TW200800870A - Sulfonic acid ester compound and use thereof - Google Patents

Abstract

Disclosed is a sulfonic acid ester compound represented by the formula (1) below. Since this sulfonic acid ester compound has high stability and high solubility in a wide range of organic solvents, it easily forms a uniform solution, thereby enabling to achieve excellent device characteristics when used in an OLED device. This sulfonic acid ester compound is suitable as an electron-accepting material or a thermal acid generator. (1) (In the formula, A represents a substituted or unsubstituted monovalent hydrocarbon group; X represents a substituted or unsubstituted divalent hydrocarbon group; Y represents O, S or a substituted or unsubstituted divalent amino group; and Z represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group.)

Description

200800870 (1) Nine, the invention belongs to the technical field of the invention. The present invention relates to a sulfonate compound and its use, and more particularly to a sulfonate compound which can form a cyclic complex in a molecule. And the use of an electron accepting substance of the compound and the use of a thermal acid generator. [Prior Art]

In the low-molecular organic EL (hereinafter referred to as OLED) device, a copper phthalocyanine (CuPC) layer as a hole injection layer is provided, and the initial characteristics such as reduction in driving voltage or luminous efficiency are improved, and life can be realized. A report of the feature draw is proposed (Non-Patent Document 1: Applied Physies Letters, USA, 1996, 69, p. 2 1 60-2 1 6 2). On the other hand, an organic EL (hereinafter abbreviated as PLED) element using a polymer light-emitting material is a polyaniline-based material (Patent Document 1: Japanese Patent Laid-Open No. Hei-3-273087, Non-Patent Document 2: Nature, United Kingdom, 1992, Vol. 357, p. 477-479), or a polythiophene-based material (Non-Patent Document 3: Applied Physics Letters, USA, 998, 72, p. 2660-2662) as a film The hole transport layer user, and the same effect as the OLED element can be published. In recent years, a charge transporting varnish which has been found to dissolve a low molecular low aniline material or a low thiophene material in an organic solvent has been obtained, and the hole injection layer obtained from the varnish is inserted into the organic EL element to obtain a substrate. A report on the planarization effect of a substrate or the characteristics of an excellent EL element has been published (Patent Document 2: 曰本特开2 0 0 2 - 1 5 1 2 7 2, Patent Document 200800870 (2) 3: WO 2004-043117 Patent Document 4: WO2005-043962). Further, in the case of using a 1,4-benzodioxanesulfonic acid compound as an electron-accepting substance (Patent Document 5: WO 2005-000832), a report that the driving voltage of the OLED element can be lowered is disclosed.

However, since the sulfonic acid compound is generally low in solubility with respect to an organic solvent, it is easy to use a solvent in the case of preparing an organic solution, and it is necessary to make N,N-dimethylacetamide, or N-A. A highly polar organic solvent having a high solubility such as pyrrolidone is used at a high ratio. When the high-polarity organic solvent contains a high ratio of the organic solution, there is a case where a part of the inkjet coating device or the organic structure such as the insulating film and the partition formed on the substrate is damaged. Further, since the sulfonic acid compound is highly polar, it is difficult to remove salts due to separatory extraction and washing operations due to refining of cerium oxide gel column chromatography. On the other hand, a sulfonate compound is highly soluble in various organic solvents, and a material which is generated by an organic strong acid due to external stimulation such as heating or chemical action is known. A report on the occurrence of a compound in which a sulfonic acid is generated by heating, a report such as cyclohexyl sulfonate has been published (Non-Patent Document 4: Chemische Berichte, Germany, 957, 90, p. 585-592), in recent years. In addition, this sulfonate is widely recognized in the so-called thermal acid proliferator (proliferatoO) (Patent Document 5: Japanese Patent Laid-Open No. Hei 7- 344 1 6, Non-Patent Document 5: Functional Materials, Japan, 2004, Volume 24, p. 72-82). However, especially in the case of aromatic disulfonic acid and other electron-deficient aromatics -5 - 200800870 (3) ring substituted sulfonate, with some heat, or water, alkali Decomposition due to the reaction of a substance or the like is apt to occur, and innovation of a highly stable sulfonate compound is desirable.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Abstract Patent Publication No. 2005/043 No. 962: International Publication No. 20/5 0 0 832 Abstract Non-Patent Document 1: Applied Physics Letters, USA, 1996, 69, p. 2160-2162 Non-Patent Document 2: Nature, UK, 1992, Vol. 3 5.7, p. 477-479 Non-Patent Document 3: Applied Physics Letters USA, 1998, Vol. 72, ρ·2660-26 6 2 Non-Patent Document 4: Chemische Berichte, Germany , 1957, 90, p. 585-592 Non-Patent Document 5: Functional Materials, Japan, 2004, 254, p. 72-82 [Invention] The present invention is to solve the problems of the present invention. In view of such circumstances, the object is to provide/species, has high stability, and at the same time, has high solubility with respect to a wide range of organic solvents, so that it is easy to form a uniform solution, which is suitable for OLED components 200800870 (4) The situation can achieve excellent component characteristics, as an electron accepting substance or Acid generator to an appropriate sulfonate compound. Means of solving problems

The inventors of the present invention, in order to achieve the above object, have repeatedly reviewed the results of repeated tests, and first discovered that a sulfonate compound having an atom at a position in which an ester substituent is coordinated to a sulfur atom is caused by coordination of the atom. The formation of a cyclic complex compound increases the electron density of the sulfur atom in the sulfonic acid ester, thereby hindering the side reaction caused by water or a basic substance in the synthesis of the compound, and at the same time hinders the thermal decomposition reaction and exhibits high stability, which can usually be It is easy to carry out the synthesis and purification of a difficult sulfonate compound, and the sulfonate compound exhibits high solubility with respect to a wide range of low polar solvents. Furthermore, it has been found that the sulfonate compound is formed into a film, and after being stimulated, it can act as a good electron-accepting substance under stimulation, and exhibits high charge transportability, and is first discovered. In the case where the film is used as a hole injection layer of a 0 LED element, a low driving voltage of the element can be made feasible, and thus the present invention has been completed. That is, the present invention provides: [1] a sulfonate compound represented by the formula (1), [Chemical Formula 1]

A

200800870 (5) (wherein A represents a substituted or unsubstituted one-valent hydrocarbon group, X represents a substituted or unsubstituted divalent hydrocarbon group, Y represents 0, s, or a substituted or unsubstituted 2 valence MSZ represents a hydrogen atom or a substitution Or an unsubstituted one-valent hydrocarbon group). Μ Applying the sulfonate compound of item i of the patent scope, which is represented by formula (2),

(wherein, Ri to R4 are each independently represented by a hydrogen atom, hydrazine is substituted or substituted with a whey hydrocarbon group or a halogen atom, and A and Z are the same as before).

[3] A sulfonate compound as claimed in claim 1 or 2 wherein the A is a substituted or unsubstituted aromatic ring. [4] A sulfonate compound represented by the formula (3) or the formula (4).

8- 200800870 (6) (wherein A' is represented by (S03H)m, X· and (S03-XYZ)n, substituted hydrocarbyl group, X represents a substituted or unsubstituted divalent hydrocarbon group, γ 〇, S Or a substituted or unsubstituted divalent amine group, Z represents a hydrogen atom or an arbitrary monovalent hydrocarbon group X' Ο, S or NH, B represents a substituted or unsubstituted hydrocarbon group, 1,3,5-trimethyl, or Substituted or unsubstituted formula (5) or (6) [Chemical 4]

The group shown (wherein W1 and W2 are each independently, 〇, s, s(0), S(〇2), or N, Si, P, P having an unsubstituted or substituted bond (〇) base), q indicates the number of bonds of B and X', and is an integer satisfying ISq, r indicates that the number of repeated units is 'the integer that satisfies, m is an integer greater than 〇, and η1 is an integer of 1 or more, n2 It is an integer of 1 or more. Further, ni + m satisfies A' in the formula (3) as the allowable substitution number, and n2 + m satisfies A' in the formula (4) as the allowable substitution number or less). [5] - a certain acid ester compound represented by the formula (7) or the formula (8). [化5]^

A" I o=s=o I OH (8) -9- 200800870 (7) (wherein W is a substituted or unsubstituted trivalent hydrocarbon group A) means a substituted or unsubstituted divalent aromatic ring group or a single bond 'x a substituted or unsubstituted divalent hydrocarbon group, γ 〇, S, or a substituted or unsubstituted divalent amine group, z represents a hydrogen atom or an arbitrary monovalent hydrocarbon group, 3 represents an integer of 2 to 100,000, j 〜1 00 An integer of 000, U represents an integer of 1 to 1 00000, and t + u is 2 to 100000) 〇 [6 ] The sulfonate compound of claim 5, which is g (9) or (10) Shown. [Chem. 6]

(wherein R5 to R7 are each independently a hydrogen atom, an unsubstituted or substituted one-valent hydrocarbon group, or a halogen atom, A,, X, Y, Z, s, t and u are the same as before). [7] The sulfonate compound of claim 5 or 6, wherein the number average molecular weight is 5000~loooooo. [8] The sulfonate compound according to claim 4, wherein the m is 0. -10- 200800870 (8) [9] An electron accepting substance which is a sulfonate compound as disclosed in claim 4 of the patent application. [10] An acid generator for a sulfonate compound according to any one of claims 1 to 8. [1 1] A charge transporting varnish containing a sulfonate compound according to any one of claims 1 to 8.

[12] A charge transporting film containing a sulfonate compound according to any one of claims 1 to 8. [1 3 ] A charge transporting film obtained from the charge transporting varnish of claim 11 of the patent application. [14] A method for producing a charge transporting film, which is characterized in that a charge transporting varnish according to claim 1 of the patent application is applied to a substrate and heated. [15] An organic electroluminescence device having a charge transporting film as disclosed in claim 12 or 13. [16] —Formula (1)

(1) (wherein, A, X, Y and Z are the same as before) A method for producing a sulfonate compound, which is characterized by the formula (1 1 ) • 11 - (9) 200800870 [Chem. 7]

A

I

〇 = S = 0 (li) OH (wherein A represents a substituted or unsubstituted one-valent hydrocarbon group) a sulfonic acid compound is reacted with a base to give a formula (12) [Chemical 8]

A

I 0 = S = 0 (12) ό ν (wherein, the same as before, V + shows sodium ion, potassium ion, pyridinium ion or fourth-order ammonium ion), the sulfonate compound shown, The sulfonate compound is reacted with a halogenated reagent to be derivatized as formula (13).

[Chemistry 9]

A

I 0=S=0 (13)

W (wherein A is the same as before, W is a halogen atom), the sulfonium halide compound is shown, and the sulfonium halide compound is represented by the formula (14) [10] (14)

HO-XYZ -12- 200800870 (10) (wherein x represents a substituted or unsubstituted divalent hydrocarbon group, Y represents ο, s, or a substituted or unsubstituted divalent amine group, z represents a hydrogen atom or a substitution or a non- Substituting a monovalent hydrocarbon group). The alcohol compound shown is the reactant. Effect of the invention

The sulfonate compound of the present invention has high stability with respect to heat or water, and exhibits high solubility with respect to a wide range of organic solvents containing a low polar solvent, so even if a low polar solvent is used, or a ratio of a highly polar solvent is used Lowering, it is also possible to modulate the charge transport varnish. As a result, the sulfonate compound of the present invention is more suitable for use as a charge transporting varnish than the conventional sulfonate compound, so that the amorphous solid film having high flatness can be produced more easily. Further, since the film obtained from the sulfonate compound of the present invention exhibits high charge transportability, it can be used as a hole injection layer or a hole transport layer to lower the driving voltage of the organic EL element. In the use of the high flatness and high charge transportability of the film, the hole transport layer of the solar cell, the electrode for a fuel cell, the capacitor electrode protective film, and the antistatic film can be further used, the sulfonate compound of the present invention. Because it has the function of a thermal acid generator or a cationic conductive substance, it can be applied to a photoresist auxiliary material, an ion conductive membrane, and a solid electrolyte. -13- 200800870 (11) BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The first sulfonate compound of the present invention is represented by the following formula (i). W 匕 12]

In the formula (1), A represents a substituted or unsubstituted one-valent hydrocarbon group, and specific examples thereof may be exemplified by methyl 'ethyl, n-propyl, isopropyl, n-butyl, isobutyl 'tertiary An alkyl group such as n-hexyl, n-octyl, 2-ethylhexyl or decyl; a cycloalkyl group such as cyclopentyl or cyclohexyl; a bicyclo ίτπ group such as a bicyclohexyl group; Alkyl 2 -propionyl 'isopropyl iodide, 1-methyl-2-propenyl, 1 or 2 or 3-butenyl, alkenyl and the like alkenyl; phenyl, methylbenzyl (xylyl An aromatic ring group (aryl group) such as a tolyl group, a biphenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylcyclohexyl group; or a part of a hydrogen atom of the group Or all further exemplified by a hydroxyl group, an amine group, a stanol group, a thiol group, a carboxyl group, a sulfonate group, a phosphate group, a phosphate group, an ester group, a thioester group, a decyl group, a nitro group, a monovalent group A hydrocarbon group, an organic oxy group, an organic amine group, an organic monoalkyl group, an organic thio group, a fluorenyl group, a fluorenyl group, a halogen atom or the like. Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. Specific examples of the organooxy group include an alkoxy group, an alkenyloxy group, an aryloxy group, etc., and the alkyl group, the alkenyl group and the aryl group may be the same as the above-exemplified substituents. Things. -14-

200800870 (12) Specific examples of the organic amine group may, for example, be a methylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, an octylamino group or a decylamino group. , mercaptoamine, lauryl-based amine; dimethylamino, diethylamino, dipropylaminoamino, dipentylamino, dihexylamino, diheptylamino, Specific examples of the dialkylamino group such as a dimethyl group, a dialkylamino group, a dicycloalkylamino group, a dicycloalkylamino group, and the like, and an organic monoalkylene group such as a morpholino may be exemplified. Trimethyl, triethylmonodecyl, tripropylmonodecyl, tributyl, tripentylmonodecyl, trihexylmonodecyl, pentyldialkyl, hexyldimethylmonodecyl, xin Dimethyl dimethyl phthalocyanine dimethyl monodecyl alkyl and the like. Specific examples of the organic sulfur group may, for example, be a methylthio 'propylthio' butylthio 'pentylthio-hexylthio group, an octylthio group, a mercaptothio group, a mercapto sulfur. Base, lauryl thiol. Specific examples of the fluorenyl group include a methyl group, an ethyl group, a butyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzene group, a monovalent hydrocarbon group, an organic oxy group, an organic amine group, and an organic single. The carbon number in the alkylene group, the organic sulfur group and the fluorenyl group is not usually from 1 to 20, preferably from 1 to 8. Among the above substituents, a fluorine, a sulfonic acid group, or a male oxy group, an alkyl group or an organic monodecyl group is more preferable. Further, unsubstituted means that a hydrogen atom is bonded to the bond. Further, an alkylamine, an alkylene such as heptylamine, a dibutyldioctylamine cyclohexylamine fluorenyl monodecyl monodecanemethylmonodecyl group, a fluorenyl group, an ethylthio 'heptylthio group, etc. An alkyl group, a propyl group, and the like. The amine group is not limited, and the substitution is the same. -15- 200800870 (13) In the substituent, the substituents are linked to each other and contain a cyclic moiety. In view of the application of the sulfonate compound of the present invention to an electron accepting substance, in the case of A, a substituted or unsubstituted aromatic ring group is preferred, and a substituted or unsubstituted phenyl group, a naphthyl group, a decyl group or the like is Suitable, substituted or unsubstituted phenyl, naphthyl is the most suitable. In the formula (1), X represents a substituted or unsubstituted divalent hydrocarbon group, and specific examples thereof may be a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms and a carbon number of φ 1 to 2 alkylene oxide. Carbon number 1 to 2 alkylene group, carbon number 1 to 2 alkylene group sulfur carbon number 1 to 2 alkylene group, carbon number 1 to 2 alkylene carbonyl carbon number 1 to 2 alkylene group, etc. Y in sulfonic acid In the ester, it is preferred to form an S atom, and a group of a ring-like complex such as the following formula is preferred. Further, as the substituent, the same as described above can be exemplified.

(wherein, A, X, Y' and Z are the same as before.) In particular, when the number of constituent atoms of the main chain is 2 or 3, the sulfonate compound (1) 'is a 5-membered ring or a 6-membered ring Therefore, it is appropriate to substitute or unsubstituted vinyl, trimethylene, methyleneoxymethylene, methylenesulfenyl, and the like. In the formula (1), Y is not particularly limited as long as it forms a cyclic complex with the S atom of the sulfonate compound, and is a divalent amine substituted by hydrazine, S, or substituted or not (14) 200800870. The basis is appropriate, especially the best. Here, the divalent substituted amine group may, for example, be -N(CH3)-, -N(C2H5)-, -N(C3H7)- or the like. In particular, a point where a cyclic complex compound can be easily formed, X is a substituted or unsubstituted vinyl group, Y is a compound represented by the following formula (2), or a formula represented by the following formula (2J) The compound is appropriate. [Chem. 14]

[Chemical 15] R2 R3

(wherein A2 represents a divalent hydrocarbon group which may have a substituent). In the formulae (2) and (2,), R1 to R4 are each independently a hydrogen atom, an unsubstituted or substituted one-valent hydrocarbon group, or a halogen atom, wherein a hydrogen atom; a methyl 'ethyl group, a propyl group' An alkyl group having 1 to 6 carbon atoms is preferred. -17- 200800870 (15) Further, specific examples of the other one-valent hydrocarbon group are as described above. In the formulae (1), (2) and (2'), Z is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and is not particularly limited. Specific examples of the monovalent hydrocarbon group are as described above. Preferred is methyl, ethyl or n-propyl. In the formula (2'), A2 is a divalent hydrocarbon group which may have a substituent, for example, an alkylene group (methylene group, vinyl group, trimethylene group, etc.) which may have a substituent, and an extended aryl group which may have a substituent ( Stretching phenyl, stretching naphthyl, stretching phenyl, etc.). The substituent may, for example, be a hydroxyl group, an amine group, a stanol group, a thiol group, a carboxyl group, a sulfonate group, a phosphate group, a phosphate group, an ester group, a thioester group, a decyl group, a nitro group, a monovalent group. A hydrocarbon group, an organic oxy group, an organic amine group, an organic monoalkyl group, an organic thio group, a fluorenyl group, a fluorenyl group, a halogen atom or the like. The method for producing the compound represented by the formula (1) may, for example, be the following method, but is not limited thereto.

That is, the sulfonic acid compound represented by the formula (1 1) is reacted with a base to be derivatized into a sulfonate compound represented by the formula (1 2), and the sulfonate compound is reacted with a halogenated reagent to be derivatized. The sulfonium halide compound shown in (13), which is reacted with an alcohol compound represented by the formula (14) to obtain a sulfonate compound of the formula (1). Further, the sulfonic acid compound represented by the formula (1 1) may be a commercially available product, or may be subjected to a known method (New Experimental Chemistry Lecture 14 Organic Compound Synthesis and Reaction III, P.1773 to 1784), etc., as needed. synthesis. 200800870 (16) [Chem. 16] Alkali

A

A

I o=s=o

I

OH

(wherein, A, X, Y, and Z are the same as before. V + is a sodium ion, a potassium ion, a pyridinium ion or a fourth-order ammonium ion, and W is a halogen " atom).

The base used for the step of reacting the sulfonic acid compound represented by the formula (11) with a base to be derivatized to the sulfonate compound represented by the formula (12) may, for example, be sodium hydride, potassium hydride, sodium carbonate or potassium carbonate. , various bases such as sodium hydrogencarbonate, pyridine, pyrimidine, triethylamine, etc., and in terms of alkali which improves the solubility with respect to the organic solvent of the sulfonate compound (11) and which does not affect the reaction of the next step Preferably, an amine such as pyridine, pyrimidine or triethylamine is used, and pyridine is particularly preferred. The amount of the base to be used is not particularly limited as long as it is 1 time or more based on the sulfonic acid compound (1 1 ), but it is preferably 1 to 5 moles. In terms of the reaction solvent, it is preferred to dissolve the sulfonic acid compound (11), water, N-methylpyrrolidone (NMP), imidazolidinone (DMI), acetic anhydride, methanol, Ethanol, isopropanol, pyridine, etc. are appropriate. -19- 200800870 (17) The reaction temperature is not particularly limited, and is preferably 0 to 150 °C. After completion of the reaction, a pure sulfonate compound can be obtained by subjecting the solvent to distillation under reduced pressure, liquid separation and extraction, reprecipitation, recrystallization, and the like. The halogenated reagent used for the step of reacting the sulfonate compound represented by the formula (12) with a halogenated reagent to be derivatized into the sulfonium halide compound represented by the formula (13) may, for example, be sulfinium chloride and oxygen. Phosphorus chloride (PHOSPHORUS OXYCHLORIDE), phosphorus chloride (V) and other rejuvenation reagents, and ruthenium chloride is appropriate. The amount of the halogenated reagent to be used is not particularly limited as long as it is 1 time or more based on the sulfonate compound, and is preferably 2 to 10 times the mass ratio of the sulfonate compound.

The solvent is preferably a solvent which does not react with the halogenated reagent, and examples thereof include chloroform, dichloroethane, carbon tetrachloride, hexane, heptane and the like, and the solvent-free is appropriate. Further, in the case where the reaction is carried out without a solvent, it is preferred to use a halogenated reagent in an amount greater than the amount of the homogeneous solution when the reaction is completed. The reaction temperature may be about 0 to F50 ° C, and is preferably 20 to 1 ° C, and preferably less than the boiling point of the halogenated reagent to be used. After completion of the reaction, in general, the resulting crude product obtained by concentration under reduced pressure is used in the next step. In the step of reacting the sulfonium halide compound represented by the formula (13) with the alcohol compound represented by the formula (?4), a base can be used. As the base which can be used, sodium hydride, pyridine, triethylamine, diisopropylethylamine and the like can be exemplified, and sodium hydride, pyridine and triethylamine are used as -20-200800870 (18). The amount of the base to be used is preferably from 1 to 2 moles to the amount of the solvent of the sulfonium halide compound (13). As the reaction solvent, various organic solvents can be used, and tetrahydrofuran, dichloroethane, and pyridine are suitable. The reaction temperature is not particularly limited, and is preferably ～80 °C. After completion of the reaction, a pure sulfonate compound can be obtained by post-treatment under reduced pressure, fractional extraction, water washing, reprecipitation, recrystallization, chromatography, and the like. Further, by subjecting the obtained pure sulfonate compound to heat treatment or the like, a high-purity sulfonic acid compound can be obtained. The second sulfonate compound of the present invention is not in the following formula (3) or (4).

In the formula (3) '(4), A, a hydrocarbon group substituted with (s〇3H)m, X, and (s〇3-X_y_z) ni 'this hydrocarbon group may be (s〇3H)m, χ, and (s〇3H_z) n, substituted with a substituent other than the substituent. The substituent may be the same as the substituent described for the above-mentioned substituted or unsubstituted one-valent hydrocarbon group. In a specific example of A, -21 - 200800870 (19), the hydrogen atom of the above A is removed, and the bond is converted into a bond bond to form a multivalent hydrocarbon group. same. X' shows, Ο, S or NH, especially 〇 is appropriate. The two X's in the formula (3) may be the same or different from each other. In addition, X, Y, and Z are the same as described above. Further, B is a substituted or unsubstituted hydrocarbon group, a 1,3,5-trimethyl group, or a substituted or unsubstituted group represented by the following formula (5) or (6). [Chem. 18]

(5) (wherein W1 and W2 are each independently, 〇, s, s(〇), s(〇2), or unsubstituted or substituted N, Si, P, P ( O) base). In consideration of the improvement in durability and the improvement of the transportability of the compound of the above formulas (3) and (4), in the case of B, the unsubstituted or substituted nicotine containing two or more valences of one or more aromatic rings, 2 A valence or a trivalent 1,3,5-trimethylidene group, a substituted or unsubstituted divalent diphenyl fluorenyl group, particularly a divalent or trivalent substituted or unsubstituted benzyl group, a divalent substitution or a non-substituted Substituted for a sub-methyl group, a divalent or trivalent substituted or unsubstituted naphthyl group, a divalent or trivalent 1,3,5-trimethyl group, a divalent substituted or unsubstituted diphenyl fluorenyl group, 2 to 4 mussels perfluorobiphenyl, divalent substituted or unsubstituted 2,2_bis((hydroxypropoxy)phenyl)propyl, substituted or unsubstituted polyvinylbenzyl-22- 200800870 (20 ) is appropriate. m indicates that the number of sulfonic acid groups bonded to A ' is an integer of 0 or more, and preferably 〇~4, and the solubility of the solvent with respect to the compound represented by the formula (3) or (4) is considered to be improved. In the case of 〇~2, it is preferred to use 1 or 2 in consideration of an increase in the electron acceptability of the compound. q indicates the number of bonds with B. If the integer of ISq is satisfied, it is not particularly limited, and 2 S q is preferred.

r is the number of the repeated units, and is not particularly limited as long as it satisfies the integer of l^r, and 2 S r is preferable. Η1 is an integer of 1 or more, preferably an integer of 1 to 4, and n2 is an integer of 1 or more, preferably an integer of 1 to 4, and all of them are optimum. Further, in the formula (3), nbm satisfies Α' as an allowable substitution number or less, and n2 + m satisfies Α· as an allowable substitution number or less in the formula (4). The method for producing the sulfonate compound represented by the formulas (3) and (4) may, for example, be the following method. In other words, the sulfonate compound (15) or (16) which is produced by the above-mentioned production method or the like can be obtained by imparting a cross-linking reagent. In this case, the method of the reaction is not particularly limited, and for example, a general nucleophile substitution reaction can be used.

-23- 200800870 (21) Examples of such a reagent include a halogen atom, a hydroxyl group, an amine group, a awake group, a carboxyl group, an ester group, or a hydrocarbon compound substituted with an alkoxy group, and the like, as described in the above B. In addition, it is preferable to improve the heat resistance, the charge transport property, or the solubility with respect to an organic solvent, and the compound containing one or more aromatic rings is preferable.

In addition, when a hydrocarbon compound containing two or more substituents such as a halogen atom, a hydroxyl group, an amine group, a ketone group, a carboxyl group, an ester group or an alkoxy group is used, since the compound acts as a cross-linking reagent, it can be used. A compound having a crosslinked structure. When the compound of the formula (15) is subjected to q quantification using a reagent having q or more reactive substituents (crosslinking portion), the amount of the reagent used is Ι/q with respect to the compound of the formula (15). Double Moore is appropriate. Specific examples of the reagent for reacting with the X'H group of the sulfonate compound (15) or (16) may, for example, benzaldehyde, benzoic acid, benzoic acid ester, 1-naphthaldehyde or 2-naphthaldehyde. ,2,4,6-trimethoxy-1,3,5-triazine, bis(4-fluorophenyl) maple, bis(4-fluoro-3-nitrophenyl)fluorene, perfluorobiphenyl , 2,2-bis(4-glycidoxyphenyl)propane, polyvinyl chloride benzyl, and the like. A catalyst may also be used in the case where the sulfonate compound (15) or (16) is allowed to react with the above reagent. The catalyst may, for example, be lithium, potassium, lithium hydride, sodium hydride, lithium tertiary hydride, sodium trisodium butoxide, potassium tertiary hydride, lithium diisopropyl guanamine, n-butyl Lithium, primary butyl lithium, butyl lithium, (lithium-hexamethy 1 disilazide? sodium-hexamethyl disilazide potassium-hexamethyl disilazide, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, cerium oxide, lithium carbonate , sodium carbonate, carbonic acid-24- 200800870 (22) potassium, carbonic acid planing, calcium carbonate, sodium hydrogencarbonate, triethylamine, diisopropylethylamine 'tetramethylethylenediamine, triethylenediamine, pyridine , dimethylaminopyridine, imidazole, etc.; hydrochloric acid, sulfuric acid, phosphorus pentoxide, aluminum (III) chloride, boron trifluoride diethyl ether complex, ethyl aluminum dichloride, chlorination A dehydrating condensing agent such as diethylaluminum or the like, wherein sodium hydride, sodium carbonate or potassium carbonate is used as appropriate. The amount of the catalyst used is not particularly limited, and is relative to the formula (15) or the formula (16). The compound is preferably used in an amount of 1 · 0 to i. 5 times Mo. The reaction solvent 'is aprotic polar organic The agent is preferably, for example, DMF, DMAc, NMP, DMI, DMSO, THF, dioxin, etc. The compound having a plurality of sulfonic acid groups is low in solubility relative to the organic solvent, so in this case, the sulfonic acid compound The DMI and NMP of the solvent with high solubility and low thermal decomposition are appropriate. The reaction temperature is usually from -50 °C to the boiling point of the solvent used, and the range of 〇~140 °C is preferred. The reaction time is usually 〇.1 ~ 1 0 0 hours.

After completion of the reaction, the reaction solvent is distilled off, and when the sulfonic acid group is present, protonation of the sulfonate by the cation exchange resin, extraction by a solvent such as methanol, reprecipitation operation, etc., can be carried out. The third sulfonate compound of the present invention is represented by the following formula (7) or (8) 0 - 25 - 200800870 (23) [Chem. 20]

(8) wherein W represents a substituted or unsubstituted trivalent hydrocarbon group having at least one bond to an A" or S atom, and a bond other than the bond, that is, if at least two are formed in association with the polymer chain The bonding bond is not particularly limited. Specific examples thereof include ethylene (-CH2CH2-), ethylene (-CH=CH-), and acetylene substituted with at least one hydrogen and substituted with A or S atoms.

-C = C - ) » propyl (-CH2CH2CH2-) 'isopropyl isopropyl (-CH2CH(CH3)·) ' vinyl-ethylene (-CH2CH(CH = CH2) ·), methoxyethylene ( _CH2CH(0CH3)-), ethoxyethylene (-CH2CH(OCH2CH3)-), (methylamino)ethylene (-ch2ch(nhch3)-), (dimethylamino)ethylene (-CH2CH (N ( CH3) 2)-), a methyl acrylate derivative (-ch2ch(c(o)och3)-), a methyl methacrylate derivative (-CH2C(CH3)(C(O)0CH3)-), Phenyl (-C6H4-), a phenyl group (-c6h4-c6h4-), etc., each of which may be further substituted with a monovalent hydrocarbon group. Preferably, the sulfonate compound represented by the following formula (9) or (10) is exemplified by 0-26-200800870 (24) [Chem. 21]

In the above formula, R5 to R7 each independently represent a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, or a halogen atom, and specific examples of the monovalent hydrocarbon group may be the same as those described above. In the specific example of the divalent hydrocarbon group or the single bond, the divalent hydrocarbon group, a bond group having a bond with hydrogen may be converted into a bond bond in the one-valent hydrocarbon group represented by the above A. The price is, in particular, a substituted or unsubstituted divalent aromatic ring group or a single bond. Further, in the case of a single bond, the W and S atoms may be directly bonded. The s is 2 to 100,000, preferably 20 An integer of ～5000. t is an integer from 1 to 100000, preferably from 20 to 5000, U is an integer from 1 to 100000, preferably an integer from 1 to 5000, and t + u is 2 to 1 〇〇〇〇 Preferably, it satisfies 20 to 500. X, Y, and Z are the same as those described in the above formula (1). The production method of the compound represented by the formula (7) or the formula (8) The following method can be exemplified, but it is not limited to the above. First, a sulfonate compound (20) is synthesized from a sulfonic acid compound (17) containing a polymerizable functional group (W') by the same method as above. Further, for -27-200800870 (25), a polymerization reaction is carried out, and a compound represented by the formula (7) is derived. At this time, a part of the sulfonic acid ester becomes a free sulfonic acid. It has become the formula (8) shown in the case of a compound.

The sulfonate compound represented by the above formulas (1) to (10) can be formed into a sulfonic acid by heat treatment or the like, and the sulfonic acid compound exhibits electron acceptability, so that it can be used as an acid generator or an electron accepting substance. Use it properly. Since the sulfonate compound exhibits high solubility with respect to a wide range of solvents containing a low polar solvent, it is possible to prepare a solution property using a wide variety of solvents, and the coating property is high. Therefore, it is preferably applied in the form of a sulfonate to cause sulfonic acid to occur when the coating film is dried or when it is fired. The temperature at which the sulfonic acid is generated from the sulfonic acid ester is stable at room temperature, and the firing temperature is preferably -28-200800870 (26) or less, so that it is preferably 40 to 300 ° C. Further, in consideration of the high stability in the varnish and the ease of detachment during firing, it is preferably 80 to 23 〇 ° C, more preferably 1 2 0 to 1 80 ° C. The sulfonate compounds represented by the above formulas (1) to (10) can be used as an electron accepting substance by themselves. In particular, in the compounds of the formulae (3) and (4), when m is 1 or more, since a sulfonic acid group exists and it exhibits strong electron acceptability, it can be suitably used as an electron accepting substance. φ The sulfonate compound represented by the above formulas (4) and (7) to (10) can be used as a high molecular weight substance. The molecular weight is not particularly limited, and when the molecular weight is increased while maintaining high solubility, the film can be expected to be stabilized during film formation, so that high molecular weight is desired. When the molecular weight is too large, there is a case where the solubility is lowered or agglutination occurs. The specific range is preferably a number average molecular weight of from 50,000 to 100,000, more preferably from 20,000 to 50,000. The sulfonate compound represented by the above formulas (1) to (10) can be dissolved or dispersed in a solvent together with a charge transporting substance which is a charge transporting mechanism, and can be a charge transporting varnish. Here, the charge-sensitive substance is used for improving the charge transporting ability and film formation uniformity, and is synonymous with the charge-sensitive dopant substance. Further, the charge transporting property is synonymous with conductivity, and in the present invention, it is synonymous with hole transportability. The charge transporting varnish may have a charge transporting property itself or a charge transporting property of the solid film obtained from the varnish. The charge transporting substance is not particularly limited as long as it is a solvent-transmissive low-oligomer or a polymer which is soluble or uniformly dispersed in a solvent, and may have a low conjugate unit of from -29 to 200800870 (27). Oligomers, low oligomers having a combination of distinct continuous conjugate units are desirable. Here, the conjugate unit is an atom capable of transporting a charge, and the aromatic ring or the conjugated group is not particularly limited, and is preferably a substituted or unsubstituted 2 to 4 valent anilino group, a thienyl group, a furyl group, a pyrrolyl group, Ethylene group, vinylene group, phenylene, naphthyl group, oxadiazolyl, quinolyl group, sil〇le group, fluorene atom 'pyridyl group, phenylvinylene group, fluorenyl group, carbazolyl group, triaryl Amino-based metal- or metal-free phthalocyanine groups, and metal- or metal-free porphyrin groups. Specific examples of the substituent are independently hydrogen, hydroxy, halo, amine, stanol, thiol, carboxyl, sulfonate, phosphate, phosphate, ester, thio Ester group, decylamino group, nitro group, monovalent hydrocarbon group 'organooxy group, organic amine group, organic monodecyl group, organic thio group, fluorenyl' fluorenyl group, etc., and these functional groups can be further substituted by any functional group Replaced.

The number of carbon atoms in the above-mentioned monovalent hydrocarbon group, organooxy group, organic amine group, organic monodecyl group 'organothio group, and mercapto group is not particularly limited, and is usually from 1 to 20 carbon atoms, preferably from 1 to 8 carbon atoms. Further, specific examples of the 'monovalent hydrocarbon group, the organic oxy group, the organic amine group, the organic monodecyl group, the organic thio group and the fluorenyl group are as described above. As the appropriate substituent, a fluorine, a sulfonic acid group, a substituted or unsubstituted organic oxy group, an alkyl group or an organic monodecyl group can be exemplified. Further, the conjugated unit is a conjugated chain formed by joining, and may contain a cyclic moiety. The number average molecular weight of the charge transporting substance is expected to increase the solubility -30-200800870 (28), which is expected to be less than 5,000, and exhibits low volatility and charge transportability. It is preferable that the solvent exhibiting high solubility with respect to at least one kind of solvent is a number average molecular weight of 5,000 to 500,000 if it is a substance exhibiting high solubility with respect to at least one kind of solvent. In the case of the charge transporting material, the low aniline derivative described in JP-A-2002-151272 can be suitably used. That is, the low aniline derivative represented by the formula (2 1 ) is suitable. Further, the following one-valent hydrocarbon group, organic oxygen group and mercapto group may be the same as those previously described. (21) r 1 r 〒91 R8—D1-NH—D2-pll—R11 sf (wherein R 8 represents a hydrogen atom, a monovalent hydrocarbon group, or an organooxy group, and R 9 and R 11 are each independently represented. a hydrogen atom or a monovalent hydrocarbon group, and D1 and D2 each independently represent the following formula (22) or (23) [Chem. 24]

The divalent group shown, R11 to R18 each independently represent a hydrogen, a hydroxyl group, a monovalent hydrocarbon group, an organooxy group, a decyl group, or a sulfonic acid group 's' and each independently an integer of 1 or more, which satisfies s' + t'€20). -31 - 200800870 (29) Further, the intramolecular ττ conjugate system can be expanded as much as possible, because the charge transportability of the obtained charge transporting film can be improved, and in particular, the low aniline derivative represented by the formula (24) can be used. Or a benzoquinone diimine derivative of its oxide is preferred. Further, in the two benzene rings of the formula (24), the substituents of the same symbols are given, and they may be the same or different.

[Chem. 25]

(wherein R8 to R14, s' and r are synonymous with the above). In the formulas (21) and (24), s' + t' can exhibit good charge transportability, preferably 4 or more, and preferably 16 or less from the viewpoint of ensuring solubility in a solvent. Further, when R8 is a hydrogen atom and R1G is a phenyl group, that is, both ends of the low aniline derivative of the formula (24) are preferably blocked with a phenyl group. These charge transporting materials may be used alone or in combination of two or more. Specific examples of the compound represented by the above formula (21) include an organic solvent such as phenyltetraphenylamine, phenylpentaniline, tetraphenylamine (aniline tetramer), and octaphenylamine (aniline 8 polymer). Soluble low aniline derivatives. Further, the synthesis method of the other charge transporting substance is not particularly limited, and examples thereof include the literature, and the 化学本化学界会报 (Bulletin Of

Chemical Society of Japan), 1985, Vol. 67, P.1 749--32-200800870 (30) 1 7 5 2, Synthetic Metal (etaphic eta 1 s), United States, 1979, Volume 84, Low Aniline Synthesis as described in ρ·11 9-1 20, or, for example, the literature, Heterocycles, 1987, Vol. 26, ρ·93 9-942, Heterocycles ), 1987, Vol. 26, Low Thiophene Synthesis Method as described in ρ·1 793 - 1 796. In the charge transporting varnish of the present invention, the highly soluble solvent which can dissolve the charge transporting substance and the charge sensitive substance can be used in a ratio of 5 to 100% by weight based on the total amount of the solvent used for the varnish. . In this case, the varnish can be completely dissolved by the highly soluble solvent, and it is preferably in a state of being uniformly dispersed. * The highly soluble solvent is not particularly limited, and examples thereof include water, methanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N. , Nf-dimethylimidazolidinone (imidazolidinone), dimethyl sulfoxide, chloroform, toluene, methanol, and the like. Further, the charge transporting varnish of the present invention has a viscosity at 20 ° C, 10 to .φ 2 〇〇 mPa · s, and at least one boiling point of 50 to 30 at normal pressure (TC is a high viscosity organic solvent. Further, the charge transporting varnish is preferably an organic solvent having a viscosity of 50 to 150 mPa·s at 20 ° C and a boiling point of 150 to 250 ° C under normal pressure. ^ High viscosity organic solvent is not particularly The definition is, for example, cyclohexanol, ethylene glycol, ethylene glycol diepoxypropyl ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1, 3-butanediol, 1,4-butanediol, propylene glycol, hexanediol, etc. -33- 200800870 (31) The ratio of addition of the high viscosity organic solvent used in the varnish of the present invention to the entire solvent, In the range where the solid does not precipitate, the addition ratio may be 5 to 80% by mass in the range where the solid does not precipitate. Further, in order to improve the wettability of the substrate, the adjustment of the surface tension of the solvent, the polarity Adjustment, adjustment of boiling point, etc., other solvents that can impart flatness to the film during firing, phase The solvent to be used in the varnish is preferably 1 to 90% by mass, preferably 1 to 50% by mass. φ The solvent is not particularly limited, and examples thereof include butyl cellosolve and diethyl phthalate. Alcohol diethyl ether, dipropylene glycol monomethyl ether, ethyl carbitol, diacetone alcohol, r-butyrolactone, ethyl lactate, etc. ' by applying the above-described charge transporting varnish to a substrate The solvent is evaporated to form a charge transporting coating film on the substrate. The coating method of the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a spray method, and an ink jet method. Printing method, roll coating method, brush coating, etc., all of which can be uniform film formation. The evaporation method of φ solvent is not particularly limited, and a hot plate or an oven is used in an appropriate atmosphere. That is, an inert gas such as the atmosphere or nitrogen may be evaporated in a vacuum to obtain a film having a uniform film-forming surface. The firing temperature is not particularly limited as long as it is an evaporable solvent, and is 40 to 250 ° C. It is better to show higher uniform film formation and on the substrate. In order to carry out the reaction, the temperature change of the charge transporting film obtained by the coating and the evaporation operation is not particularly limited, and it is used as a charge injection layer in the organic EL device. ～20 0 nm is expected. In the method of changing the film thickness, the method of -34-200800870 (32) has a change in the solid content concentration in the varnish or a change in the amount of the solution on the substrate during coating. The method for producing the OLED element of the transport varnish may be exemplified by the following methods and materials, but the method is not limited thereto. The electrode substrate used can be washed with a lotion, alcohol, pure water or the like. It is preferable to perform surface treatment in advance on the anode substrate for the treatment of odor φ oxygen, oxygen-plasma treatment, etc. before use. However, in the case where the organic material is mainly composed of the anode material, the surface treatment may not be performed. In the case where a hole transport varnish is used for the OLED element, for example, the following method can be employed. In other words, the hole transporting varnish is used for the anode substrate to form a hole transporting film on the electrode by the film forming method. This is introduced into a vacuum evaporation apparatus, and a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited to form an OLED element. ^ # At this time, the carrier block layer can be set between any layers to control the light-emitting area. The anode material may, for example, be a transparent electrode represented by indium tin oxide (ITO) or indium zinc oxide (IZO), and is preferably planarized. Polythiophene derivatives having high charge transportability, or polyanilines can be used. The material for forming the hole transport layer may, for example, be a (triphenylamine) dimer derivative (TPD) or an (α-naphthyldiphenylamine) dimer (a-NPD), [(3) Phenylamine) Dimer] Spiral Dimer (Spiro-TAD) and other triarylamines: 4,4'54"-three [3-methylphenyl(phenyl)amino]triphenyl Amine (m- -35 - 200800870 (33) MTDATA), 4,4',4"-tris-naphthyl (phenyl)amino]triphenylamine (1-TNATA) Amines: 5,5"-bis-{4-[bis(4-methylphenyl)amino)phenyl]-2 5 2':5,2"trithiophene (16 to 11 丨〇?1 ^1^) (6 PCT - 3 butyl) and other low thiophenes. In terms of the material for forming the light-emitting layer, tris(8-quinolinol) aluminum (III) (Alq3), bis(8-quinolinol) zinc (II) (Znq2), bis (2-A) Alkyl-8-quinolinol) (p-phenylphenolate) aluminum (III) (BAlq), 4,4'-bis(2,2-diphenylethylene)biphenyl (DPVBi) or the like. Further, a light-emitting layer can be formed by co-evaporation with an illuminating dopant by an electron transporting material or a hole transporting material. As the electron transporting material, Alq3, BAlq, DPVBi, (2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole) (PBD) can be exemplified. ), triterpenoid derivatives (TAZ), bathocuproin (BCP), silole derivatives, and the like. As the luminescent dopant, quinacridone, quaternary, coumarin 540, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylamino) can be mentioned. Styryl)-4H-pyran (DCM), tris(2-phenylpyridine)indole (in) (lr(PPy)3), (1,10-phenanthroline)·three (4,4,4 -Trifluoro-1-(2-thienyl)-butylene-1,3-diolate) ruthenium (III) (Eu(TTA)3phen) and the like. The material for forming the carrier blocking layer may, for example, be PBD, TAZ, and BCP ° electron injecting layer, and may be exemplified by lithium oxide (Li20), magnesium oxide (Mg02), aluminum oxide (A12 03 ), and lithium fluoride ( LiF), magnesium fluoride (MgF2), strontium fluoride (SrF〇, Liq, ethionyl acetonyl acetonide lithium complex (L i (acac)), lithium acetate, lithium benzoate, etc. -36 - 200800870 (34) The cathode material may, for example, be aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, planer, etc. In the case where the charge transporting varnish of the present invention is used for an OLED element, For example, the electron transporting film is formed on the cathode substrate by using the electron transporting varnish, and introduced into a vacuum vapor deposition apparatus, and an electron transporting layer, a light emitting layer, and a hole transporting are formed using the same material as described above. After the hole is injected into the layer φ, the anode material is formed into a OLED element by sputtering or the like. The method for producing the PLED element using the charge transporting varnish of the present invention may, for example, be the following method. Not limited to this. 'The above OL In the fabrication of the ED device, instead of the vacuum evaporation operation of the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer, the formation of the luminescent charge-transporting polymer layer can be made to contain the present invention. The PLED element of the charge transporting film formed by the charge transporting varnish. φ Specifically, the hole transporting varnish is applied to the electrode by the above method to form a hole transporting film with respect to the anode substrate, and An illuminating charge transporting polymer layer is formed on the upper portion, and the cathode electrode is vapor-deposited to form a PLED element. Alternatively, the electron transporting varnish is used for the cathode substrate, and an electron transporting film is formed on the electrode by the above method. An illuminating charge transporting polymer layer is formed on the upper portion, and the anode electrode is formed into a PLED element by sputtering, vapor deposition, spin coating, etc. For the cathode and anode materials, the OLED element can be used as an example -37-200800870 ( 35) The substance shown is the same substance, and the same washing treatment and surface treatment are carried out. Formation of the luminescent charge transporting polymer layer In addition, a solvent may be added to the luminescent charge transporting polymer material or a material to which the luminescent dopant is added, and a solvent may be added thereto to be dissolved or uniformly dispersed, and applied to the hole transporting film formed thereon. A method of forming a film by evaporation of a solvent after the electrode substrate. The luminescent charge transporting polymer material may, for example, be a polyfluorene derivative such as poly(9,9- φ dialkyl fluorene) (PDAF). Poly(phenylene vinylene) supported by poly(2-methoxy-5-(2'-ethylhexyloxy)-i,4·phenylene vinylene) (meh-ppv) A derivative, a polythiophene derivative such as poly(3-alkylthiophene) (PAT), polyvinyl carbazole (PVCz) or the like. The solvent may, for example, be toluene, xylene or chloroform. In the case of the dissolvable or uniform dispersion method, a method of dissolving or uniformly dispersing by stirring, heating and stirring, ultrasonic dispersion or the like may be mentioned. The coating method is not particularly limited, and examples thereof include a dipping method, a rotary φ coating method, a transfer printing method, a roll coating method, and a brush coating. Coating is carried out under an inert gas such as nitrogen or argon. The evaporation method of the solvent can be exemplified by heating in an oven or a hot plate under an inert gas or in a vacuum. [Embodiment] Hereinafter, the present invention will be more specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. -38- (36) (36) 200800870 [Synthesis Example 1] Naphthalene disulfonic acid compound oligomer 2 (hereinafter, abbreviated as NSO-2) was synthesized according to the following reaction formula. [Chem. 26]

934 mg of 1-naphthol-3,6-disulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) which was well-dried, and a perfluorobiphenyl 450 mg, 60% sodium hydride 166 mg, and anhydrous in a nitrogen atmosphere. 50 ml of hydrazine, imidazolidinone, and the reaction was replaced with nitrogen, and then stirred at 80 ° C for 43 hours. After allowing to cool to room temperature, water was added to stop the reaction, and the dried mash was concentrated under reduced pressure. 5 ml of methanol was added to the residue, and the resulting suspension was added to 100 ml of diethyl ether while stirring. After stirring at room temperature for 1 hour, the precipitated solid was collected by filtration, and 25 ml of methanol was added to the filtrate to supersonic suspension. The insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure and dried. Add methanol-water (1:2) 1 2 m 1 to the residue and dissolve it, add about 2 ml of cation exchange resin DOWEX 6 5 0C (H type), filter after stirring for 10 minutes, and use the cation exchange resin for the filtrate. The DOWEX 650C (H-type about -39-200800870 (37) 40 ml, distillate solvent: methanol·water (1:2)) was purified by column chromatography. The mixture was concentrated to dryness under reduced pressure at a pH of 1 or less. After azeotropy with isopropyl alcohol, 2 ml of isopropyl alcohol was added to the residue, and the obtained solution was added while stirring in 50 ml of diethyl ether. After stirring at room temperature for 1 hour, the supernatant liquid was removed, and the residue was dried under reduced pressure to give 984 mg (yield: 81%). The yellow powder was analyzed by MALDI-TOF-MS to detect the main peak which was considered to be derived from NSO-2. MS (MALDI-TOF-MS-): m/z 901 (M-H)' [Example 1] [Chem. 27]

Public. 〇2 〇2 0

I 998 mg of 1,3-benzenedisulfonium dichloride (manufactured by Aldrich Co., Ltd.) was dissolved in 20 mL of dehydrated tetrahydrofuran (hereinafter referred to as THF) under a nitrogen atmosphere. In this solution, 0.85 mL of dehydrated propylene glycol monomethyl ether (hereinafter referred to as PGME) and 60 mg of 60% sodium hydride were added in this order in an ice bath, and the mixture was stirred for 15 minutes. The mixture was stirred at room temperature for 40 minutes, and further added with 6 〇% sodium hydride 5 2 6 mg, and stirred at room temperature for 3 minutes. The reaction mixture was filtered with a fluorite, and washed in the order of dichloroethane PGME. CG-50 (manufactured by Aldrich) and water were added to the filtrate to be added to pH 7, and the fluorite was again subjected to 40 mg (40-38). ) 200800870 Filtering. The filtrate was concentrated, dichloroethane was added, and cerium dioxide gel filtration (18 g of cerium oxide gel) was carried out. After washing with dichloroethane, the combined filtrate was concentrated and dried to make the residue hexane. After washing three times, it was dried under reduced pressure to obtain 93 6 mg of a sulfonic acid ester compound (yield: 68%). !H_NMR (3 00MHz, CDC13) 5 (ppm): 1.35(6H,d), 3·19(6Η,s),3.3-3.5(4Η,m),4.83(2Η,ddt),7.72(1Η, dd ), 8.16 (2Η, dd), 8.5 0 (1 Η » dd).

Rf 値 (1,2-dichloroethane (DCE)): 0·13-0·36. [Embodiment 2] [Chem. 28]

(9) 99 8 mg of 1,3-benzenedisulfonium dichloride (manufactured by Aldrich Co., Ltd.) was added to dehydrated THF 2 OmL under a nitrogen atmosphere to dissolve. In this solution, 0.58 mL of a sugar alcohol was added in a water bath (20 ° C), and 60% of sodium hydride 35 Img was stirred for 2.5 hours. After the reaction mixture was filtered through a solution of fluorite, washed with dichloroethane, the combined filtrate was concentrated to dryness under reduced pressure. Dichloroethane was added to the residue, and the mixture was filtered through a cerium oxide gel (8 g of a cerium dioxide gel), and washed with dichloroethane. The filtrates which were added together were concentrated to dryness under reduced pressure, and the residue was washed with hexane three times, and then dried under reduced pressure -41 - 200800870 (39) 涸' to obtain a sulfonate compound represented by the formula (26). 472 ng (colorless oil, yield 37%).

Rf 値(DCE): 0.22_0.54 '(DCE: EtOAc = 10:1): 0.50-0.67 [Example 3] 2.76 g of NSO-2 obtained in Synthesis Example 1 and acetic anhydride 1 was added under nitrogen atmosphere 1 · 7 m L, uniformly dispersed by ultrasonic waves, in a water bath

(20 ° C), 4·8 mL of dehydrated pyridine was added, and the mixture was stirred at room temperature for 26 hours. Thereafter, 80 mL of diethyl ether was added to the reaction system, uniformly dispersed by ultrasonic wave, and then suction-filtered, and the filtrate was dried under reduced pressure to obtain a sulfonic acid pyridinium salt of the formula (27). (White powder, yield 83%). [化29]

S〇3 Bu 4HiQ (27) Into the obtained sulfonic acid pyridinium salt 1.50 6 g, 7.5 mL of thionyl chloride was added thereto under nitrogen atmosphere, and the mixture was stirred at 80 ° C for 8 hours. The reaction mixture was concentrated to dryness under reduced pressure to give a crude product (yellow powder) of the sulfonic acid chloride of formula (28). [化30]

(28) -42· 200800870 (40) In the obtained brown powder, 15 mL of dehydrated pyridine was added in a water bath (20 ° C), and 3 mL of PGME was dehydrated, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated to dryness under reduced pressure, and then azeotroped twice with dichloroethane, and the residue was subjected to cerium oxide gel column chromatography (cerium oxide gel 50 g, dichloroethane-dichloro Ethane: Ethyl acetate 1 〇: 1) Purification, Rf 値 (dichloroethane: ethyl acetate 10:1) 0.4~0.5 fractions are fractionated and concentrated under reduced pressure to obtain the formula ( 2 9) The sulfonate compound shown was 712 mg (yellow oil, yield 48%).

Ms (ESI+, MeOH - 0.02M NH4OAc): 1 207 [M + NH3] +

[Comparative Example 1] [Chem. 32]

In 1,3-benzenesulfonate dichloride (manufactured by Aldrich) l. 〇〇 3g, in a nitrogen atmosphere, add pyridine l〇mL to dissolve, and then in a water bath (2 〇. under the ,, add cyclohexanol 0 · 9 OmL, stirred at room temperature for 20 hours. The reaction mixture was poured into 50 mL of diethyl ether, and the insoluble solid was removed by suction filtration to remove -43-200800870 (41). The filtrate was concentrated under reduced pressure. After the azeotrope was carried out once, the toluene was subjected to azeotropic gel filtration (20 g of a cerium oxide gel), and the mixture was washed with dichloroethane. The combined filtrate was concentrated under reduced pressure to dryness. The sulfonate compound represented by the formula (30) was 529 mg (colorless oil, yield 36%). h-NMR (300 MHz, CDC13) 5 (ppm): 1.2 - 1·9 (20 Η, m), 4.63 ( 2Η, dddd), 7.75 (1Η, dd), 8.16(2Η, dd), • 8·45(1Η, dd) °

Rf 値(DCE) : 0·5 — 0·6 [Comparative Example 2] [Chem. 33]

A crude product of sulfonic acid chloride (28) was obtained from 260 mg of the sulfonic acid pyridinium salt (27) by the method described in Example 3. Add 2.5 mL of dehydrated pyridine to the obtained sulfonate chloride (28) in a water bath (15 ° C), uniformly disperse it by ultrasonic wave, and add dehydrated cyclohexanol in a water bath (15 ° C). 0.5 mL was stirred at room temperature for 7 hours. The reaction mixture was poured (pou oxime in 15 mL of diethyl ether, and the insoluble solid was removed by filtration under reduced pressure, and the filtrate was dried under reduced pressure, and the toluene was azeotroped twice to obtain the compound represented by the formula (3 1). Oil of sulfonate compound 326 mg. MS) ESI+, in MeOH-0.02M NH4 OAc) : 1247 [M + NH3] + -44 - 200800870 (42) , 1165 ([M-C6H10 + HN3]+, 1 083 [M-2C6H10 + NH3] + 値 by the above MS analysis 値, during the reaction or purification operation, the cyclohexyl group is detached, it is known that the final product contains free sulfonic acid. Decomposition occurs by liquid separation washing treatment by ethyl acetate or water or gelation of cerium oxide gel, and further purification cannot be performed. By virtue of these facts, the detachability of cyclohexyl group is higher than that of PGME group. The difficulty in refining is self-evident. [Comparative Example 3] [Chem. 34]

A crude product of 25 1 mg of sulfonic acid chloride (28) derived from pyridinium sulfonate (27) was obtained by the method described in Example 3. Add 2.0 mL of dehydrated pyridine to the obtained sulfonate chloride (28) in a water bath (15 ° C), uniformly disperse it by ultrasonic wave, and add 0.5 mL of dehydrated isobutanol in a water bath (15 t). Stir at room temperature for 20 hours. The reaction mixture was poured (pour) in 12.5 mL of diethyl ether, and the insoluble solid was removed by filtration under reduced pressure. The filtrate was dried under reduced pressure, and toluene was azeotroped once to obtain a sulphur of the formula (32). The oil of the acid ester compound was 84 mg. The obtained oily substance can be decomposed by a liquid separation washing treatment by toluene or water or a cerium oxide gel refining treatment, and further purification of -45-200800870 (43) can no longer be carried out. Due to these facts, it is known that it is difficult to refine the isobutyl ester.

[Comparative Example 4] [Chem. 35]

The crude product of the sulfonate (28) was obtained from 101 mg of the sulfonic acid pyridinium salt (27) by the method described in Example 3. Add the dehydrated pyridinium 1. 〇ml to the obtained sulfonate (28) in a water bath (15 ° C), uniformly disperse it by ultrasonic wave, and add dehydration in a water bath (15 ° C). N-butanol oxime 2tnL was stirred at room temperature for 4 hours. Although the TLC can track the reaction, the low polarity point from the target only ends. Therefore, based on the fact, in order to lower the reactivity or to improve the decomposability of n-butyl ester (3 3 ), it is difficult to obtain a synthesis with good yield. [Comparative Example 5] [Chem. 36]

(34) -46-200800870 (44) A crude product of the sulfonate compound (28) was obtained from the sulfonic acid pyridinium salt (27) (10 mg) in the method described in Example 3. Adding dehydrated pyridine 1.0 mL to the obtained sulfonate (28) in a water bath (15 ° C), uniformly dispersing it by ultrasonic wave, and adding 0.2 mL of dehydrated cycloheptanol in a water bath (15 t). Stir at room temperature for 4 hours. Although the reaction can be followed by TLC, the low polarity point from the target only ends. Based on the fact, in order to make the cycloheptyl ester (34) have low reactivity or high decomposability, it is difficult to synthesize a good yield. [Embodiment 4] [Chem. 37]

(35) Into 50.00 g of sodium 4-styrenesulfonate (manufactured by Aldrich Co., Ltd.), 250 mL of pure water was added and dissolved, and 25 ml of a cation exchange resin Dowex 6 5 0C (H type, hereinafter abbreviated as 650 C) was added thereto, followed by stirring for 5 minutes. Fractionate the supernatant, add 6 50C 25ml for 5 minutes to stir, and then distillate the solution, add 650C 50ml for 5 minutes to stir, finally fractionate the supernatant, use 650C (500ml, distillate solvent: Water) is purified by column chromatography. -47- 200800870 (45) 100 mL of methanol and 27 mL of pyridine were added sequentially to the aqueous solution of 4-styrenesulfonic acid obtained by the ion father. After stirring for a while, the dried hydrazine was concentrated under reduced pressure, and methanol was used. After sub-azeotropic operation, 58 mL of methanol was added and dissolved. The obtained solution was dropped while stirring in diethyl ether 116 Torr. After stirring at room temperature for 15 minutes, the supernatant liquid was removed, and the residue was dried under reduced pressure to yield 50.20 g (yield of white powder, yield: 85%). To 38.41 g of the crude 4-styrenesulfonate salt obtained by the above method, 115 mL of thionylsulfonate was added, and the mixture was heated under reflux for 12 minutes. After cooling to room temperature, the dried hydrazine was concentrated under reduced pressure. After dissolving 4 mL of anhydrous pyridine with respect to the obtained pale yellow oil, water-free PGME 1.0 mL was added, and the mixture was suspended by ultrasonic waves and a glass rod, and stirred at room temperature for 30 minutes. The reaction system was concentrated to dryness under reduced pressure, and azeotroped with 1,2-dichloroethane for 1 time, and then filtered through a cerium oxide gel (8 g of cerium oxide gel, solvent and washing liquid: 1, 2) - Dichloroethane). The filtrate was concentrated to dryness under reduced pressure to give 22,77 g of crude material of the sulfonic acid ester compound. The obtained monomer crude product is purified by cerium oxide gel column chromatography (solvent: dichloroethane-dichloroethane: ethyl acetate = 20:1 - 10:1) to obtain a sulfonate. 11.98 g of compound monomer (colorless liquid, yield 32%). 9.31 g of the sulfonate compound monomer obtained by the above method was added to 37 mL of ethyl acetate anhydride under a nitrogen atmosphere to dissolve. After degassing by nitrogen foaming, AIBN 23.5 mg of ethyl acetate anhydride was obtained. 38 mL of the solution was added under a nitrogen atmosphere, and stirred at 8 (TC for 6 hours. After cooling to room temperature, the concentration was reduced to -30 mL by subtracting -48-200800870 (46), and pouring was carried out while stirring at 20 mL of methanol. After stirring at room temperature for 20 minutes, it was suction-filtered, and the filtrate was dried under reduced pressure to obtain 5.01 g (white powder, yield 54%) of the polystyrene sulfonate compound represented by formula (3). -NMR (300MHz » CDC13) δ (ppm) : 1.1 - 1.9(6Η » br),3·1—3·3(3Η,br),3·3—3·6(2Η,br),4.6— 4.9 (1Η, br), 6·4—6·9 (2Η, br), 7.5—7·9 (2Η, br) GPC: Mn (number average molecular weight) 26408; Mw (weight average molecular weight) 7 1 420; Mz (Z average molecular weight) 235 146 TG-DTA was measured for the sulfonate compounds obtained in the above Examples 1 to 4 and Comparative Example 1. The evaluation results are shown in Table 1. The measurement apparatus and conditions are as follows. Measuring device Thermal analyzer system WS002, Macscience Company Ltd. temperature rise rate: 5t: / min [Table 1]

Decomposition point (fever peak) Example 1 1 3 8 °C Example 2 22 2 °C Example 3 13 4〇C Example 4 14 1 °C Comparison Example 1 8 6〇C

Further, the solubility of each of the sulfonic acid ester compounds obtained in Examples 1 to 4 and various solvents of -49 - 200800870 (47) NSO-2 was evaluated by the following method. The results are shown in Table 2. <Solubility evaluation method> Each solvent having a mass ratio of 20 times was added to each sample, and stirred at room temperature, heated and stirred, or dissolved by ultrasonic vibration test. The object which was heated and stirred was observed after cooling to room temperature. In the table, 0 indicates complete dissolution, and there is no solid precipitation or residual of solid. In the table, X indicates solid precipitation or solid residue. [Table 2] Dimethylacetamide acetone ethyl acetate dichloroethane toluene isobutanol Example 1 〇〇〇〇〇X Example 2 〇〇〇〇〇X Example 3 〇〇〇〇〇X implementation Example 4 〇〇〇〇〇X NSO-2 〇XXXX 〇

As shown in Table 2, the ratio of the mineral acid vinegar compound 'obtained in Examples 1 to 4 to NSO-2 having a free sulfonic acid' showed high solubility with respect to various organic solvents. [Example 5] The mineral acid vinegar compound (29) obtained in Example 3 (1) 6 3 mg 'and Japanese-50-200800870 (48) The Bulletin of Chemical Society of Japan, 194, The method described in Vol. 67, p. 1 749-1 752 is synthesized, and dimethylacetamide (DMAc) is added to a mixture of phenyltetraphenylamine (PTA) 50 mg as shown in the following formula. 44 ml was added and dissolved under a nitrogen atmosphere, and 4.28 ml of cyclohexanol was added under a nitrogen atmosphere and stirred at room temperature to obtain a green transparent varnish (solid content: 3.3% by mass). The obtained varnish could not be solidified even when it was cooled to -25 °C. [Example 38] The varnish obtained in Example 5 was spin-coated on an IT0 substrate which was subjected to ozone cleaning for 40 minutes to the front of the eye, and then fired to form a film thickness of 22 nm. The charge transporting film (hole transporting film) obtained by the charge transporting film is an amorphous solid. [Example 7] The varnish obtained in Example 5 was subjected to 'spin coating' on an IT0 substrate which was subjected to ozone cleaning for 40 minutes, and then "fired" to form a charge transporting film having a film thickness of 67 nm (electrical Hole transport film). The resulting charge transporting film is an amorphous solid. [Example 8] -51 - 200800870 (49) A mixture of 11 6 mg of the sulfonate compound (3 5) obtained in Example 4 and 50 mg of the PTA shown above, dimethylacetamide (DMAc) 2.40 The solution was dissolved under a nitrogen atmosphere, and then 2.40 ml of cyclohexanol was added under a nitrogen atmosphere and stirred at room temperature to obtain a green transparent varnish (solid content: 3.5% by mass). The resulting varnish did not show solid precipitation even after cooling to 0 °C. The obtained varnish was spin-coated on a φ ITO substrate which was washed with ozone for 40 minutes, and then fired to form a charge transporting film (hole transporting film) having a film thickness of 36 nm. The obtained charge transporting film was an amorphous solid. [Comparative Example 6] (+)·1〇· In a mixture of 206 mg of camphorsulfonic acid and 100 mg of PTA, DM Ac 1.8 7 ml was added and dissolved in a nitrogen atmosphere, and further 5.53 ml of cyclohexanol was added and stirred at room temperature. A green transparent varnish (solid content of 4.2% by mass) was obtained. Using the obtained varnish, a charge transporting film (hole transporting film) having a film thickness of 12 nm was obtained by the method described in Example 6. The obtained charge transporting film was an amorphous solid. [Comparative Example 7] A charge transporting film (hole transporting film) having a film thickness of 24 nm was obtained in the same manner as in Comparative Example 6. The obtained charge transporting film was an amorphous solid. -52- 200800870 (50) [Comparative Example 8] In PTA 1.00 g, 2.128 g of 5-sulfosalicylic acid dihydrate, and hydrazine, hydrazine dimethyl acetamide (DMA 〇 17.50 g in nitrogen) The mixture was added and dissolved in an atmosphere, and 52.50 g of cyclohexanol was added to the resulting solution and stirred to prepare a varnish (solid content of 4.1% by mass). The obtained varnish was subjected to spin coating for 40 minutes of ozone washing. After coating on a glass substrate, it was fired at 180 ° C for 2 hours in air to obtain a charge transporting film (hole transporting film) having a film thickness of 21 nm. The above Examples 6 to 8 and Comparative Example 6 were The varnish viscosity used in 8 films, the firing conditions during film production, the film thickness of the film, and the free potential (hereinafter referred to as Ip) are shown in Table 3. In addition, the varnish viscosity, film thickness, IP値 can be as follows [1] Viscosity • E-type viscometer (ELD-50, manufactured by Tokyo Keiki Co., Ltd.), measuring temperature

Degree: 2 0 °C

[2] The film thickness was measured by a surface shape measuring device (DEKTAK3ST, manufactured by Nippon Vacuum Technology Co., Ltd.). [3] IP 测定 Measured by a photoelectron spectroscopic device (AC-2, manufactured by Sigma). -53- (51) 200800870 [Table 3] varnish solid concentration concentration varnish viscosity firing condition film thickness Ip replenishment %) (mPa · s) (nm) Example 6 3.3 10.5 220 ° C, 30 minutes 22 5.56 Example 7 3.3 10.5 220 ° C, 30 min 67 5.56 Example 8 3.5 4.8 220 ° C, 30 min 36 5.57 Comparative Example 6 4.2 11.5 180 ° C, 2 hours 12 5.49 Comparative Example 7 4.2 11.5 140 ° C, 2 hours 24 5.47 Comparative Example 8 4.1 11.8 180 ° C, 2 hours 21 5.37

As shown in Table 3, the Ip of the films obtained in Examples 6 to 8 showed sufficiently high enthalpy, and the sulfonate compounds (29) and (35) were treated as a good charge-sensitive substance by heat treatment after coating. The function is self-evident. [Example 9] An ITO substrate formed of the hole transporting film formed by the method of Example 6 was introduced into a vacuum vapor deposition apparatus, and α-NPD, Alq3, LiF, and A1 were sequentially subjected to vapor deposition to obtain an OLED element. The film thicknesses were 40 nm, 60 nm, 0.5 nm, and 100 nm, respectively, and the vapor deposition operation was performed at a pressure of 8×1 (T4Pa or less. The vapor deposition rate was 0.3 to 0.4 nm/s for removing LiF and 0.02 to 1 for LiF). 0.04 nm/s. The moving operation of the vapor deposition operation was carried out in a vacuum. [Example 10] -54- 200800870 (52) The ITO substrate on which the hole transporting film was formed by the method of Sinus 8 was introduced into a vacuum steaming. In the plating apparatus, α-NPD, Alq3, LiF, and A1 were sequentially vapor-deposited under the same conditions as in Example 9 to obtain an OLED device. [Comparative Example 9] The ITO glass substrate was washed with ozone for 40 minutes, and then introduced into a vacuum. In the vapor deposition apparatus, a-NPD, Alqs, LiF, and A1 were sequentially vapor-deposited in the same manner as in Example 9 to obtain an OLED device. [Comparative Example 10] A hole transporting film was formed in the same manner as in Comparative Example 6. The ITO substrate was introduced into a vacuum vapor deposition apparatus, and a-NPD, Alq3, LiF, and A1 were sequentially vapor-deposited under the same conditions as in Example 9 to obtain a ruthenium LED element. [Comparative Example 1 1] φ The method of Comparative Example 7 was used. The ITO substrate on which the hole transporting film was formed was introduced into a vacuum vapor deposition apparatus, and a_NPD was carried out under the same conditions as in Example 9. , Alq3, LiF, and A1 were sequentially vapor-deposited to obtain a ruthenium LED element. [Comparative Example 1 2] An ITO substrate in which a hole transporting film was formed by the method of Comparative Example 8 was introduced into a vacuum vapor deposition apparatus, and was the same as in Example 9. Under the conditions, a-NPD, Alq3, LiF'A1 were sequentially vapor-deposited to obtain a ruthenium LED element. The OLED element obtained in the above-mentioned Example 9, 1 〇, Comparative Examples 9 to 12 was -55-200800870 (53) The characteristics were measured using the following apparatus. The results are shown in Table 4. [1] EL measurement system = luminescence quantum efficiency measurement device (ELI 003, manufactured by Precise Gauges)

[2] Voltmeter (voltage generation source): Programmable (P rogrammable) DC voltage/current source (R6145, manufactured by Advantest) [3] Ammeter: digital multimeter (R65 8 1 D, Advantest company)

[4] Luminance meter: LS-1 10 (manufactured by Minolta Co., Ltd.) [Table 4] Film thickness Current density Voltage Luminance Current efficiency Luminescence start maximum brightness (nm) (mA/cm2) (V) (cd/m2) (cd/ A) Voltage (V) (cd/m2) Example 9 22 10.1 7.0 317 3.13 2.75 29830 Example 10 36 0.21 7.0 7.0 3.41 4.00 4167 10 10.5 285 2.85 Comparative Example 9 — 0.37 7.0 1.2 0.32 4.50 10640 10 9.2 330 3.3 4.50 10640 Comparative Example 10 24 0.419 7.0 8.89 2.12 4.00 5540 Comparative Example π 12 10 10.2 239 2.39 6.50 4410 Comparative Example 12 21 2.86 7.0 101 3.5 2.75 18799 10 8.1 410 4.1 2.75 18799 As shown in Table 4, obtained from Example 6 The OLED element of the hole transporting film produced by the varnish (Example 9) has the same reduction rate and maximum brightness as the OLED element without the hole-56-200800870 (54) transport film. The above is self-evident. Further, in the OLED device of Example 9, the sulfonate compound which is not a predetermined dopant as compared with the comparative example using 5-SSA, the driving voltage is lowered to increase the maximum luminance to be self-evident. The uniformity of the light-emitting surface of the OLED element produced in Example 9 was unrecognizable. φ The OLED element of Example 10, in conjunction with the embodiment 9, showed good current efficiency as self-evident. That is, the sulfonate compound of the example can be effectively used as a hole in the hole injection layer after film formation. [Example 11] The sulfonate compound (29) obtained in Example 3 (24.5 mg) The mixture of the charge transporting main substance synthesized by the method described in the literature 4, 19. mg, was added with 3.24 ml of toluene, and the mixture was stirred at room temperature. Varnish (solid content concentration: 1.5% by mass). The obtained solid matter was not observed even when it was cooled to -25 °C. by! It is known that the sulfonate compound is used for the charge transporting host material having a low polarity and a high solubility as BBD, and even if it is only a low-polar solvent, the charge paint can be prepared without self-precipitating. . , the current effect of the present invention, in addition to the fact that the black OLED element 4 recorded the acceptability, and the patent, quality BBD mixed to obtain a red varnish, compared to the results of the solvent in the use of toluene transportability clear.

Claims (1)

200800870 (1) X. Application for Patent Park 1· A sulfonate compound represented by formula (1) (1) (wherein A represents a substituted or unsubstituted one-valent hydrocarbon group, X represents a substituted or unsubstituted valence hydrocarbon group, γ represents hydrazine, S, or a substituted or unsubstituted 2 valent amine group 'Z non-hydrogen atom or substitution Or an unsubstituted one-valent hydrocarbon group). 2. The sulfonate compound according to item 1 of the patent application, which is represented by the formula (2), [Chemical 2] (2) (wherein R 1 to R 4 are each independently a hydrogen atom, an unsubstituted or substituted valence hydrocarbon group or a functional atom, and A and Z are the same). 3. A mineral acid vinegar compound as claimed in claim 1 or 2, wherein the A is a substituted or unsubstituted aromatic ring. 4·~ The type of mineral acid vinegar compound of formula (3) or formula (4), -58- 200800870 (2) [Chem. 3] (3) (4) (wherein A' is represented by (S03H)m, X' and (S〇3-XYZ)n, substituted hydrocarbyl group, X represents substituted or unsubstituted divalent hydrocarbon group, γ represents 〇, S or substituted Or an unsubstituted divalent amine group, Z represents a hydrogen atom or an arbitrary monovalent hydrocarbon group, X ' indicates Ο, S or Ν, B indicates a substituted or unsubstituted hydrocarbon group, 1,3,5-tridecyl, or Substituted or unsubstituted formula (5) or (6), [Chemical 4] The group shown (wherein W1 and w2 are each independently, indicating Ο, S, S(O) groups, S(0 fluorenyl, or ν, Si, Ρ, Ρ with unsubstituted or substituted bonds) 0) base), q shows the number of bonds of B and X, is an integer satisfying 14, r is the number of repeated units, is an integer satisfying, ❿ is an integer above ,, η1 is an integer of 1 or more, n2 is An integer of 1 or more, and + m satisfies Α in the formula (3), and is an allowable substitution number or less, and n2 + m satisfies A' in the formula (4) as an allowable substitution number or less). 5. The sulfonate compound of the formula (7) or the formula (8), -59- 200800870 (3) [Chemical 5] (wherein W represents a substituted or unsubstituted trivalent hydrocarbon group, a" represents a substituted or unsubstituted divalent aromatic ring group or a single bond, X represents a substituted or unsubstituted divalent hydrocarbon group, and Y represents Ο, S, or a substituted or unsubstituted divalent amine group, z is not a hydrogen atom or an arbitrary monovalent hydrocarbon group, s represents an integer of 2 to 100000, t represents an integer of 1 to 1000, and u represents an integer of 1 to 100,000, t + u To satisfy 2~looooo), 6 · The sulfonate compound of claim 5, which is represented by formula (9) or formula (10), [Chemical 6] (wherein R5 to R7 are each independently, and represent a hydrogen atom, an unsubstituted or -60-200800870 (4) substituted one-valent hydrocarbon group, or a halogen atom, A&quot;, X, Y, Z, s, t, and u before). 7. The sulfonate compound according to claim 5 or 6, wherein the number average molecular weight is from 5,000 to 100,000. 8. The sulfonate compound according to claim 4, wherein the m is 0 〇 9. A sulfonate compound as claimed in claim 4 is an electron accepting substance. 1 0. An acid generator for a sulfonate compound as claimed in any one of claims 1 to 8. * 1 1 A charge transporting varnish containing a sulfonate compound according to any one of claims 1 to 8. A charge transporting film comprising a sulfonate compound according to any one of claims 1 to 8 of the patent application. A charge transporting film obtained by a charge transporting φ varnish as described in claim 1 of the patent application. A method of producing a charge transporting film, which comprises applying a charge transporting varnish according to claim 1 of the patent application to a substrate and heating the substrate. An organic electroluminescence device having a charge transporting film as disclosed in claim 12 or 13 of the patent application. 1 6 · - (1) -61 - 200800870 (5) [Chemical Formula 11] A 〇 ( /Υ^ζ (1) χκ (wherein, Α, χ, γ and Ζ are the same as before) Manufacturing method 'characterized by 'making equation (11) [化7] (11) I OH (wherein A represents a substituted or unsubstituted one-valent hydrocarbon group) and the sulfonic acid compound is reacted with a base to be derivatized as the formula (12) [Chemical 8] A OV+ (wherein, the same as before, V+ indicates sodium ion, potassium ion, pyridinium ion or fourth-order money ion), the sulfonate compound shown, reacts the sulfonate compound with a halogenated reagent Derived from the formula (1 3 ), -62· 200800870 (6) [: 9] AI Μ 0=S=0 (13) I w (wherein A is the same as before, w is a halogen atom), as shown Sulfonium halide compound, this sulfonium halide compound and formula (1 4) HO—X—Y—Z (14) (wherein X represents a substituted or unsubstituted divalent hydrocarbon group, Y represents hydrazine, S, or a substituted or unsubstituted divalent amine group, and z represents a hydrogen atom; Or a substituted or unsubstituted one-valent hydrocarbon group), the alcohol compound shown. -63- 200800870 VII Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is a simple description: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: