formed by a vacuum deposition method or a coating method similar to the method for forming the active layer.

As shown in FIG. 1, the photoelectric conversion device of this embodiment preferably has an electron transport layer between the first electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the electrode.
In another embodiment, the photovoltaic device may not have an electron-transporting layer.

The electron-transporting layer provided in contact with the first electrode is sometimes called an electron-injecting layer. An electron transport layer (electron injection layer) provided in contact with the first electrode has a function of promoting injection of electrons into the first electrode. The electron transport layer (electron injection layer) may be in contact with the active layer.

The electron-transporting layer contains an electron-transporting material. Examples of electron-transporting materials include polyalkyleneimine and derivatives thereof, high-molecular compounds having a fluorene structure, metals such as calcium, and metal oxides.

Examples of polyalkyleneimines and derivatives thereof include alkyleneimine having 2 to 8 carbon atoms, especially alkyleneimine having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine. Polymers obtained by conventionally polymerizing one or more of 2 to 4 alkyleneimines, and polymers chemically modified by reacting them with various compounds can be mentioned. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

Examples of polymer compounds containing a fluorene structure include poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9 ,9′-dioctylfluorene)] (PFN) and PFN-P2.

Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable.

Examples of other electron-transporting materials include poly(4-vinylphenol) and perylene diimide.

In the photoelectric conversion element according to this embodiment, the intermediate layer is the electron transport layer, and the substrate (supporting substrate), the first electrode, the electron transport layer, the active layer, the hole transport layer, and the second electrode are arranged in this order. It is preferred to have a configuration that is stacked against each other.

As shown in FIG. 1, the photoelectric conversion device of the present embodiment preferably has a hole transport layer as an intermediate layer between the second electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the second electrode. The hole transport layer may be in contact with the second electrode. The hole transport layer may be in contact with the active layer.
In another embodiment, the photoelectric conversion device may not have a hole transport layer.

A hole-transporting layer provided in contact with the second electrode may be particularly referred to as a hole-injecting layer. A hole transport layer (hole injection layer) provided in contact with the second electrode has a function of promoting injection of holes generated in the active layer into the second electrode.

The hole-transporting layer contains a hole-transporting material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing constitutional units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO ₃ ) and molybdenum oxide. (MoO ₃ ).

(sealing member)
Preferably, the photoelectric conversion element of the present embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.

Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.

The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include gas barrier layers and gas barrier films.

The sealing layer is preferably formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the sealing layer include polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer, and the like. Examples include organic materials, inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

The sealing member is usually made of a material that can withstand a heat treatment to which the photoelectric conversion element is applied, for example, when it is incorporated into a device of application examples described later.

(2) Manufacturing Method of Photoelectric Conversion Element The photoelectric conversion element of the present embodiment can be manufactured by any suitable conventionally known manufacturing method. The photoelectric conversion element of the present embodiment may be manufactured by combining processes suitable for materials selected for forming constituent elements.

Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (supporting substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order. explain.

(Process of preparing substrate)
In this step, for example, a support substrate provided with a first electrode is prepared. Alternatively, a substrate provided with a conductive thin film formed of the electrode material already described is obtained from the market, and if necessary, the conductive thin film is patterned to form a first electrode, A support substrate provided with a first electrode can be prepared.

In the method for manufacturing the photoelectric conversion element according to this embodiment, the method for forming the first electrode when forming the first electrode on the support substrate is not particularly limited. The first electrode is a structure in which the first electrode is formed by any suitable conventionally known method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a coating method, etc., using the material already described ( (e.g., supporting substrate, active layer, hole transport layer).

(Step of forming hole transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.

A method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventionally known coating method. The hole transport layer can be formed, for example, by a coating method or a vacuum deposition method using a coating liquid containing a material capable of forming the hole transport layer and a solvent.

(Step of forming active layer)
In the method for manufacturing the photoelectric conversion element of this embodiment, the active layer is formed on the hole transport layer. The active layer can be formed by any suitable conventionally known formation process. In this embodiment, the active layer can be produced by a coating method using the ink composition already described.

The active layer can be formed in the same manner as the "solidified film" already described. In this embodiment, a step of applying an ink composition containing a p-type semiconductor material, an n-type semiconductor material, and a solvent onto a hole transport layer to form a coating film, and then drying the coating film. An active layer can be formed by a process including a process.

(Step of forming electron transport layer)
The method for manufacturing the photoelectric conversion element of this embodiment can include a step of forming an electron transport layer (electron injection layer) provided so as to be in contact with the active layer.

A method for forming the electron transport layer is not particularly limited. From the viewpoint of making the step of forming the electron transport layer simpler, it is preferable to form the electron transport layer by any suitable conventionally known vacuum vapor deposition method.

(Step of forming second electrode)
A method for forming the second electrode is not particularly limited. The second electrode can be formed, for example, from the materials of the electrodes exemplified above by any suitable conventionally known method such as a coating method, a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.

(Step of forming sealing body)
In forming the sealing body, in the present embodiment, a conventionally known and suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied to the support substrate so as to surround the manufactured photoelectric conversion element, and then the sealing material is bonded without any gaps, and then selected. A photoelectric conversion element sealed body can be obtained by sealing the photoelectric conversion element in the gap between the support substrate and the sealing substrate using a method such as irradiation of UV light, which is suitable for the sealing material. can.

(3) Applications of Photoelectric Conversion Element Applications of the photoelectric conversion element of the present embodiment include photodetection elements and solar cells.
More specifically, the photoelectric conversion element of the present embodiment allows a photocurrent to flow by irradiating light from the transparent or translucent electrode side while a voltage (reverse bias voltage) is applied between the electrodes. and can be operated as a photodetector (optical sensor). Also, it can be used as an image sensor by integrating a plurality of photodetectors. The photoelectric conversion element of this embodiment can be suitably used particularly as a photodetector.

Moreover, the photoelectric conversion element of this embodiment can generate a photovoltaic force between the electrodes by being irradiated with light, and can be operated as a solar cell. A solar cell module can also be obtained by integrating a plurality of photoelectric conversion elements.

(4) Application Examples of Photoelectric Conversion Element The photoelectric conversion element according to the present embodiment can be used as a photodetector in various electronic devices such as workstations, personal computers, personal digital assistants, entrance/exit management systems, digital cameras, and medical equipment. It can be suitably applied to the detection unit provided in the device.

The photoelectric conversion element of the present embodiment is provided in the above-exemplified electronic device, for example, an image detection unit for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor (e.g., an image sensor such as an X-ray sensor), a fingerprint Detection units of biometric information authentication devices that detect predetermined features of a part of a living body, such as detection units, face detection units, vein detection units, and iris detection units (e.g., near-infrared sensors), and optical biosensors such as pulse oximeters. It can be suitably applied to a detection unit or the like.

The photoelectric conversion element of this embodiment can be suitably applied as an image detection unit for a solid-state imaging device, and further to a time-of-flight (TOF) type distance measurement device (TOF type distance measurement device).

A TOF rangefinder measures a distance by causing a photoelectric conversion element to receive reflected light emitted from a light source and reflected by an object to be measured. Specifically, the distance to the object to be measured is obtained by detecting the time of flight until the irradiation light emitted from the light source is reflected by the object to be measured and returns as reflected light. The TOF type includes a direct TOF method and an indirect TOF method. The direct TOF method directly measures the difference between the time when the light is irradiated from the light source and the time when the reflected light is received by the photoelectric conversion element. to measure the distance. The distance measurement principle used in the indirect TOF method to obtain the time of flight by charge accumulation includes a continuous wave (especially sine wave) modulation method in which the time of flight is obtained from the phases of the light emitted from the light source and the reflected light reflected by the measurement target. and pulse modulation method.

Hereinafter, among detection units to which the photoelectric conversion element according to the present embodiment can be preferably applied, an image detection unit for a solid-state imaging device, an image detection unit for an X-ray imaging device, a biometric authentication device (for example, a fingerprint authentication device, a vein Configuration examples of a fingerprint detection unit and a vein detection unit for an authentication device, etc., and an image detection unit of a TOF rangefinder (indirect TOF method) will be described with reference to the drawings.

(Image detector for solid-state imaging device)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.

The image detection unit 1 includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion element provided on the interlayer insulating film 30 according to the embodiment of the present invention. It is provided so as to penetrate the element 10 and the interlayer insulating film 30 , and is provided so as to cover the photoelectric conversion element 10 and the interlayer wiring part 32 electrically connecting the CMOS transistor substrate 20 and the photoelectric conversion element 10 . and a color filter 50 provided on the sealing layer 40 .

The CMOS transistor substrate 20 has a conventionally known arbitrary and suitable configuration in a design-appropriate manner.

The CMOS transistor substrate 20 includes functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions, including transistors and capacitors formed within the thickness of the substrate.

Functional elements include, for example, floating diffusions, reset transistors, output transistors, and selection transistors.

A signal readout circuit and the like are built into the CMOS transistor substrate 20 by such functional elements, wiring, and the like.

The interlayer insulating film 30 can be made of any suitable conventionally known insulating material such as silicon oxide and insulating resin. The interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

The sealing layer 40 may be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10. can be done. The sealing layer 40 can have the same configuration as the sealing member 17 already described.

As the color filter 50, for example, a primary color filter made of any conventionally known suitable material and corresponding to the design of the image detecting section 1 can be used. Further, as the color filter 50, a complementary color filter that can be thinner than the primary color filter can be used. As complementary color filters, for example, three types of (yellow, cyan, magenta), three types of (yellow, cyan, transparent), three types of (yellow, transparent, magenta), and three types of (transparent, cyan, magenta) A combination of types of color filters can be used. These can be arranged in any suitable arrangement corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition that color image data can be generated.

The light received by the photoelectric conversion element 10 through the color filter 50 is converted by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and is output as a light reception signal, that is, the object to be imaged, to the outside of the photoelectric conversion element 10 through the electrodes. is output as an electrical signal corresponding to

Next, the received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and further Image information based on the object to be imaged is generated by performing signal processing by an arbitrary suitable conventionally known functional unit.

(fingerprint detector)
FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.

The display device 2 of the mobile information terminal includes a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component, and a display panel provided on the fingerprint detection unit 100 and displaying a predetermined image. 200.

In this configuration example, the fingerprint detection section 100 is provided in an area that matches the display area 200 a of the display panel section 200 . In other words, the display panel section 200 is integrally laminated above the fingerprint detection section 100 .

In the case where fingerprint detection is performed only in a partial area of the display area 200a, the fingerprint detection section 100 may be provided so as to correspond only to the partial area.

The fingerprint detection section 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional section that performs essential functions. The fingerprint detection unit 100 includes any suitable conventionally known members such as a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film. It may be provided in a manner corresponding to the design to obtain the properties. The fingerprint detection unit 100 may adopt the configuration of the image detection unit already described.

The photoelectric conversion element 10 can be included in any manner within the display area 200a. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

As already described, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrodes or second electrodes) in a matrix, for example.

The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of received light, and the received light signal, that is, the electricity corresponding to the imaged fingerprint, is output outside the photoelectric conversion element 10 via the electrodes. output as a signal.

In this configuration example, the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel. The display panel unit 200 may be configured by, for example, a display panel having an arbitrary and suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight, instead of the organic EL display panel.

The display panel section 200 is provided on the already-described fingerprint detection section 100 . The display panel section 200 includes an organic electroluminescence element (organic EL element) 220 as a functional section that performs an essential function. The display panel unit 200 further includes an arbitrary and suitable substrate such as a conventionally known glass substrate (support substrate 210 or sealing substrate 240), a sealing member, a barrier film, a polarizing plate such as a circularly polarizing plate, and an arbitrary substrate such as a touch sensor panel 230. Suitable conventionally known members may be provided in a manner corresponding to the desired properties.

In the configuration example described above, the organic EL element 220 is used as a light source for the pixels in the display area 200a and also as a light source for imaging a fingerprint in the fingerprint detection section 100. FIG.

Here, the operation of fingerprint detection unit 100 will be briefly described.
When performing fingerprint authentication, fingerprint detection unit 100 detects a fingerprint using light emitted from organic EL element 220 of display panel unit 200 . Specifically, the light emitted from the organic EL element 220 passes through the constituent elements existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and the display in the display area 200a is displayed. The light is reflected by the skin (finger surface) of the fingertip placed in contact with the surface of the panel section 200 . At least part of the light reflected by the finger surface is transmitted through intervening components and received by the photoelectric conversion element 10 , and converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Image information about the fingerprint on the surface of the finger is constructed from the converted electric signal.

The portable information terminal equipped with the display device 2 performs fingerprint authentication by comparing the obtained image information with prerecorded fingerprint data for fingerprint authentication by any suitable conventionally known step.

(Image detector for X-ray imaging device)
FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging apparatus.

An image detection unit 1 for an X-ray imaging device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and an interlayer insulating film 30 provided on the interlayer insulating film 30. a photoelectric conversion element 10 according to the embodiment; , a scintillator 42 provided on the sealing layer 40, a reflective layer 44 provided to cover the scintillator 42, and a reflective layer 44 provided to cover the and a protective layer 46 having a

The CMOS transistor substrate 20 has a conventionally known arbitrary and suitable configuration in a design-appropriate manner.

The CMOS transistor substrate 20 includes functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions, including transistors and capacitors formed within the thickness of the substrate.

Functional elements include, for example, floating diffusions, reset transistors, output transistors, and selection transistors.

A signal readout circuit and the like are built into the CMOS transistor substrate 20 by such functional elements, wiring, and the like.

The interlayer insulating film 30 can be made of any suitable conventionally known insulating material such as silicon oxide and insulating resin. The interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

The sealing layer 40 may be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10. can be done. The sealing layer 40 can have the same configuration as the sealing member 17 already described.

The scintillator 42 can be constructed of any suitable conventionally known material that corresponds to the design of the image detector 1 for an X-ray imaging apparatus. Examples of suitable materials for the scintillator 42 include inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadolinium oxysulfide), and GSO (gadolinium silicate). , organic crystals of organic materials such as anthracene, naphthalene, and stilbene; organic liquids obtained by dissolving organic materials such as diphenyloxazole (PPO) and terphenyl (TP) in organic solvents such as toluene, xylene, and dioxane; and organic materials such as xenon and helium. Gases, plastics, etc. can be used.

The above components correspond to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition that the scintillator 42 converts incident X-rays into light having a wavelength centered in the visible region to generate image data. Any suitable arrangement can be used.

The reflective layer 44 reflects the light converted by the scintillator 42 . The reflective layer 44 can reduce the loss of converted light and increase detection sensitivity. In addition, the reflective layer 44 can also block light that is directly incident from the outside.

The protective layer 46 can be made of any suitable material known in the art, provided that it prevents or inhibits permeation of harmful substances such as oxygen and water that may functionally degrade the scintillator 42 .

Here, the operation of the image detection unit 1 for the X-ray imaging apparatus having the above configuration will be briefly described.

When radiation energy such as X-rays or γ-rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) with wavelengths in the ultraviolet to infrared range centered on the visible range. The light converted by the scintillator 42 is received by the photoelectric conversion element 10 .

In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and the received light signal is output outside the photoelectric conversion element 10 via the electrodes. That is, it is output as an electrical signal corresponding to the object to be imaged. Radiation energy (X-rays) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.

Next, the received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and further Image information based on the object to be imaged is generated by performing signal processing by an arbitrary suitable conventionally known functional unit.

(Vein detector)
FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device.
The vein detection unit 300 for the vein authentication device includes a cover unit 306 defining an insertion unit 310 into which a finger to be measured (eg, one or more fingertips, fingers and palm) is inserted during measurement, and a cover unit 306 . A light source unit 304 provided in a unit 306 for irradiating light onto an object to be measured, a photoelectric conversion element 10 for receiving the light emitted from the light source unit 304 through the object to be measured, and a support for supporting the photoelectric conversion element 10 . The glass substrate 302 is arranged so as to face the substrate 11 and the support substrate 11 with the photoelectric conversion element 10 interposed therebetween, is separated from the cover portion 306 at a predetermined distance, and defines an insertion portion 310 together with the cover portion 306 . consists of

In this configuration example, the light source unit 304 is configured integrally with the cover unit 306 so that the photoelectric conversion element 10 is separated from the photoelectric conversion element 10 while sandwiching the object to be measured during use. , the light source unit 304 is not necessarily positioned on the cover unit 306 side.

On the condition that the object to be measured can be efficiently irradiated with the light from the light source unit 304, for example, a reflection imaging method in which the object to be measured is irradiated from the photoelectric conversion element 10 side may be employed.

The vein detection section 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional section that performs essential functions. The vein detection unit 300 includes any suitable conventionally known members such as a protection film (not shown), a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light cut film, and a finger placement guide. can be provided in a manner corresponding to the design to obtain the desired properties. The vein detection unit 300 may employ the configuration of the image detection unit 1 already described.

Photoelectric conversion element 10 may be included in any manner. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

As already described, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrodes or second electrodes), for example, in a matrix.

The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of light received, and the received light signal, that is, the electricity corresponding to the imaged vein, is output outside the photoelectric conversion element 10 via the electrodes. output as a signal.

During vein detection (during use), the object to be measured may or may not be in contact with the glass substrate 302 on the photoelectric conversion element 10 side.

Here, the operation of the vein detection unit 300 will be briefly described.
During vein detection, the vein detection unit 300 detects the vein pattern of the measurement target using light emitted from the light source unit 304 . Specifically, the light emitted from the light source unit 304 is transmitted through the measurement target and converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Image information of the vein pattern to be measured is constructed from the converted electrical signal.

The vein authentication device performs vein authentication by comparing the obtained image information with pre-recorded vein data for vein authentication by any suitable conventionally known step.

(Image detector for TOF rangefinder)
FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF rangefinder.

The image detection unit 400 for the TOF type distance measuring device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and an interlayer insulating film 30 provided on the interlayer insulating film 30. The photoelectric conversion element 10 according to the embodiment, the two floating diffusion layers 402 spaced apart to sandwich the photoelectric conversion element 10, and the photoelectric conversion element 10 and the floating diffusion layer 402 are provided to cover the photoelectric conversion element 10. It comprises an insulating layer 401 and two photogates 404 provided on the insulating layer 401 and spaced apart from each other.

A part of the insulating layer 401 is exposed from the gap between the two photogates 404 separated from each other, and the remaining area is shielded from light by the light shielding portion 406 . The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by an interlayer wiring portion 32 provided so as to penetrate the interlayer insulating film 30 .

The interlayer insulating film 30 can be made of any suitable conventionally known insulating material such as silicon oxide and insulating resin. The interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

Insulating layer 401, in this structural example, can have any conventionally known and suitable structure such as a field oxide film made of silicon oxide.

Photogate 404 may be constructed of any suitable material known in the art, such as, for example, polysilicon.

The TOF rangefinder image detection unit 400 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs essential functions. The image detector 400 for the TOF-type rangefinder uses any suitable conventional film such as a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, an infrared cut film, and the like. Known components may be provided in a manner corresponding to the design to obtain the desired properties.

Here, the operation of the image detection section 400 for the TOF rangefinder will be briefly described.

Light is emitted from the light source, the light from the light source is reflected from the object to be measured, and the photoelectric conversion element 10 receives the reflected light. Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402 , and by alternately applying pulses, signal charges generated by the photoelectric conversion element 10 are transferred to the two floating diffusion layers 402 . The charge is transferred to either one and accumulated in the floating diffusion layer 402 . When the light pulse arrives so as to equally straddle the timing of opening the two photogates 404, the amount of charge accumulated in the two floating diffusion layers 402 becomes equal. If the light pulse arrives at the other photogate 404 with a delay with respect to the timing at which the light pulse arrives at the one photogate 404, the amount of charge accumulated in the two floating diffusion layers 402 will differ.

The difference in charge amount accumulated in the floating diffusion layer 402 depends on the delay time of the light pulse. The distance L to the object to be measured has a relationship of L=(1/2) ctd using the round trip time td of light and the speed of light c. If it can be estimated, the distance to the measurement target can be obtained.

The amount of light received by the photoelectric conversion element 10 is converted into an electrical signal as the difference between the amounts of charge accumulated in the two floating diffusion layers 402, and the received light signal, that is, the electricity corresponding to the object to be measured, is output outside the photoelectric conversion element 10. output as a signal.

Next, the received light signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and read out by a signal readout circuit (not shown). Distance information based on the measurement object is generated through signal processing by an arbitrary suitable conventionally known functional unit.

8. Photodetection element As described above, the photoelectric conversion element of the present embodiment can have a photodetection function capable of converting irradiated light into an electric signal corresponding to the amount of received light and outputting the signal to an external circuit via an electrode. . Therefore, the photoelectric conversion element according to the embodiment of the present invention can be particularly suitably applied as a photodetector having a photodetection function. Here, the photodetector element of this embodiment may be a photoelectric conversion element itself, or may further include a functional element for voltage control in addition to the photoelectric conversion element.

Examples are given below to describe the present invention in more detail. The invention is not limited to the following examples.

<Synthesis of compound 4>
Compound 4 was synthesized according to the following procedure.

First, compound 2 was synthesized according to the following scheme.

Magnesium (3.22 g, 0.133 mol), THF (93.7 g), and iodine (63.5 mg) were added to a 1 L four-necked flask in which the internal atmosphere was replaced with nitrogen gas, and stirred. After the purple color of iodine disappeared, 10 wt% of a solution containing 1-bromo-4-dodechylbenzene (40.7 g, 0.125 mmol) and THF (72.9 g) was added dropwise to a four-necked flask, Heat to 55° C. to generate the Grignard reagent. Then, after cooling to 35°C, a solution containing 1-Bromo-4-dodechylbenzene and THF was added dropwise to the four-necked flask so as not to exceed 45°C. After that, the mixture was stirred at room temperature for 2 hours.

A solution containing compound 1 (10.4 g, 0.050 mol) and THF (213 g) synthesized by the method described in International Publication No. 2011/136311 so that the internal temperature does not exceed 35 ° C., a four-necked flask dripped into. After that, the mixture was stirred for 1 hour and allowed to stand overnight.

The obtained reaction solution was quenched by pouring a 6% NH ₄ Cl aqueous solution, and the organic layer was extracted. After toluene was added to the obtained organic layer, it was washed once with saturated brine, dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. was obtained as a yellow liquid in an amount of 42.65 g.

Next, compound 3 was synthesized according to the following scheme.

Crude Compound 2 (42.65 g) and heptane (321 g) were placed in a 1 L four-necked flask, and the internal atmosphere was replaced with nitrogen gas for 30 minutes. After charging trifluoroacetic acid (0.986 g, 0.0087 mmol) into a four-necked flask, the temperature was raised to 60°C. After reaching 60° C., the mixture was stirred for 30 minutes and then cooled to room temperature to obtain a reaction solution.

The reaction solution was washed twice with water, dried over magnesium sulfate, purified with a silica gel column using heptane as a developing solvent, and then concentrated with a rotary evaporator to give 33 g of crude compound 3 as a yellow liquid. Obtained.

Next, compound 4 was synthesized according to the following scheme.

In a 300 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas, the crude compound 3 (8.56 g) obtained as described above, tetramethylethylenediamine (1.16 g, 0.010 mol) and dehydrated THF were added. (106 g) was charged and dissolved, and after confirming that the oxygen concentration was below 0.02%, the flask was immersed in a cooling bath containing dry ice and acetone until the internal temperature became -60 ° C. or less. cooled.

Next, a 1.6 mol/L nBuLi hexane solution (16 mL, 2.5 eq, 0.025 mmol) was slowly added dropwise to the four-necked flask so that the internal temperature did not exceed -60°C. Then, after keeping the temperature for 2 hours, a solution prepared by diluting isopropyl borate (5.27 g, 2.8 eq, 0.028 mmol) with 9.6 g of dehydrated THF was slowly added to the flask so that the internal temperature did not exceed -60°C. Dropped into the flask. After further keeping the temperature for 1 hour, the temperature was naturally raised to room temperature. Next, 75.6 g of hydrochloric acid having a concentration of 2% was added dropwise to the four-necked flask to quench the solution, and the aqueous layer was removed by liquid separation.

Toluene, magnesium sulfate, and trimethylene (3.60 g, 0.030 mmol, 3.0 eq.) were added to the obtained organic layer, stirred at room temperature for 1 hour, and allowed to stand overnight. Magnesium sulfate was removed by filtration, the filtrate was concentrated by an evaporator, toluene was added, and insoluble matter was removed by filtration.

After the obtained solution was again concentrated by an evaporator, ethanol and hexane were added to the obtained concentrate for recrystallization, followed by filtration and washing with cooled hexane. The resulting solid was dried overnight at 40° C. under reduced pressure. As a result, 5.19 g of compound 4 was obtained as a white solid.

<Synthesis of compound 7>
Synthesis of compound 7 was carried out according to the following procedure.

First, compound 5 was synthesized according to the following scheme.

Magnesium (9.79 g), THF (316 mL), and iodine (2 grains) were added to a 2 L four-necked flask in which the internal atmosphere was replaced with nitrogen gas, and stirred. After the purple color of iodine disappeared, a THF (221 mL) solution of 1-bromo-3-hexylbenzene (91.6 g) was added dropwise over 30 minutes. After that, the temperature was raised to 30° C. and the mixture was stirred for 1 hour.

A solution containing Compound 1 (31.6 g) and THF (649 mL) synthesized by the method described in International Publication No. 2011/136311 was added dropwise to a four-neck flask so that the internal temperature did not exceed 35 ° C., and then Stir overnight.

The resulting reaction solution was quenched by pouring a 10% concentration NH ₄ Cl aqueous solution, and the organic layer was extracted. After toluene was added to the obtained organic layer, the organic layer was washed once with water, dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated with a rotary evaporator. 78.5 g of compound 5 was obtained by purifying the resulting crude product with a silica gel column (using hexane and ethyl acetate as a developing solvent).

Compound 6 was then synthesized according to the scheme below.

The resulting compound 5 (78.5 g), p-toluenesulfonic acid monohydrate (4.67 g) and toluene (785 mL) were placed in a 2 L four-necked flask whose internal atmosphere was replaced with nitrogen gas. After heating to 100° C. and stirring for 1.5 hours, the mixture was cooled. After stopping the reaction by adding water, the organic layer was further washed once with water. The obtained organic layer was dried over anhydrous magnesium sulfate and then filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was purified with a silica gel column (hexane was used as a developing solvent) to obtain 71.8 g of compound 6.

Next, compound 7 was synthesized according to the following scheme.

The obtained compound 6 (42.9 g), tetramethylethylenediamine (12.4 mL) and dehydrated THF (1073 mL) were placed in a 2 L four-necked flask whose internal atmosphere was replaced with nitrogen gas, dissolved, and oxygen was added. After confirming that the concentration was below 0.02%, the flask was immersed in a cooling bath containing dry ice and acetone to cool the inside temperature to -60°C or below. Then, a 1.6 mol/L nBuLi hexane solution (132 mL, 2.5 eq) was slowly added dropwise so that the internal temperature did not exceed -60°C. After the resulting solution was kept warm for 2 hours, a solution obtained by diluting isopropyl borate (43.88 g, 2.8 eq) with 27 mL of dehydrated THF was slowly added dropwise to the four-necked flask so that the internal temperature did not exceed -60°C. bottom.

Next, after keeping the obtained solution warm for 1 hour, the flask was removed from the bath and the temperature was naturally raised to room temperature. After that, 629 mL of a hydrochloric acid solution having a concentration of 2% was added dropwise to quench the solution, and after adding 536 mL of THF, the layers were separated and the aqueous layer was removed.

Subsequently, magnesium sulfate and trimethylene (30.4 g, 3.0 eq.) were added to the obtained organic layer, stirred at room temperature for 1 hour, and then allowed to stand overnight. Next, magnesium sulfate was removed by filtration, the filtrate was concentrated by an evaporator, toluene was added, and insoluble matter was removed by filtration.

The resulting solution was concentrated by an evaporator, recrystallized by adding hexane, filtered, and washed with cooled hexane. The resulting solid was dried overnight at 40° C. under reduced pressure. As a result, 53.7 g of compound 7 was obtained.

<Synthesis of compound 11>
Compound 11 was synthesized according to the following procedure.

First, compound 8 was synthesized according to the following scheme.

Magnesium (65.2 g, 2.68 mol), THF (275 mL), and iodine (2 grains) were added to a flask whose internal atmosphere was replaced with nitrogen gas, and stirred. After the purple color of iodine disappeared, a solution of 1-Bromo-3-hexylbenzene (612.9 g, 2.54 mol) in THF (4730 mL) was added dropwise to generate a Grignard reagent.

Then 1,3-Dibromobenzene (550 g, 2.33 mol), THF (2783 mL), PdCl ₂ (dppf).CH ₂ Cl ₂ (7.62 g, 9.33 mmol) were added to another flask and stirred, Cool to 10°C. A prepared Grignard reagent was added dropwise to the flask so that the internal temperature did not exceed 10° C. to obtain a reaction solution. After that, the mixture was stirred for 1 hour, water was poured into the reaction mixture to stop the reaction, and the mixture was separated.

The obtained organic layer was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated with a rotary evaporator.

The resulting filtrate was further purified by silica gel column chromatography (hexane solvent) to obtain 532.2 g (1.68 mol, yield 67%) of Compound 8.

The ¹ H-NMR measurement results of compound 8 are as follows.
δ (ppm): 7.73 (t, 1H), 7.52-7.50 (dt, 1H), 7.48-7.45 (dq, 1H), 7.38-7.28 (m, 4H), 7.21-7.18 (m, 1H), 2.67 (t, 2H), 1.69-1.58 (m, 2H), 1.40-1.28 (m, 6H) , 0.89 (t, 3H)

Next, compound 9 was synthesized according to the following scheme.

Magnesium (1.61 g, 0.066 mol), THF (47 g), and iodine (32 mg) were added to a 1 L four-necked flask in which the internal atmosphere was replaced with nitrogen gas, and stirred. After the purple color of iodine disappeared, a THF (36 g) solution of the resulting compound 8 (19.8 g, 0.063 mmol) was added dropwise to generate a Grignard reagent.

A solution containing compound 1 (5.21 g, 0.025 mol) and THF (107 g) synthesized by the method described in International Publication No. 2011/136311 is added dropwise to a four-necked flask so that the internal temperature does not exceed 40 ° C. to obtain a reaction solution. After that, the mixture was stirred for 1 hour, an aqueous ammonium chloride solution was poured into the reaction mixture to stop the reaction, and the mixture was separated. The organic layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated using a rotary evaporator.

Then, 14.21 g (20.7 mmol, yield 83%) of compound 9 was obtained by purification by silica gel column chromatography using hexane and ethyl acetate as a developing solvent.

The ¹ H-NMR measurement results of compound 9 are as follows.
δ (ppm): 7.82-7.76 (m, 1H), 7.64 (s, 2H), 7.43 (m, 2H), 7.31 (m, 10H), 7.25 (m , 2H), 7.21 (m, 1H), 7.13 (m, 2H), 6.91 (d, 1H), 6.64 (d, 1H), 6.43 (d, 1H), 3 .72-3.64 (m, 1H), 2.63 (t, 4H), 1.61 (m, 4H), 1.22-1.34 (m, 12H), 0.86 (t, 6H) )

Next, compound 10 was synthesized according to the scheme below.

The resulting compound 9 (14.21 g, 0.0208 mmol) and heptane (130 g) were placed in a 500 mL four-necked flask, and the atmosphere in the reaction vessel was replaced with nitrogen gas. 409 g, 0.0036 mmol) was charged, heated to 60° C., stirred for 30 minutes, and then cooled to room temperature to obtain a reaction solution.

After washing the obtained reaction solution twice with water, the organic layer was dehydrated with magnesium sulfate, passed through a Kiriyama funnel filled with silica gel, and the filtrate was concentrated with a rotary evaporator to obtain 13.37 g of compound 10. (yield 96.6%) was obtained.

¹ H-NMR measurement results of compound 10 are as follows.
δ (ppm): 7.73 (s, 2H), 7.64 (s, 2H), 7.45-7.43 (m, 7H), 7.33-7.31 (m, 2H), 7 .26 (s, 2H), 7.22 (s, 1H), 7.16-7.13 (m, 1H), 6.93 (d, 1H), 6.65 (d, 1H), 44 (d, 1H), 2.64 (t, 4H), 1.67-1.58 (m, 4H), 1.34-1.26 (m, 12H), 0.86 (t, 6H)

Then, compound 11 was synthesized according to the scheme below.

The resulting compound 10 (25.0 g), tetraethylethylenediamine (5.6 mL), and dehydrated tetrahydrofuran (436 mL) were placed in a flask whose internal atmosphere was replaced with argon gas, and dissolved by stirring. Then, after cooling the resulting solution to -65 ° C. in a cooling bath containing dry ice and acetone, 1.6 mol / L nBuLi hexane solution (58.9 mL) was added dropwise to the flask, and -65 ° C. for 2 hours. Stirred. A solution of triisopropoxyborane (19.74 g) dissolved in 40 mL of THF was added dropwise to the flask while the temperature was maintained at −65° C., and the mixture was further stirred at −65° C. for 1 hour and then warmed to room temperature to dilute the reaction solution. Obtained. Next, 290 mL of hydrochloric acid having a concentration of 2% was added to the obtained reaction solution, and the solution was separated.

Magnesium sulfate and trimethylolethane (13.5 g) were added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour. Magnesium sulfate was removed by filtration to obtain a filtrate. The solvent was distilled off under reduced pressure from the resulting filtrate, toluene (700 mL) was added, the precipitated solid was further removed by filtration, hexane was added to remove the supernatant, and the solvent was removed under reduced pressure. 37.7 g of compound 11 was obtained (yield 109%).

<Synthesis of compound 14>
Compound 14 was synthesized according to the following procedure.

First, compound 12 was synthesized according to the following scheme.

Magnesium (12.37 g), THF (360 mL), and iodine (two grains) were added to a flask whose internal atmosphere was replaced with argon gas, and the mixture was stirred. After the purple color of iodine disappeared, a solution containing 1-bromo-3,5-diphenylbenzene (148.48 g) and THF (280 mL) was added dropwise to generate a Grignard reagent.

A THF (820 mL) solution of compound 1 (35.88 g) synthesized by the method described in International Publication No. 2011/136311 was added dropwise so that the internal temperature did not exceed 40° C. to obtain a reaction solution. After that, the mixture was stirred overnight, an aqueous solution of ammonium chloride (450 mL) having a concentration of 10% was poured into the reaction mixture to stop the reaction, and the mixture was separated.

The obtained organic layer was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated with a rotary evaporator.

Purification by silica gel column chromatography using hexane and ethyl acetate as developing solvents gave 128.6 g of compound 12 (yield 99%).

Next, compound 13 was synthesized according to the following scheme.

The obtained compound 12 (128.6 g) and toluene (1376 mL) were charged into a flask whose internal atmosphere was replaced with argon gas, and after replacing the atmosphere in the reaction vessel with nitrogen gas, p-toluenesulfonic acid monohydrate was added. A soda (5.39 g) was charged, heated to 100° C., stirred for 1.5 hours, and then cooled to room temperature to obtain a reaction solution.

After the obtained reaction solution was washed with water, the organic layer was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated with a rotary evaporator.

Next, hexane (150 mL) was added to the concentrated filtrate to precipitate a solid, then toluene (50 mL) and hexane (50 mL) were added, and after cooling with ice for 60 minutes, the precipitated solid was filtered and dried. As a result, 106 g of compound 13 was obtained (yield 96%).

Then, compound 14 was synthesized according to the following scheme.

The resulting compound 13 (28.38 g), tetraethylethylenediamine (6.5 mL), and 568 mL of dehydrated THF were placed in a flask whose internal atmosphere was replaced with argon gas, and dissolved by stirring. Then, after cooling the resulting solution to -65 ° C. in a cooling bath containing dry ice and acetone, 1.6 mol / L nBuLi hexane solution (69.9 mL) was added dropwise and stirred at -65 ° C. for 1 hour. . While maintaining the temperature at −65° C., a solution of triisopropoxyborane (22.96 g) dissolved in 11.4 mL of THF was added dropwise, and the mixture was further stirred at −65° C. for 1 hour and then warmed to room temperature.

Next, 329 mL of hydrochloric acid having a concentration of 10% was added to the obtained reaction solution, and the solution was separated. Magnesium sulfate and trimethylolethane (15.72 g) were added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour, and magnesium sulfate was removed by filtration. The resulting filtrate was evaporated under reduced pressure to remove the solvent, added with chloroform (480 mL), stored overnight in a refrigerator, and after removing the precipitated solid, the filtrate was evaporated under reduced pressure to remove the solvent. Obtained. The resulting crude product was recrystallized with ethanol and hexane to obtain 36.18 g of compound 14 (yield 91.5%).

<Synthesis of compound 16>
Compound 16 was synthesized according to the scheme below.

Compound 15 (20.27 g) synthesized by the method described in literature (Dyes and Pigments, 2015, 112, 145.), tetraethylethylenediamine (5.87 mL) and dehydrated THF were added to a flask whose internal atmosphere was replaced with argon gas. (506 mL) and stirred to dissolve. Then, after cooling the resulting solution to -65 ° C. in a cooling bath containing dry ice and acetone, 1.6 mol / L nBuLi hexane solution (62.7 mL) was added dropwise and stirred at -65 ° C. for 1 hour. . Next, while maintaining the temperature at −65° C., a solution obtained by dissolving triisopropoxyborane (20.73 g) in THF (28.4 mL) was added dropwise. A reaction liquid was obtained by warming.

Next, 296 mL of hydrochloric acid having a concentration of 10% was added to the obtained reaction solution, and the solution was separated. Magnesium sulfate and trimethylolethane (120.15 g) were added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour, and the magnesium sulfate was removed by filtration. The solvent was distilled off under reduced pressure from the resulting filtrate, hexane (480 mL) was added, the mixture was cooled with ice water, and the precipitated solid was collected by filtration.

The obtained solid was dissolved in toluene (480 mL), and the insoluble component was removed by further filtration. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain a crude product. The obtained crude product was recrystallized with ethanol and hexane to obtain 26.94 g of compound 16 (yield 88.8%).

(Example 1)
Polymer compounds P-1 and P-2 were synthesized according to the scheme below.

First, compound 17 was synthesized by the method described in WO2014/112656.

Next, in a glass reaction vessel equipped with a cooling device, compound 18 (2.5 mmol), compound 16 (1.023 mmol), compound 17 (1.023 mmol), water (65.4 g) were added as starting materials at room temperature. , 40 wt% aqueous potassium phosphate solution (7.9 mL), THF (51.3 mL), tetralin (22 mL), and bis(tri-tert-butylphosphine) palladium (0) (0.02 mmol) were added, Stirred at 65° C. for 1 hour. A mixed solution of phenylboric acid (2.2 mmol) and a potassium phosphate aqueous solution (11.57 mL) with a concentration of 40% by mass was further added to the reactor as raw materials, and the mixture was stirred at 65° C. for 1 hour.

Next, the resulting organic layer was washed with an aqueous solution of sodium diethyldithiocarbamate, aqueous acetic acid, and water, and then the washed organic layer was added to methanol and the precipitated solid was collected by filtration to obtain a crude polymer.

The resulting crude polymer was dissolved in tetralin, passed through a 5B (JIS P 3801: 5 type B) filter paper, added again to methanol, and the precipitated solid was collected by filtration to obtain a polymer compound P. -1 was obtained.

(Example 2)
The raw materials added to the glass reaction vessel were compound 18 (2.2 mmol), compound 16 (1.023 mmol), compound 17 (1.023 mmol), water (65.4 g), and potassium phosphate having a concentration of 40% by mass. aqueous solution (7.9 mL), THF (51.3 mL), tetralin (22 mL), bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol), and phenylboric acid (2.2 mmol) and concentration 40 mass % potassium phosphate aqueous solution (11.57 mL) was used to synthesize polymer compound P-2 in the same manner as in Example 1.

(Example 3)
Polymer compound P-3 was synthesized according to the scheme below.

The raw materials added to the glass reaction vessel were compound 18 (2.1 mmol), compound 4 (0.987 mmol), compound 17 (0.987 mmol), water (62.4 g), and an aqueous potassium phosphate solution having a concentration of 40% by mass. (7.6 mL), THF (49 mL), tetralin (21 mL), bis(tri-1ert-butylphosphine)palladium(0) (0.02 mmol), and phenylboronic acid (2.1 mmol) and phosphorus at a concentration of 40% by weight. A polymer compound P-3 was synthesized in the same manner as in Example 1, except that a mixed solution of an aqueous potassium acid solution (11.0 mL) was used.

(Example 4)
Polymer compound P-4 was synthesized using compounds 17, 18 and 19 as shown in the following formula.

First, compound 17 and compound 19 were synthesized by the method described in International Publication No. 2014/112656.

Then, in a glass reaction vessel equipped with a cooling device, at room temperature, compound 17 (12.91 mmol), compound 19 (12.91 mmol), compound 18 (26.50 mmol), water (788 mL), 40 mass% phosphoric acid Potassium aqueous solution (93.5 mL), ortho-xylene (441 mL), cyclohexanone (441 mL), and chloride (methanide) {bis(1,1-dimethylethyl)[3,5-bis(1,1-dimethylethyl)phenyl] Phosphane}palladium (0.32 mmol) was added and mixed.

The resulting mixture was stirred at 65° C. for 2 hours. After washing the resulting organic layer with water and aqueous acetic acid, the washed organic layer was added to methanol and the precipitated solid was collected by filtration to obtain a crude polymer.

The obtained crude polymer is dissolved in ortho-xylene, passed through a 5B (JIS P 3801: 5 type B) filter paper, and then added to methanol again and the precipitated solid is collected by filtration to obtain a polymer compound P. -4 was obtained.

(Example 5)
A polymer compound P-5 having a molecular weight different from that of the polymer compound P-4 according to Example 4 was synthesized in the same manner as in Example 4, except that 12.94 mmol of each of the compounds 17 and 19 were used.

(Example 6)
Polymer compound P-6 was synthesized in the same manner as in Example 4, except that 12.94 mmol of compound 17 and compound 19 were used. The polymer compound P-6 according to Example 6 was synthesized under the same conditions as the synthesis process of the polymer compound P-5 according to Example 5, but the physical properties were slightly different.

(Example 7)
Polymer compound P-7 was synthesized in the same manner as in Example 4, except that 13.25 mmol of compound 17 and compound 19 were used.

(Example 8)
Polymer compound P-8 was synthesized according to the scheme below.

The raw materials added to the glass reaction vessel were compound 18 (2.1 mmol), compound 17 (0.977 mmol), compound 4 (0.977 mmol), water (62.4 g), and an aqueous potassium phosphate solution having a concentration of 40% by mass. (7.6 mL), THF (49 mL), tetralin (21 mL), bis(tri-1ert-butylphosphine)palladium(0) (0.02 mmol), and phenylboronic acid (2.1 mmol) and phosphorus at a concentration of 40% by weight. A polymer compound P-8 was synthesized in the same manner as in Example 1, except that a mixed solution of an aqueous potassium acid solution (11.0 mL) was used.

(Example 9)
Polymer compound P-9 was synthesized according to the following scheme.

The raw materials added to the glass reaction vessel were compound 18 (2.6 mmol), compound 7 (1.235 mmol), compound 17 (1.235 mmol), water (77.3 g), and an aqueous potassium phosphate solution having a concentration of 40% by mass. (9.4 mL), THF (60.7 mL), tetralin (26 mL), bis(tri-1ert-butylphosphine)palladium(0) (0.03 mmol), and phenylboric acid (2.6 mmol) and a concentration of 40% by mass. A polymer compound P-9 was synthesized in the same manner as in Example 1, except that a mixed solution of an aqueous potassium phosphate solution (13.7 mL) was used.

(Example 10)
Polymer compound P-10 was synthesized according to the scheme below.

The raw materials added to a glass reaction vessel were compound 18 (1.2 mmol), compound 16 (1.164 mmol), water (35.7 g), a 40% by mass potassium phosphate aqueous solution (4.3 mL), THF ( 28.0), tetralin (23.5 mL), bis(tri-1ert-butylphosphine) palladium (0) (0.01 mmol), and phenylboric acid (1.2 mmol) and an aqueous potassium phosphate solution with a concentration of 40% by mass ( Polymer compound P-10 was synthesized in the same manner as in Example 1, except that a mixed solution of 6.3 mL) was used.

(Comparative example 1)
Compound 17 and compound 19 were synthesized by the method described in International Publication No. 2014/112656.

Then, in a glass reaction vessel equipped with a cooling device at room temperature, compound 17 (8.89 mmol), compound 19 (8.89 mmol), compound 18 (18.00 mmol), water (540 mL), 40 mass% potassium phosphate Aqueous solution (60 mL), tetralin (300 mL), 1-methylcyclohexanol (441 mL), and chloride (methanide) {bis(1,1-dimethylethyl)[3,5-bis(1,1-dimethylethyl)phenyl] Phosphane}palladium (0.32 mmol) was added to give a mixture.

The organic layer obtained by stirring the resulting mixture at 65° C. for 2 hours was washed with water and acetic acid water, and then the washed organic layer was added to methanol, and the precipitated solid was collected by filtration as a crude polymer. .

The resulting crude polymer was dissolved in tetralin, passed through a 5B filter paper, added again to methanol, and the precipitated solid was filtered to synthesize polymer compound C-1.

(Comparative example 2)
Polymer compound C-2 was synthesized in the same manner as in Comparative Example 1, except that 8.87 mmol of compound 17 and compound 19 were used.

(Comparative Example 3)
Polymer compound C-3 was synthesized in the same manner as in Comparative Example 1, except that 8.82 mmol of compound 17 and compound 19 were used.

(Comparative Example 4)
Compound 17 (13.02 mmol), Compound 19 (13.02 mmol), Compound 18 (26.50 mmol), water (794 mL), 40 wt% potassium phosphate aqueous solution (88 mL), tetralin (441 mL), 1-methylcyclohexanol (441 mL), and chloride (methanide){bis(1,1-dimethylethyl)[3,5-bis(1,1-dimethylethyl)phenyl]phosphane}palladium (0.32 mmol). Polymer compound C-4 was synthesized in the same manner as in 1.

<Preparation of sample for viscosity measurement>
Tetralin was used as a solvent, and each of the polymer compounds of Examples 1 to 10 and Comparative Examples 1 to 4 was dissolved in the solvent at a concentration of 15 mg/mL, followed by heat treatment at 100°C for 3 hours. was performed to obtain a sample (composition) for viscosity measurement.

<Measurement of viscosity with E-type viscometer>
0.7 mL of a sample for viscosity measurement, which is a composition containing each of the polymer compounds according to Examples 1 to 10 and Comparative Examples 1 to 4, was weighed with a micropipette and measured with an E-type viscometer (Brookfield DV-2 Pro ), the temperature of the sample for viscosity measurement in the cup was kept constant (30° C.), and the viscosity was measured by rotating the spindle at 15 rpm.

<Calculation of thickening rate>
After storing the sample for viscosity measurement, which is the composition prepared as described above, at room temperature for 7 days after preparation, the viscosity value measured as described above (after 7 days) is changed to the viscosity value measured on the day of preparation (Init ) and multiplied by 100 to obtain a viscosity increase rate (%). The results are shown in Table 1 below.

<Measurement of proportion of terminal structure containing amide structure by infrared spectroscopy>
Using a mortar and pestle, the polymer compounds of Examples 1 to 4 and Comparative Examples 1 to 4 were each ground until fine, and potassium bromide and the polymers of Examples 1 to 4 and Comparative Examples 1 to 4 were obtained. Each of the compounds was mixed until the color became uniform so that the concentration of the polymer compound was 5% by mass, and a sample for measurement was prepared. The obtained sample was placed in a tablet forming machine to form a tablet, and the ratio of the terminal structure including the amide structure of the polymer compound was measured by infrared spectroscopy (transmission method) under the following measurement conditions. A tablet formed only from potassium bromide was used as a blank.

[Measurement condition]
Measurement method: infrared spectroscopy (transmission method)
Apparatus: Nicolet iS50 FT-IR manufactured by ThermoFisher
Accumulation times: 32 Contents: Polymer compound 10 mg, KBr 200 mg

Dividing the C═O stretching peak intensity derived from the terminal structure containing the amide structure contained in some of the polymer compounds contained in the composition by the peak intensity derived from the main chain contained in all polymer compounds, Further, the value obtained by multiplying by 100 was defined as the ratio (%) of the terminal structure containing the amide structure. The results are shown in Table 1 below. The C═O stretching peak derived from the terminal structure including the amide structure contained in some polymer compounds is shifted in the range of 1700 cm ⁻¹ or ±10 cm ⁻¹ when the peak is shifted. The intensity at the wave number identified as the C=O stretching peak contained in the polymer compound was adopted. In addition, the peak derived from the main chain contained in all polymer compounds is a peak shifted in the range of 954 cm ^-1 or ± 10 cm ^-1 when the peak is shifted, and the polymer The intensity at the wave number identified as the peak derived from the main chain contained in the compound was adopted.

The polymer compound P-1 according to Example 1, the polymer compound P-2 according to Example 2, the polymer compound P-3 according to Example 3, the polymer compound P-4 according to Example 4, Both the polymer compound P-5 according to Example 5 and the polymer compound P-6 according to Example 6 contain a compound having a terminal structure represented by formula (II). was below the detection limit, the proportion of terminal structures containing amide structures could not be calculated. In Table 1, "N.D." indicates that the ratio of the terminal structure containing the amide structure could not be calculated because the C=O stretching peak intensity was below the detection limit.

REFERENCE SIGNS LIST 1 image detection unit 2 display device 10 photoelectric conversion element 11, 210 support substrate 12 first electrode 13 electron transport layer 14 active layer 15 hole transport layer 16 second electrode 17 sealing member 20 CMOS transistor substrate 30 interlayer insulating film 32 Interlayer Wiring Section 40 Sealing Layer 42 Scintillator 44 Reflective Layer 46 Protective Layer 50 Color Filter 100 Fingerprint Detection Section 200 Display Panel Section 200a Display Area 220 Organic EL Element 230 Touch Sensor Panel 240 Sealing Substrate 300 Vein Detection Section 302 Glass Substrate 304 Light source section 306 Cover section 310 Insertion section 400 Image detection section for TOF rangefinder 401 Insulating layer 402 Floating diffusion layer 404 Photogate 406 Light shielding section

Claims (11)

Containing two or more polymer compounds containing structural units represented by the following formula (I),
At least one of the two or more polymer compounds is a polymer compound having a terminal structure represented by the following formula (II) bonded to a divalent organic group represented by A,
The ratio of the peak intensity derived from the terminal structure represented by the following formula (II) to the peak intensity derived from the main chain contained in all polymer compounds measured by infrared spectroscopy is 3.7% or less. ,Composition.

(In formula (I),
A represents a divalent organic group which may have a substituent,
B represents a ring structure containing a thiadiazole skeleton, an oxadiazole skeleton, or a triazole skeleton,
Y represents a group represented by -CH- or a nitrogen atom. )

(In formula (II),
B and Y are as defined above. ) The ratio of the peak intensity derived from the terminal structure represented by the formula (II) to the peak intensity derived from the main chain contained in all polymer compounds when measured by infrared spectroscopy is 2% or less. A composition according to claim 1 . The composition according to claim 1 or 2, wherein A is a divalent organic group represented by the following formula (IV).

(In formula (IV),
Ar ² and Ar ³ each independently represent an optionally substituted trivalent aromatic heterocyclic group,
Z represents a group represented by any one of the following formulas (Z-1) to (Z-7). )

(In the formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^c or a group represented by —SO ₂ —R ^d ,
R ^c and R ^d are each independently
hydrogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
In formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different. ) The composition according to claim 1 or 2, wherein said B contains a thiadiazole skeleton. The composition according to claim 1 or 2, wherein said A contains a thiophene skeleton. 3. The composition of claim 1 or 2, further comprising an organic solvent, said organic solvent comprising an aromatic hydrocarbon. An ink composition comprising the composition according to claim 1 or 2 and an n-type semiconductor material. A solidified film obtained by solidifying the ink composition according to claim 7 . A photoelectric conversion device comprising the solidified film according to claim 8 as an active layer. 3. A method for producing the composition according to claim 1, comprising a polymerization step using a solvent that does not contain alcohols as a polymerization solvent. 11. The method for producing a composition according to claim 10, wherein a ketone solvent is used as the polymerization solvent.

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