PHOTOCROSSLINKABLE POLYMER, INSULATING FILM, PLANARIZATION FILM, LYOPHILIC/LIQUID REPELLENT PATTERNED FILM, AND ORGANIC FIELD EFFECT TRANSISTOR DEVICE COMPRISING SAME

20210135115 · 2021-05-06

Assignee

Tosoh Corporation (Shunan-shi, Yamaguchi, JP)

Inventors

Cpc classification

International classification

Abstract

Provided is a resin which is excellent in terms of solubility in common solvents, crosslinking temperature, time required for crosslinking, solvent resistance (cracking resistance), breakdown voltage, leakage current, solvent wettability, and planarity in cases where the resin is formed into a thin film. A resin which comprises repeating units represented by formula (1) and formula (2), and wherein the repeating unit represented by formula (2) is contained in an amount of 20% by mole or more relative to the total amount of the repeating units represented by formula (1) and formula (2).

##STR00001##

Claims

1. A resin,. comprising: a plurality of repeating units represented by formula (1); and a plurality of repeating units represented by formula (2), wherein the resin includes 20% by mole or more of the repeating units represented by the formula (2) with respect to a total amount of the repeating units represented by the formulae (1) and (2): ##STR00046## wherein in the formula (1), R.sub.1 represents hydrogen or a C1-C6 alkyl group; S.sub.1 represents —O— or —C(O)—; p represents 0 or 1; A.sub.1 represents a C6-C19 aryl group; Y represents halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group; and k represents an integer from 0 to (s-1), wherein s represents the number of carbon atoms constituting the A.sub.1, ##STR00047## wherein in the formula (2), R.sub.2 represents hydrogen or a C1-C6 alkyl group; S.sub.2 represents —O— or —C(O)—; q represents 0 or 1; A.sub.2 represents a C6-C19 aryl group; Y represents a substituent as defined in formula (1); j represents an integer from 0 to (r-2) and m represents an integer from 1 to (r-j-1), wherein r represents the number of carbon atoms constituting the A.sub.2, and Z represents at least one organic group selected from the formulae (A) to (D): ##STR00048## wherein in the formulae (A) to (D), R.sub.3 and R.sub.4 each independently represents hydrogen, a C1-C6 alkyl group, an aryl group, or a carboxyalkyl group; and R.sub.5 to R.sub.29 independently represent hydrogen, halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group.

2. An insulating film, comprising: a crosslinked product of the resin according to claim 1.

3. An organic field effect transistor device, comprising: a substrate; an organic semiconductor layer; a gate electrode; and the gate insulating layer comprising the insulating film of claim 2, wherein, on the substrate, the organic semiconductor layer and the gate electrode are stacked to each other via the gate insulating layer, and a source electrode and a drain electrode are attached on the organic semiconductor layer.

4. A planarization film comprising the resin according to claim 1 and/or a crosslinked product of the resin according to claim 1.

5. A lyophilic/liquid-repellent patterned film comprising the resin according to claim 1 and/or a crosslinked product of the resin according to claim 1.

6. A film, comprising: the resin of claim 1; and a crosslinked product of the resin of claim 1, wherein the film is a planarization film.

7. A film, comprising: the resin of claim 1; and a crosslinked product of the resin of claim 1, wherein the film is a lyophilic/liquid-repellent patterned film.

8. The resin of claim 1, further comprising: a plurality of repeating units represented by formula (18), ##STR00049## where R.sub.2, S.sub.2, A.sub.2, and Y each represent a substituent defined in the formula (2), q represents an integer defined in the formula (2), n represents an integer from 0 to (t-4), t represents the total number of the carbon atoms constituting A.sub.2, d and e represent single bonds that are located in the ortho positions to each other (bonded to adjacent carbons) on the aromatic group A.sub.2, and R.sub.3 to R.sub.9 are the same as those defined in the formula (A), and Z is the formula (A).

9. The resin of claim 1, wherein the organic group of the formula (A) is one of followings: ##STR00050## ##STR00051##

10. The resin of claim 1, further comprising: a plurality of repeating units represented by formula (19), ##STR00052## where A.sub.3 represents a C6-C19 aryl group, Y represents substituent defined in the formula (1), R.sub.30 represents hydrogen or a C1-C6 alkyl group, R.sub.f represents a C1-C18 fluoroalkyl group, v represents an integer from 0 to (u-2), w represents an integer from 1 to (u-v-1), and u represents the number of carbon atoms constituting A.sub.3.

11. The resin of claim 10, wherein R.sub.30 in the formula (19) is the C1-C6 alkyl group which is one of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a n-butyl group.

12. A film, comprising: the resin of claim 10, wherein the film is a lyophilic/liquid-repellent patterned film.

13. A film, comprising: a crosslinked product of the resin of claim 10, wherein the film is a lyophilic/liquid-repellent patterned film.

14. A film, comprising: the resin of claim 10; and a crosslinked product of the resin of claim 10, wherein the film is a lyophilic/liquid-repellent patterned film.

15. A film, comprising: the resin of claim 11, wherein the film is a lyophilic/liquid-repellent patterned film.

16. A film, comprising: a crosslinked product of the resin of claim 11, wherein the film is a lyophilic/liquid-repellent patterned film.

17. A film, comprising: the resin of claim 11; and a crosslinked product of the resin of claim 11, wherein the film is a lyophilic/liquid-repellent patterned film.

18. A film, comprising: the resin of claim 8, wherein the film is a planarization film.

19. A film, comprising: a crosslinked product of the resin of claim 8, wherein the film is a planarization film.

20. A film, comprising: the resin of claim 8; and a crosslinked product of the resin of claim 8, wherein the film is a planarization film.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0129] FIG. 1 is a view showing a cross-sectional shape of a bottom-gate bottom-contact (BGBC) type device.

[0130] FIG. 2 is a graph showing a .sup.1H-NMR chart of a resin 1 produced in Example 1.

[0131] FIG. 3 is a graph showing that in an OFET device produced in Example 1, hysteresis is not observed in a source-drain current (I.sub.SD) (solid line) observed when a gate voltage (V.sub.GS) is changed, and that a leakage current value (I.sub.L) (broken line) is very small as 0.01 nA or less.

[0132] FIG. 4 is a view showing a cross-sectional shape of a top-gate bottom-contact (TGBC) type device.

[0133] FIG. 5 is a view showing a test pattern of Ag wiring formed by lyophilic/liquid-repellent patterning in Example 9.

EXAMPLES

[0134] Hereinafter, the present invention is described in more detail with reference to Examples, but the present invention is not limited to these Examples alone. Note here that the organic semiconductor (di-n-hexyl dithienobenzodithiophene) used in Examples was synthesized according to the production method of Japanese Patent Application Unexamined Publication No. 2015-224238. Among the use photocyclizable compounds, 2-oxo-2H-1-benzopyran-6-carbonyl chloride (represented by the following formula (G)) was synthesized according to CN103183634, 4-[2-(4-pyridinyl)ethenyl]benzoyl chloride (represented by the following formula (H)) was synthesized according to the method described in Journal fúr Practitioner tipper Chez Chemie, Vol. 6, page 72 (1958). Furthermore, cinnamic acid chloride which is a reagent made of Tokyo Chemical Industry Co., Ltd (represented by the following formula (I)) was used. A compound (represented by the following formula (J)) having a fluoroalkyl group was synthesized according to the method described in Journal of Fluorine Chemistry, vol. 131, page 621 (2010). Furthermore, as Ag nanoink (ink containing silver nanoparticle), silver nanocolloid H-1 manufactured by Mitsubishi Materials was used.

##STR00022##

[0135] In Examples, NMR, spin coating, film thickness measurement, dispenser printing, UV irradiation, vacuum deposition, the amount of UV irradiation necessary for crosslinking, wettability of a polymer dielectric layer to a solvent, breakdown voltage, evaluation of an OFET device, evaluation of solvent resistance (cracking resistance) were carried out under the following conditions and using the following devices.

<NMR>

[0136] NMR was measured using JNM-ECZ400S FT-NMR (manufactured by JEOL Ltd.). Note here that the molar fraction X of a photocyclization group in an aromatic group can be calculated by the following expression using integrated intensity of a peak obtained by the .sup.1H-NMR measurement.

X=(P−1)×I.sub.2/{(N+1)×I.sub.2−M×I.sub.1}

(herein, I.sub.1 represents an integral value of peaks that are present in δ0.8 to δ2.04 ppm, I.sub.2 represents an integral value of peaks that are present in δ6.50 to δ7.6 ppm, P represents the total number of hydrogen atoms that are present in the photocyclization group, N represents the number of the total of methylene, methine, and methyl groups, and M represents the total number of hydrogen atoms of the aromatic group.)

[0137] MS-A100 manufactured by Mikasa Co., Ltd was used.

[0138] Measurement was carried out using DektakXT stylus profiler manufactured by Bruker Corporation.

[0139] IMAGE MASTER 350PC SMART manufactured by Musashi Engineering, Inc. was used.

[0140] UV irradiation was carried out using UV-System, CSN-40A-2 manufactured by GS Yuasa Corporation under the condition of UV intensity of 4.0 kW, and UV irradiation time was adjusted by changing the conveying speed.

[0141] Small-sized vacuum evaporation equipment VTR-350M/ERH manufactured by ULVAC KIKO was used.

[0142] On a washed and dried glass having a size of 30×30 mm.sup.2 (Eagle XG manufactured by Corning Inc.), a resin solution was applied to form a spin-coated film having a film thickness of 500 nm, followed by drying sufficiently. Initial film thickness (A) at this time was measured, and a crosslinked film obtained with an amount of UV irradiation changed was soaked in toluene for one hour, and dried. Then, a film thickness (B) of the resultant film was measured. Using these film thicknesses, from the following expression:

Film remaining rate=Film thickness (B)/Initial film thickness(A)×100,

the amount of UV irradiation in which the film remaining rate was 95% or more was made to be a UV irradiation amount necessary for crosslinking.

[0143] Five types of solvents (toluene, tetralin, xylene, mesitylene, and chlorobenzene) having different surface tension was dropped in an amount of 1 μL onto a crosslinked film of a resin. When coating of an appropriate amount of the organic semiconductor solution covering the S electrode and the D electrode is carried out, if a shape at instant time of coating of droplet is maintained or wettability is widened, the solution can cover the electrodes entirely. Thus, this case was evaluated as good (score 1). On the other hand, when the droplet was contracted, and/or moved, electrode was not covered. Therefore, a case where the liquid was contracted and/or moved was evaluated as failure (score 0). When good results are obtained in all the solvents, the score was 5.

[0144] On the washed and dried glass having a size of 30×30 mm.sup.2 (Eagle XG manufactured by Corning Inc.), silver was deposited to form an electrode having a thickness of 30 nm. Thereafter, on the substrate on which the electrode was formed, a film of a dielectric material (insulator) was formed, gold electrode was deposited on the dielectric layer to prepare an MIM capacitor, and a voltage was applied between the above silver-gold electrodes. A voltage at which an electric current starts to flow inside the dielectric layer by dielectric breakdown was measured, and a value obtained by dividing the value by a thickness of the measured dielectric layer referred to a breakdown voltage.

[0145] A bottom-gate bottom-contact (BGBC) type device as one embodiment of the organic field effect transistor was prepared, and mobility, leakage current, on-current/off-current ratio, hysteresis of source/drain current, and threshold voltage were evaluated using Semiconductor Parameter Analyzer SCS4200 manufactured by Keithley Instruments, Inc., with a source-drain voltage be −60 volts and a gate voltage changed.

[0146] On a PET film (manufacture by Teijin DuPont Films Japan) having a size of 5 cm×5 cm and a thickness of 100 micron, an insulating film having a thickness of 600 nm was formed using a spin coater, and then a photocyclization (photocrosslinking) was carried out. The film was soaked in toluene for one hour, then the film was taken out to volatilize toluene at ordinary temperature, and the presence or absence of micro-cracks on the surface of the film was checked by observing the surface of the film using a shape-measurement laser microscope (VK-X100 manufactured by Keyence Corporation).

[0147] Hereinafter, Examples are shown. All of reaction, purification, and drying were carried out under yellow light or under shading. Note here that Examples were carried out under yellow light or under shading, in order to prevent photocyclization reaction of a photocyclizable compound and photocyclization reaction of a resin into which a photocyclizable compound has been introduced.

[0148] Irradiation was carried while the irradiation time was adjusted using SUS740 manufactured by USHIO INC.

[0149] Blade coating was carried out using Automatic film applicator 100-5 and a film applicator 064-13 having film thickness-adjustment function, manufactured by Allgood Co., Ltd.

[0150] A parylene dimer was put into PDS 2010 manufactured by Japan Parylene Limited Liability Company, and a film was formed by chemical vapor deposition.

[0151] To a washed and dried glass (substrate) (Eagle XG manufactured by Corning Inc.) having a size of 30×30 mm.sup.2, a xylene solution of a resin (3 wt %) was spin-coated under the conditions of 500 rpm×5 seconds and 1500 rpm×20 seconds, and dried at 50° C. for one minute to form a planarization film which had been irradiated with ultraviolet ray and cross-linked. Thereafter, irradiation of vacuum ultraviolet ray (VUV) was carried out via a photomask having chromium patterns having line-and-space of 5 micron to 50 micron to pattern the surface of the planarization film into a lyophilic region and a hydrophobic region. This substrate was set to a main body of an automatic film applicator that had been heated to 70° C., Ag nanoink was dropped thereto, and then applied by moving a film applicator having a film thickness adjustment function at a speed of 140 mm/s and baked at 120° C. for 30 minutes. All the formed patterns were observed. A value of a pattern having the minimum line-and-space among patterns formed without defects was made to be a resolution.

Example 1

[0152] In a nitrogen box, in 300-mL Schlenk tube, 5.0 g of polystyrene having a weight-average molecular weight of 280,000 (hereinafter, referred to as a “raw material polymer A”), 150 mL of dehydrated methylene chloride, and 4.0 g of cinnamic acid chloride were charged and dissolved at room temperature under stirring. Into a 30-mL dropping funnel equipped with a 3-way cock at the upper part, and sealed at the lower part, 9.0 g of trifluoromethanesulfonic acid (hereinafter, referred to as “TFMS”) was charged. The Schlenk tube and the dropping funnel mentioned above were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were linked to each other in a nitrogen sealed state. Flow of nitrogen to the Schlenk tube was stopped, and the 3-way cock in the upper part of the dropping funnel was linked to a calcium chloride tube, and the flow of nitrogen was stopped. Next, the Schlenk tube was cooled in ice water, and TFMS was dropped from the dropping funnel over 10 minutes. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 28 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 10.6 g of saturated sodium hydrogen carbonate was added to neutralize TFMS and hydrochloric acid in the system. The reacted product was transferred to a separation funnel and the methylene chloride layer was separated. Furthermore, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of a polymer. An operation of filtering the solution through 3-μm Teflon (registered trademark) filter, and precipitating again in 1.5 L of methanol, and isolating the polymer by filtration was carried out twice, followed by drying at 50° C. under reduced pressure to obtain 6.8 g of resin 1.

[0153] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 1 (the following formula) included 59% by mole and 41% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00023##

[0154] Note here that the .sup.1H-NMR of the resin 1 was shown in FIG. 2.

[0155] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 2.04 (brs, —CH.sub.2—CH—), 1.78 to 1.40 (bm, —CH.sub.2—)

[0156] To a washed and dried glass (substrate) (Eagle XG manufactured by Corning Inc.) having a size of 30×30 mm.sup.2, aluminum was deposited so as to form a gate electrode having a thickness of 50 nm. The substrate on which an electrode was formed was spin-coated with a toluene solution of the obtained resin 1 (3 wt %) under the conditions of 500 rpm×5 seconds and 1000 rpm×20 seconds, and dried at 50° C. for 5 minutes (formation of an insulating film), then irradiated with 250 mJ/cm.sup.2 of ultraviolet ray so as to form a cross-linked polymer dielectric layer having a film thickness of 520 nm. On the substrate on which a gate electrode and a polymer dielectric layer were formed, gold was deposited to form a source electrode and a drain electrode, having a thickness of 50 nm, a channel length of 100 μm and a channel width of 500 μm, were formed. Thereafter, immediately, the substrate was soaked in 30 mmol/L isopropanol solution of pentafluorobenzenethiol, taken out after 5 minutes had passed, washed with isopropanol, and blow-dried. Thereafter, 60 nL of 0.8 wt % toluene solution of an organic semiconductor (di-n-hexyldithienobenzodithiophene) printed by a dispenser. The solvent was volatilized and dried at 50° C. for one hour, and then a bottom-gate bottom-contact (BGBC) type organic field effect transistor device was prepared. Evaluation results of the prepared organic field effect transistor device are shown in Table 1.

TABLE-US-00001 TABLE 1 Polymer dielectric layer Organic field effect transistor (OFET) device performance Cross linking conditions On- Dielectric UV Surface current/ Leakage layer Film formation/drying irradiation roughness Solvent Threshold Mobility off- current Breakdown thickness Temperature Time Temperature Time Pressure amount Ra wettability Occurrence voltage [cm/ current density voltage Resin [nm] [° C.] [min] [° C.] [min] [Pa] [mJ/cm.sup.2] [nm] [Score] of crack [V] V .Math. s] [-] Hysteresis [nA] [MV/cm] Example 1 1 520 50 5 Room 1.0 Normal 250 0.2 5 Absent 1.2 0.36 10.sup.7 Absent 0.01 4.1 temperature pressure 2 2 510 50 5 Room 0.6 Normal 150 0.2 5 Absent 1.4 0.32 10.sup.7 Absent 0.01 4.1 temperature pressure 3 3 510 50 5 Room 0.9 Normal 230 0.2 5 Absent 1.1 0.35 10.sup.7 Absent 0.01 4.1 temperature pressure 4 4 510 50 5 Room 0.8 Normal 200 0.2 5 Absent 1.0 0.28 10.sup.7 Absent 0.01 4.1 temperature pressure 5 5 510 50 5 Room 1.0 Normal 250 0.2 5 Absent 1.4 0.30 10.sup.7 Absent 0.01 4.1 temperature pressure 6 6 510 50 5 Room 0.9 Normal 230 0.2 5 Absent 2.0 0.25 10.sup.7 Absent 0.01 4.1 temperature pressure 7 7 520 50 5 Room 0.8 Normal 200 0.2 5 Absent 1.5 0.32 10.sup.7 Absent 0.01 4.1 temperature pressure 8 8 510 50 5 Room 0.6 Normal 160 0.2 5 Absent 1.6 0.22 10.sup.7 Absent 0.01 4.1 temperature pressure 9 9 430 50 5 Room 0.4 Normal 100 0.2 5 Absent −7.7 0.3 10.sup.7 Absent 0.01 4.2 temperature pressure 10 10 430 50 5 Room 0.4 Normal 100 0.2 5 Absent −6.2 0.3 10.sup.7 Absent 0.01 4.2 temperature pressure 11 11 430 50 5 Room 0.4 Normal 100 0.2 5 Absent −7 0.3 10.sup.7 Absent 0.01 4.2 temperature pressure 12 12 540 50 5 Room 0.8 Normal 200 0.2 5 Absent 1.6 0.3 10.sup.7 Absent 0.01 4.2 temperature pressure 13 13 430 50 5 Room 0.4 Normal 100 0.3 5 Absent 1.2 0.36 10.sup.7 Absent 0.01 4.2 temperature pressure Comparative 1 14 510 50 5 Room 2.3 Normal 600 0.2 5 Present 1.5 0.23 10.sup.7 Absent 0.01 3.1 Example temperature pressure 2 15 520 50 5 Room 4.6 Normal 1200 03 5 Present 1 0.20 10.sup.7 Absent 0.01 3.1 temperature pressure 3 16 520 50 5 Room 3.1 Normal 800 0.3 5 Present 1.1 0.25 10.sup.7 Absent 0.01 3.1 temperature pressure 4 17 520 50 5 Room 4.2 Normal 1100 0.3 5 Present 1.1 0.30 10.sup.7 Absent 0.01 3.1 temperature pressure 5 18 520 50 5 Room 3.1 Normal 800 03 5 Present 1 0.30 10.sup.7 Absent 0.01 3.1 temperature pressure 6 19 530 50 5 Room 4.2 Normal 1100 0.3 5 Present 1.3 0.32 10.sup.7 Absent 0.01 3.1 temperature pressure 7 20 520 50 5 Room 3.1 Normal 800 0.3 5 Present 1.2 0.29 10.sup.7 Absent 0.01 3.1 temperature pressure 8 21 530 50 5 Room 4.6 Normal 1200 0.3 5 Present 1.1 0.29 10.sup.7 Absent 0.01 3.1 temperature pressure 9 22 530 50 5 Room 3.1 Normal 800 0.3 5 Present 1.1 0.29 10.sup.7 Absent 0.01 3.1 temperature pressure

[0157] The device was evaluated by setting a drain-source voltage V.sub.DS at −60 volts and varying a gate-source voltage. As a result, the mobility was 0.36 cm.sup.2/V.s, the leakage current was 0.01 nA, no hysteresis was observed in a source-drain current, the on-current/off-current ratio was 10.sup.7 or more, and the breakdown voltage was 4 MV/cm or more. Thus, the device was excellent in the leakage current, hysteresis, the on-current/off-current ratio, and breakdown voltage, and had no cracks in the organic semiconductor layer and insulating film. FIG. 3 shows that the hysteresis was not observed.

Example 2

[0158] In a nitrogen box, in 300-mL Schlenk tube, 10 g of raw material polymer A, 260 mL of dehydrated methylene chloride, and 19.2 g of cinnamic acid chloride were charged and dissolved at room temperature under stirring. Into a 100-mL dropping funnel equipped with a 3-way cock at the upper part, and sealed at the lower part, 26 g of TFMS was charged. The Schlenk tube and the dropping funnel mentioned above were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were linked to each other in a nitrogen sealed state. Flow of nitrogen to the Schlenk tube was stopped, and the 3-way cock in the upper part of the dropping funnel was linked to a calcium chloride tube, and the flow of nitrogen was stopped. Next, the Schlenk tube was cooled in ice water, and TFMS was dropped from the dropping funnel over 10 minutes. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 55 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 3.6 g of saturated sodium hydrogen carbonate was added to neutralize TFMS and hydrochloric acid in the system. The reacted product was transferred to a separation funnel and the methylene chloride layer was separated. Furthermore, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of a polymer. The solution was filtered through a 3-μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities, decolorized, and reprecipitated with 3 L of methanol. In addition, the polymer was reprecipitated and thereby purified, and dried at 50° C. under reduced pressure to obtain 18.2 g of resin 2.

[0159] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 2 (the following formula) included 30% by mole and 70% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00024##

[0160] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 2.04 (brs, —CH.sub.2—CH—), 1.78 to 1.40 (bm, —CH.sub.2—)

[0161] An insulating film was formed using the resin 2 produced in Example 2 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0162] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 3

[0163] A resin 3 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to coumarin -6-carboxylate chloride.

[0164] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 3 (the following formula) included 75% by mole and 25% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00025##

[0165] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.82 (brs, —CH═CH—C(O)—), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0166] An insulating film was formed using the obtained resin 3 in the same manner as in Example 1, and then, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0167] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 4

[0168] A resin 4 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylate chloride.

[0169] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 4 (the following formula) included 60% by mole and 40% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00026##

[0170] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.82 (brs, —CH═CH—C(O)—), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0171] An insulating film was formed using the obtained resin 4 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0172] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 5

[0173] A resin 5 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to pyridinylethenyl benzoic acid chloride.

[0174] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 5 (the following formula) included 72% by mole and 28% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00027##

[0175] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0176] An insulating film was formed using the obtained resin 5 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0177] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 6

[0178] A resin 6 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to pyridinylethenyl benzoic acid chloride.

[0179] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 6 (the following formula) included 58% by mole and 42% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00028##

[0180] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0181] An insulating film was formed using the obtained resin 6 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0182] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 7

[0183] A resin 7 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to phenylethenyl benzoic acid chloride.

[0184] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 7 (the following formula) included 60% by mole and 40 by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00029##

[0185] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0186] An insulating film was formed using the obtained resin 7 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0187] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 8

[0188] A resin 8 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to phenylethenyl benzoic acid chloride.

[0189] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 8 (the following formula) included 40% by mole and 60% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00030##

[0190] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0191] An insulating film was formed using the obtained resin 8 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0192] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 9

[0193] In a nitrogen box, in 300-mL Schlenk tube, 4.01 g of polystyrene-b-poly(ethylene/propylene)-b-polystyrene (SEPS) having a weight-average molecular weight of 150,000 and polystyrene content of 65 wt % (hereinafter, referred to as “raw material polymer B”), 150 mL of dehydrated methylene chloride, and 4.5 g of cinnamic acid chloride were charged and dissolved at room temperature under stirring. Next, the Schlenk tube was cooled to 0° C. or less, and 6.2 g of TFMS was dropped using a syringe. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 24 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 6.9 g of saturated sodium hydrogen carbonate was added to neutralize TFMS and hydrochloric acid in the system. The reacted product was transferred to a separation funnel and the methylene chloride layer was separated. Furthermore, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of a polymer. The solution was filtered through 3-μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities, decolorized, and reprecipitated with 1.5 L of methanol. In addition, the polymer was reprecipitated and thereby purified twice, and dried at 40° C. under reduced pressure to obtain 5.6 g of resin 9.

[0194] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 9 (the following formula) included 27% by mole and 29% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00031##

[0195] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.59 (brs, —CH═CH—Ph), 7.36 (brs, aromatic),6.99 (brs, aromatic), 6.45 (brs, —CH═CH—Ph), 1.90 to 1.00 (bm, —CH.sub.2—), 0.84 (bm, —CH.sub.3)

[0196] Excellent drawings were made in all line-and-space patterns of 5 to 50 micron, it was observed that the resolution was 5 micron. Furthermore, the surface roughness of the obtained film was 0.3 nm, and excellent planarity was exhibited.

[0197] To a washed and dried glass (substrate) (Eagle XG manufactured by Corning Inc.) having a size of 30×30 mm.sup.2, a xylene solution of the obtained resin 9 (3 wt %) was spin-coated under the conditions of 500 rpm×5 seconds and 1500 rpm×20 seconds, and dried at 50° C. for 5 minutes and irradiated with 100 mJ/cm.sup.2 ultraviolet ray to form an under-layer having a film thickness of 100 nm and cross-linked. Thereafter, irradiation of VUV was carried out via a photomask for 180 seconds to pattern the surface of the under-layer to have lyophilicity and liquid-repellency. The substrate was set to a main body of an automatic film applicator which had been heated to 70° C., Ag nanoink was dropped thereto, and applied by moving a film applicator having a film thickness adjustment function at a speed of 140 mm/s, and then baked at 120° C. for 30 minutes to form a source electrode and a drain electrode having a thickness of 500 nm, a channel length of 5 μm, a channel width of 500 μm, and an electrode width of 100 μm. Then, immediately, the substrate was soaked in an isopropanol solution of 30 mmol/L pentafluorobenzenethiol, taken out at the time 5 minutes had passed, washed with isopropanol, and blow-dried. Thereafter, 0.8 wt % xylene/tetralin mixture solution of an organic semiconductor (di-n-hexyl dithienobenzothiophene) was spin-coated so as to form a film. In order to volatilize a solvent, drying was carried out at 90° C. for 20 minutes. Thereafter, the obtained substrate and 0.6 g of a Parylene dimer were put into a vacuum evaporator, and heated in a vacuum to vaporize the Parylene dimer to polymerize on the substrate to form a gate insulating layer having a thickness of 430 nm and made of polyparaxylylene. Thereafter, irradiation with VUV was carried out via a photomask for 180 seconds to pattern the surface of the insulating film to have lyophilicity and hydrophobicity. The substrate was set to a main body of an automatic film applicator which had been heated to 70° C., Ag nanoink was dropped, applied at a speed of 140 mm/s, baked at 90° C. for 20 minutes to form a gate electrode having a thickness of 500 nm to prepare a top-gate bottom-contact (TGBC) type organic field effect transistor device. A configuration of the prepared organic field effect transistor is shown in FIG. 4, and evaluation results are shown in Table 1.

[0198] The device was evaluated by setting a drain-source voltage VDS at -60 volts and varying a gate-source voltage. As a result, the mobility was 0.3 cm.sup.2/V.s, the leakage current was 0.01 nA, no hysteresis was observed in a source-drain current, the on-current/off-current ratio was 10.sup.7 or more, and the breakdown voltage was 4 MV/cm or more. The device was excellent in the leakage current, hysteresis, on-current/off-current ratio, and breakdown voltage, and had no cracks in the organic semiconductor layer and the under-layer.

Example 10

[0199] In a nitrogen box, in 300-mL Schlenk tube, 4.01 g of raw material polymer B, 150 mL of dehydrated methylene chloride, and 5.99 g of cinnamic acid chloride were charged and dissolved at room temperature under stirring. Next, the Schlenk tube was cooled to 0° C. or less, and 8.2 g of TFMS was dropped using a syringe. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 25 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 9.14 g of saturated sodium hydrogen carbonate was added to neutralize TFMS and hydrochloric acid in the system. The reacted product was transferred to a separation funnel and the methylene chloride layer was separated. In addition, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of a polymer. The solution was filtered through 3-μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities, decolorized, and reprecipitated with 1.5 L of methanol. In addition, the polymer was reprecipitated and thereby purified, and dried at 40° C. under reduced pressure to obtain 6.0 g of resin 10.

[0200] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 10 (the following formula) included 21% by mole and 32% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00032##

[0201] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.59 (brs, —CH═CH—Ph), 7.36 (brs, aromatic), 6.99 (brs, aromatic), 6.45 (brs, —CH═CH—Ph), 1.90 to 1.00 (bm, —CH.sub.2—), 0.84 (bm, —CH.sub.3)

[0202] Evaluation was carried out in the same manner as in Example 9. It was demonstrated that excellent drawings are made in all line-and-space pattern of 5 to 50 micron, and resolution of 5 micron. The surface roughness of the obtained film was 0.3 nm, thus exhibiting excellent planarity.

[0203] A top-gate bottom-contact (TGBC) type organic field effect transistor device was prepared in the same manner as in Example 9. Evaluation results of the prepared organic field effect transistor are also shown in Table 1.

[0204] As in Example 9, excellent performance as the organic field effect transistor device was observed.

Example 11

[0205] In a nitrogen box, in 300-mL Schlenk tube, 3.0 g of raw material polymer B, 150 mL of dehydrated methylene chloride, and 6.3 g of cinnamic acid chloride were charged and dissolved at room temperature under stirring. Next, the Schlenk tube was cooled to 0° C. or less, and 8.44 g of TFMS was dropped using a syringe. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 29 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 9.45 g of saturated sodium hydrogen carbonate was added to neutralize TFMS and hydrochloric acid in the system. The reacted product was transferred to a separation funnel and the methylene chloride layer was separated. Furthermore, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of a polymer. The solution was filtered through 3-μm Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities, decolorized, and reprecipitated with 1.5 L of methanol. In addition, the polymer was reprecipitated and thereby purified, and dried at 40° C. under reduced pressure to obtain 4.9 g of resin 11.

[0206] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 11 (the following formula) included 17% by mole and 39% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00033##

[0207] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.59 (brs, —CH═CH—Ph), 7.36 (brs, aromatic), 6.99 (brs, aromatic), 6.45 (brs, —CH═CH—Ph), 1.90 to 1.00 (bm, —CH.sub.2—), 0.84 (bm, —CH.sub.3)

[0208] Evaluation was carried out in the same manner as in Example 9. It was demonstrated that excellent drawings are made in all line-and-space pattern of 5 to 50 micron, and resolution of 5 micron. The surface roughness of the obtained film was 0.3 nm, thus exhibiting excellent planarity.

[0209] A top-gate bottom-contact (TGBC) type organic field effect transistor device was prepared in the same manner as in Example 9. Evaluation results of the prepared organic field effect transistor are also shown in Table 1.

[0210] As in Example 9, excellent performance as the organic field effect transistor device was observed.

Example 12

[0211] In a nitrogen box, in 300-mL Schlenk tube, 10 g of the raw material polymer A, 260 mL of dehydrated methylene chloride, and 19.2 g of cinnamic acid chloride were charged and dissolved at room temperature under stirring. Into a 100-mL dropping funnel equipped with a 3-way cock at the upper part and sealed at the lower part, 26 g of TFMS was charged. The Schlenk tube and the dropping funnel mentioned above were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were linked to each other in a nitrogen sealed state. Flow of nitrogen to the Schlenk tube was stopped, and the 3-way cock in the upper part of the dropping funnel was linked to a calcium chloride tube, and the flow of nitrogen was stopped. Next, the Schlenk tube was cooled in a low-temperature incubator, and TFMS was dropped from the dropping funnel over 10 minutes under stirring with a magnetic stirrer. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, reaction was performed at 1° C. for 55 hours. From 360 mL of a saturated aqueous solution dissolving 36 g of saturated sodium hydrogen carbonate, 100 mL of the solution was dropped slowly. The remaining saturated sodium hydrogen carbonate solution was put into a 1-L beaker, and cooled by adding 100 g of ice thereto. To the beaker, a reaction solution was poured, and the reaction solution was stirred for 2 hours, and then transferred to a separation funnel to separate a methylene chloride layer. In addition, a water layer was washed with methylene chloride three times, separated to obtain a methylene chloride solution of a polymer. An operation of reprecipitating this polymer solution with 3 L of methanol was carried out twice, and then the obtained solution was filtered and dried at 50° C. under reduced pressure to obtain 17.9 g of resin 12.

[0212] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 12 (the following formula) included 36.5% by mole, 62.5% by mole, and 1.0% by mole of the structural units represented by the formulae (1), (2), and (18), respectively.

##STR00034##

[0213] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), δ4.5 (brs, —C(O)CH.sub.2—CH(Ph)—), δ2.57 (brs, —C(O)CH.sub.2—CH(Ph)—), δ3.14 (brs, —C(O)CH.sub.2—CH(Ph)—), 2.04 (brs, —CH.sub.2—CH—),1.78 to 1.40 (bm, —CH.sub.2—)

[0214] An insulating film was formed using the obtained resin 12 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0215] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

Example 13

[0216] In a nitrogen box, in a 300-mL Schlenk tube, 1.1 g of the raw material polymer B, 30 mL of dehydrated methylene chloride, and 1.3 g of 3-(perfluorohexyl)propionyl chloride were charged and dissolved at room temperature under stirring. Next, the Schlenk tube was cooled in ice water, and 1.2 g of TFMS was dropped using a syringe under the flow of nitrogen. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 48 hours. The reaction solution was cooled in ice water again, and then an aqueous solution dissolving 1.2 g of sodium hydrogen carbonate was dropped so as to neutralize TFMS and hydrochloric acid in the system. The reacted solution was transferred to a separation funnel, and the water phase was separated. Furthermore, a methylene chloride phase was washed with water three times, and separated to obtain a methylene chloride solution of a polymer. The solution was reprecipitated in 300 mL of methanol. In addition, the polymer was reprecipitated and thereby purified twice, and dried at 40° C. under reduced pressure to obtain 1.7 g of resin 13-a (the following formula).

##STR00035##

[0217] In addition, in a nitrogen box, 100-mL Schlenk tube was charged with 1.0 g of the obtained resin 13-a, 40 mL of dehydrated methylene chloride, and 0.59 g of cinnamic acid chloride were charged, and dissolved at room temperature under stirring. Next, the Schlenk tube was cooled in ice water, and 1.3 g of TFMS was dropped using a syringe under the flow of nitrogen. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 48 hours. The reaction solution was cooled in ice water again, and then an aqueous solution dissolving 1.2 g of sodium hydrogen carbonate was dropped so as to neutralize TFMS and hydrochloric acid in the system. The reacted solution was transferred to a separation funnel, and the water phase was separated. Furthermore, a methylene chloride phase was washed with water three times, and separated to obtain a methylene chloride solution of a polymer. The solution was reprecipitated in 350 mL of methanol. In addition, the polymer was reprecipitated and thereby purified twice, and dried at 40° C. under reduced pressure to obtain 1.1 g of resin 13.

[0218] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 1 (the following formula) included 3% by mole, 29% by mole, and 24% by mole of the structural units represented by the formulae (1), (2), and (19), respectively.

##STR00036##

[0219] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, aromatic, —CH═CH—Ph), 7.39 to 6.51 (m, aromatic, —CH═CH—Ph), 3.12 (brs, —CH.sub.2—C(═O)—), 2.52(brs, —CF.sub.2—CH.sub.2—), 1.90 to 1.00 (bm, —CH.sub.2—), 0.84 (bm, —CH.sub.3)

[0220] An insulating film was formed using the obtained resin 13 in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0221] As in Example 1, excellent performance as the organic field effect transistor device was demonstrated.

[0222] Evaluation was carried out in the same manner as in Example 9. It was demonstrated that excellent drawings are made in all line-and-space pattern of 5 to 50 micron, and resolution of 5 micron. The surface roughness of the obtained film was 0.3 nm, thus exhibiting excellent planarity.

Comparative Example 1

[0223] In a nitrogen box, in a 300-mL Schlenk tube, 5.0 g of raw material polymer A, 150 mL of dehydrated methylene chloride, and 3.9 g of anhydrous aluminum chloride were charged and dissolved at room temperature under stirring. Into a 300-mL dropping funnel equipped with a 3-way cock at the upper part and sealed at the lower part, 30 mL of methylene chloride solution of 4.0 g of cinnamic acid chloride was charged. The Schlenk tube and the dropping funnel mentioned above were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were linked to each other in a nitrogen sealed state. Flow of nitrogen to the Schlenk tube was stopped, and the 3-way cock in the upper part of the dropping funnel was linked to a calcium chloride tube, and the flow of nitrogen was stopped. Next, the Schlenk tube was cooled in ice water, and cinnamic acid chloride was dropped from the dropping funnel over 10 minutes. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 28 hours. The reaction solution was cooled in ice water again, and then 20 mL of 35% hydrochloric acid aqueous solution was dropped. Stirring was carried out in this state for 5 hours, and then the reaction solution was transferred to a separation funnel to separate a methylene chloride layer. The methylene chloride layer was washed with water four times repeatedly. The water layer was extracted with methylene chloride three times, and separated. An operation of combining the obtained methylene chloride layer thereto, filtering the resultant through 3-μm Teflon (registered trademark) filter to reprecipitate 1.5 L of methanol, and isolating the polymer by filtration was carried out twice, followed by drying at 50° C. under reduced pressure to obtain 5.9 g of resin 14.

[0224] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 14 (the following formula) included 86% by mole and 14% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00037##

[0225] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, —CH═CH—Ph),7.39 to 6.51(m, aromatic, —CH═CH—Ph), 2.04 (brs, —CH.sub.2—CH—), 1.78 to 1.40 (bm, —CH.sub.2—)

[0226] The organic field effect transistor device was prepared using the obtained resin in the same manner as in Example 1. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0227] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 2

[0228] In a nitrogen box, a 300-mL Schlenk tube was charged with 5.0 g of raw material polymer A, 150 mL of dehydrated methylene chloride, and 1.2 g of anhydrous aluminum chloride. A 30-mL dropping funnel, equipped with a 3-way cock at the upper part, and sealed at the lower part, was charged with a solution in which 1.3 g of cinnamic acid chloride was dissolved in 20 mL of methylene chloride solution. The Schlenk tube and the dropping funnel mentioned above were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were linked to each other in a nitrogen sealed state. Flow of nitrogen to the Schlenk tube was stopped, and the 3-way cock in the upper part of the dropping funnel was linked to a calcium chloride tube, and the flow of nitrogen was stopped. Next, the Schlenk tube was cooled in ice water, and cinnamic acid chloride was dropped from the dropping funnel over 10 minutes. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 28 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 2.1 g of saturated sodium hydrogen carbonate was added to neutralize hydrochloric acid in the system. The reacted product was transferred to a separation funnel, and a methylene chloride layer was separated. In addition, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of the polymer. An operation of filtering the solution through 3-μm Teflon (registered trademark) filter, and precipitating again in 1.5 L of methanol, and isolating the polymer by filtration was carried out twice, followed by drying at 50° C. under reduced pressure to obtain 4.7 g of resin 15.

[0229] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 15 (the following formula) included 92% by mole and 8% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00038##

[0230] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, —CH═CH—Ph),7.39 to 6.51(m, aromatic, —CH═CH—Ph), 2.04 (brs, —CH.sub.2—CH—), 1.78 to 1.40 (bm, —CH.sub.2—)

[0231] The organic field effect transistor device was prepared using the obtained resin in the same manner as in Example 1. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0232] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 3

[0233] In a nitrogen box, a 300-mL Schlenk tube was charged with 5 g of raw material polymer A, 150 mL of dehydrated methylene chloride, and 2.2 g of anhydrous aluminum chloride. A 20-mL dropping funnel, equipped with a 3-way cock at the upper part, and sealed at the lower part, was charged with a solution in which 2.3 g of cinnamic acid chloride was dissolved in 50 mL of methylene chloride solution. The Schlenk tube and the dropping funnel mentioned above were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were linked to each other in a nitrogen sealed state. Flow of nitrogen to the Schlenk tube was stopped, and the 3-way cock in the upper part of the dropping funnel was linked to a calcium chloride tube, and the flow of nitrogen was stopped. Next, the Schlenk tube was cooled in ice water, and cinnamic acid chloride was dropped from the dropping funnel over 9 minutes. With dropping, the color of the polymer solution was changed to reddish purple. After completion of dropping, the ice water bath was removed, and reaction was performed at room temperature for 28 hours. The reaction solution was cooled in ice water again, and then a saturated aqueous solution dissolving 3.9 g of saturated sodium hydrogen carbonate was added to neutralize hydrochloric acid in the system. The reacted product was transferred to a separation funnel, and a methylene chloride layer was separated. In addition, a water layer was washed with methylene chloride three times, and separated to obtain a methylene chloride solution of the polymer. An operation of filtering the solution through 3-μm Teflon (registered trademark) filter, and precipitating again in 1.5 L of methanol, and isolating the polymer by filtration was carried out twice, followed by drying at 50° C. under reduced pressure to obtain 4.9 g of resin 16.

[0234] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 16 (the following formula) included 87% by mole and 13% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00039##

[0235] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.62 (brs, —CH═CH—Ph),7.39 to 6.51(m, aromatic, —CH═CH—Ph), 2.04 (brs, —CH.sub.2—CH—), 1.78 to 1.40 (bm, —CH.sub.2—)

[0236] The organic field effect transistor device was prepared using the obtained resin in the same manner as in Example 1. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0237] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 4

[0238] A resin 17 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylate chloride. Analysis results of .sup.1H-NMR (400 MHz, CDCl.sub.3) and a structural formula of the polymer are shown below.

[0239] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 17 (the following formula) included 94% by mole and 6% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00040##

[0240] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.82 (brs, —CH═CH—C(O)—), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0241] An insulating film was formed using the obtained resin 3 in the same manner as in Example 1, and then, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0242] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 5

[0243] A resin 18 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylate chloride.

[0244] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 18(the following formula) included 88% by mole and 12% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00041##

[0245] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.82 (brs, —CH═CH—C(O)—), 7.70 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0246] An insulating film was formed using the obtained resin in the same manner as in Example 1, and then, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0247] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 6

[0248] A resin 19 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to pyridinylethenyl benzoic acid chloride.

[0249] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 19 (the following formula) included 94% by mole and 6% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00042##

[0250] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0251] An insulating film was formed using the obtained resin in the same manner as in Example 1, and then the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0252] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 7

[0253] A resin 20 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to pyridinylethenyl benzoic acid chloride.

[0254] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 20 (the following formula) included 86% by mole and 14% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00043##

[0255] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.80 (brs, Py—CH═CH—), 7.76 to 6.60 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0256] An insulating film was formed using the obtained resin in the same manner as in Example 1, and then the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0257] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 8

[0258] A resin 21 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to phenylethenyl benzoic acid chloride.

[0259] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 21 (the following formula) included 95% by mole and 5% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00044##

[0260] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

[0261] An insulating film was formed using the obtained resin in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0262] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

Comparative Example 9

[0263] A resin 22 was obtained in the same manner as in Comparative Example 1 except that cinnamic acid chloride was changed to phenylethenyl benzoic acid chloride.

[0264] The results of analysis by .sup.1H-NMR demonstrated that the obtained resin 22 (the following formula) included 85% by mole and 15% by mole of the structural units represented by the formulae (1) and (2), respectively.

##STR00045##

[0265] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ7.67 (brs, —CH═CH—), 7.10 to 6.32 (m, aromatic, —CH═CH—Ph), 2.15 (brs, —CH.sub.2—CH—), 1.90 to 1.48 (bm, —CH.sub.2—)

An insulating film was formed using the obtained resin in the same manner as in Example 1, the organic field effect transistor device was prepared. Evaluation results etc. of the prepared organic field effect transistor device are also shown in Table 1.

[0266] It was demonstrated that cross-linking time, solvent resistance (cracking resistance), and breakdown voltage were inferior to those in Examples 1 to 8.

[0267] Although the present invention has been described in detail and with reference to specific embodiments, it is clear to a person skilled in the art that various changes and modifications can be made without departing from the nature and scope of the present invention.

[0268] The entire content of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2017-051670 filed on Mar. 16, 2017, No. 2017-199489 filed on Oct. 13, 2017, No. 2018-011579 filed on Jan. 26, 2018, No. 2018-011580 filed on Jan. 26, 2018 is incorporated herein by reference as the disclosure of the specification of the present invention.

PHOTOCROSSLINKABLE POLYMER, INSULATING FILM, PLANARIZATION FILM, LYOPHILIC/LIQUID REPELLENT PATTERNED FILM, AND ORGANIC FIELD EFFECT TRANSISTOR DEVICE COMPRISING SAME

Assignee

Inventors

Cpc classification

Classification Explorer

C08F112/08

CHEMISTRY; METALLURGY

Classification Explorer

C08F8/18

CHEMISTRY; METALLURGY

Classification Explorer

C08J2353/00

CHEMISTRY; METALLURGY

Classification Explorer

C08J5/18

CHEMISTRY; METALLURGY

Classification Explorer

H01B3/307

ELECTRICITY

Classification Explorer

H10K85/111

ELECTRICITY

Classification Explorer

C08F2810/50

CHEMISTRY; METALLURGY

Classification Explorer

H10K85/151

ELECTRICITY

Classification Explorer

C08F212/26

CHEMISTRY; METALLURGY

Classification Explorer

C08F8/04

CHEMISTRY; METALLURGY

Classification Explorer

C09D125/18

CHEMISTRY; METALLURGY

Classification Explorer

C08J2325/06

CHEMISTRY; METALLURGY

Classification Explorer

C08F8/18

CHEMISTRY; METALLURGY

Classification Explorer

C08F212/08

CHEMISTRY; METALLURGY

Classification Explorer

C08F212/22

CHEMISTRY; METALLURGY

Classification Explorer

C08F212/32

CHEMISTRY; METALLURGY

Classification Explorer

H10K85/6576

ELECTRICITY

Classification Explorer

C08F8/48

CHEMISTRY; METALLURGY

Classification Explorer

C08F8/10

CHEMISTRY; METALLURGY

Classification Explorer

C08F212/22

CHEMISTRY; METALLURGY

Classification Explorer

C08F297/046

CHEMISTRY; METALLURGY

Classification Explorer

C08F212/08

CHEMISTRY; METALLURGY

Classification Explorer

C08F8/48

CHEMISTRY; METALLURGY

Classification Explorer

C08F112/08

CHEMISTRY; METALLURGY

Classification Explorer

C08F297/00

CHEMISTRY; METALLURGY

Classification Explorer