JP2021038161A - Ionic compound, organic electronic material, ink composition, and organic electronic element - Google Patents

Abstract

To provide an ionic compound that can achieve improved solubility to a solvent when an ink composition is prepared, and an organic electronic material, an ink composition and an organic electronic element comprising the ionic compound.SOLUTION: An ionic compound contains a cation and an anion, represented by the following formula, where C is a cation, Rd, Re, Rf and Rg independently represent a C1-5 perfluoroalkyl group; l, m, n and o independently represent an integer of 1-5.SELECTED DRAWING: None

Description

Embodiments of the present invention relate to ionic compounds, organic electronic materials, ink compositions, and organic electronic devices.

Organic electronics devices are devices that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are an alternative technology to conventional silicon-based inorganic semiconductors. Attention has been paid.

Examples of organic electronics devices include organic electroluminescence devices (hereinafter, also referred to as organic EL devices), organic photoelectric conversion devices, and organic transistors.

Among organic electronic devices, organic EL devices are attracting attention as large-area solid-state light source applications as alternatives to, for example, incandescent lamps and gas-filled lamps. It is also attracting attention as the most promising self-luminous display that can replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and its commercialization is progressing.

In recent years, attempts have been made to mix an electron-accepting compound with a charge-transporting compound for the purpose of improving the luminous efficiency and life of the organic EL device.

For example, in Patent Document 1, a hole-injection layer is obtained by mixing a hole-transporting polymer compound with Tris (pentafluorophenyl) borane as an electron-accepting compound by a wet film formation method. Is disclosed to form.

Further, Patent Document 2 discloses a composition comprising an ionic compound and a charge transporting compound as a composition for a charge transporting membrane.

On the other hand, organic EL devices are roughly classified into two types, low molecular weight organic EL devices and high molecular weight organic EL devices, depending on the material used. Since the organic material of the high molecular weight organic EL element is composed of the high molecular weight material, it is possible to form a simple film by inkjet or the like as compared with the low molecular weight organic EL element which requires the film formation in a vacuum system. , Is expected as an indispensable element for future large-screen organic EL displays.

Further, in the organic EL element, in order to improve the luminous efficiency and the element life, the organic layer is multi-layered.

In the production of low-molecular-weight organic EL devices, multi-layering can be easily achieved by performing vapor deposition while sequentially changing the materials used. On the other hand, in the production of a polymer-type organic EL device, since a film is formed by using a wet process such as an inkjet, a method in which the lower layer is not dissolved when the upper layer is applied is required.

In order to cope with this requirement, in Patent Documents 3 and 4, a siloxane compound or a compound having a functional group such as an oxetane group or a vinyl group is used, and the solubility of the compound is changed by utilizing a polymerization reaction to form a thin film. A method of insolubilizing in a solvent is being studied.

To utilize the polymerization reaction, usually, an appropriate polymerization initiator that reacts or decomposes with a stimulus such as light or heat to generate an acid, a base, a radical, or the like is added.

Patent Document 5 discloses that an iodonium compound is used as the polymerization initiator and an acid is generated by light.

Japanese Unexamined Patent Publication No. 2003-31365 Japanese Unexamined Patent Publication No. 2006-233162 International Publication No. 2008/010487 JP-A-2009-196982 JP-A-2007-302886

However, although the conventional polymerization initiator having a thermoacid generation mechanism has high solubility in a polar solvent, it often has low solubility in a non-polar solvent such as toluene, which may reduce the selectivity of the ink solvent. There is.

The present invention has been made in view of the above, and an embodiment of the present invention aims to provide an ionic compound capable of improving solubility. Another embodiment of the present invention aims to provide an organic electronics material, an ink composition, and an organic electronics element using the ionic compound.

As a result of diligent studies, the present inventors have found that an ionic compound having a specific structure can solve the above-mentioned problems, and have completed the present invention.

Embodiments of the present invention relate to:

<1> An ionic compound containing a cation and an anion represented by the following formula.

In the formula, C represents a cation, and R ^d , ^Re , R ^f and R ^g each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms. l, m, n and o each independently represent an integer of 1-5.

<2> The ionic compound according to <1>, wherein the anion is represented by the following formula.

In the formula, R ^d , ^Re , R ^f and R ^g each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms. l, m, n and o each independently represent an integer of 0 to 3.

<3> The ionic compound according to <1> or <2>, wherein each of ^{R d} , ^Re , R ^f and R ^{g is the same as each other.}

<4> The ionic compound according to any one of <1> to <3>, wherein each of ^{R d} , ^Re , R ^f and R ^{g is a trifluoromethyl group.}

<5> The ionic compound according to any one of <1> to <4>, wherein the anion is represented by the following formula.

<6> The ionic compound according to any one of <1> to <5>, wherein the cation is represented by the following formula.

In the formula, R ^a , R ^b and R ^c each independently represent a monovalent organic group.

<7> An organic electronics material containing the ionic compound according to any one of <1> to <6> and a charge transporting compound.

<8> The organic according to <7>, wherein the charge transporting compound contains at least one selected from the group consisting of a unit containing an aromatic amine structure, a unit containing a carbazole structure, and a unit containing a thiophene structure. Electronics material.

<9> The organic electronic material according to <7> or <8>, wherein the charge transporting compound is a polymer or an oligomer.

<10> The organic electronic material according to any one of <7> to <9>, wherein the charge transporting compound has one or more polymerizable functional groups.

<11> The organic electronic material according to <10>, wherein the polymerizable functional group contains at least one selected from the group consisting of an oxetane group, an epoxy group, and a vinyl ether group.

<12> An ink composition containing the organic electronic material according to any one of <7> to <11> and a solvent.

<13> The ink composition according to <12>, wherein the solvent is a non-polar organic solvent.

<14> Organic electronics including the organic electronics material according to any one of <7> to <11> or an organic layer formed by using the ink composition according to <12> or <13>. element.

<15> The organic electronic device according to <14>, wherein the organic layer is a layer insolubilized by polymerization.

<16> The organic electronic device according to <15>, wherein another layer is formed on the organic layer to form a multi-layered structure.

<17> The organic electronic device according to any one of <14> to <16>, further comprising a substrate, wherein the substrate is a resin film.

According to an embodiment of the present invention, it is possible to provide an ionic compound capable of improving solubility. Further, according to another embodiment of the present invention, it is possible to provide an organic electronics material, an ink composition and an organic electronics element using the ionic compound.

FIG. 1 is a schematic view showing an example of an organic EL device according to an embodiment of the present invention.

<Ionic compound>
The ionic compound of the present embodiment comprises a cation and an anion represented by the following formula described later. Hereinafter, cations and anions will be described.

(Cation)
The cation portion is not particularly limited and may be a known cation, and examples of the cation that can be used for the ionic compound of the present embodiment include iodonium, sulfonium, phosphonium, carbenium (trityl), anilinium, and bismutnium. Ammonium, selenium, pyridinium, imidazolium, oxonium, quinolinium, pyrrolidinium, aminium, imonium, tropylium and the like can be mentioned.

Examples of sulfonium include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and tris (4-fluoro). Phenyl) Sulfonium, Tri-1-naphthylsulfonium, Tri-2-naphthylsulfonium, Tris (4-hydroxyphenyl) Sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-trilthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4 -(Phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4 -[Bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methoxyphenyl) sulfonio] phenyl} sulfide , 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenylbis (4-Fluorophenyl) Sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7 -Isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthiol) )] Phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, 5-tolylthiaanthrenium, Triarylsulfoniums such as 5- (4-ethoxyphenyl) thiaanthrenium, 5- (2,4,6-trimethylphenyl) thiaanthrenium; diphenylphenacil sulfonium, diphenyl4-nitrophenacil sulfonium, diphenylbenzyl sulfonium, Diarylsulfoniums such as diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) Ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetcarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacyl Monoarylsulfoniums such as sulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthrasenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphena Examples thereof include trialkylsulfoniums such as silsulfonium, which are described in the following literature.

Regarding triarylsulfonium, for example, US Pat. No. 4,231,951, US Pat. No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922. Japanese Patent Application Laid-Open No. 8-27208, Japanese Patent Application Laid-Open No. 8-27209, Japanese Patent Application Laid-Open No. 8-165290, Japanese Patent Application Laid-Open No. 8-301991, Japanese Patent Application Laid-Open No. 9-143212, Japanese Patent Application Laid-Open No. 9-278813, Japanese Patent Application Laid-Open No. 10-7680, Japanese Patent Application Laid-Open No. 10-287643, Japanese Patent Application Laid-Open No. 10-245378, Japanese Patent Application Laid-Open No. 8-157510, Japanese Patent Application Laid-Open No. 10-204083, Japanese Patent Application Laid-Open No. 8-245566, Japanese Patent Application Laid-Open No. 8-157451, Japanese Patent Application Laid-Open No. 7-324069, Japanese Patent Application Laid-Open No. 9-268205, Japanese Patent Application Laid-Open No. 9-278935, Japanese Patent Application Laid-Open No. 2001-288205, Japanese Patent Application Laid-Open No. 11-80118, Japanese Patent Application Laid-Open No. 10- 182825, Japanese Patent Application Laid-Open No. 10-330353, Japanese Patent Application Laid-Open No. 10-152495, Japanese Patent Application Laid-Open No. 5-239213, Japanese Patent Application Laid-Open No. 7-333834, Japanese Patent Application Laid-Open No. 9-12537, Japanese Patent Application Laid-Open No. 8-325259, Japanese Patent Application Laid-Open No. 8-160606, Japanese Patent Application Laid-Open No. 2000-186071 (US Pat. No. 6,368,769), etc .; Regarding diarylsulfonium, for example, Japanese Patent Application Laid-Open No. 7-300504, Japanese Patent Application Laid-Open No. 64-45357, Japanese Patent Application Laid-Open No. No. 64-29419, etc .; Regarding monoarylsulfonium, for example, JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6,093753), JP-A-2. -196812, Japanese Patent Application Laid-Open No. 2-1470, Japanese Patent Application Laid-Open No. 2-196812, Japanese Patent Application Laid-Open No. 3-237107, Japanese Patent Application Laid-Open No. 3-17101, Japanese Patent Application Laid-Open No. 6-228086, Japanese Patent Application Laid-Open No. 10-152469 No. 7, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; Regarding trialkylsulfonium, for example, JP-A-4-308563 and JP-A-5-140210. Japanese Patent Application Laid-Open No. 5-140209, Japanese Patent Application Laid-Open No. 5-230189, Japanese Patent Application Laid-Open No. 6-271532, Japanese Patent Application Laid-Open No. 58-37003, Japanese Patent Application Laid-Open No. 2-178303, Japanese Patent Application Laid-Open No. 10-338688 , JP-A-9-328506, JP-A-11-22 8534, 8-27102, 7-333834, 5-222167, 11-21307, 11-35613, US Pat. No. 6031014, etc. It is described in.

Examples of iodonium ions include diphenyl iodonium, di-p-tolyl iodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, and bis (4-decyl). Examples thereof include oxyphenyl) iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyl iodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, and the like, which are Macromolecules, 10, 1307 (1977), JP-A-6-184170, US Pat. No. 4,256,828, US Pat. No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117. , JP 2001-139539, JP 2000-510516, JP 2000-119306, and the like.

Examples of the selenium ion include triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium, and tri. Triaryl selenium such as -1-naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyldiphenyl selenium, 4- (p-trilthio) phenyldi-p-tolyl selenium; Diaryl selenium such as diphenyl phenacyl selenium, diphenyl benzyl selenium, diphenyl methyl selenium; phenyl methyl benzyl selenium, 4-hydroxyphenyl methyl benzyl selenium, phenyl methyl phenacil selenium, 4-hydroxyphenyl methyl phenacil selenium, 4-methoxyphenyl methyl Monoaryl selenium such as phenacyl selenium; trialkyl selenium such as dimethyl phenacyl selenium, phenyl tetrahydro selenophenium, dimethyl benzyl selenium, benzyl tetrahydro selenophenium, octadecyl methyl phenacil selenium, etc. It is described in Japanese Patent Application Laid-Open No. 50-151997, Japanese Patent Application Laid-Open No. 50-151976, Japanese Patent Application Laid-Open No. 53-22597 and the like.

Examples of ammonium ions include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, and trimethyl-. Tetraalkylammonium such as t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium, methyltriisopropylammonium; Pyrrolidiniums such as N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N, N-diethylpyrrolidinium; N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1,2-diethyl-3-methylimidazolium, 1-methyl- 3-n-propyl-2,4-dimethylimidazolium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4-methylimidazolinium, 1,2,3,4-tetramethyl Imidazolinium such as imidazolinium; N, N'-dimethyltetrahydropyrimidinium, N, N'-diethyltetrahydropyrimidinium, N-ethyl-N'-methyltetrahydropyrimidinium, 1,2,3- Tetrahydropyrimidinium such as trimethyltetrahydropyrimidinium; morpholinium such as N, N'-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium; N, N-dimethyl Piperidinium such as piperidinium, N-ethyl-N'-methylpiperidinium, N, N'-diethylpiperidinium; N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, N-isopropylpyridinium , N-n-butylpyridinium, N-benzylpyridinium, N-phenacylpyridium and other pyridiniums; N-methylquinolium, N-ethylquinolium, Nn-propylquinolium, N-isopropylquinolium, N -N-butyl quinolium, Kinoliums such as N-benzyl quinolium and N-phenacyl quinolium; N-methylisoquinolium, N-ethylisoquinolium, Nn-propylisoquinolium, N-isopropylisoquinolium, Nn- Isoquinolium such as butylisoquinolium, N-benzylisoquinolium, N-phenacylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; acridium such as benzylacrydium and phenacylacrydium And so on.

These include US Pat. No. 4069055, Japanese Patent No. 2519480, Japanese Patent Application Laid-Open No. 5-222112, Japanese Patent Application Laid-Open No. 5-222111, Japanese Patent Application Laid-Open No. 5-262813, Japanese Patent Application Laid-Open No. 5-255256, Japanese Patent Application Laid-Open No. 7- 109303, 10-101718, 2-268173, 9-328507, 5-132461, 9-221652, 7-43854. Japanese Patent Application Laid-Open No. 7-43901, Japanese Patent Application Laid-Open No. 5-262831, Japanese Patent Application Laid-Open No. 4-327574, Japanese Patent Application Laid-Open No. 2-433202, Japanese Patent Application Laid-Open No. 60-203628, Japanese Patent Application Laid-Open No. 57-209931 It is described in Japanese Patent Application Laid-Open No. 9-221652 and the like.

Examples of the phosphonium ion include tetraarylphosphoniums such as tetraphenyl phosphonium, tetra-p-tolyl phosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium; Triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium; triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacilphosphonium, Examples thereof include tetraalkylphosphoniums such as tributylphenacilphosphonium, which are described in JP-A-6-157624, JP-5-105692, JP-A-7-82283, JP-A-9-202873 and the like. Have been described.

Examples of the oxonium ion include trimethyloxonium, triethyloxonium, tripropyloxonium, tributyloxonium, trihexyloxonium, triphenyloxonium, pyririnium, chromenilium, xanthylium and the like.

Examples of the bismutnium ion include those described in Japanese Patent Application Laid-Open No. 2008-214330.

Examples of the tropylium ion include J. cerevisiae. Polym. Sci. PartA; Polym. Chem. , 42, 2166 (2004) and the like.

(Ammonium cation)
The ionic compound of the present embodiment preferably contains an ammonium cation represented by the following formula (1A).

The ammonium cation represented by the following formula (1A) will be described.

In the above formula (1A), ^Ra , R ^b and R ^c each independently represent a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group and the like. These groups may further have a substituent, and examples of the substituent include an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable. At ^{least two of R a} , R ^b and R ^c may be bonded to each other to form a ring. R ^a , R ^b and R ^c may be the same or different from each other.

In the present specification and the like, the organic group means an atomic group having one or more carbon atoms.
In the present specification and the like, the aryl group means an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Examples of the aromatic hydrocarbon include a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more selected from an independent monocyclic ring and a condensed ring are bonded via a single bond.
In the present specification and the like, the heteroaryl group refers to an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. Examples of the aromatic heterocycle include a monocyclic ring, a condensed ring, and a polycyclic ring in which two or more selected from an independent monocyclic ring and a condensed ring are bonded via a single bond.

Specific examples of R ^a , R ^b, and R ^c will be described, but the present invention is not limited to the following.

The alkyl group may be linear, branched or cyclic and may have a substituent. The alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 18 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and an octyl group. 2-Ethylhexyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group , Perfluorooctyl group and the like.

The alkenyl group may be linear, branched or cyclic and may have a substituent. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-octenyl group and a 1-decenyl group. Examples thereof include a 1-octadecenyl group.

The alkynyl group may be linear, branched or cyclic and may have a substituent. The alkynyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. And so on.

The aryl group may further have a substituent, and examples of the substituent include an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable. The monovalent aryl group in the unsubstituted state preferably has 6 to 60 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 18 carbon atoms. Specifically, a phenyl group, a C1 to C12 alkoxyphenyl group (C1 to C12 indicate that the substituent has 1 to 12 carbon atoms; the same applies hereinafter), a C1 to C12 alkylphenyl group, Examples thereof include 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, phenanthrene-yl group, pyrene-yl group, perylene-yl group, pentafluorophenyl group and the like.

Specific examples of C1-C12 alkyl include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3 , 7-Dimethyloctyl, lauryl and the like are exemplified.

The heteroaryl group may further have a substituent, and examples of the substituent include an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable. The monovalent heteroaryl group in the unsubstituted state preferably has 4 to 60 carbon atoms, more preferably 4 to 40 carbon atoms, and further preferably 4 to 20 carbon atoms. Specifically, a thienyl group, a C1-C12 alkylthenyl group, a pyrrolyl group, a frill group, a pyridyl group, a C1-C12 alkylpyridyl group and the like are exemplified, and a thienyl group, a C1-C12 alkylthenyl group, a pyridyl group, a C1- A C12 alkylpyridyl group is preferred. Examples of C1 to C12 alkyl are as described above.

The arylalkyl group is a group in which at least one hydrogen atom of the alkyl group is substituted with an aryl group. The arylalkyl group may further have a substituent, and examples of the substituent include an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable. The monovalent arylalkyl group in the unsubstituted state preferably has 7 to 19, more preferably 7 to 16, and even more preferably 7 to 13. Examples of the alkyl group include the above-mentioned alkyl group, and examples of the aryl group include the above-mentioned aryl group. Specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a diphenylmethyl group and the like are exemplified.

In the formula (1A), ^{at least one of Ra} , R ^b and R ^c is an organic group having 5 or more carbon atoms (more preferably 6 or more carbon atoms, still more preferably 8 or more carbon atoms). preferable. When ^{at least one of R a} , R ^b and R ^c is an organic group having 5 or more carbon atoms, the temperature is low when an ionic compound is used together with a charge transporting compound having a polymerizable functional group described later. The curability can be improved and the film forming property can be improved.

Further, from the viewpoint of solubility, in the formula (1A), ^Ra , R ^b and R ^c are monovalent organic groups independently selected from the group consisting of an alkyl group, an alkenyl group and an alkynyl group, respectively. Is preferable, and more preferably, ^Ra , R ^b, and R ^c are independently alkyl groups.

For example, in the formula (1A), ^Ra , R ^b and R ^c are monovalent organic groups independently selected from the group consisting of an alkyl group, an alkenyl group and an alkynyl group, respectively, and ^Ra , R ^b. It ^{is also preferable that at least one of R c is} a monovalent organic group having 5 or more carbon atoms (more preferably 6 or more carbon atoms, still more preferably 8 or more carbon atoms).

(Anion)
The anion of the ionic compound of this embodiment is represented by the following formula (1B).

In the above formula (1B), R ^d , ^Re , R ^f and R ^g each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms. l, m, n and o each independently represent an integer of 1-5.

Specific examples of R ^d , ^Re , R ^f and R ^g include the groups shown below. In the present specification and the like, "*" in the structural formula represents a binding site with another structural unit.

Further, from the viewpoint of solubility, it is preferable to make the anion bulky. When the anion has a bulky substituent, the steric strain becomes large and the solubility in a solvent becomes high. I deleted it a little.

Examples of the bulky anion include a configuration in which R ^d , ^Re , R ^f and R ^g are perfluoroalkyl groups having 3 to 5 carbon atoms in the formula (1B).

Further, in the formula (1B), a bulky anion having a steric strain due to the proximity of the ^{substituents R d} , ^Re , R ^f and R ^{g of the phenyl group bonded to boron (B) is used.} Is preferable. For example, in the formula (1B), it is represented by the following formula (2B) having ^{substituents R d} , ^Re , R ^f and R ^g at the 3- and 5-positions of the phenyl group bonded to boron (B). Anions can be used.

In the above formula (2B), R ^d , ^Re , R ^f and R ^g each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms. l, m, n and o each independently represent an integer of 0 to 3.

Examples of R ^d , ^Re , R ^f and R ^g include the substituents exemplified in the above formula (1B).

Further, from the viewpoint of easily producing anions, ^{it is preferable that each of R d} , ^Re , R ^f and R ^g is the same as each other, and each of l, m, n and o is the same as each other. Is preferable. Further, from the viewpoint of easily producing an anion, each of R ^d , ^Re , R ^f and R ^g is preferably a trifluoromethyl group. For example, an anion represented by the following formula (3B) can be used.

The ionic compound of the present embodiment can improve the selectivity of the ink solvent when used in an ink composition.

<Organic electronics materials>
The organic electronic material of the present embodiment contains the ionic compound of the above-described embodiment, and may contain only one type of ionic compound or two or more types of ionic compound. The organic electronic material of the present embodiment may further contain a charge transporting compound. By using the organic electronic material containing the ionic compound of the above-described embodiment, it is possible to obtain an organic electronic device provided with an organic layer having excellent solvent resistance.

[Charge transporting compound]
The organic electronics material may contain a charge transporting compound. The charge transporting compound may be a low molecular weight compound or a polymer. From the viewpoint of solubility in an organic solvent, a polymer is preferable, and from the viewpoint of easy purification by sublimation, recrystallization, etc., a low molecular weight compound is preferable. The "polymer" includes an oligomer having a low degree of polymerization (for example, a number average degree of polymerization of 2 or more and 20 or less) and a polymer having a high degree of polymerization (for example, a number average degree of polymerization of more than 20). The charge transporting compound may be a commercially available compound or may be synthesized by a known method, and is not particularly limited.

The charge transporting compound preferably contains at least one unit selected from the group consisting of a unit containing an aromatic amine structure, a unit containing a carbazole structure, and a unit containing a thiophene structure.
The charge transporting compound preferably has one or more polymerizable functional groups in the molecule. The polymerizable functional group is not particularly limited, and preferred polymerizable functional groups include an oxetane group, an epoxy group, and a vinyl ether group.
When the charge transporting compound has a polymerizable functional group, the curability at low temperature is improved when the organic electronics material containing the charge transporting compound and the ionic compound of the above-described embodiment is used as an ink composition. Therefore, the film forming property at a low temperature can be improved.

(Charge transport polymer)
Hereinafter, the charge transporting polymer will be described.
Charge-transporting polymers have the ability to transport charges. The charge-transporting polymer may be linear or may have a branched structure. The charge-transporting polymer preferably contains at least a divalent structural unit D having charge transportability and a monovalent structural unit M constituting the terminal portion, and contains a trivalent or higher-valent structural unit T constituting the branch portion. Further may be included. The charge-transporting polymer may contain only one type of each structural unit, or may contain a plurality of types of each structural unit. Each structural unit is bound to each other at a binding site of "monovalent" to "trivalent or higher".

(Structure of charge transport polymer)
Examples of the partial structure contained in the charge transport polymer include the following. The charge-transporting polymer is not limited to those having the following partial structures. In the partial structure, "D" represents the structural unit D, "M" represents the structural unit M, and "T" represents the structural unit T. In the partial structure contained in the charge-transporting polymer shown below, "*" in the formula represents a binding site with another structural unit. In the following substructures, the plurality of Ds may be the same structural unit or different structural units from each other. The same applies to M and T.

Linear charge transport polymer

Charge-transporting polymer with branched structure

(Structural unit D)
The structural unit D is a divalent structural unit having charge transportability. The structural unit D is not particularly limited as long as it includes an atomic group capable of transporting electric charges. For example, the structural unit D is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, biphenyl structure, terphenyl structure, naphthalene structure, anthracene structure, tetracene structure, phenanthrene structure, dihydro. Phenanthrene structure, pyridine structure, pyrazine structure, quinoline structure, isoquinoline structure, quinoxalin structure, aclysine structure, diazaphenanthrene structure, furan structure, pyrrole structure, oxazole structure, oxaziazole structure, thiazole structure, thiazazole structure, triazole structure, benzo It is selected from a thiophene structure, a benzoxazole structure, a benzoxaziazole structure, a benzothiazole structure, a benzothiazazole structure, a benzotriazole structure, and a structure containing one or more of these. The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.

In the present embodiment, the structural unit D is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, and these, from the viewpoint of obtaining excellent hole transportability. It is preferable to select from a structure containing one or more of these, and select from a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, and a structure containing one or more of these. It is more preferable to be done. The structural unit D is derived from a substituted or unsubstituted fluorene structure, benzene structure, phenanthrene structure, pyridine structure, quinoline structure, and a structure containing one or more of these, from the viewpoint of obtaining excellent electron transportability. It is preferably selected.

Specific examples of the structural unit D include the following. The structural unit D is not limited to the following.

R independently represents a hydrogen atom or a substituent. When R is a substituent, the substituents are independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , and a halogen atom, and It is preferably selected from the group consisting of groups containing polymerizable functional groups, which will be described later. R ^{1 to} R ⁸ independently represent a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or a heteroaryl group having 2 to 30 carbon atoms. The alkyl group may be further substituted with an aryl group or a heteroaryl group having 2 to 20 carbon atoms, and the aryl group or the heteroaryl group may be further substituted with a linear, cyclic or branched having 1 to 22 carbon atoms. It may be substituted with an alkyl group. R is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkyl-substituted aryl group. Ar represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. In the present specification and the like, the arylene group means an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. Further, in the present specification and the like, the heteroarylene group means an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. The description of the aromatic hydrocarbon and the aromatic heterocycle is the same as that of the aryl group and the heteroaryl group.

(Structural unit M)
The structural unit M is a monovalent structural unit constituting the terminal portion of the charge-transporting polymer. The structural unit M is not particularly limited, and is selected from, for example, a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure, and a structure containing one or more of these. The structural unit M may have the same structure as the structural unit D except for the valence. In the present embodiment, the structural unit M is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without lowering the charge transportability, and is preferably a substituted or unsubstituted benzene. The structure is more preferable. Further, as will be described later, when the charge-transporting polymer has a polymerizable functional group at the terminal portion, the structural unit M has a polymerizable structure (that is, a polymerizable functional group such as a pyrrole-yl group). May be good. Specific examples of the structural unit M include the following.

In the above formula, R includes a hydrogen atom or a substituent mentioned as R in the structural unit D. When the charge-transporting polymer has a polymerizable functional group at the terminal portion, it is preferable that at least one of R is a group containing a polymerizable functional group.

(Structural unit T)
The structural unit T is a trivalent or higher structural unit that constitutes a branched portion when the charge-transporting polymer has a branched structure. From the viewpoint of improving the durability of the organic electronic device, the structural unit T is preferably a hexavalent or lower structural unit, more preferably a tetravalent or lower structural unit, and further preferably a trivalent or tetravalent structural unit. Is. The structural unit T is preferably a unit having charge transportability. For example, the structural unit T is a substituted or unsubstituted triphenylamine structure, a carbazole structure, a condensed polycyclic aromatic hydrocarbon structure, and one or two of these, from the viewpoint of improving the durability of the organic electronic device. Includes at least one selected from structures containing more than one species. The structural unit T may have the same structure as the structural unit D except for the valence, and may have the same structure as the structural unit M except for the valence.

Specific examples of the structural unit T include the following. The structural unit T is not limited to the following.

W represents a trivalent linking group, for example, an arene triyl group having 2 to 30 carbon atoms or a heteroarene triyl group. In the present specification and the like, the arene triyl group refers to an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. In the present specification and the like, the heteroarene triyl group refers to an atomic group obtained by removing three hydrogen atoms from an aromatic heterocycle. Ar independently represents a divalent linking group, and for example, each independently represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group, for example, from the group having one or more hydrogen atoms among the substituents listed as R (excluding the group containing a polymerizable functional group) in the structural unit D. Examples thereof include a divalent group excluding one hydrogen atom. Z represents either a carbon atom, a silicon atom, or a phosphorus atom. In the structural unit, the fused ring, W, Y, and Ar may have a substituent, and examples of the substituent include the substituent mentioned as R in the structural unit D.

(Polymerizable functional group)
In the present embodiment, the charge-transporting polymer is preferably cured by a polymerization reaction and has at least one polymerizable functional group from the viewpoint of changing the solubility in a solvent. The "polymerizable functional group" refers to a functional group capable of forming a bond with each other by applying at least one of heat and light.

The polymerizable functional group includes a group having a carbon-carbon multiple bond (for example, a vinyl group, an allyl group, a butenyl group, an ethynyl group, an acryloyl group, an acryloyloxy group, an acryloylamino group, a methacryloyl group, a methacryloyloxy group, and a methacryloylamino group. Group, vinyloxy group, vinylamino group, etc.), group having a small ring (for example, cyclic alkyl group such as cyclopropyl group, cyclobutyl group; cyclic ether group such as epoxy group (oxylanyl group), oxetan group (oxetanyl group)) Examples thereof include a diketen group; an episulfide group; a lactone group; a lactam group, etc.), a heterocyclic group (for example, a furan-yl group, a pyrrole-yl group, a thiophen-yl group, a silol-yl group) and the like. These groups may further have a substituent, and examples of the substituent include an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable. As the polymerizable functional group, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are particularly preferable, and a vinyl group, an oxetan group, or an epoxy group is more preferable from the viewpoint of reactivity and characteristics of the organic electronic device. preferable.

From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the occurrence of a polymerization reaction, it is preferable that the main skeleton of the charge-transporting polymer and the polymerizable functional group are linked by an alkylene chain.
Further, for example, when an organic layer is formed on an electrode, a hydrophilic chain such as an ethylene glycol chain or a diethylene glycol chain is used from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO (indium oxide-tin oxide). It is preferable that they are connected by. Further, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group, the charge transport polymer is used with at least one of the ends of the alkylene chain and the hydrophilic chain, that is, with these chains. At least one of the linking portion with the polymerizable functional group and the connecting portion between these chains and the skeleton of the charge-transporting polymer may have an ether bond or an ester bond. The above-mentioned "group containing a polymerizable functional group" means a polymerizable functional group itself or a group in which a polymerizable functional group and an alkylene chain are combined. As the group containing the polymerizable functional group, for example, the group exemplified in International Publication No. 2010/1405553 can be preferably used.

The polymerizable functional group is introduced at the terminal portion (that is, the structural unit M) of the charge-transporting polymer or at a portion other than the terminal portion (that is, the structural unit D or T). It may be introduced in both the and non-terminal parts. From the viewpoint of curability, it is preferable that it is introduced at least at the terminal portion, and from the viewpoint of achieving both curability and charge transportability, it is preferable that it is introduced only at the terminal portion. Further, when the charge-transporting polymer has a branched structure, the polymerizable functional group may be introduced into the main chain or the side chain of the charge-transporting polymer, and both the main chain and the side chain may be introduced. It may be introduced in.

From the viewpoint of contributing to the change in solubility, the polymerizable functional group is preferably contained in a large amount in the charge-transporting polymer. On the other hand, the polymerizable functional group preferably contains a small amount in the charge-transporting polymer from the viewpoint of not hindering the charge-transporting property. The content of the polymerizable functional group can be appropriately set in consideration of these.

For example, the number of polymerizable functional groups per molecule of the charge-transporting polymer is preferably 2 or more, and more preferably 3 or more, from the viewpoint of obtaining a sufficient change in solubility. The number of polymerizable functional groups is preferably 1,000 or less, more preferably 700 or less, and even more preferably 500 or less, from the viewpoint of maintaining charge transportability.

The number of polymerizable functional groups per molecule of the charge-transporting polymer is the amount of the polymerizable functional group charged (for example, the amount of the monomer having the polymerizable functional group) used for synthesizing the charge-transporting polymer, and each structure. It can be obtained as an average value by using the amount of the monomer charged corresponding to the unit, the weight average molecular weight of the charge-transporting polymer, and the like. The number of polymerizable functional groups is the ratio of the integrated value of the signal derived from the polymerizable functional group in ^{the 1} H NMR (nuclear magnetic resonance) spectrum of the charge transport polymer to the integrated value of the entire spectrum, and the charge transport polymer. It can be calculated as an average value by using the weight average molecular weight of. When the amount to be charged is clear, it is preferable to adopt the value obtained by using the amount to be charged because it is convenient.

(Number average molecular weight)
The number average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming property, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more, from the viewpoint of excellent charge transportability. The number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and more preferably 50,000 or less, from the viewpoint of maintaining good solubility in the solvent and facilitating the preparation of the ink composition. The following is more preferable.

(Weight average molecular weight)
The weight average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming property, and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, from the viewpoint of excellent charge transportability. The weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and more preferably 400,000 or less, from the viewpoint of maintaining good solubility in the solvent and facilitating the preparation of the ink composition. The following is more preferable.

The number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

(Ratio of structural units)
The ratio of the structural unit D contained in the charge-transporting polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on all the structural units, from the viewpoint of obtaining sufficient charge transportability. Is more preferable. Further, the ratio of the structural unit D is preferably 95 mol% or less, more preferably 90 mol% or less, more preferably 85 mol% or less, based on all the structural units, in consideration of the structural unit M and the structural unit T to be introduced as needed. More preferably, it is mol% or less.

The ratio of the structural unit M contained in the charge-transporting polymer is based on all the structural units from the viewpoint of improving the characteristics of the organic electronic device or from the viewpoint of suppressing the increase in viscosity and satisfactorily synthesizing the charge-transporting polymer. 5 mol% or more is preferable, 10 mol% or more is more preferable, and 15 mol% or more is further preferable. The ratio of the structural unit M is preferably 60 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less, based on all structural units, from the viewpoint of obtaining sufficient charge transportability.

When the charge transporting polymer contains the structural unit T, the ratio of the structural unit T is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the structural units, from the viewpoint of improving the durability of the organic electronic device. It is preferable, and 10 mol% or more is more preferable. The ratio of the structural unit T is 50 mol% or less based on all structural units from the viewpoint of suppressing an increase in viscosity and satisfactorily synthesizing a charge-transporting polymer or obtaining sufficient charge-transporting property. Is preferable, 40 mol% or less is more preferable, and 30 mol% or less is further preferable.

When the charge-transporting polymer has a polymerizable functional group, the ratio of the polymerizable functional group is preferably 0.1 mol% or more based on all structural units from the viewpoint of efficiently curing the charge-transporting polymer. 1 mol% or more is more preferable, and 3 mol% or more is further preferable. The proportion of the polymerizable functional group is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, based on all structural units, from the viewpoint of obtaining good charge transportability. .. The "ratio of polymerizable functional groups" here means the ratio of structural units having polymerizable functional groups.

Considering the balance of charge transportability, durability, productivity, etc., the ratio (molar ratio) of the structural unit D and the structural unit M is preferably D: M = 100: 1 to 70, more preferably 100: 3 to 50. It is preferable, and 100: 5 to 30 is more preferable. When the charge transporting polymer contains the structural unit T, the ratio (molar ratio) of the structural unit D, the structural unit M, and the structural unit T is D: M: T = 100: 10 to 200: 10 to 100. Preferably, 100: 20 to 180: 20 to 90 is more preferable, and 100: 40 to 160: 30 to 80 is even more preferable.

The ratio of the structural units can be determined by using the amount of the monomer charged corresponding to each structural unit used for synthesizing the charge-transporting polymer. Further, the ratio of the structural units can be calculated as an average value by using the integrated value of the spectrum derived from each structural unit in ^{the 1 H NMR spectrum of the charge transport polymer.} When the amount to be charged is clear, it is preferable to adopt the value obtained by using the amount to be charged because it is convenient.

(Production method)
The charge-transporting polymer can be produced by various synthetic methods and is not particularly limited. For example, known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Still coupling, and Buchwald-Hartwig coupling can be used. Suzuki coupling causes a Pd-catalyzed cross-coupling reaction between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki Coupling, a charge-transporting polymer can be easily produced by binding desired aromatic rings to each other.

In the coupling reaction, for example, a Pd (0) compound, a Pd (II) compound, a Ni compound and the like are used as the catalyst. Further, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like as a precursor and mixing with a phosphine ligand can also be used. Regarding the method for synthesizing the charge-transporting polymer, for example, the description of International Publication No. 2010/1405553 can be incorporated.

(Charge transporting low molecular weight compound)
Hereinafter, the charge transporting low molecular weight compound will be described.
The charge-transporting low-molecular-weight compound is not particularly limited as long as it contains an atomic group capable of transporting charges. The charge transporting low molecular weight compound may have a polymerizable functional group. The charge-transporting low molecular weight compound preferably contains at least one unit selected from the group consisting of a unit containing an aromatic amine structure, a unit containing a carbazole structure, and a unit containing a thiophene structure.

(Structure of charge transporting low molecular weight compound)
Examples of the structure of the charge transporting low molecular weight compound include the following. “D” represents the structural unit D, and “M” represents the structural unit M. The structural unit D and the structural unit M are as described above.

The organic electronics material may contain only one type of charge transporting compound (including a charge transporting low molecular weight compound), or may contain two or more types.

When the organic electronics material contains an ionic compound and a charge transporting compound, the content of the ionic compound is 0.1% by mass or more based on the mass of the charge transporting compound from the viewpoint of film forming property. Is preferable, 0.2% by mass or more is more preferable, and 0.5% by mass or more is further preferable. The content of the ionic compound is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less, based on the mass of the charge transporting compound, from the viewpoint of the driving voltage of the organic electronics element. More preferred.

[solvent]
The organic electronics material may further contain a solvent. The solvent-containing organic electronics material is preferably used as an ink composition in the production of organic electronics devices.

As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetraline and diphenylmethane; ethylene glycol. Alibo ethers such as dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetone; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, Aromatic ethers such as 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate and propionic acid Aromatic esters such as phenyl, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide; dimethylsulfoxide, tetrahydrofuran, acetone , Chloroform, methylene chloride and the like. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers and the like. As the solvent, a non-polar organic solvent is preferable.

The content of the solvent in the ionic compound can be determined in consideration of application to various coating methods. For example, the ionic compound preferably contains an amount of the solvent having a charge-transporting polymer ratio of 0.1% by mass or more with respect to the solvent, and preferably contains an amount of the solvent having an amount of 0.2% by mass or more. It is more preferable that the solvent is contained in an amount of 0.5% by mass or more. Further, the ionic compound preferably contains a solvent in an amount such that the ratio of the charge transport polymer to the solvent is 20% by mass or less, and more preferably 15% by mass or less. It is more preferable to contain the solvent in an amount of 10% by mass or less.

[Additive]
The organic electronics material may further contain an additive as an optional component. Additives include, for example, polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, antioxidants, oxidizing agents, reducing agents, surface modifiers, emulsifiers, defoamers, etc. Dispersants, surfactants and the like can be mentioned.

<Organic layer>
The organic layer of the present embodiment is obtained by polymerizing a layer formed by a coating method using the organic electronic material of the above-described embodiment or an ink composition containing the organic electronic material, and further, the formed layer. It is a layer that has been allowed to insolubilize. By using an organic electronic material containing a solvent, an organic layer can be satisfactorily formed by a coating method. Examples of the coating method include a spin coating method; a casting method; a dipping method; a letterpress printing, a concave plate printing, an offset printing, a flat plate printing, a letterpress reversal offset printing, a screen printing, a plate printing method such as gravure printing; an inkjet method and the like. Known methods such as a plateless printing method can be mentioned. When the organic layer is formed by the coating method, the organic layer (coating layer) obtained after coating may be dried using a hot plate or an oven to remove the solvent.

When the organic electronics material contains a charge-transporting compound having a polymerizable functional group, these polymerization reactions can be allowed to proceed by light irradiation, heat treatment, or the like to change the solubility of the organic layer. In organic electronics materials, ionic compounds can function as polymerization initiators. By stacking organic layers having different solubilities, it is possible to easily increase the number of layers of organic electronic devices. As for the method of forming the organic layer, for example, the description of International Publication No. 2010/1405553 can be incorporated.
When the organic electronics material contains a charge-transporting compound having a polymerizable functional group, the curability at a low temperature can be improved when the ink composition is prepared. In addition, good stacking of organic layers is possible, and when an organic electronic device is used, the life of the organic electronic device can be extended.

The thickness of the organic layer after drying or curing is preferably 0.1 nm or more, more preferably 1 nm or more, still more preferably 3 nm or more, from the viewpoint of improving the efficiency of charge transport. The thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less from the viewpoint of reducing the electric resistance.

<Organic electronics element>
The organic electronic device of the present embodiment has at least the organic layer of the above-described embodiment. Examples of the organic electronics element include an organic EL element such as an organic light emitting diode (OLED), an organic photoelectric conversion element, and an organic transistor. The organic electronic device preferably has a structure in which an organic layer is arranged between at least a pair of electrodes.

[Organic EL element]
The organic EL device of the present embodiment has at least one or more organic layers of the above-described embodiment. The organic EL device usually includes a light emitting layer, an anode, a cathode, and a substrate, and if necessary, provides other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. I have. Each layer may be formed by a thin-film deposition method or a coating method. The organic EL device preferably has an organic layer as a light emitting layer or another functional layer, more preferably as a functional layer, and further preferably as at least one of a hole injection layer and a hole transport layer.

FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic EL device. The organic EL device shown in FIG. 1 is a multi-layered device, and has a substrate 8, an anode 2, a hole injection layer 3, a hole transport layer 6, a light emitting layer 1, an electron transport layer 7, an electron injection layer 5, and a cathode. It has a multi-layer structure in which 4 are laminated in this order. Note that FIG. 1 is an example, and the organic EL element of the present embodiment is not limited to this figure.
In FIG. 1, the hole injection layer 3 is an organic layer formed by using the above-mentioned organic electronic material, but the organic EL device of the present embodiment is not limited to such a structure, and other organic layers may be used. , It may be an organic layer formed by using the above-mentioned organic electronic material. For example, it is preferable to include an organic layer formed by using the above-mentioned organic electronics material as at least one layer selected from the group consisting of a hole transport layer, a hole injection layer, and a light emitting layer. Hereinafter, each layer will be described.

[Light emitting layer]
As the material used for the light emitting layer, a light emitting material such as a low molecular weight compound, a polymer, or a dendrimer can be used. Polymers are preferred because they are highly soluble in solvents and suitable for coating methods. Examples of the light emitting material include fluorescent materials, phosphorescent materials, thermal activated delayed fluorescent materials (TADF) and the like.

Low molecular weight compounds such as perylene, coumarin, rubrene, quinacridone, stilbene, dyes for dye lasers, aluminum complexes, and derivatives thereof as fluorescent materials; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinylcarbazole, fluorene-benzothiazol copolymer , Fluorene-triphenylamine copolymers, polymers such as derivatives thereof; mixtures thereof and the like.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. Examples of the Ir complex include FIr (pic) (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate) that emits blue light, and Ir (ppy) _{3 that emits green light.} (Factris (2-phenylpyridine) iridium), exhibiting red luminescence (btp) ₂ Ir (acac) (bis [2- (2'-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] Iridium (acetyl-acetonate)), Ir (piq) ₃ (tris (1-phenylisoquinoline) iridium) and the like can be mentioned. Examples of the Pt complex include PtOEP (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-forfin platinum) that emits red light.

When the light emitting layer contains a phosphorescent material, it is preferable that the light emitting layer further contains a host material in addition to the phosphorescent material. As the host material, a low molecular weight compound, a polymer, or a dendrimer can be used. Examples of low molecular weight compounds include CBP (4,4'-bis (9H-carbazole-9-yl) biphenyl), mCP (1,3-bis (9-carbazolyl) benzene), and CDBP (4,4'-. Bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), derivatives thereof and the like, and as the polymer, the organic electronics material of the above-described embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof and the like can be used. Can be mentioned.

Examples of thermally activated delayed fluorescent materials include Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012). Appl. Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); Nature, 492, 234 (2012) ); Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. Chem. Chem. Phys., 15, 15850 (2013); Chem. Comm., 49, 10385 (2013); Chem. Lett., 43, 319 (2014), etc. can be incorporated.

[Hole transport layer, hole injection layer]
The above-mentioned organic layer is preferably used as at least one of the hole injection layer and the hole transport layer, and more preferably at least as the hole transport layer. When the organic EL device has the above-mentioned organic layer as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. Further, when the above-mentioned organic layer is provided as a hole injection layer and further has a hole transport layer, a known material can be used for the hole transport layer.

Examples of the material that can be used for the hole injection layer and the hole transport layer include aromatic amine compounds, phthalocyanine compounds, and thiophene compounds.

[Electron transport layer, electron injection layer]
Materials used for the electron transport layer and the electron injection layer include, for example, fused ring tetracarboxylic acid anhydrides such as phenanthroline derivative, bipyridine derivative, nitro-substituted fluorene derivative, diphenylquinone derivative, thiopyrandioxide derivative, naphthalene and perylene, and carbodiimide. , Fluolenilidene methane derivative, anthraquinodimethane and antron derivative, oxadiazole derivative, thiadiazole derivative, benzoimidazole derivative, quinoxalin derivative, aluminum complex (for example, BAlq, Alq ₃ ) and the like. Further, the organic electronic material of the above-described embodiment can also be used.

[cathode]
As the cathode material, for example, a metal or a metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, CsF is used.

[anode]
As the anode material, for example, a metal (for example, Au) or another conductive material is used. Other materials include, for example, oxides (eg, ITO), conductive polymers (eg, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[substrate]
Glass, plastic, etc. can be used as the substrate. The substrate is preferably transparent and preferably has flexibility. Quartz glass, light-transmitting resin film and the like are preferably used.

As the resin film, for example, a film containing polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate and the like. Can be mentioned.

When a resin film is used, the resin film may be coated with an inorganic substance such as silicon oxide or silicon nitride in order to suppress the permeation of water vapor, oxygen and the like.

[Emission color]
The emission color of the organic EL element is not particularly limited. An organic EL element exhibiting white light emission (also referred to as a white organic EL element) is preferable because it can be used for various lighting fixtures such as household lighting, vehicle interior lighting, clocks, and liquid crystal backlights.

As a method for forming the white organic EL element, a method can be used in which a plurality of luminescent materials are used to simultaneously emit a plurality of luminescent colors to mix the colors. The combination of a plurality of emission colors is not particularly limited, but for example, a combination containing three emission maximum wavelengths of blue, green and red, and a complementary color relationship such as blue and yellow and yellow-green and orange. Examples thereof include a combination containing the two maximum emission wavelengths used. The emission color can be controlled by adjusting the type and amount of the emission material.

<Display element, lighting device, display device>
The display element of the present embodiment includes the organic EL element of the above-described embodiment. For example, by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB), a color display element can be obtained. There are two methods for forming an image: a simple matrix type in which individual organic EL elements arranged on a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which a thin film transistor is arranged and driven in each element.

Further, the lighting device of the present embodiment includes the organic EL element of the above-described embodiment. Further, the display device of the present embodiment includes a lighting device and a liquid crystal element as a display means. For example, the display device can be a display device using the lighting device of the above-described embodiment as a backlight and a known liquid crystal element as a display means, that is, a liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Synthesis of ionic compounds>
[Example 1]
(Synthesis of Ionic Compound 1)
Ionic compound 1 having the following structure was synthesized as follows.
Add 25 g of acetone and 5 g of pure water to 1.954 g (10 mmol) of N, N-dicyclohexylmethylamine and stir to make a uniform solution, then slowly add 3.653 g of a 10% hydrogen chloride aqueous solution and stir for 1 hour after the completion of the dropping. did. The solvent was distilled off from this solution under reduced pressure. Then, 9.745 g (11 mmol) of Sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] -borate was mixed and stirred for 1 hour. This was washed with water 5 times and dried to prepare a white solid.

[Example 2]
(Synthesis of Ionic Compound 2)
Ionic compound 2 having the following structure was synthesized as follows.
To 1.292 g (10 mmol) of N, N-diisopropylethylamine, 25 g of acetone and 5 g of pure water were added and stirred to make a uniform solution, then 3.653 g of a 10% hydrogen chloride aqueous solution was slowly added dropwise, and the mixture was stirred for 1 hour after the completion of the addition. .. The solvent was distilled off from this solution under reduced pressure. Then, 9.745 g (11 mmol) of Sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] -borate was mixed and stirred for 1 hour. This was washed with water 5 times and dried to prepare a white solid.

[Comparative Example 1]
(Synthesis of Ionic Compound 3)
The ionic compound 3 having the following structure was synthesized as follows.
Add 25 g of acetone and 5 g of pure water to 1.954 g (10 mmol) of N, N-dicyclohexylmethylamine and stir to make a uniform solution, then slowly add 3.653 g of a 10% hydrogen chloride aqueous solution and stir for 1 hour after the completion of the dropping. did. The solvent was distilled off from this solution under reduced pressure. Then, 77.49 g (11 mmol) of a 10% aqueous solution of Sodium tetrakis (pentafluorophenyl) borate was mixed, and the mixture was stirred for 1 hour. This was washed with water 5 times and dried to prepare a white solid.

[Comparative Example 2]
(Synthesis of Ionic Compound 4)
The ionic compound 4 having the following structure was synthesized as follows.
To 1.292 g (10 mmol) of N, N-diisopropylethylamine, 25 g of acetone and 5 g of pure water were added and stirred to make a uniform solution, then 3.653 g of a 10% hydrogen chloride aqueous solution was slowly added dropwise, and the mixture was stirred for 1 hour after the completion of the addition. .. The solvent was distilled off from this solution under reduced pressure. Then, 77.49 g (11 mmol) of a 10% aqueous solution of Sodium tetrakis (pentafluorophenyl) borate was mixed, and the mixture was stirred for 1 hour. This was washed with water 5 times and dried to prepare a white solid.

<Evaluation of solubility>
The solubility of each of the ionic compounds of Examples 1 and 2 (ionic compounds 1 and 2) and the ionic compounds of Comparative Examples 1 and 2 (ionic compounds 3 and 4) was evaluated. 5 mg of each ionic compound was weighed into a 6 mL screw tube, and 100 μL of each solvent was added until it was visually dissolved. Table 1 shows the amount of solvent required for the ionic compound to dissolve. In addition, "-" in the table indicates that the ionic compound was not dissolved in the solvent.

Examples 1 and 2 using the ionic compound of the present embodiment were compared with Comparative Examples 1 and 2, and all showed good evaluation results in terms of solubility.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples, and includes various modifications.

<Preparation of hole-transporting polymer>
(Preparation of Pd catalyst)
Tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed in a sample tube at room temperature in a glove box under a nitrogen atmosphere, toluene (15 mL) was added, and the mixture was stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, toluene (5 mL) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes before use as a catalyst. All solvents were degassed by nitrogen bubbles for at least 30 minutes before use.

(Preparation of hole transporting polymer 1)
In a three-necked round-bottom flask, the following monomer A1 (5.0 mmol), the following monomer B1 (2.0 mmol), the following monomer C1 (4.0 mmol), methyltri-n-octylammonium chloride (“Alicoat 336” manufactured by Alfa Aesar). (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL) are added, and the Pd-catalyzed toluene solution (3.0 mL) prepared above is further added and mixed. Then, the reaction was carried out by heating and refluxing this mixed solution for 2 hours. All operations up to this point were performed under a nitrogen stream. In addition, all the solvents were used after being degassed by nitrogen bubbles for 30 minutes or more.

After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene, poured into methanol and reprecipitated. The obtained precipitate was collected by suction filtration, dissolved in toluene, and a metal adsorbent (“Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer” manufactured by Strem Chemicals, 200 mg with respect to 100 mg of the precipitate) was added to 80. The mixture was stirred at ° C. for 2 hours. After the stirring was completed, the metal adsorbent and the insoluble matter were removed by filtration, and the filtrate was poured into methanol for reprecipitation. The resulting precipitate was collected by suction filtration and washed with methanol. The obtained precipitate was vacuum dried to prepare a hole-injectable compound 1. The hole-transporting polymer 1 had a number average molecular weight of 14,700 and a weight average molecular weight of 46,100.

The number average molecular weight and the weight average molecular weight were measured by GPC (polystyrene conversion) using tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.
Equipment: High Performance Liquid Chromatograph Prominence Shimadzu Corporation
Liquid transfer pump (LC-20AD)
Degassing unit (DGU-20A)
Autosampler (SIL-20AHT)
Column oven (CTO-20A)
PDA detector (SPD-M20A)
Differential Refractometer Detector (RID-20A)
Column: Gelpack®
GL-A160S (serial number: 686-1J27)
GL-A150S (serial number: 685-1J27) Hitachi Kasei Co., Ltd. Eluent: tetrahydrofuran (THF) (for HPLC, containing stabilizer) Fujifilm Wako Pure Chemical Industries, Ltd. Flow velocity: 1 mL / min
Column temperature: 40 ° C
Detection wavelength: 254 nm
Molecular weight standard substance: PStQuick A / B / C Tosoh Corporation

(Preparation of hole transporting polymer 2)
In a three-necked round-bottom flask, the following monomer A2 (5.0 mmol), the following monomer B1 (2.0 mmol), the following monomer C1 (3.6 mmol), the following monomer C2 (0.4 mmol), methyltri-n-octylammonium chloride ( Alfa Aesar "Alicoat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL) were added, and the Pd-catalyzed toluene solution prepared above (50 mL) was added. 3.0 mL) was added and mixed, and the reaction was carried out by heating and refluxing the mixed solution for 2 hours. All operations up to this point were performed under a nitrogen stream. In addition, all the solvents were used after being degassed by nitrogen bubbles for 30 minutes or more. After that, the same operation as that for the hole transporting polymer 1 was carried out to prepare the hole transporting polymer 2. The hole-transporting polymer 2 had a number average molecular weight of 12,000 and a weight average molecular weight of 67,000.

[Solvent resistance evaluation]
An organic layer was formed using the hole-transporting polymers 1 and 2, and the solvent resistance (that is, the curability of the hole-transporting polymer + the ionic compound) was evaluated by measuring the residual film ratio.

(Measurement of residual film ratio)
The ionic compound (10 mg) used in Example 1 was weighed into a 20 mL screw tube, chlorobenzene (10 mL) was added, and the mixture was stirred to prepare an ionic compound solution. Then, the hole-transporting polymer (10 mg) and chlorobenzene (792 μL) were added to the 9 mL screw tube to dissolve the hole-transporting polymer. Then, 101 μL of the ionic compound solution was added to the above-mentioned 9 mL screw tube and stirred to prepare an ink composition. The ink composition is filtered through a polytetrafluoroethylene (PTFE) filter (pore diameter 0.2 μm), dropped onto a quartz substrate (length 22 mm × width 29 mm × thickness 0.7 mm), and a coating film is formed by a spin coater. Filmed. Subsequently, heat curing was carried out at 200 ° C. for 30 minutes in a nitrogen atmosphere to form an organic layer having a film thickness of 30 nm on a quartz substrate.

The absorbance A of the organic layer formed on the quartz substrate was measured using a spectrophotometer (“UV-2700” manufactured by Shimadzu Corporation). Subsequently, the mixture was immersed in anisole (10 mL, 25 ° C.) for 10 minutes in an environment of 25 ° C. so that the organic layer after measurement was on the upper surface. The absorbance B of the organic layer after immersion in anisole was measured, and the residual film ratio was calculated from the absorbance A of the formed organic layer and the absorbance B of the organic layer after immersion in anisole using the following formula. As the value of absorbance, the value at the maximum absorption wavelength of the organic layer was used. The larger the residual film ratio, the better the solvent resistance.

[Number 1]

Residual film ratio (%) = (absorbance B / absorbance A) x 100

Table 2 shows the measurement results of the residual film ratio.

The organic layer using the ionic compounds 1 and 2 in the above-described embodiment has the same residual film ratio as the organic layer using the ionic compounds 3 to 4, and gives a good measurement result in terms of film forming property. Indicated.

1 Light emitting layer 2 Anode 3 Hole injection layer 4 Cathode 5 Electron injection layer 6 Hole transport layer 7 Electron transport layer 8 Substrate

Claims (17)

An ionic compound containing cations and anions represented by the following formula.

(In the formula, C represents a cation, R ^d , ^Re , R ^f and R ^g each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms. L, m, n and o are respectively. Independently represents an integer of 1-5.) The ionic compound according to claim 1, wherein the anion is represented by the following formula.

(In the formula, R ^d , ^Re , R ^f and R ^g each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms. L, m, n and o independently represent 0 to 3, respectively. Represents an integer of.) The ionic compound according to claim 1 or 2, wherein each of R ^d , ^Re , R ^f and R ^{g is the same as each other.} The ionic compound according to any one of claims 1 to 3, wherein each of R ^d , ^Re , R ^f and R ^{g is a trifluoromethyl group.} The ionic compound according to any one of claims 1 to 4, wherein the anion is represented by the following formula.

The ionic compound according to any one of claims 1 to 5, wherein the cation is represented by the following formula.

(In the formula, R ^a , R ^b and R ^c each independently represent a monovalent organic group.) An organic electronics material containing the ionic compound according to any one of claims 1 to 6 and a charge transporting compound. The organic electronics material according to claim 7, wherein the charge transporting compound comprises at least one selected from the group consisting of a unit containing an aromatic amine structure, a unit containing a carbazole structure, and a unit containing a thiophene structure. The organic electronic material according to claim 7 or 8, wherein the charge transporting compound is a polymer or an oligomer. The organic electronic material according to any one of claims 7 to 9, wherein the charge-transporting compound has one or more polymerizable functional groups. The organic electronic material according to claim 10, wherein the polymerizable functional group comprises at least one selected from the group consisting of an oxetane group, an epoxy group, and a vinyl ether group. An ink composition containing the organic electronic material according to any one of claims 7 to 11 and a solvent. The ink composition according to claim 12, wherein the solvent is a non-polar organic solvent. An organic electronic device comprising the organic electronic material according to any one of claims 7 to 11 or an organic layer formed by using the ink composition according to claim 12 or 13. The organic electronic device according to claim 14, wherein the organic layer is a layer insolubilized by polymerization. The organic electronic device according to claim 15, wherein another layer is formed on the organic layer to form a multi-layered structure. The organic electronic device according to any one of claims 14 to 16, further comprising a substrate, wherein the substrate is a resin film.

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