JP5957313B2 - Film containing organic antimony compound and polymer compound - Google Patents

Description

  The present invention relates to a film containing an organic antimony compound and a polymer compound.

  It is known that an organic antimony compound is used for a living radical polymerization initiator (see Patent Document 1), a carbon dioxide fixing material (see Patent Document 2), and the like.

Japanese Patent No. 4477636 JP 2008-255049 A

  However, the light emission characteristics and the like of organic antimony compounds are not yet well known, and organic antimony compounds are not effectively used for electronic devices such as organic electroluminescence devices (sometimes referred to as “organic EL devices”). . Furthermore, the organic antimony compound is applied to an electronic device such as a coexisting component that can be used to improve the properties such as film formation and film forming properties in order to apply to an electronic device such as an organic EL device. There has not yet been studied to construct the resulting film.

  Then, an object of this invention is to provide the film | membrane containing an organic antimony compound and a high molecular compound which can be used as a functional layer of electronic devices, such as an organic EL element.

  As a result of intensive studies, the present inventors have completed the present invention.

（式（１）中、
Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又は有機基である。
Ｒ^３は、水素原子又は有機基である。
Ｒ^１とＲ^２は結合して、それぞれが結合する炭素原子とともに環構造を形成していてもよく、Ｒ^４とＲ^５は結合して、それぞれが結合する炭素原子とともに環構造を形成していてもよい。
Ａは、−Ｏ−で表される基、−Ｓ−で表される基、−Ｎ（Ｒ^６）−で表される基、−Ｃ（Ｒ^７）_２−で表される基、−Ｓｉ（Ｒ^８）_２−で表される基、又は−Ｐ（Ｒ^９）−で表される基である。複数個存在するＡは、同一であっても異なっていてもよい。Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、置換基を有していてもよいヒドロカルビル基である。）
［４］ 前記Ａが、−Ｓ−で表される基である、［３］に記載の膜。
［５］ 前記Ｒ^３が、置換基を有していてもよいアリール基である、［３］又は［４］に記載の膜。
［６］ 前記式（１）で表される化合物が、下記式（２）で表される化合物であるか、又は下記式（３）で表される化合物である、［３］〜［５］のいずれか１つに記載の膜。

（式（２）中、
Ｒ^１及びＲ^５は、それぞれ独立に、水素原子又は有機基である。
Ａｒ^１は、置換基を有していてもよいアリール基である。）

（式（３）中、
Ｒ^１０及びＲ^１１は、それぞれ独立に、有機基である。
ｍ及びｎは、それぞれ独立に、０〜４の数である。
Ａｒ^２は、置換基を有していてもよいアリール基である。）
［７］ 前記高分子化合物が、ポリスチレン誘導体、ポリメチルメタクリレート、ポリカルバゾール誘導体、ポリアリールアミン誘導体、ポリアリールアルカン誘導体、ポリビニルカルバゾール誘導体、ポリオキサジアゾール誘導体、ポリトリアジン誘導体、ポリフルオレン誘導体、又はこれらの組み合わせである、［１］〜［６］のいずれか１つに記載の膜。
［８］ 下記式（１）で表される化合物。

（式（１）中、
Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又は有機基である。
Ｒ^３は水素原子又は有機基である。Ｒ^１とＲ^２は結合して、それぞれが結合する炭素原子とともに環構造を形成していてもよく、Ｒ^４とＲ^５は結合して、それぞれが結合する炭素原子とともに環構造を形成していてもよい。
Ａは、−Ｏ−で表される基、−Ｓ−で表される基、−Ｎ（Ｒ^６）−で表される基、−Ｃ（Ｒ^７）_２−で表される基、−Ｓｉ（Ｒ^８）_２−で表される基、又は−Ｐ（Ｒ^９）−で表される基である。複数個存在するＡは、同一であっても異なっていてもよい。
Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、置換基を有していてもよいヒドロカルビル基である。）
［９］ 下記式（２）で表されるか、又は下記式（３）で表される化合物。

（式（２）中、
Ｒ^１及びＲ^５は、それぞれ独立に、水素原子又は有機基である。
Ａｒ^１は、置換基を有していてもよいアリール基である。）

（式（３）中、
Ｒ^１０及びＲ^１１は、それぞれ独立に、有機基である。
ｍ及びｎは、それぞれ独立に、０〜４の数である。
Ａｒ^２は、置換基を有していてもよいアリール基である。） The present invention provides the following [1] to [9].
[1] A film containing an organic antimony compound and a polymer compound.
[2] The film according to [1], wherein the organic antimony compound is a compound in which two or three sp ² carbon atoms are bonded to an antimony atom.
[3] The film according to [1] or [2], wherein the organic antimony compound is a compound represented by the following formula (1).

(In the formula (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an organic group.
R ³ is a hydrogen atom or an organic group.
R ¹ and R ² may be bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to form a ring structure with the carbon atoms to which they are bonded. May be.
A represents a group represented by -O-, a group represented by -S-, a group represented by -N (R ⁶ )-, a group represented by -C (R ⁷ ) _2- , -Si It is a group represented by (R ⁸ ) ₂ — or a group represented by —P (R ⁹ ) —. A plurality of A may be the same or different. R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbyl group optionally having a substituent. )
[4] The film according to [3], wherein A is a group represented by -S-.
[5] The film according to [3] or [4], wherein R ³ is an aryl group which may have a substituent.
[6] The compound represented by the formula (1) is a compound represented by the following formula (2) or a compound represented by the following formula (3) [3] to [5] The membrane according to any one of the above.

(In the formula (2),
R ¹ and R ⁵ are each independently a hydrogen atom or an organic group.
Ar ¹ is an aryl group which may have a substituent. )

(In formula (3),
R ¹⁰ and R ¹¹ are each independently an organic group.
m and n are each independently a number of 0 to 4.
Ar ² is an aryl group which may have a substituent. )
[7] The polymer compound is a polystyrene derivative, polymethyl methacrylate, polycarbazole derivative, polyarylamine derivative, polyarylalkane derivative, polyvinylcarbazole derivative, polyoxadiazole derivative, polytriazine derivative, polyfluorene derivative, or these The film according to any one of [1] to [6], which is a combination of
[8] A compound represented by the following formula (1).

(In the formula (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an organic group.
R ³ is a hydrogen atom or an organic group. R ¹ and R ² may be bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to form a ring structure with the carbon atoms to which they are bonded. May be.
A represents a group represented by -O-, a group represented by -S-, a group represented by -N (R ⁶ )-, a group represented by -C (R ⁷ ) _2- , -Si It is a group represented by (R ⁸ ) ₂ — or a group represented by —P (R ⁹ ) —. A plurality of A may be the same or different.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbyl group optionally having a substituent. )
[9] A compound represented by the following formula (2) or represented by the following formula (3).

(In the formula (2),
R ¹ and R ⁵ are each independently a hydrogen atom or an organic group.
Ar ¹ is an aryl group which may have a substituent. )

(In formula (3),
R ¹⁰ and R ¹¹ are each independently an organic group.
m and n are each independently a number of 0 to 4.
Ar ² is an aryl group which may have a substituent. )

  ADVANTAGE OF THE INVENTION According to this invention, the film | membrane which contains an organic antimony compound and a high molecular compound, and has a luminescent property can be provided. Since the film of the present invention is flat and has little film thickness unevenness, it can be suitably used as a light emitting layer of an organic EL element.

  Hereinafter, the film | membrane containing the organic antimony compound and polymer compound concerning embodiment of this invention is demonstrated.

<Explanation of terms>
In the present specification, Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, n-Bu represents a normal butyl group, and n-Hex represents a normal hexyl group. And Ph represents a phenyl group.

  In this specification, when propyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, octadecyl group, docosyl group are described, May be linear or branched, but is preferably linear.

  In the present specification, examples of the substituent in the case where “optionally substituted” or “optionally substituted” are described are as follows unless otherwise described. , A halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms, among these, a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms, or 1 to 1 carbon atom. 18 hydrocarbyloxy groups are preferred, halogen atoms, hydrocarbyl groups having 1 to 12 carbon atoms or hydrocarbyloxy groups having 1 to 12 carbon atoms are more preferred, and halogen atoms or hydrocarbyl groups having 1 to 12 carbon atoms are more preferred. Particularly preferred are hydrocarbyl groups having 1 to 8 carbon atoms.

  In the present specification, the case where “the Z group in which the number of carbon atoms which may have a substituent is X to Y (X and Y are positive integers, X <Y.)” Is described. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferably, the total number of carbon atoms with the number of carbon atoms in the substituent is X to Y.

<Organic antimony compound>
The film of this embodiment contains an organic antimony compound and a polymer compound other than the organic antimony compound.
The organic antimony compound contained in the film of this embodiment is usually an antimony compound containing one or more carbon atoms, preferably a compound having 2 to 200 carbon atoms, more preferably a compound having 3 to 150 carbon atoms. More preferably, it is a compound having 6 to 100 carbon atoms, particularly preferably a compound having 10 to 75 carbon atoms, and particularly preferably a compound having 14 to 50 carbon atoms.

  The organic antimony compound of this embodiment may contain one antimony atom or two or more, but preferably contains one.

  The organic antimony compound of this embodiment contains a transition metal atom, and the antimony atom may be coordinated to the transition metal atom, but preferably does not contain a transition metal atom.

In the organic antimony compound of this embodiment, one or more carbon atoms are usually bonded to an antimony atom. Since the solubility in an organic solvent can be improved, the film-formability can be further improved, and a flat and uniform film thickness can be obtained, so that three carbon atoms are bonded to the antimony atom. It is preferable. The carbon atom bonded to the antimony atom is preferably an sp ³ carbon atom or an sp ² carbon atom, and more preferably two or three sp ² carbon atoms are bonded to the antimony atom. More preferably, the organic antimony compound has three sp ² carbon atoms bonded to the antimony atom.

  Since the organic antimony compound of the present embodiment is excellent in light emission when contained as a component of the film, it is preferably a structure represented by the following formula (1).

In formula (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an organic group.
R ³ is a hydrogen atom or an organic group.
R ¹ and R ² may be bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ may be bonded to form a ring structure with the carbon atoms to which they are bonded. Good.
A represents a group represented by -O-, a group represented by -S-, a group represented by -N (R ⁶ )-, a group represented by -C (R ⁷ ) _2- , -Si It is a group represented by (R ⁸ ) ₂ — or a group represented by —P (R ⁹ ) —. A plurality of A may be the same or different.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbyl group optionally having a substituent.

In the organic antimony compound represented by the formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an organic group. Examples of the organic group in R ¹ , R ² , R ⁴ and R ⁵ include a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent, and a substituent. A good hydrocarbyloxy group having 1 to 30 carbon atoms, an optionally substituted hydrocarbylthio group having 1 to 30 carbon atoms, and a substituted silyl group having 1 to 30 carbon atoms (substituted silyl group) The substituent which may have a substituent further may be mentioned. The substituent which the substituted silyl group may have is preferably a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms which may have a substituent, or the number of carbon atoms which may have a substituent. Is a hydrocarbyloxy group having 1 to 18 carbon atoms or a substituted silyl group having 1 to 30 carbon atoms, more preferably a halogen atom or a hydrocarbyl group having 1 to 18 carbon atoms which may have a substituent. Or a substituted silyl group having 1 to 18 carbon atoms, more preferably a hydrocarbyl group having 1 to 18 carbon atoms which may have a substituent, or a substitution having 1 to 18 carbon atoms. A silyl group.

  Each of the hydrocarbyl group, the hydrocarbyloxy group and the hydrocarbylthio group may be linear, branched or cyclic, and is preferably linear or branched.

Examples of the halogen atom that R ¹ , R ² , R ^4, and R ⁵ can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom is preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom or a chlorine atom, and still more preferably a fluorine atom.

Examples of the hydrocarbyl group in the “hydrocarbyl group optionally having substituent (s)” that R ¹ , R ² , R ⁴ and R ⁵ can take include, for example, a methyl group, an ethyl group, a 1-propyl group, and a 2-propyl group. 1-butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclopropyl group , Cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, benzyl group, α, α-dimethylbenzyl group, 1-phenethyl group, 2-phenethyl group, vinyl group, propenyl group, butenyl group, Oleyl group, eicosapentaenyl group, docosahexaenyl group, 2,2-diphenylvinyl group, 1,2,2-to Riphenylvinyl group, 2-phenyl-2-propenyl group, phenyl group, 2-tolyl group, 4-tolyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, terphenyl group, 3,5- Diphenylphenyl group, 3,4-diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1 -A naphthyl group, 2-naphthyl group, 9-anthryl group, 2-anthryl group, 9-phenanthryl group, 1-pyrenyl group, chrycenyl group, naphthacenyl group and coronyl group are mentioned.

  Among these hydrocarbyl groups, preferably, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Octyl group, decyl group, dodecyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, benzyl group, α, α-dimethylbenzyl group, 1-phenethyl group, 2-phenethyl group, vinyl group, propenyl group, butenyl Group, oleyl group, eicosapentaenyl group, docosahexaenyl group, 2,2-diphenylvinyl group, 1,2,2-triphenylvinyl group, 2-phenyl-2-propenyl group, phenyl group, 2-tolyl Group, 4-tolyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, terphenyl group, 3,5-diphenylphenyl Group, 3,4-diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1-naphthyl Group, 2-naphthyl group, 9-anthryl group, 2-anthryl group, or 9-phenanthryl group, more preferably methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2 -Butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, benzyl group or phenyl group, more preferably methyl group, ethyl Group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, tert-butyl group, pentyl group, hexyl group, or 2-ethyl group. A hexyl group, particularly preferably a methyl group.

Examples of the hydrocarbyloxy group in the “hydrocarbyloxy group optionally having substituent (s)” that R ¹ , R ² , R ⁴ and R ⁵ can take include, for example, a methoxy group, an ethoxy group, a 1-propanoxy group, 2- Propanoxy group, 1-butoxy group, 2-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, 3,7- Dimethyloctyloxy group, cyclopropanoxy group, cyclopentyloxy group, cyclohexyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, norbornyloxy group, benzyloxy group, α, α-dimethylbenzyloxy group, 2-phenethyloxy group, 1-phenethyloxy group, pheno Xyl group, 1-naphthyloxy group, and 2-naphthyloxy group can be mentioned.

  Among these hydrocarbyloxy groups, preferably methoxy group, ethoxy group, 1-propanoxy group, 2-propanoxy group, 1-butoxy group, 2-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy Group, octyloxy group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, or 3,7-dimethyloctyloxy group, more preferably methoxy group or ethoxy group.

Examples of the hydrocarbylthio group in the “hydrocarbylthio group optionally having substituent (s)” that R ¹ , R ² , R ⁴ and R ⁵ can take include, for example, methylthio group, ethylthio group, 1-propylthio group, 2- Propylthio group, 1-butylthio group, 2-butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio Group, cyclopropylthio group, cyclopentylthio group, cyclohexylthio group, 1-adamantylthio group, 2-adamantylthio group, norbornylthio group, benzylthio group, α, α-dimethylbenzylthio group, 2-phenethylthio group, 1- Phenethylthio group, phenylthio group, 1-naphthyl A thio group and a 2-naphthylthio group are mentioned.

  Among these hydrocarbylthio groups, preferably methylthio group, ethylthio group, 1-propylthio group, 2-propylthio group, 1-butylthio group, 2-butylthio group, isobutylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group Group, dodecylthio group, 2-ethylhexylthio group, or 3,7-dimethyloctylthio group, more preferably methylthio group or ethylthio group.

The substituted silyl group in the “substituted silyl group” that R ¹ , R ² , R ⁴ and R ⁵ can take is one, two or three hydrogen atoms in the silyl group having 1 to 30 carbon atoms. A silyl group substituted with one, two or three groups selected from the group consisting of an alkyl group, an aryl group having 6 to 30 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms . Preferably, it refers to a silyl group substituted with three groups selected from the above group. Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, tert-butyldimethylsilyl group, pentyldimethylsilyl group, Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, tri Examples include phenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, and dimethylmonophenylsilyl group.

  Among these substituted silyl groups, a trimethylsilyl group, a triethylsilyl group, and a tripropylsilyl group are preferable. Or it is a tert-butyldimethylsilyl group, More preferably, it is a trimethylsilyl group.

In the organic antimony compound represented by the formula (1), A represents a group represented by —O—, a group represented by —S—, a group represented by —N (R ⁶ ) —, —C A group represented by (R ⁷ ) ₂ —, a group represented by —Si (R ⁸ ) ₂ —, or a group represented by —P (R ⁹ ) —.

Among these groups, when an organic antimony compound having such a group is contained in the film, the emission intensity is excellent. Therefore, a group represented by —O—, a group represented by —S—, and —C (R ⁷ ) A group represented by _2- or a group represented by -Si (R ⁸ ) _2- is preferred, a group represented by -O- or a group represented by -S- is more preferred, and -S A group represented by-is more preferred.

In the organic antimony compound represented by the formula (1), R ³ is a hydrogen atom or an organic group. Examples of the organic group for R ³ include a saturated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and a hydrocarbyl having 1 to 30 carbon atoms which may have a substituent. Examples thereof include an oxy group, an aryl group which may have a substituent, and a monovalent heterocyclic group having 2 to 50 carbon atoms which may have a substituent. The organic group for R ³ is preferably an aryl group which may have a substituent, or a monovalent heterocyclic group having 2 to 50 carbon atoms which may have a substituent, More preferably, it is an aryl group which may have a substituent. The number of carbon atoms of the aryl group in the aryl group which may have a substituent is preferably 6 to 50, more preferably 6 to 36, and still more preferably 6 to 12.

Examples of the saturated hydrocarbon group in the “saturated hydrocarbon group optionally having substituent (s)” that R ³ can have include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, Alkyl groups having 1 to 30 carbon atoms such as tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, octadecyl group and docosyl group And cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group, and adamantyl group. Is an alkyl group having 1 to 12 carbon atoms.

Specific examples and preferred examples of the hydrocarbyloxy group in the “hydrocarbyloxy group optionally having substituent (s)” that R ³ can have are the same as the hydrocarbyloxy group in R ¹ , R ² , R ^4, and R ⁵ . It is.

Examples of the aryl group in the “aryl group optionally having substituent (s)” that R ³ can have include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-methylphenyl group, and a 3-methylphenyl group. 4-methylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-hexyl Examples include a phenyl group, a 4-cyclohexylphenyl group, a 4-adamantylphenyl group, a 4-phenylphenyl group, a 1-anthracenyl group, a 2-anthracenyl group, and a 9-anthracenyl group.

  Among these aryl groups, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4 -Ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, or 4-hexylphenyl group, more preferably phenyl group, 1-naphthyl Group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, or 3,5-dimethylphenyl group.

Examples of the monovalent heterocyclic group in the “monovalent heterocyclic group optionally having substituent (s)” that R ³ can have include a pyrazolyl group, a benzopyrazolyl group, a thienyl group, a benzothienyl group, and a pyrrolyl group. Benzopyrrolyl group, furyl group, benzofuryl group, phosphoryl group, pyridyl group, piperidyl group, piperazyl group, quinolyl group, isoquinolyl group, triazyl group, quinazolinyl group, imidazolyl group, benzimidazolyl group, oxazolyl group, and thienyl group, A pyridyl group, a piperidyl group, a piperazyl group, a quinolyl group, an isoquinolyl group, an imidazolyl group, or a benzoimidazolyl group is preferable, and a pyridyl group, a quinolyl group, or an isoquinolyl group is more preferable.

R ¹ and R ⁵ are preferably organic groups.

R ² and R ⁴ are preferably hydrogen atoms.

R ¹ and R ² may be bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to form a ring structure with the carbon atoms to which they are bonded. However, when a ring structure is formed, R ¹ and R ² are bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to each other. It is preferable to form a ring structure with the carbon atoms to be bonded. When these form a ring structure, it is preferable to form a benzene ring, and the benzene ring may further have a substituent.

As the organic antimony compound of this embodiment when R ¹ and R ² do not form a ring structure and R ⁴ and R ⁵ do not form a ring structure, a compound represented by the following formula (2) is preferable.

In formula (2),
R ¹ and R ⁵ represent the same meaning as described above.
Ar ¹ is an aryl group which may have a substituent.

This embodiment in which R ¹ and R ² are bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to form a ring structure with the carbon atoms to which they are bonded. An example of a preferable structure of the organic antimony compound is represented by the following formula (3).

In formula (3),
R ¹⁰ and R ¹¹ are each independently an organic group.
m and n are each independently a number of 0 to 4.
Ar ² is an aryl group which may have a substituent.

In Formula (2), Ar ¹ is an aryl group which may have a substituent, and specific examples and preferred examples of the aryl group include an aryl which may have a substituent which R ³ can take. Same as group.

In formula (3), R ¹⁰ and R ¹¹ are each independently an organic group. Specific examples and preferred examples of the organic group are the same as the organic groups which R ¹ , R ² , R ⁴ and R ⁵ can take.

  In formula (3), m and n are each independently a number of 0 to 4, preferably a number of 0 to 2, more preferably a number of 0 to 1, and still more preferably 0.

  Specific examples of the organic antimony compound contained in the film of the present embodiment are represented by the following formula 1-1 to formula 1-21, formula 2-1 to formula 2-8, and formula 3-1 to formula 3-9. And organic antimony compounds.

  In the organic antimony compounds represented by the above formula 1-1 to formula 1-21, formula 2-1 to formula 2-8, and formula 3-1 to formula 3-9, preferably formula 2-1 to formula 2 -8, or organic antimony compounds represented by Formula 3-1 to Formula 3-9, and more preferably Formula 2-1, Formula 2-2, Formula 2-3, Formula 2-6, Formula 2-8. , Formula 3-1, Formula 3-3, Formula 3-3, Formula 3-4, Formula 3-7, or an organic antimony compound represented by Formula 3-8.

The structure of the organic antimony compound of the present invention can be confirmed by analytical methods such as melting point measurement, molecular weight measurement, ¹ H NMR measurement, ¹³ C NMR measurement, and CHN elemental analysis.

  The organic antimony compound of the present invention can be synthesized by combining generally known reactions, and is not particularly limited. The organic antimony compound of this embodiment can be suitably manufactured by the method shown below, for example.

  The compound represented by the formula (1) is represented by the following formula (4):

（式（４）中、
Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５及びＡは前記と同じ意味を表す。
Ｘ^２は、臭素原子又はヨウ素原子である。複数個存在するＸ^２は、同一であっても異なっていてもよい。）
で表される化合物に、Ｘ^２が結合する炭素原子にアニオン性の電荷特性を与える化合物（例えば、ｎ−ブチルリチウム等の有機リチウム化合物や、マグネシウム等）を２当量加えてジアニオンを生成させた後、下記式（５）：

（式（５）中、
Ｒ^３は前記と同じ意味を表す。
Ｘ^３は、塩素原子又は臭素原子である。複数個存在するＸ^３は、同一であっても異なっていてもよい。）
で表される化合物と反応させることにより、得ることができる。

(In formula (4),
R ¹ , R ² , R ⁴ , R ⁵ and A have the same meaning as described above.
X ² is a bromine atom or an iodine atom. A plurality of X ² may be the same or different. )
A dianion was produced by adding 2 equivalents of a compound (for example, an organic lithium compound such as n-butyllithium or magnesium) that gives an anionic charge characteristic to the carbon atom to which X ² is bonded. Then, following formula (5):

(In Formula (5),
R ³ represents the same meaning as described above.
X ³ is a chlorine atom or a bromine atom. A plurality of X ³ may be the same or different. )
It can obtain by making it react with the compound represented by these.

The compound represented by the formula (5) can be produced, for example, by reacting Sb (R ³ ) ₃ and Sb (X ³ ) _{3 at} a molar ratio of 1: 2.

<Membrane>
The thickness of the film of the present embodiment is usually 1 nm to 50 μm, preferably 2 nm to 10 μm, more preferably 3 nm to 3 μm, and further preferably 5 nm to 1 μm. When used as a layer, the current is more likely to flow, so the thickness is particularly preferably 10 nm to 150 nm.

  The film of this embodiment may have pinholes and irregularities on the surface as long as it is within the allowable range. However, from the viewpoint of the electrical characteristics of the electronic element, the film should have pinholes and irregularities as much as possible. However, it is preferably flat.

  The film of this embodiment is, for example, a method including a step of depositing the organic antimony compound and the coexisting component on the substrate in an arbitrary ratio, or the organic antimony compound and the coexisting component in an arbitrary ratio in a solvent. It can be produced by a method comprising a step of suspending or dissolving and applying the obtained coating solution to a substrate. The film of the present embodiment is preferably produced by a method including a step of suspending or dissolving the organic antimony compound and the coexisting component in a solvent at an arbitrary ratio and applying the obtained coating solution.

Examples of the solvent used in the coating step include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and other chlorine solvents, tetrahydrofuran. , Ether solvents such as 2-methyltetrahydrofuran, 1,4-dioxane and anisole, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, phenylcyclohexane and bicyclohexylbenzene, cyclohexane, methylcyclohexane, n-pentane and n-hexane Aliphatic hydrocarbon solvents such as n-heptane, n-octane, n-nonane, n-decane, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, methyl benzoate, vinegar Ester solvent such as phenyl, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol Polyhydric alcohols and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide, Examples include nitrile solvents such as acetonitrile and benzonitrile. These solvents may be used alone or in combination of a plurality of types.
Among these solvents, since the film thickness of the film of this embodiment becomes more uniform, a chlorine solvent, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent, or a ketone solvent is preferable, and chloroform, 1,2-dichloroethane, 1 , 1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzenetoluene, xylene, mesitylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butyl Benzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, ethoxybenzene, methyl benzoate, cyclohexanone, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octane Non, 2-nonanone, 2-decanone, dicyclohexyl ketone, or acetophenone is more preferable.

  Examples of the method for drying the solvent include air drying, heat drying, vacuum drying, heat vacuum drying, and drying performed by spraying a nitrogen gas on the coating film. Air drying or heat drying is preferable, and heat drying is more preferable. . The atmosphere in drying the solvent is not particularly limited. The atmosphere for drying the solvent is preferably an inert gas atmosphere such as nitrogen gas or argon gas.

  Examples of the coating method include spin coating, casting, dip coating, gravure printing, bar coating, roll coating, spray coating, screen printing, flexographic printing, inkjet printing, and offset printing. A spin coating method, a casting method, a roll coating method, a spray coating method, a screen printing method, a flexographic printing method, an ink jet printing method, or an offset printing method is preferable.

  The film of the present invention contains the organic antimony compound and a coexisting component. This coexisting component contains at least a polymer compound (sometimes referred to as “polymer organic material”). As other coexisting components, a low molecular organic material, an organic-inorganic composite material, an inorganic material, and a mixture thereof can be used, and can be arbitrarily selected according to applications.

  Examples of the coexisting polymer compound include carbazole derivatives, pyrazoline derivatives, pyrazolone derivatives, stilbene derivatives, triphenyldiamine derivatives, phenylenediamine derivatives, styrylanthracene derivatives, styrylamine derivatives, aromatic dimethylidyne derivatives, hydrazone derivatives, Polymers containing residues of hole transport materials such as amino-substituted chalcone derivatives; polyarylalkane derivatives, polyarylamine derivatives, polyvinylcarbazole derivatives, polysilane derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain Polymer hole transport materials such as polyaniline derivatives, poly (2,5-thienylene vinylene) derivatives, aniline copolymers, and conductive polymer oligomers such as polythiophene; Azole derivatives, imidazole derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic carboxylic acid anhydride derivatives (naphthalene, perylene), metal complexes (for example, 8- Metal complexes of quinolinol derivatives, metal complexes with benzoxazole ligands, metal complexes with benzothiazole ligands, naphthoquinone derivatives, anthraquinone derivatives, tetracyanoanthraquinodimethane derivatives, fluorenone derivatives, diphenylenedicyanoethylene Derivatives, polymers containing residues of electron transport materials such as diphenoquinone derivatives, 8-hydroxyquinoline derivatives, phthalocyanine derivatives, metalloporphyrin derivatives, polytriazine derivatives, polyoxazoles Electron transport materials such as conductors, polynaphthalene derivatives, polythienylene vinylene derivatives, polyquinoline derivatives, polyquinoxaline derivatives, polymers containing aromatic amine structures in the main chain or side chain; polyvinyl chloride, polycarbonate, polystyrene derivatives, polymethyl Methacrylate (PMMA), polybutyl methacrylate and derivatives thereof, polyfluorene derivatives, polyester and derivatives thereof, polysulfone and derivatives thereof, polyphenylene oxide derivatives, polybutadiene derivatives, hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, polyethylene oxide and its derivatives, polyacrylonitrile And a polymer matrix such as ril and derivatives thereof, a copolymer of vinylidene fluoride and propylene hexafluoride.

Examples of other coexisting components include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, organosilane derivatives, amino Substituted chalcone derivatives, anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, styrylamine derivatives, aromatic dimethylidine derivatives, porphyrin derivatives, thiophene oligomers, conductive polymers oligomers such as polythiophene, anthraquinodimethane derivatives, anthrone Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, di- Tyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides, phthalocyanine derivatives, metal complexes (eg, metal complexes using platinum group elements, metal complexes using rare earth elements, aluminum complexes coordinated with 8-quinolinol derivatives, metal phthalocyanines , Metal complexes with benzoxazole as ligands, metal complexes with benzothiazole as ligands), alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, alkalis Metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide or rare earth metal halide, alkali metal complex, alkaline earth metal complex, rare earth metal complex, fluorene skeleton Compound, pyridine skeleton, triazine skeleton Compound, compound having arylsilane skeleton, compound having naphthacene skeleton, compound having dicyanoethylene skeleton, compound having coumarin skeleton, compound having quinacridone skeleton, compound having phenylene vinylene skeleton, compound having naphthalene skeleton, supporting salt (Lithium trifluoromethanesulfonate, lithium perchlorate, tetrabutylammonium perchlorate, potassium hexafluorophosphate, tetra-n-butylammonium tetrafluoroborate, etc.) (propylene carbonate, acetonitrile, 2-methyltetrahydrofuran, 1,3-dioxofuran, nitrobenzene, N, N-dimethylformamide, dimethyl sulfoxide, glycerin, propyl alcohol, water, etc.), and mixtures thereof. Preferably, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, organosilane derivatives, styrylamine derivatives, porphyrins Derivatives, thiophene oligomers, diphenylquinone derivatives, tetracarboxylic anhydrides of aromatic rings (naphthalene, perylene, etc.), phthalocyanine derivatives, metal complexes (for example, metal complexes of 8-quinolinol derivatives, metal complexes having metal phthalocyanine as a ligand) , Metal complexes having benzoxazole as a ligand and metal complexes having benzothiazole as a ligand), compounds having a fluorene skeleton, compounds having a pyridine skeleton, triazi A compound having a skeleton or a compound having an arylsilane skeleton, more preferably a carbazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a phenylenediamine derivative, an arylamine derivative, an organic silane derivative, a porphyrin derivative, or a phthalocyanine derivative , A compound having a fluorene skeleton, a compound having a pyridine skeleton, a compound having a triazine skeleton, or a compound having an arylsilane skeleton, more preferably a carbazole derivative, an oxadiazole derivative, an arylamine derivative, a compound having a fluorene skeleton , A compound having a triazine skeleton, or a compound having an arylsilane skeleton.
The coexisting component contained in the film of the present embodiment may be one type or a combination of two or more types.

  The content of the organic antimony compound in the film of this embodiment is usually 0.01% to 99.9% by weight, preferably 0.1% to 99% by weight, based on the weight of the entire film. %, More preferably 1% by weight to 90% by weight, still more preferably 5% by weight to 80% by weight, and particularly preferably 10% by weight to 50% by weight.

  The film of the present invention contains at least a polymer compound as a coexisting component. The polymer compound that can be included in the film of the present embodiment is preferably a polycarbazole derivative, a polyarylamine derivative, a polyphenylenediamine derivative, a polyhydrazone derivative, a polyarylalkane derivative, a polyvinylcarbazole derivative, a polysilane derivative, a side chain, or a main chain. Residues of polysiloxane derivatives having an aromatic amine structure, poly (2,5-thienylene vinylene) derivatives, aniline copolymers, polytriazole derivatives, polyoxadiazole derivatives, polyimidazole derivatives, 8-hydroxyquinoline derivatives Group-containing polymer, polyphthalocyanine derivative, polymer containing metal porphyrin derivative residue, polytriazine derivative, polyoxazole derivative, polynaphthalene derivative, polyaniline derivative, polythiophene derivative, polythienille Vinylene derivatives, polyquinoxaline derivatives, polymers containing aromatic amine structures in the main chain or side chain, polyvinyl chloride, polycarbonate, polystyrene derivatives, polymethyl methacrylate derivatives, polyfluorene derivatives, polyphenylene oxide derivatives, hydrocarbon resins, polyamides, Polyethylene oxide and its derivatives.

  The polymer compound that can be included in the film of the present embodiment is more preferably a polycarbazole derivative, a polyarylamine derivative, a polyarylalkane derivative, a polyvinylcarbazole derivative, a polysilane derivative, a polythiophene derivative, a polyoxadiazole derivative, or a metal porphyrin derivative. Polymers containing residues of, polytriazine derivatives, polyoxazole derivatives, polynaphthalene derivatives, polymers containing aromatic amine structures in the main chain or side chain, polystyrene derivatives, polymethyl methacrylate derivatives, polyfluorene derivatives, polyphenylene oxide derivatives It is.

  More preferably, the polymer compound that can be included in the film of the present embodiment is a polystyrene derivative, polymethyl methacrylate, polycarbazole derivative, polyarylamine derivative, polyarylalkane derivative, polyvinylcarbazole derivative, polyoxadiazole derivative, polytriazine. A derivative, a polyfluorene derivative, or a combination thereof.

  The polymer compound that can be included in the film of the present embodiment may be one kind or a combination of two or more kinds.

The weight average molecular weight in terms of polystyrene of the polymer compound that can be contained in the membrane of the present embodiment is usually 1 × 10 ³ to 1 × 10 ⁸ , preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably. Is 2 × 10 ³ to 1 × 10 ⁶ , more preferably 3 × 10 ^{3 to} 5 × 10 ⁵ , and particularly preferably 5 × 10 ³ to 1 × 10 ⁵ .

  The film | membrane of this invention can be used as a film | membrane laminated | stacked as a functional layer of electronic elements, such as a light emitting element and a photoelectric conversion element.

[Light emitting element]
Hereinafter, the light emitting element among the electronic elements will be described. A light-emitting element is usually a light-emitting element in which a pair of electrodes composed of an anode and a cathode and a layer (film) composed of one or more layers each having a light-emitting layer provided between the electrodes are sandwiched. One or more of these layers is a light emitting element (organic EL element) which is the film of this embodiment.

Examples of the light emitting element include a single layer type light emitting element (anode / light emitting layer / cathode) and a multilayer type light emitting element. Examples of the layer configuration of the multilayer light emitting element include the following layer configurations (a) to (e).
(A) anode / hole injection layer / (hole transport layer) / light emitting layer / cathode (b) anode / light emitting layer / electron injection layer / (electron transport layer) / cathode (c) anode / hole injection layer / (Hole transport layer) / light emitting layer / electron injection layer / (electron transport layer) / cathode (d) anode / light emitting layer / (electron transport layer) / electron injection layer / cathode (e) anode / hole injection layer / (Hole transport layer) / light emitting layer / (electron transport layer) / electron injection layer / cathode

  In the light-emitting element, any layer constituting the light-emitting element may be the film of this embodiment, and the layer is not limited. The film of this embodiment is preferably a light emitting layer.

  In the layer configurations of (a) to (e), “(hole transport layer)” and “(electron transport layer)” in parentheses indicate that these layers are present at the indicated positions, respectively. It represents an optional layer that may not be present.

  The anode has a function of supplying holes to layers such as a hole injection layer, a hole transport layer, and a light emitting layer. As the material of the anode, for example, a metal, an alloy, a metal oxide, an electrically conductive compound, and a combination thereof can be used. Preferably, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), etc. Conductive metal oxides; metals such as gold, silver, chromium and nickel; mixtures and laminates of the conductive metal oxides and the metals; inorganic conductive materials such as copper iodide and copper sulfide; polyanilines and polythiophenes Organic conductive materials such as polypyrrole (polyethylenedioxythiophene), polypyrrole, etc., and combinations thereof with ITO.

  The cathode has a function of supplying electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like. Examples of the cathode material include metals, alloys, metal halides, metal oxides, electrically conductive compounds, and combinations thereof. Preferably, alkali metals (Li, Na, K, Cs, etc.) and their Fluorides and oxides; alkaline earth metals (Mg, Ca, Ba, etc.) and their fluorides and oxides; gold, silver, lead, aluminum, alloys and mixed metals (sodium-potassium alloys, sodium-potassium mixed metals) Lithium-aluminum alloy, lithium-aluminum mixed metal, magnesium-silver alloy, magnesium-silver mixed metal, etc.); rare earth metal (ytterbium, etc.); indium;

  The hole injection layer and the hole transport layer have a function of injecting holes from the anode toward the light emitting layer, a function of transporting holes, or a function of blocking electrons injected from the cathode. Examples of materials used for these layers include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted Chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine derivatives, styrylamine derivatives, aromatic dimethylidine derivatives, porphyrin derivatives, polysilane derivatives, poly (N-vinylcarbazole) derivatives , Organosilane derivatives, and polymers containing these residues; conductive polymer oligomers such as aniline copolymers, thiophene oligomers, and polythiophene And the like. The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of them, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  The electron injection layer and the electron transport layer have a function of injecting electrons from the cathode, a function of transporting electrons, or a function of blocking holes injected from the anode. Examples of materials used for these layers include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, and carbodiimide derivatives. , Fluorenylidenemethane derivatives, distyrylpyrazine derivatives, tetracarboxylic anhydrides of aromatic rings (eg, naphthalene, perylene), phthalocyanine derivatives, metal complexes (eg, metal complexes of 8-quinolinol derivatives, metal phthalocyanines as ligands) Metal complexes having benzoxazole as a ligand and metal complexes having benzothiazole as a ligand) and organosilane derivatives. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of these, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  As materials for the electron injection layer and the electron transport layer, inorganic compounds such as insulators and semiconductors can also be used. If the electron injection layer and the electron transport layer are made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved. Examples of such an insulator include one or more metal compounds selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides, CaO, BaO, SrO, BeO, BaS or CaSe is preferred. Examples of semiconductors include oxides of one or more elements selected from the group consisting of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn, Nitride and oxynitride are mentioned.

  In the light emitting element, a reducing dopant may be added to an interface region between the cathode and the film in contact with the cathode. Examples of the reducing dopant include alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal. And oxides or rare earth metal halides, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes.

  The light emitting layer is capable of injecting holes from the anode, hole injection layer or hole transport layer when an electric field is applied, and a function capable of injecting electrons from the cathode, electron injection layer or electron transport layer, It has a function of moving the injected charge by the force of an electric field, and a function of providing a field for recombination of electrons and holes and connecting it to light emission. When the light emitting layer contains the film of the present embodiment, or when the light emitting layer is the film of the present embodiment, the organic antimony compound contained in the film of the present embodiment is contained as a guest material in the light emitting layer, and further the host A material may be contained in the light emitting layer. The host material may be a low molecular compound or a high molecular compound, a composition thereof, or a high molecular compound contained in the film of the present embodiment. Examples of the host material include a compound having a fluorene skeleton, a compound having a carbazole skeleton, a compound having a diarylamine skeleton, a compound having a pyridine skeleton, a compound having a pyrazine skeleton, a compound having a triazine skeleton, and an arylsilane skeleton Compounds.

  Furthermore, the organic antimony compound contained in the film of the present embodiment may be contained in the light emitting layer as a host material, and further a guest material may be contained in the light emitting layer. The guest material may be a low molecular compound or a high molecular compound, a composition thereof, or a high molecular compound contained in the film of the present embodiment. Examples of guest materials include metal complexes using platinum group elements (for example, iridium complexes coordinated with phenylpyridine derivatives), metal complexes using rare earth elements (for example, europium complexes coordinated with phenanthroline derivatives), 8 -Aluminum complexes coordinated with quinolinol derivatives, naphthacene derivatives, dicyanoethylene derivatives, coumarin derivatives, quinacridone derivatives, anthracene derivatives, perylene derivatives, phenylene vinylene derivatives, fluorene derivatives, naphthalene derivatives.

  In the light-emitting element, examples of a method for forming each layer include a vacuum deposition method (resistance heating deposition method, electron beam method, etc.), a sputtering method, an LB method, a molecular lamination method, and a coating method (casting method, spin coating method, bar coating method). Coating method, blade coating method, roll coating method, gravure printing method, screen printing method, ink jet printing method and the like. Among these film forming methods, the coating method is preferable because the manufacturing process can be simplified. In the coating method, a coating solution is prepared by mixing the organic antimony compound, the coexisting components (including a polymer compound), a mixture thereof, and the like, which are materials for each layer, with a solvent, and the coating solution is desired. It can be formed by coating on the layer (film) or electrode and drying the obtained coating film. The coating solution may contain a resin as a host material and / or a binder.

  The thickness of each layer of the light emitting element is preferably 0.5 nm to 100 μm, and more preferably 1 nm to 1 μm.

  The light emitting element can be used in, for example, an illumination light source, a sign light source, a backlight light source, a display device, a printer head, and the like. As an example of the display device, a device having a segment type, a dot matrix type, or the like using a known driving technique, a driving circuit, or the like can be given.

[Photoelectric conversion element]
The photoelectric conversion element usually has an anode, a cathode, and a charge separation layer. The charge separation layer is located between the anode and the cathode. The photoelectric conversion element may have an arbitrary layer other than the charge separation layer between the anode and the cathode. The organic antimony compound may be used as a material for the charge separation layer, or may be used as a material for any layer other than the charge separation layer.

  Examples of the cathode and anode materials are the same as those of the cathode and anode materials described in the section of the light emitting element. The shape of the anode and the cathode is not particularly limited, and may be, for example, a comb shape. The anode and the cathode may be either transparent or translucent.

  The charge separation layer of the photoelectric conversion element usually contains an electron donating compound and an electron accepting compound.

  Examples of the electron donating compound include conjugated polymer compounds. Examples of the conjugated polymer compound include a conjugated polymer compound containing a thiophenediyl group and a conjugated polymer compound containing a fluorenediyl group.

  As an electron-accepting compound, a fullerene and a fullerene derivative are mentioned, for example.

  The photoelectric conversion element is usually formed using a substrate. The example of the substrate is the same as the example of the substrate described in the section of the light emitting element.

  The photoelectric conversion element is preferably a solar cell.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example.

<Measurement device>
For NMR measurement, Varian 400-MR or Varian 500-MR was used.

  LTQ Orbitrap XL manufactured by Thermo Fisher Scientific was used for atmospheric pressure chemical ionization mass spectrometry (APCI-MS) measurement. For other mass spectrometry measurements, GCMS-QP5050A manufactured by SHIMADZU was used.

  For the melting point measurement, EXSTAR 6000-DSC6200 manufactured by SII was used.

  For molecular sieve type liquid chromatography, LC-908 MODEL 576 manufactured by Nippon Analytical Industry equipped with a column of Kf001 manufactured by Shodex and a column of Kf002 manufactured by Shodex was used.

  For the fluorescence spectrophotometer, RF-5000 manufactured by SHIMADZU or FP-6500 manufactured by JASCO Corporation was used.

  ET3000 manufactured by Kosaka Laboratory was used for film thickness measurement and film thickness unevenness measurement.

<Synthesis of raw materials>
4,4′-Dibromo-2,2′-bis (trimethylsilyl) bithiophene was synthesized in the same manner as described in Organometallics 18, 1453-1459 (1999).

  (3,5-dimethylphenyl) dichloroantimony was prepared according to J. Am. Am. Chem. Soc. 131, 3418-3419 (2009).

<Example 1>
According to the following scheme, 1- (3,5-dimethylphenyl) -3,6-bis (trimethylsilyl) dithienostibol (the above compound 2-3) was synthesized.

  To a 30 mL Schlenk tube equipped with a dropping funnel, 0.119 g (0.255 mmol) of 4,4′-dibromo-2,2′-bis (trimethylsilyl) bithiophene and 2.5 mL of diethyl ether were added and cooled to −80 ° C. To this, 0.509 mL of sec-butyllithium (1.00 mol / L of a mixed solvent of cyclohexane and normal hexane) was added dropwise, followed by stirring for 1 hour. Thereafter, a suspension of 0.0758 g (0.255 mmol) of (3,5-dimethylphenyl) dichloroantimony in 0.5 mL of THF was slowly dropped from the dropping funnel, and then 2.5 mL of THF was added thereto. Thereafter, the temperature was slowly returned to room temperature, and after stirring for about 1 hour, diethyl ether was distilled off by heating with an oil bath. After refluxing overnight, the solvent was distilled off with an evaporator, and the resulting residue was hydrolyzed with water and extracted with toluene. The obtained organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off with an evaporator. The obtained residue was passed through molecular sieve type liquid chromatography using toluene as a developing solvent to give 1- (3,5-dimethylphenyl) -3,6-bis (trimethylsilyl) dithienostibol (compound 2-3). ) As a yellow oily substance, 0.033 g, 24% yield.

¹ H NMR, ¹³ C NMR and APCI-MS measurement data of the obtained compound 2-3 are shown below.

¹ H NMR (in C ₆ D ₆ ) δ (ppm) = 0.22 (s, 18H, TMS protons), 1.85 (s, 6H, methyl protons), 6.59 (t, 1H, J = 0.4 Hz, xyl-ring proton ), 7.16 (s, 2H, thiophene-ring protons), 7.20-7.21 (m, 2H, xyl-ring protons).
¹³ C NMR (in C ₆ D ₆ ) δ (ppm) = -0.02, 21.04, 131.16, 133.64, 137.27, 138.25, 138.50, 141.67, 146.39, 153.55.
APCI Exact MS calcd for C ₂₂ H ₃₀ S ₂ SbSi ₂ : [M + H ⁺ ] = 535.03595. Found = C ₂₂ H ₃₀ S ₂ SbSi ₂ : 535.03595.

<Synthesis Example 1>
(4-Methylphenyl) dichloroantimony was synthesized according to the following scheme.

  Magnesium (3.12 g, 128 mmol) and THF (30 mL) were added to a 100 mL three-necked flask equipped with a dropping funnel and a reflux tube, and cooled to 0 ° C. Thereto, 13.8 mL (113 mmol) of p-methylbromobenzene was dropped from a dropping funnel, and then stirred at room temperature for 2 hours to synthesize a Grignard reagent. On the other hand, to a 200 mL capacity three-necked flask equipped with a dropping funnel and a reflux tube, 7.12 g (31.2 mmol) of trichloroantimony and 60 mL of THF were added and stirred, and then the above-mentioned Grignard reagent with 40 mL of THF was added at room temperature. After dropwise addition, the mixture was stirred for 12 hours. Then, the solvent was distilled off with an evaporator, water was added to the obtained residue to hydrolyze, and after extraction with hexane, the obtained organic layer was dried over anhydrous magnesium sulfate, and the solvent was again distilled off with an evaporator. Tris (tolyl) antimony was obtained in 8.12 g, 65.8% yield.

The mass spectrometry and ¹ H NMR measurement data of tris (tolyl) antimony are shown below.

MS (m / z) 394 (M ⁺ ).
¹ H NMR (in CDCl ₃ ) δ (ppm) = 2.34 (s, 9H), 7.13 (d, 6H, J = 8.0 Hz), 7.32 (d, 6H, J = 8.0 Hz).

  To a 100 mL flask equipped with a reflux tube, antimony (III) chloride (22.7 mmol) and 4.49 g (11.4 mmol) of the above tris (tolyl) antimony were added and heated with a heat gun until the mixture was completely dissolved. After stirring for 30 minutes at room temperature, the mixture was allowed to stand for 10 minutes to obtain (4-methylphenyl) dichloroantimony as a pale yellow solid in 9.18 g in a yield of 95.0%.

Mass spectrometry, ¹ H NMR and melting point measurement data of (4-methylphenyl) dichloroantimony are shown below.

MS (m / z) 282 (M ⁺ ).
¹ H NMR (in CDCl ₃ ) δ (ppm) = 2.42 (s, 3H), 7.40 (d, 2H, J = 6.8 Hz), 7.76 (d, 2H, J = 6.8 Hz).
T _m = 72.8 ° C (DSC).

<Example 2>
According to the following scheme, 1- (4-methylphenyl) -3,6-bis (trimethylsilyl) dithienostibol (the above compound 2-2) was synthesized.

  To a 30 mL Schlenk tube equipped with a dropping funnel, 0.241 g (0.513 mmol) of 4,4′-dibromo-2,2′-bis (trimethylsilyl) bithiophene and 5 mL of diethyl ether were added and cooled to −80 ° C. Thereto, 0.633 mL of n-butyllithium (1.62 M hexane solution; 1.03 mmol as n-butyllithium) was added dropwise, followed by stirring for about 1 hour. Thereafter, a suspension of 0.142 g (0.500 mmol) of (4-methylphenyl) dichloroantimony in 2.5 mL of THF was slowly dropped from the dropping funnel, and then 2.5 mL of THF was added thereto. Thereafter, the temperature was slowly returned to room temperature, and after stirring for about 1 hour, diethyl ether was distilled off by heating with an oil bath. After refluxing overnight, the solvent was distilled off with an evaporator, and the resulting residue was hydrolyzed with water and extracted with toluene. The obtained organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off with an evaporator. The obtained residue was passed through a silica gel column using hexane / ethyl acetate = 4/1 (volume ratio) as a developing solvent, and passed through molecular sieve type liquid chromatography using toluene as a developing solvent. Then, by recrystallizing with ethanol, Compound 2-2 was obtained as a yellow powder in 0.038 g in a yield of 13%.

¹ H NMR, ¹³ C NMR, melting point measurement, and APCI-MS measurement data of the obtained compound 2-2 are shown below.

¹ H NMR (in C ₆ D ₆ ) δ (ppm) = 0.22 (s, 18H, TMS protons), 1.88 (s, 3H, methyl protons), 6.71 (d, 2H, J = 6.1 Hz, m-phenyl protons ), 7.09 (s, 2H, thiophene-ring protons), 7.40 (d, 2H, J = 6.1 Hz, o-phenyl protons).
¹³ C NMR (in C ₆ D ₆ ) δ (ppm) = -0.34, 20.77, 129.77, 133.24, 135.64, 137.85, 138.50, 141.31, 146.40, 153.21.
T _m = 117.5 ° C.
APCI Exact MS calcd for C ₂₁ H ₂₈ S ₂ SbSi ₂ : [M + H ⁺ ] = 521.02036; Found [M + H ⁺ ] = C ₂₁ H ₂₈ S ₂ SbSi ₂ : [M + H ⁺ ] = 521.02032.

<Synthesis Example 2>
According to the following scheme, 3,3′-dibromo-2,2′-bibenzo [b] thiophene was synthesized.

  To a 300 mL three-necked flask equipped with a reflux tube, 4.74 g (35.3 mmol) of benzo [b] thiophene, 80 mL of dichloromethane and 80 mL of acetic acid were added and cooled to 0 ° C. Thereto was added 12.5 g (70.6 mmol) of N-bromosuccinimide over 1 hour, and the mixture was stirred for 1 hour while being kept at 0 ° C., and then left overnight at room temperature. Thereafter, the mixture was neutralized with an aqueous sodium hydrogen carbonate solution, and subsequently extracted with dichloromethane. The obtained organic layer was dried over magnesium sulfate, and the solvent was distilled off with an evaporator. Thereafter, the solution of hexane / chloroform = 4/1 (volume ratio) was passed through a silica gel column using a developing solvent, and 2,3-dibromobenzo [b] thiophene was obtained in a yield of 8.63 g and 83.7%.

The mass spectrometry and ¹ H NMR measurement data of the obtained 2,3-dibromobenzo [b] thiophene are shown below.

MS (m / z) 290 (M ⁺ ).
¹ H NMR (in CDCl ₃ ) δ (ppm) = 7.38 (td, 1H), 7.43 (td, 1H), 7.73 (dd, 1H), 7.74 (dd, 1H).

  To a 250 mL three-necked flask equipped with a reflux tube and a dropping funnel, 8.63 g (29.6 mmol) of 2,3-dibromobenzo [b] thiophene and 80 mL of THF were added and cooled to −80 ° C. Thereto was added dropwise 16.5 mL of n-butyllithium (1.62 M hexane solution; 26.7 mmol as n-butyllithium), and the mixture was stirred at -80 ° C. for 1 hour. Thereafter, 6.79 g (50.5 mmol) of copper (II) chloride was added in 5 portions, and the mixture was allowed to warm to room temperature over 1 hour and stirred overnight. Thereafter, extraction with toluene was performed, and the obtained organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off with an evaporator. Thereafter, the solution was passed through a silica gel column using hexane as a developing solvent, recrystallized with a mixed solvent of methanol and chloroform, and then 3,3′-dibromo-2,2′-bibenzo [b] thiophene as green crystals, 2.00 g, 15.9 % Yield.

The mass spectrometry and ¹ H NMR measurement data of the obtained 3,3′-dibromo-2,2′-bibenzo [b] thiophene are shown below.

MS (m / z) 422 (M ⁺ ).
¹ H NMR (in CDCl ₃ ) δ (ppm) = 7.46-7.54 (m, 4H), 7.86 (d, 2H, J = 6.4 Hz), 7.92 (dd, 2H, J = 6.0 Hz, 0.5 Hz).

<Example 3>
According to the following scheme, 1- (4-methylphenyl) -2,2′-di (benzo [b] thieno) stivol (compound 3-1) was synthesized.

  To a 30 mL Schlenk tube equipped with a dropping funnel, 0.206 g (0.486 mmol) of 3,3′-dibromo-2,2′-bibenzo [b] thiophene and 5 mL of diethyl ether were added and cooled to −80 ° C. Thereto was added 0.60 mL of n-butyllithium (1.62 mol / L hexane solution; 0.97 mmol as n-butyllithium), and the mixture was slowly returned to room temperature and stirred for 1 hour. Thereto was added dropwise 0.142 g (0.500 mmol) of (4-methylphenyl) dichloroantimony dissolved in 5 mL of THF at −80 ° C., followed by stirring overnight at room temperature. Thereafter, the solvent was distilled off by an evaporator, and the resulting residue was hydrolyzed by adding water and extracted with hot toluene. The obtained organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled off with an evaporator. The obtained residue was purified by passing through a molecular sieve type liquid chromatography using toluene as a developing solvent to obtain Compound 3-1 as a pale yellow powder in a yield of 0.029 g and 13%.

¹ H NMR, ¹³ C NMR, melting point measurement, and APCI-MS measurement data of the obtained compound 3-1 are shown below.

¹ H NMR (in C ₆ D ₆ ) δ = 1.82 (s, 3H, Me-protons), 6.64 (d, J = 8.0 Hz, 2H, Tol-ring protons), 6.99 (td, J = 7.5 Hz, 1.0 Hz, 2H, benzothiophene-ring protons), 7.08 (td, J = 8.0 Hz, 1.0 Hz, 2H, benzothiophene-ring protons), 7.37 (d, J = 8.0 Hz, 2H, Tol-ring protons), 7.48 (d , J = 8.0 Hz, 2H, benzothiophene-ring protons), 7.53 (d, J = 7.5 Hz, 2H, benzothiophene-ring protons).
¹³ C NMR (in C ₆ D ₆ ) δ = 20.72, 123.12, 123.72, 124.33, 125.17, 130.02, 133.04, 135.27, 138.69, 142.31, 142.40, 142.77, 147.70.
T _m = 204.7 ° C.
APCI Exact MS calcd for C ₂₃ H ₁₆ S ₂ Sb: [M + H ⁺ ] = 476.97261; Found [M + H ⁺ ] = C ₂₃ H ₁₆ S ₂ Sb: [M + H ⁺ ] = 476.97305.

<Synthesis Example 3>
According to the following scheme, (2-naphthyl) dichloroantimony was synthesized.

  Magnesium (0.440 g, 18.1 mmol) was added to a 50 mL capacity two-necked flask equipped with a dropping funnel and a reflux tube, and activated by heating with a heat gun. After returning to room temperature, 5 mL of THF was added thereto, followed by several drops of dibromoethane, and 5 mL of a solution of 3.72 g (18.0 mmol) of 2-bromonaphthalene was added dropwise over 30 minutes, and then at room temperature for 2 hours. A Grignard reagent was prepared by stirring. On the other hand, 1.37 g (6.01 mmol) of trichloroantimony and 5 mL of THF were added to a 50 mL two-necked flask equipped with a dropping funnel and a reflux tube. And refluxed for 1 hour. The resulting reaction solution was hydrolyzed with water, and extracted with toluene. The obtained organic layer was dried over magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain 2.99 g of trinaphthylantimony as a pale yellow powder in a yield of 99.1%.

The mass spectrometry, ¹ H NMR and ¹³ C NMR measurement data of trinaphthylantimony are shown below.

MS (m / z) 502 (M ⁺ ).
¹ H NMR (in CDCl ₃ ) δ (ppm) = 7.45-7.52 (m, 6H), 7.56 (dd, J = 8.4 Hz, 1.2 Hz, 3H), 7.73-7.86 (m, 9H), 8.06 (s, 3H).
¹³ C NMR (in CDCl ₃ ) δ (ppm) = 126.11, 126.45, 127.82, 127.86, 128.18, 132.41, 133.42, 133.74, 135.89, 137.00.

  To a 100 mL flask equipped with a reflux tube, 2.71 g (11.9 mmol) of antimony (III) chloride and 2.99 g (5.95 mmol) of trinaphthylantimony were added and heated with a heat gun until the mixture was completely dissolved. Then, it stirred at room temperature for 30 minutes, and left still for 10 minutes, and obtained 5.42 g and 95.0% of yield as (2-naphthyl) dichloroantimony as pale yellow solid.

Mass spectrometry, ¹ H NMR, ¹³ C NMR and melting point measurement data of (2-naphthyl) dichloroantimony are shown below.

MS (m / z) 318 (M ⁺ ).
¹ H NMR (in CDCl ₃ ) δ (ppm) = 7.57-7.61 (m, 2H), 7.88-7.94 (m, 2H), 7.97 (dd, J = 8.0 Hz, 1.0 Hz, 1H), 8.06 (d, J = 5.5 Hz, 1H), 8.31 (s, 1H).
¹³ C NMR (in CDCl ₃ ) δ (ppm) = 125.86, 127.13, 127.90, 128.03, 128.08, 128.58, 129.69, 133.02, 134.05, 134.64.
T _m = 87.5 ° C.

<Example 4>
According to the following scheme, 1- (2-naphthyl) -di (benzo [b] thieno) [3,2-b] stivol (compound 3-2) was synthesized.

  To a 30 mL Schlenk tube equipped with a dropping funnel, 0.33 g (0.785 mmol) of 3,3′-dibromo-2,2′-bibenzo [b] thiophene and 8 mL of diethyl ether were added and cooled to −80 ° C. Thereto was added 1.0 mL of n-butyllithium (1.62 mol / L hexane solution; 1.57 mmol as n-butyllithium), and then slowly returned to room temperature and stirred for 1 hour. Thereafter, (2-naphthyl) dichloroantimony 0.259 g (0.810 mmol) dissolved in THF 8 mL at −80 ° C. was added dropwise thereto, followed by stirring at room temperature overnight. Thereafter, the solvent was distilled off by an evaporator, and the resulting residue was hydrolyzed by adding water, and then extracted with hot toluene. The obtained organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled off with an evaporator. Then, by recrystallizing with toluene, Compound 3-2 was obtained as a pale yellow crystal in a yield of 0.081 g and 20%.

¹ H NMR, ¹³ C NMR, melting point measurement, and APCI-MS measurement data of the obtained compound 3-2 are shown below.

¹ H NMR (in C ₄ D ₈ O) δ = 7.28-7.39 (m, 7H, naph-ring protons and bibenzothiophene-ring protons), 7.56 (d, J = 8.5 Hz, 1H, naph-ring proton), 7.66 -7.72 (m, 2H, naph-ring protons), 7.91 (d, J = 7.5 Hz, 2H, bibenzothiophene-ring protons), 7.95 (d, J = 7.5 Hz, 2H, bibenzothiophene-ring protons), 7.21 (s , 1H, naph-ring proton).
¹³ C NMR (in C ₄ D ₈ O) δ = 123.96, 124.81, 125.34, 126.11, 126.81, 127.19, 128.44, 128.46, 129.05, 131.87, 134.61, 134.90, 135.84, 137.29, 143.41, 143.47, 143.57, 148.36.
T _m = 248.5 ° C.
APCI Exact MS calcd for C ₂₆ H ₁₆ S ₂ Sb: [M + H ⁺ ] = 521.97261; Found [M + H ⁺ ] = C ₂₆ H ₁₆ S ₂ Sb: [M + H ⁺ ] = 512.97278.

<Luminescent characteristics>
When the compound synthesized in Example 1 was dissolved in chloroform and irradiated with ultraviolet rays having a wavelength of 355 nm, the compound emitted light having a maximum emission wavelength of 395 nm.

  When the compound synthesized in Example 2 was dissolved in chloroform and irradiated with ultraviolet rays having a wavelength of 355 nm, the compound emitted light having a maximum emission wavelength of 420 nm.

  When the compound synthesized in Example 3 was dissolved in chloroform and irradiated with ultraviolet rays having a wavelength of 374 nm, the compound emitted light having a maximum emission wavelength of 437 nm.

  When the compound synthesized in Example 4 was dissolved in chloroform and irradiated with ultraviolet rays having a wavelength of 374 nm, the compound emitted light having a maximum emission wavelength of 443 nm.

<Example 5>
0.90 mg of the compound synthesized in Example 2 (Compound 2-2) and 3.0 mg of PMMA (Polysciences, weight average molecular weight 25000) were dissolved in a mixed solvent of 200 mg of chloroform and 100 mg of 1,2-dichloroethane, and spin coated. The film was rotated at 1000 rpm for 10 seconds by the above method, and subsequently applied to a quartz substrate by rotating at 2000 rpm for 60 seconds, followed by drying to prepare a film. The thickness of the obtained film was 115 nm. The surface of the obtained film was flat and the film thickness unevenness was 5 nm or less.
When the obtained film was irradiated with ultraviolet rays having a wavelength of 355 nm, light emission with a maximum emission wavelength of 416 nm was exhibited.

  From these results, the compounds synthesized in Example 1, Example 2, Example 3 and Example 4 can be mixed and coated with a polymer compound to form a film. It had luminescent properties. Therefore, the organic antimony compound of the present invention is useful as a light emitting material, and a film containing such an organic antimony compound and a polymer compound can be suitably used as a functional layer of an electronic device.

Claims (7)

A film containing an organic antimony compound represented by the following formula (1) and a polymer compound.

(In the formula (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an organic group.
R ³ is a hydrogen atom or an organic group.
R ¹ and R ² may be bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to form a ring structure with the carbon atoms to which they are bonded. May be.
A represents a group represented by -O-, a group represented by -S-, a group represented by -N (R ⁶ )-, a group represented by -C (R ⁷ ) _2- , -Si It is a group represented by (R ⁸ ) ₂ — or a group represented by —P (R ⁹ ) —. A plurality of A may be the same or different. R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbyl group optionally having a substituent. ) The film according to claim 1 , wherein A is a group represented by —S—. The film according to claim 1 or 2 , wherein R ³ is an aryl group which may have a substituent. The compound represented by the formula (1) is either a compound represented by the following formula (2), or a compound represented by the following formula (3), any one of claims 1 to 3 The membrane according to 1.

(In the formula (2),
R ¹ and R ⁵ are each independently a hydrogen atom or an organic group.
Ar ¹ is an aryl group which may have a substituent. )

(In formula (3),
R ¹⁰ and R ¹¹ are each independently an organic group.
m and n are each independently a number of 0 to 4.
Ar ² is an aryl group which may have a substituent. ) The polymer compound is a polystyrene derivative, polymethyl methacrylate, polycarbazole derivative, polyarylamine derivative, polyarylalkane derivative, polyvinylcarbazole derivative, polyoxadiazole derivative, polytriazine derivative, polyfluorene derivative, or a combination thereof. The film according to any one of claims 1 to 4 , wherein: A compound represented by the following formula (1).

(In the formula (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an organic group.
R ³ is a hydrogen atom or an organic group.
R ¹ and R ² may be bonded to form a ring structure with the carbon atoms to which they are bonded, and R ⁴ and R ⁵ are bonded to form a ring structure with the carbon atoms to which they are bonded. May be.
A represents a group represented by -O-, a group represented by -S-, a group represented by -N (R ⁶ )-, a group represented by -C (R ⁷ ) _2- , -Si It is a group represented by (R ⁸ ) ₂ — or a group represented by —P (R ⁹ ) —. R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbyl group optionally having a substituent. ) A compound represented by the following formula (2) or represented by the following formula (3).

(In the formula (2),
R ¹ and R ⁵ are each independently a hydrogen atom or an organic group.
Ar ¹ is an aryl group which may have a substituent. )

(In formula (3),
R ¹⁰ and R ¹¹ are each independently an organic group.
m and n are each independently a number of 0 to 4.
Ar ² is an aryl group which may have a substituent. )