Composition, film production method, and light emitting device

Abstract

A composition having excellent dischargeability by an ink jet method and reduced clogging of an ink jet apparatus is provided. The composition contains a fluorinated alcohol A represented by the formula (1) and having a boiling point of 50 C. or more and less than 150 C., a fluorinated alcohol B represented by the formula (1) and having a boiling point of 150 C. or more and less than 300 C., and a charge transportable compound, in which the ratio rate of the fluorinated alcohol B with respect to 100 parts by mass of the sum of the fluorinated alcohol A and the fluorinated alcohol B is 10 parts by mass to 90 parts by mass:
C.sub.nFH.sub.2nF+1-mFF.sub.nFOH (1)
In formula (1), nF is an integer of 1 to 12 and mF is an integer of 1 to 25, provided that 2nF+1mF.

Claims

1. A composition comprising a fluorinated alcohol A represented by the formula (1) and having a boiling point of 50 C. or more and less than 150 C., a fluorinated alcohol B represented by the formula (1) and having a boiling point of 150 C. or more and less than 300 C. and a charge transportable compound, wherein a ratio of said fluorinated alcohol B with respect to 100 parts by mass of the sum of said fluorinated alcohol A and said fluorinated alcohol B is 10 parts by mass to 90 parts by mass:
C.sub.nFH.sub.2nF+1-mFF.sub.nFOH (1) in the formula (1), nF is an integer of 1 to 12 and mF is an integer of 1 to 25, provided that 2nF+1mF.

2. The composition according to claim 1, wherein a difference between the boiling point of said fluorinated alcohol A and the boiling point of said fluorinated alcohol B is 50 C. or less.

3. The composition according to claim 1, wherein nF in said fluorinated alcohol A is an integer of 1 to 10 and nF in said fluorinated alcohol B is an integer of 4 to 10.

4. The composition according to claim 3, wherein mF in said fluorinated alcohol A is an integer of 4 to 12 and mF in said fluorinated alcohol B is an integer of 4 to 12.

5. The composition according to claim 1, wherein said fluorinated alcohol A and said fluorinated alcohol B are each a linear alcohol.

6. The composition according to claim 1, wherein said charge transportable compound is at least one selected from the group consisting of aromatic hydrocarbon compounds, aromatic heterocyclic compounds, organic silane compounds, alkali metal salts and alkaline earth metal salts of aromatic hydrocarbon compounds, alkali metal salts and alkaline earth metal salts of aromatic heterocyclic compounds, alkali metal salts and alkaline earth metal salts of organic silane compounds, halides, oxide salts and carbonates of alkali metals, halides, oxide salts and carbonates of alkaline earth metals, and metal complexes.

7. The composition according to claim 1 wherein said charge transportable compound is a polymer compound.

8. The composition according to claim 1, further comprising water.

9. The composition according to claim 1, further comprising a solvent having a surface tension higher than that of said fluorinated alcohol A and said fluorinated alcohol B and having a boiling point higher than that of said fluorinated alcohol A and said fluorinated alcohol B.

10. A production method of a film, comprising a step of forming a film by an application method using the composition according to claim 1.

11. A production method of a light emitting device, comprising a step of forming a layer by an application method using the composition according to claim 1.

Description

EXAMPLES

(1) The present invention will be illustrated in detail by examples below, but the present invention is not limited to these examples.

(2) In examples, the polystyrene-equivalent number-average molecular weight (Mn) and polystyrene-equivalent weight-average molecular weight (Mw) of a polymer compound were determined according to the measurement condition of size exclusion chromatography (SEC) described below using tetrahpdrofuran as a mobile phase.

(3) <Measurement Condition>

(4) A polymer compound to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 pL of the resultant solution was injected into SEC. The mobile phase was flowed at a flow rate of 1.0 mL/min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories, Ltd.) was used. As a detector, UV-VIS Detector (trade name: UV-8320 GPC, manufactured by Tosoh Corp.) was used.

(5) NMR was measured by the following method

(6) A measurement sample (5 to 10 mg) was dissolved in about 0.5 mL of heavy chloroform, heavy tetrahydrofuran, heavy dimethyl sulfoxide, heavy acetone, heavy N,N-dimethylformamide, heavy toluene, heavy methanol, heavy ethanol, heavy 2-propanol or heavy methylene chloride, and NMR thereof was measured using an NMR apparatus (trade name: INOVA300 or MERCURY400VX, manufactured by Agilent).

(7) As an indicator of the purity of a compound, the value of high performance liquid chromatography (HPLC) area percentage was used. This value is a value at UV=254 nm in HPLC (trade name: LC-20A, manufactured by Shimadzu Corp.) unless otherwise stated. In this operation, a compound to be measured was dissolved in tetrahydrofuran or chloroform to a concentration of 0.01 to 0.2% by mass, and 1 to 10 L of the solution was injected into HPLC depending on the concentration. As the mobile phase of HPLC, a mixture of acetonitrile/tetrahydrofuran was used while changing the ratio thereof from 100/0 to 0/100 (volume ratio) and flowed at a flow rate of 1.0 mL/min. As a column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having the equivalent ability was used. As a detector, Photodiode Array Detector (trade name: SPD-M20A, manufactured by Shimadzu Corp.) was used.

(8) The viscosity of the composition was measured using a viscosity measuring apparatus (manufactured by Brookfield, Inc., US, trade name: LVDV-II+Pro CP).

(9) The dischargeability of the composition by an ink jet method and clogging of an ink jet apparatus were evaluated using an inkjet application apparatus (manufactured by Fujifilm Corp, trade name: Dymatics material printer, DMP-2831; cartridge: DMCLCP-11610).

Synthesis Example 1

Synthesis of Monomers CM1 and CM2

(10) Monomers CM1 and CM2 were synthesized in accordance with methods described in the following documents, and those showing an HPLC area percentage value of 99.5% or more were adopted.

(11) The monomer CMI was synthesized in accordance with a method described in JP-A. No. 2012-033845.

(12) The monomer CM2 was synthesized in accordance with a method described in JP-A No. 2010-189630.

(13) ##STR00025##

Synthesis Example 2

Synthesis of Polymer Compound 1

(14) An inert gas atmosphere was prepared in a reaction vessel, then, the monomer CM1 (9.23g), the monomer CM2 (4.58 g), dichlorobis(tris-o-methoxyphenylphoshpine)palladium (8.6 mg) and toluene (175 mL) were added, and heated at 105 C.

(15) Thereafter, into this was dropped a 12% by mass sodium carbonate aqueous solution (40.3 mL), and the mixture was refluxed for 29 hours.

(16) Thereafter, to this were added phenylboronic acid (0.47 g) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (8.7 mg), and the mixture was refluxed for 14 hours.

(17) Then, to this was added a sodium diethyldithiacarbamate aqueous solution, and the mixture was stirred at 80 C. for 2 hours. The resultant reaction solution was cooled, then, dropped into methanol, to generate a precipitate. The resultant precipitate was isolated filtration, and washed with methanol and water respectively, then, dried, to obtain a solid. The resultant solid was dissolved in chloroform, and purified by passing sequentially through an alumina column and a silica gel column through which chloroform had passed previously. The resultant purified solution was dropped into methanol, and the mixture was stirred, to generate a precipitate. The resultant precipitate was isolated by filtration, and dried, to obtain a polymer compound P1 (7.15 g). The polymer compound P1 had an Mn of 3.210.sup.4 and an Mw of 6.010.sup.4.

(18) The polymer compound P1 is a copolymer constituted of a constitutional unit derived from the monomer CM1 and a constitutional unit derived from the monomer CM2 at a molar ratio of 50:50 according to the theoretical values calculated from the amounts of the charged raw materials.

(19) An argon gas atmosphere was prepared in a reaction vessel, then, the polymer compound P1 (3.1 g), tetrahydrofuran (130 mL), methanol (66 mL), cesium hydroxide monohydrate (2.1 g) and water (12.5 mL) were added, and stirred at 60 C. for 3 hours.

(20) Thereafter, to this was added methanol (220 mL), and the mixture was stirred for 2 hours. The resultant reaction mixture was concentrated, then, dropped into isopropyl alcohol, and the mixture was stirred, to generate a precipitate. The resultant precipitate was isolated by filtration, and dried, to obtain a polymer compound 1 (3.5 g). By .sup.1H NMR analysis of the polymer compound 1, it was confirmed that a signal of an ethyl ester portion in the polymer compound P1 disappeared and the reaction was completed.

(21) The polymer compound 1 is a copolymer constituted of a constitutional unit represented by the following formula and a constitutional unit derived from the monomer CM2 at a molar ratio of 50:50 according to the theoretical values calculated from the amounts of the charged raw materials.

(22) ##STR00026##

Example 1

Preparation of Composition 1

(23) The polymer compound 1 was dissolved at a concentration of 0.05% by mass in a mixed solvent of 1H,1H,5H-octafluoropentanol (boiling point: 140 to 141 C., surface tension: 22.1 mN/m) and 1H,1H,7H-dodecafluoroheptanol (boiling point: 169 to 170 C., surface tension: 18.2 mN/m) (mass ratio 70:30), to prepare a composition 1 (viscosity: 0.0177 Pa.Math.s)

Example 2

Preparation of Composition 2

(24) A composition 2 (viscosity: 0.0221 Pa.Math.s) was prepared in the same manner as in Example 1, except that the mass ratio of the mixed solvent was 50:50 in Example 1.

Example 3

Preparation of Composition 3

(25) A composition 3 (viscosity: 0.0247 Pa.Math.S) was prepared in the same manner as in Example 1, except that the mass ratio of the mixed solvent was 30:70 in Example 1.

Example 4

Preparation of Composition 4

(26) A composition 4 (viscosity: 0.0111 Pa.Math.S) was prepared in the same manner as in Example 1, except that the mixed solvent was changed to a mixed solvent of 1H,1H,5H-octafluoropentanol, 1H,1H,7H-dodecafluoroheptanol and water (mass ratio 27:70:3).

Example 5

Preparation of Composition 5

(27) The polymer compound 2 (a polymer compound containing a constitutional unit represented by the formula (ET-1), Ar.sup.E1 is a 2,7-fluorenediyl group, nE1 is 1) synthesized by the same method as for the polymer compound 1 was dissolved at a concentration of 0.2% by mass in a mixed solvent of 1H,1H,5H-octafluoropentanol and 1H,1H,7H-dodecafluoroheptanol (mass ratio 60:40), to prepare a composition 5 (viscosity: 0.020 Pa's).

Example 6

Preparation of Composition 6

(28) A mixture (mass ratio 50:50) of the polymer compound 2 and the polymer compound 3 (a polymer compound containing a constitutional unit represented by the formula (E2-1), Ar.sup.E1 is a 2,7-fluorenediyl group, nE1 is 1) synthesized by the same method as for the polymer compound 1 was dissolved at a concentration of 0.2% by mass in a mixed solvent of 1H,1H,5H-octafluoropentanol, 1H,1H,7H-dodecafluoroheptanol, propyrene glycol (boiling point: 188 to 189 C., surface tension 72.0 mN/m) and water (mass ratio 53:38.5:4.8:3.7), to prepare a composition 6 (viscosity: 0.016 Pa.Math.s).

Comparative Example 1

Preparation of Composition C1

(29) The polymer compound 1 was dissolved at a concentration of 0.05% by mass in 1H,1H,5H-octafluoropentanol, to prepare a composition C1 (viscosity: 0.0143 Pa.Math.s).

Comparative Example 2

Preparation of Composition C2

(30) The polymer compound 1 was dissolved at a concentration of 0.05% by mass in 1H,1H,7H-dodecafiuoroheptanol, to prepare a composition C2 (viscosity: 0.0329 Pa.Math.s).

Synthesis Example 3

Synthesis of Polymer Compound 4

(31) The polymer compound 4 was synthesized in accordance with a method described in Chemistry of Materials, 2004, vol. 16, p. 708. The polymer compound 4 had an Mn of 2.510.sup.3 and an Mw of 3.110.sup.3.

(32) The polymer compound 4 is a polymer compound composed of a constitutional unit represented by the following formula.

(33) ##STR00027##

Example 7

Preparation of Composition 7

(34) The polymer compound 1 was dissolved at a concentration of 0.05% by mass in a mixed solvent of 13,1H-pentafluoropropanol (boiling point: 81 to 83 C., surface tension: 17.3 mN/m) and 1H,1H,7H-dodecafluoroheptanol (mass ratio 60:40), to prepare a composition 7 (viscosity: 0.0090 Pa.Math.s).

Example 8

Preparation of Composition 8

(35) The polymer compound 4 was dissolved at a concentration of 0.05% by mass in a mixed solvent of 1H,1H,5H-octafluoropentanol and 1H,1H,7H-dodecafluoroheptanol (mass ratio 60:40), to prepare a composition 8 (viscosity: 0.0200 Pa.Math.s).

Comparative Example 3

Preparation of Composition C3

(36) The polymer compound 1 was dissolved at a concentration of 0.05% by mass in 1H,1H-pentafluoropropanol, to prepare a composition C3 (viscosity: 0.0041 Pa.Math.s).

Comparative Example 4

Preparation of Composition C4

(37) The polymer compound 4 was dissolved at a concentration of 0.05% by mass in 1H,1H,5H-octafluoropentanol, to prepare a composition C4 (viscosity :0.0170 Pa.Math.s).

Comparative Example 5

Preparation of Composition C5

(38) The polymer compound 4 was dissolved at a concentration of 0.05% by mass in 1H,1H,7H-dodecafluoroheptanol, to prepare a composition C5 (viscosity: 0.0315 Pa.Math.s).

(39) <Evaluation of ink jet dischargeability>

(40) Liquid droplets of each composition were discharged by an ink jet method, and dischargeability was evaluated according to the following criteria. The results are shown in Table 1.

(41) : Discharge as a droplet was obtained continuously for 5 minutes or more from the discharge start.

(42) : Discharge is charge as a droplet was not obtained, or discharge was not obtained as a droplet within 5 minutes from the discharge start.

(43) <Evaluation of Occurrence of Ink Jet Clogging>

(44) After droplets of each composition were discharged by an ink jet method for 1 minute, the discharge was stopped, and the occurrence of clogging of the ink jet head while the discharge was stopped was evaluated according to the following criteria. The obtained results are shown in Table 1.

(45) : No clogging occurred when left for 1 hour in an environment of 23 C. and 60% humidity, after 1 minute of discharge.

(46) : Clogging occurred when left for 1 hour in an environment of 23 C. and 60% humidity, after 1 minute of discharge.

(47) TABLE-US-00001 TABLE 1 viscosity composition (Pa .Math. s) dischargeability clogging Example 1 1 0.0177 Example 2 2 0.0221 Example 3 3 0.0247 Example 4 4 0.0111 Example 5 5 0.0200 Example 6 6 0.0160 Example 7 7 0.0090 Example 8 8 0.0200 Comparative C1 0.0143 x Example 1 Comparative C2 0.0329 x Example 2 Comparative C3 0.0041 x Example 3 Comparative C4 0.0170 x Example 4 Comparative C5 0.0315 x Example 5
<Evaluation of Film Formability>

(48) A phosphorescent material was dissolved as a solid component in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mass ratio 20:80) to a concentration of 1.5% by mass, to prepare a solution. The prepared solution was applied on a glass substrate by an ink jet method, then, vacuum-dried at 10 Pa, then, calcined for 10 minutes at 130 C. under standard pressure, to form a phosphorescent material layer having a thickness of 100 nm. The composition 5 was applied in a rectangle form of 30 mm length and 50 mm width on the phosphorescent material layer by an ink jet method, then, vacuum-dried at 10 Pa, then, calcined for 10 minutes at 130 C. under standard pressure, to form a film 1 with a thickness of 10 nm.

(49) Films 2 to 8 were formed in the same manner as for the film 1, except that the kind of the composition and the thickness of the film were changed as shown in Table 2.

(50) For each of the films 1 to 8, the difference between the width (50 mm) at the time of ink jet application and the width of each film after carrying out vacuum-drying and calcination was measured as the shrink amount (indicator for evaluation of film formability). The obtained results are shown in Table 2.

(51) TABLE-US-00002 TABLE 2 film composition thickness (nm) shrink amount (mm) 1 5 10 2 2 5 20 3 3 5 30 6 4 5 40 7.5 5 6 10 0 6 6 20 0.5 7 6 30 0.5 8 6 40 0.5

INDUSTRIAL APPLICABILITY

(52) According to the present invention, a composition that is excellent in dischargeability by an ink jet method and is less likely to cause clogging of an ink jet apparatus and production methods of a film and a light emitting device using the composition can be provided.