Components for forming protective film

Abstract

To provide a composition for forming a protective film capable of preventing reduction of performance without damaging an organic semiconductor.SOLUTION: A composition for forming a protective film includes: a fluorine-based resin including 30 mol% or more of at least one of (meth)acrylates having a specific perfluoroalkyl group, a perfluoroalkylene group, or a double bond containing a conjugated bond on its side chain; and a fluorine-based solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a protective film that is suitable for forming a film by coating on an organic semiconductor film. [Background technology]

[0002] In recent years, technological developments have been actively pursued for the low-cost, highly productive fabrication of organic electronic devices using all-printing methods. One example of such electronic devices is the development of organic transistors. These organic transistors are manufactured through a number of processes, including a process in which a protective resin film protects the organic transistor and forms a pattern of an EL light-emitting element. This pattern is formed to cover, for example, the source electrode, the drain electrode, and the organic semiconductor layer or polymer layer, but is not present on the electrodes that form the EL light-emitting element.

[0003] Typically, the EL light-emitting section is formed using photolithography, a technique in which a substrate surface coated with a photosensitive material (resist) is exposed to a pattern through a photomask or reticle to form a pattern consisting of exposed and unexposed areas, and the EL light-emitting section is then opened using dry etching or wet etching.

[0004] There is a demand for a material that can be patterned by photolithography, which can be used to apply an ink containing the material to open the EL light-emitting area, dry it, and then become insoluble in solvents through photocrosslinking at room temperature and short-term exposure.

[0005] Patent Document 1 lists such materials, including a negative photosensitive resin composition that is highly photoreactive, allows for patterning, and can form a coating with excellent dielectric properties, as well as a photocured pattern produced from the composition. However, this resin is an alkali-soluble polymer, and requires the use of water during development. Furthermore, the composition requires the use of an organic solvent such as xylene or PGMEA (1-methoxy-2-propanol acetate). Organic solvents and water can degrade the performance of electronic devices, so solubility in a fluorine-containing solvent is necessary.

[0006] To prevent the performance of electronic devices from being reduced by water or organic solvents, there is a method for forming patterns using fluorine-based resins that are soluble in fluorine solvents, as described in Patent Document 2 and Non-Patent Document 1. However, there is a problem with fluorine-based resins that are not photocrosslinkable.

[0007] Examples of fluororesins that dissolve in fluorine solvents and undergo photocrosslinking include fluororesins that use anthracene crosslinking groups, such as those described in Non-Patent Document 2. However, because they are soluble in fluorine solvents, they have a problem of a high proportion of fluorine residues and low crosslinkability.

[0008] One method for increasing solubility in fluorine solvents is to use compounds having eight or more perfluoroalkyl groups, but their use is being reconsidered due to their potential for accumulation in the environment and the human body, as well as their harmfulness, and as a result, studies are being conducted to replace them with compounds having perfluoroalkyl groups with six or fewer carbon atoms (see, for example, Patent Document 3 or Patent Document 4).

[0009] Given the above background, there has been a demand for a composition that is a compound containing a perfluoroalkyl group having six or fewer carbon atoms, yet is highly soluble in fluorine solvents, and can be made insoluble in solvents by photocrosslinking with exposure to light, allowing for pattern formation, while preventing a decrease in the performance of electronic devices. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] JP 2017-167513 A [Patent Document 2] Patent No. 6281427 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-185869 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-006273 [Non-patent literature]

[0011] [Non-Patent Document 1] Appl. Phys. Express 7, 101602 (2014) [Non-patent document 2] J Polym Sci A Polym Chem 53, 1252(2015) Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above problems, and an object of the present invention is to provide a composition for forming a protective film that can prevent a decrease in performance without damaging an organic semiconductor. [Means for solving the problem]

[0013] As a result of intensive research into solving the above problems, the inventors have found that the above problems can be solved by using the protective film-forming composition shown below, and have thus completed the present invention.

[0014] That is, the present invention provides a composition for forming a protective film, comprising a fluorine-based resin and a fluorine-based solvent, characterized in that the composition contains 30 mol % or more of at least one member selected from the group consisting of a residue unit represented by formula (1), a residue unit represented by formula (2), or a residue unit represented by formula (3).

[0015] [ka]

[0016] [ka]

[0017] [ka]

[0018] In formulas (1) to (3), R1 represents one of the group consisting of a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. Rf1 represents one of the group consisting of a linear perfluoroalkyl group having 1 to 6 carbon atoms and having a terminal CF3, a branched perfluoroalkyl group having 3 to 6 carbon atoms and having a terminal CF3, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms and having a terminal CF3. Rf2 represents one of the group consisting of a linear perfluoroalkylene group having 1 to 6 carbon atoms, a branched perfluoroalkylene group having 3 to 6 carbon atoms, or a cyclic perfluoroalkylene group having 3 to 6 carbon atoms. Rf3 represents one of the group consisting of a linear perfluoroalkylene group having 1 to 6 carbon atoms, a branched perfluoroalkylene group having 3 to 6 carbon atoms, or a cyclic perfluoroalkylene group having 3 to 6 carbon atoms. Rf4 represents a linear perfluoroalkyl group having 1 to 5 carbon atoms and having CF3 at its terminal, a branched perfluoroalkyl group having 3 to 5 carbon atoms and having CF3 at its terminal, or a cyclic perfluoroalkyl group having 3 to 5 carbon atoms and having CF3 at its terminal. Rf4 represents a linear perfluoroalkylene group having 1 to 5 carbon atoms, a branched perfluoroalkylene group having 3 to 5 carbon atoms, or a cyclic perfluoroalkylene group having 3 to 5 carbon atoms. R2 to R5 each independently represent a hydrogen atom or a fluorine atom. n represents an integer of 1 to 5. X represents one member of the group consisting of a single bond, CH2, an oxygen atom, or a sulfur atom. L represents a linking group. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a protective film-forming composition that is soluble in a fluorine solvent and becomes insoluble in the solvent by photocrosslinking at room temperature with a low exposure dose, and that can form a pattern while preventing a decrease in the performance of the electronic device, and an electronic device using the same. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a diagram showing the cross-sectional shape of an organic transistor. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be described in detail below.

[0022] The composition for forming a protective film of the present invention contains a fluorine-based resin containing 30 mol % or more of at least one member selected from the group consisting of a residue unit represented by formula (1), a residue unit represented by formula (2), or a residue unit represented by formula (3), and a fluorine-based solvent.

[0023] The composition for forming a protective film in the present invention contains a fluorine-based resin containing 30 mol % or more of at least one member selected from the group consisting of a residue unit represented by formula (1), a residue unit represented by formula (2), and a residue unit represented by formula (3), which allows the resin to dissolve in a fluorine-based solvent.

[0024] The resin composition for forming a protective film of the present invention contains a fluorine-based solvent, which allows a pattern to be formed on the organic semiconductor without damaging it.

[0025] In formulas (1) to (3), R1 represents a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. Rf1 represents a C1-6 linear perfluoroalkyl group having a terminal CF3, a C3-6 branched perfluoroalkyl group having a terminal CF3, or a C3-6 cyclic perfluoroalkyl group having a terminal CF3. Rf2 represents a C1-6 linear perfluoroalkylene group, a C3-6 branched perfluoroalkylene group, or a C3-6 cyclic perfluoroalkylene group. Rf3 represents a C1-5 linear perfluoroalkyl group having a terminal CF3, a C3-5 branched perfluoroalkyl group having a terminal CF3, or a C3-5 cyclic perfluoroalkyl group having a terminal CF3. Rf4 represents a linear perfluoroalkylene group having 1 to 5 carbon atoms, a branched perfluoroalkylene group having 3 to 5 carbon atoms, or a cyclic perfluoroalkylene group having 3 to 5 carbon atoms. R2 to R5 each independently represent a hydrogen atom or a fluorine atom. n represents an integer of 1 to 5. X represents one member of the group consisting of a single bond, CH2, an oxygen atom, or a sulfur atom. L represents a linking group.

[0026] The residue units represented by formulas (1) to (3) contain fluorine atoms, which gives the fluororesin high affinity with fluorine solvents. Furthermore, because formulas (1), (2), and (3) have ester bonds, which are polar groups, adjacent to the main chain, the fluororesin film formed by coating is highly flexible, and a flat, crack-free fluororesin film can be obtained. Furthermore, because the side chains contain fluorinated hydrocarbon groups, the fluororesin has excellent solubility in fluorine solvents.

[0027] Specific structures of the Rf1-(CR3=CR2-X-Rf2)n- moiety in formula (1) and formula (2) include, for example, C2F5-CH=CH-C4F8-, C2F5-CH=CF-C4F8-, C2F5-CF=CH-C4F8-, C2F5-CF=CF-C4F8-, C2F5-(CH=CH-C4F8)2-, C2F5-(CH=CH-C4F8)3-, C2F5-CH=CH-C6F12-, C4F9-CH=CH-C4F8-, C4F9-CH=CH-C6F12, C6F13-CH=CH-C4F8-, C6F13-CH=CH-C6F12-, C2F5-CH=CH-C4F8-, CF3-CF=CHCH2C4 F8-, CF3-CF=CHCH2C6F12-, C3F7-CF=CHCH2C4F8-, C3F7-CF=CHCH2C6F12-, C5F11-CF=CHCH2C4F8-, C5F11-CF=CHCH2C6F12-, C2F5-CH2CH=CF-C3F6-, C2F5-CH2CH=CF-C5F10-, C4F9-CH2CH=CF-C3F6-, C4F9-CH2CH=CF-C5F10-, C6F13-CH2CH=CF-C3F6-, C6F13-CH2CH=CF-C5F10-, C6F13-(CH2CH=CF-C3F6)2-, C6F13-(CH2CH=CF-C3F6)3- and the like.

[0028] In the present invention, the linking group L is preferably represented by the following general formula (4) because it can be easily synthesized.

[0029] [ka]

[0030] Here, in formula (4), the sum of l and m is an integer of 2 to 6, and when l and / or m is 2 or more, it may contain a -CH=CH- structure instead of -CH2CH2-.

[0031] Q is a single bond, -OCONH-, -CONH-, -O-, -NH-, -CO-O-, -O-CO-, -NHCONH- or -C6H4-. When Q is -C6H4-, examples of the isomer include the ortho isomer, meta isomer and para isomer, with the para isomer being preferred.

[0032] In the fluororesin, the Rf3 group in the residue unit represented by formula (3) is preferably a linear perfluoroalkyl group having 1 to 5 carbon atoms and having a CF3 terminal. This makes it easier to form a self-associated structure. The Rf4 group is preferably a linear perfluoroalkylene group having 1 to 5 carbon atoms.

[0033] Specific structures of the Rf3-(CF=CR5-CR4=CF-Rf4)n- moiety in formula (3) include, for example, CF3-CF=CH—CH=CF-C3F6-, CF3-CF=CH—CH=CF-C5F10-, C3F7-CF=CH—CH=CF-C3F6-, C3F7-CF=CH—CH=CF-C5F10-, C5F11-CF=CF—CH=CF-C5F10-, C5F11-CF= CH―CF=CF-C5F10-, C5F11-CF=CF―CF=CF-C5F10-, C5F11-CF=CH―CH=CF-C3F6-, C5F11-CF=CH―CH=CF-C5F10- , CF3-(CF=CH-CH=CF-C5F10)2-, C3F7-(CF=CH-CH=CF-C5F10)2-, C5F11-(CF=CH-CH=CF-C5F10)2-, and the like.

[0034] In formula (3), R4 and / or R5 are preferably hydrogen atoms.

[0035] Specific examples of the residue unit represented by formula (1) include the following structures:

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] Specific examples of the residue unit represented by formula (2) include the following structures:

[0040] [ka]

[0041] Specific examples of the residue unit represented by formula (3) include the following structures:

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] The fluorine-based resin contained in the protective film-forming composition of the present invention contains one or more repeating units represented by formulas (1) to (3) and may also contain repeating units having structures other than those represented by formulas (1) to (3).

[0046] The fluorine-based resin contained in the composition for forming a protective film of the present invention has sufficient solubility in fluorine-based solvents and therefore contains 30 mol % or more, more preferably 40 mol % or more, of repeating units represented by formulas (1) to (3).

[0047] The fluorine-based solvent contained in the composition for forming a protective film of the present invention may be any solvent that can dissolve the above-mentioned fluorine-based resin.

[0048] The fluorine content of the fluorine-based solvent is not particularly limited, but to ensure rapid dissolution, it should be 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 80% by mass or less, and more preferably 65% ​​by mass or more and 80% by mass or less, based on the total mass of the fluorine-based solvent. If the fluorine content exceeds 90% by mass, the fluorine-based resin will not dissolve sufficiently. If the fluorine content is less than 50% by mass, the surface of the organic semiconductor film may dissolve or swell when applied or printed on the organic semiconductor film. As the fluorine-based solvent contained in the composition for forming a protective film of the invention, the following fluorine-containing hydrocarbons, fluorine-containing ethers, or fluorine-containing alcohols can be preferably used.

[0049] Fluorine-containing hydrocarbons have a low ozone depletion potential and are therefore preferred as fluorine-based solvents contained in the protective film-forming composition of the present invention. In particular, linear, branched, or cyclic hydrocarbons having 4 to 8 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom are preferred because they are easy to apply.

[0050] Specific examples of such fluorine-containing hydrocarbons include butane, pentane, hexane, heptane, octane, cyclopentane, and cyclohexane in which at least one hydrogen atom has been substituted with a fluorine atom.Specific examples include fluorine-containing hydrocarbons such as 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 2H,3H-decafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, hexafluorocyclopentane, and 1,1,2,2,3,3,4-heptafluorocyclopentane.

[0051] The boiling point of the fluorine-containing hydrocarbon must be higher than the substrate temperature when the protective film-forming composition is applied, preferably at least 20°C higher than the substrate temperature, more preferably at least 50°C higher. If the boiling point of the fluorine-containing hydrocarbon is lower than the substrate temperature when the protective film-forming composition is applied, the fluorine-containing hydrocarbon will rapidly volatilize during the application process, making it difficult to obtain a fluorine-based resin film with sufficient flatness. Furthermore, the fluorine-containing hydrocarbon used preferably has a boiling point of 60°C or higher and 200°C or lower, more preferably 80°C or higher and 180°C or lower. If the boiling point of the fluorine-containing hydrocarbon is 60°C or higher and 200°C or lower, the fluorine-containing hydrocarbon can be easily evaporated and removed by heating from the fluorine-based resin film formed by applying the protective film-forming composition.

[0052] Among the above-mentioned fluorine-containing hydrocarbons, the following can be given as examples having particularly preferable boiling points.

[0053] Examples include 2H,3H-decafluoropentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane.

[0054] Furthermore, due to its low ozone depletion potential, a fluorinated ether can be used as the fluorine-based solvent. In particular, the boiling point of the fluorinated ether must be higher than the substrate temperature when the protective film-forming composition is applied, preferably 20°C or more higher, more preferably 50°C or more higher than the substrate temperature. If the boiling point of the fluorinated ether is lower than the substrate temperature when the protective film-forming composition is applied, the fluorinated aliphatic ether will rapidly volatilize during the application process, making it difficult to obtain sufficient flatness in the fluorine-based resin film that is formed. Furthermore, the boiling point of the fluorine-containing ether used is preferably 200°C or less, more preferably 180°C or less. If the boiling point of the fluorinated ether is 200°C or less, the fluorine-containing ether can be easily evaporated and removed by heating from the fluorine-based resin film formed by applying the protective film-forming composition.

[0055] Examples of preferred fluorine-containing ethers include 1,1,2,3,3,3-hexafluoro-1-(2,2,2-trifluoroethoxy)propane, 1,1,2,3,3,3-hexafluoro-1-(2,2,3,3,3-pentafluoropropoxy)propane, 1,1,2,3,3,3-hexafluoro-1-(2,2,3,3-tetrafluoropropoxy)propane, 2,2,3,3,3-pentafluoro-1-(1,1,2,2-tetrafluoroethoxy)propane, 1,1,1,2,2,3,3-heptafluoro- Examples of such fluorocarbons include 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, (1,1,1,2,3,3-hexahexafluoropropoxy)pentane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, and methoxyperfluoroheptene.

[0056] Examples of fluorine-containing ethers having a preferred boiling point include ethyl nonafluorobutyl ether, methyl perfluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, (1,1,1,2,3,3-hexahexafluoropropoxy)pentane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, and methoxyperfluoroheptene.

[0057] Furthermore, since it can be applied evenly by a coating method such as spin coating, a fluorine-containing alcohol can be used as the fluorine-based solvent. In particular, the boiling point of the fluorine-containing alcohol must be higher than the substrate temperature when the protective film-forming composition is applied, preferably 20°C or more higher than the substrate temperature, more preferably 50°C or more higher. If the boiling point of the fluorine-containing alcohol is lower than the substrate temperature when the protective film-forming composition is applied, the fluorine-containing aliphatic alcohol will rapidly volatilize during the application process, making it difficult to obtain sufficient flatness in the fluorine-based resin film that is formed. Furthermore, the boiling point of the fluorine-containing alcohol used is preferably 200°C or less, more preferably 180°C or less. If the boiling point of the fluorine-containing alcohol is 200°C or less, the fluorine-containing alcohol can be easily evaporated and removed by heating from the fluorine-based resin film formed by applying the protective film-forming composition.

[0058] Preferred examples of the fluorine-containing alcohol include 1H,1H-trifluoroethanol, 1H1H-pentafluoropropanol, 1H,1H-heptafluorobutanol, 2-(perfluorobutyl)ethanol, 3-(perfluorobutyl)propanol, 2-(perfluorohexyl)ethanol, 3-(perfluorohexyl)propanol, 1H,1H,3H-tetrafluoropropanol, 1H,1H,5H-octafluoropentanol, 1H,1H,7H-dodecafluoroheptanol, 2H-hexafluoro-2-propanol, and 1H,1H,3H-hexafluorobutanol.

[0059] The fluorine-based solvents mentioned above are selected from 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,2,2,3,3,4-heptafluorocyclopentane, ethyl nonafluorobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, methoxyperfluoroheptene, 1H1H-pentafluoropropanol, 1H,1H-heptafluorobutanol, 2-(perfluoromethyl)-3-ethoxydodecafluorohexane ... Preferred are 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, methoxyperfluoroheptene, 1H,1H,3H-tetrafluoropropanol, 1H,1H,5H-octafluoropentanol and 1H,1H,7H-dodecafluoroheptanol, and more preferred are 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, methoxyperfluoroheptene, 1H,1H,3H-tetrafluoropropanol, 1H,1H,5H-octafluoropentanol and 1H,1H,7H-dodecafluoroheptanol.

[0060] Furthermore, two or more kinds of fluorine solvents may be contained in order to flatten the coated film, and a mixed solvent of the above-mentioned fluorine-containing hydrocarbon and the above-mentioned fluorine-containing alcohol, or the above-mentioned fluorine-containing ether and the above-mentioned fluorine-containing alcohol, is preferred.

[0061] The protective film-forming composition of the present invention, which is made of a fluorine-based resin and a fluorine-based solvent, preferably contains 1 wt% to 50 wt% of the fluorine-based resin and 50 wt% to 99 wt% of the fluorine-based solvent, and more preferably contains 1 wt% to 30 wt% of the fluorine-based resin and 70 wt% to 99 wt% of the fluorine-based solvent.

[0062] In the ethylenically unsaturated monomer residue unit having a photocrosslinkable group in a side chain in the fluororesin contained in the protective film-forming composition of the present invention, the photocrosslinkable group refers to a functional group that can form a crosslinked structure between functional groups when exposed to light such as ultraviolet light or visible light. By including the photocrosslinkable group in the side chain of the resin, the fluororesin of the present invention selectively insolubilizes only the site irradiated with light. Examples of photocrosslinkable groups include photodimerization-reactive groups; radical-reactive groups such as methacryloyl groups, acryloyl groups, aromatic vinyl groups, and vinyl ether groups; and cation-reactive groups such as epoxy groups and oxetane groups. Photodimerization-reactive groups are preferred because they do not require the use of a photoradical generator or photocation generator and provide excellent long-term stability when formed into a film.

[0063] Examples of photodimerization reactive groups include cinnamic acid groups, chalcone groups, stilbenyl groups, stilbazolyl groups, coumarinyl groups, anthracenyl groups, naphthoquinonyl groups, acenaphthyl groups, maleimidyl groups, phenylcyclohexenonyl groups, tetracenyl groups, benzazepinyl groups, naphthalenonyl groups, etc. Among these, at least one photodimerization reactive group selected from the group consisting of the following general formulas (5), (6), (7), and (8) is preferred because of its high photocrosslinkability, economical efficiency, and ease of introduction as a functional group.

[0064] [ka]

[0065] In formula (5), A1 represents hydrogen, a hydroxyl group, an amino group, a C1-C6 alkyl group, a C1-C6 primary or secondary alkylamino group, a C1-C6 alkoxy group, or a single bond; A2 may be the same or different and represent hydrogen, halogen, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C 18represents an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a single bond. B1 may be the same or different and represent hydrogen, a C1-C6 alkyl group, a halogen, a cyano group, or an aryl group. However, this indicates that only one of one A1 and five A2 is bonded to another substituent via a single bond.)

[0066] [ka]

[0067] In formula (6), A3 may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C 18 B2 may be the same or different and represent hydrogen, a C1-C6 alkyl group, a halogen atom, a cyano group, or an aryl group. L is absent or represents a carbonyl group. However, this indicates that only one of the ten A3 is bonded to another substituent via a single bond.

[0068] [ka]

[0069] In formula (7), A4 may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C 18 B3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl group, a halogen atom, a cyano group, or an aryl group. However, only one of the four A4's is bonded to another substituent via a single bond.)

[0070] [ka]

[0071] In formula (8), A5 may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1 to C 18 represents an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a single bond. However, this indicates that only one of the ten A5s is bonded to another substituent via a single bond.)

[0072] Specific examples of the group represented by formula (5) include the following: In the formula, * represents the moiety that bonds to the side chain.

[0073] [ka]

[0074] [ka]

[0075] Specific examples of the group represented by formula (6) include the following.

[0076] [ka]

[0077] [ka]

[0078] Specific examples of the group represented by formula (7) include the following.

[0079] [ka]

[0080] Specific examples of the photodimerization reactive group represented by formula (8) include the following.

[0081] [ka]

[0082] The acrylic resin residue unit in the fluorine-based resin contained in the composition for forming a protective film of the present invention preferably has a group represented by formula (5) in its side chain. The residue unit represented by formula (5) is preferably a residue unit represented by the following formula (9), since this makes it easier to synthesize a monomer that is a raw material for the residue unit.

[0083] [ka]

[0084] In formula (9), R1 represents a hydrogen atom or a methyl group; B4 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl group, a halogen atom, a cyano group, or an aryl group; D may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C 18 represents an alkyl group, a fluoroalkyl group, or a cycloalkyl group; M represents a halogen or an aryl ether group.

[0085] In formula (9), R1 represents either a hydrogen atom or a methyl group, and is preferably a methyl group.

[0086] In formula (9), B4 may be the same or different and represents one of the group consisting of a hydrogen atom, a C1-C6 alkyl group, a halogen atom, a cyano group, or an aryl group, preferably a hydrogen atom or a C1-C6 alkyl group, and more preferably a hydrogen atom.

[0087] In formula (9), D may be the same or different and is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1 to C 18 is preferably a hydrogen atom or a C1-C18 and more preferably a hydrogen atom.

[0088] In formula (9), M represents either a halogen atom or an aryl ether group, and is preferably a halogen atom.

[0089] The protective film-forming composition of the present invention may contain a photosensitizer. Any photosensitizer may be used as long as it accelerates the crosslinking reaction of the photocrosslinkable groups. When a photosensitizer is contained, the protective film-forming composition may be a composition containing the fluororesin of the present invention and the photosensitizer, or the above-described solution of the present invention may further contain the photosensitizer.

[0090] Examples of photosensitizers include acyloins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; carbonyls such as anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, and cyclohexanone; diketones such as diacetyl and benzil; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, and tetramethylthiuram disulfide; phenones such as acetophenone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, o-methoxybenzophenone, and 2,4,6-trimethoxybenzophenone; p-toluenesulfonyl chloride, 1-naphthalene Examples of suitable photosensitizers include sulfonyl halides such as sulfonyl chloride, 1,3-benzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl bromide, and p-acetamidobenzenesulfonyl chloride; aromatic nitro compounds such as 5-nitrofluorene, 5-nitroacenaphthene, N-acetyl-4-nitro-1-naphthylamine, and biclamide; coumarins such as 7-diethylamino-3-thenoylcoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, and 1,1,2,2-tetrabromoethane; nitrogen derivatives such as diazomethane, bisisobutyronitrile, hydrazine, and trimethylbenzylammonium chloride; and dyes such as ethionine, thionine, and methylene blue. The addition of a photosensitizer allows the fluororesin of the present invention to be crosslinked (insolubilized) at lower exposure doses. Furthermore, two or more of these sensitizers can be used in combination as needed.

[0091] When the composition for forming a protective film of the present invention further contains a photosensitizer, it preferably contains 1 wt% to 50 wt% of a fluorine-based resin, 50 wt% to 99 wt% of a fluorine-based solvent, and 0.001 wt% to 5 wt% of a sensitizer, and more preferably contains 1 wt% to 30 wt% of a fluorine-based resin, 70 wt% to 99 wt% of a fluorine-based solvent, and 0.01 wt% to 3 wt% of a sensitizer.

[0092] A pattern made of a fluorine-based resin, which is one embodiment of the present invention, will be described below.

[0093] The fluorine-based resin contained in the composition for forming a protective film of the present invention can form a pattern.

[0094] First, a pattern forming method using the composition for forming a protective film of the present invention will be described.

[0095] First, a coating film of a fluorine-based resin is formed on the surface of a substrate by a known coating film forming method. Examples of substrates include various glass plates; polyesters such as polyethylene terephthalate; polyolefins such as polypropylene and polyethylene; thermoplastic plastic sheets such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide; epoxy resins; polyester resins; and thermosetting plastic sheets such as poly(meth)acrylic resins.

[0096] Examples of methods that can be used to form the coating film include spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, flow coating, gravure printing, flexographic printing, superflexographic printing, screen printing, inkjet printing, letterpress reverse printing, reverse offset printing, and adhesion contrast printing.

[0097] The coating is then dried. By drying, the solvent evaporates, resulting in a non-sticky coating. Drying conditions vary depending on the boiling point and blending ratio of the solvent used, but can be preferably used in a wide range of temperatures from 50 to 150°C for 10 to 2000 seconds.

[0098] When a predetermined pattern is formed by a printing method during the formation of a coating film, the pattern is photocrosslinked and fixed by exposure to light, thereby forming the pattern.

[0099] On the other hand, if no pattern is formed when the coating film is formed, a predetermined pattern can be formed in the coating film using photolithography. When using photolithography, the dried coating film is first exposed to light through a mask with a predetermined pattern to cause photocrosslinking.

[0100] When the fluorine-based resin contained in the protective film-forming composition of the present invention is cured by photocrosslinking, radiation such as ultraviolet light or visible light is used, for example, ultraviolet light having a wavelength of 245 to 435 nm. The irradiation dose is appropriately changed depending on the composition of the resin, but for example, it is 10 to 5000 mJ / cm. 2 In order to prevent a decrease in the degree of crosslinking and improve economic efficiency by shortening the process time, the dose is preferably 100 to 4000 mJ / cm 2 Specific examples of light irradiation devices or light sources include germicidal lamps, ultraviolet fluorescent lamps, carbon arc lamps, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, and metal halide lamps.

[0101] UV irradiation is usually carried out in the atmosphere, but can also be carried out in an inert gas atmosphere or under a constant flow of inert gas if necessary. If necessary, the photosensitizer can be added to promote the photocrosslinking reaction. The film is then developed with a developer to remove the unexposed areas. The developer can be any solvent that dissolves the uncured fluororesin, including, for example, aromatic solvents such as benzene, toluene, and xylene; ether-based solvents such as dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol dimethyl ether; ketone-based solvents such as acetone and methyl ethyl ketone; and ester-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether acetate.

[0102] The development time is preferably 30 to 300 seconds. The development method may be either a puddle method or a dipping method. After development, the substrate is washed with a solvent and air-dried with compressed air or compressed nitrogen to remove the solvent from the substrate. Subsequently, a pattern is formed by heat treatment using a heating device such as a hot plate or oven, preferably at 40 to 150°C for 5 to 90 minutes.

[0103] After forming a pixel pattern through the above-mentioned photolithography process, contamination on the substrate surface within the pixels may be removed. For example, the substrate surface may be cleaned by irradiating it with short-wavelength ultraviolet light such as a low-pressure mercury lamp or excimer UV, or by photo-ashing treatment. Photo-ashing treatment is a treatment in which short-wavelength ultraviolet light is irradiated in the presence of ozone gas. The short-wavelength ultraviolet light is light having a main peak at a wavelength of 100 to 300 nm.

[0104]

[0033] In this way, the fluorine-based resin contained in the composition for forming a protective film of the present invention is itself soluble in a fluorine-based solvent or an organic solvent, and upon irradiation with light, the photocrosslinkable groups in the side chains are crosslinked and cured, making the composition insoluble in the fluorine-based solvent or the organic solvent. By utilizing this property, the fluorine-based resin contained in the composition for forming a protective film of the present invention can be used as a negative resist in which, when crosslinked by light irradiation, the non-irradiated portions are removed by the fluorine-based solvent or the organic solvent.

[0105] After patterning the fluororesin contained in the protective film-forming composition of the present invention, the portion where the fluororesin remains after crosslinking (outside the pattern) preferably has a contact angle with the organic solvent of 50° or more to prevent the organic solvent from wetting and spreading.

[0106] The fluororesin contained in the protective film-forming composition of the present invention has excellent liquid repellency and can be used as a pattern material when producing organic transistor elements, color filters, and organic EL elements. The fluororesin of the present invention can also be used in electronic devices including the organic transistor elements, color filters, and organic EL elements.

[0107] The electronic device according to one embodiment of the present invention will be described in detail below.

[0108] The protective film-forming composition of the present invention can be used in electronic devices, such as organic transistors, because it causes less damage to organic semiconductors.

[0109] When the protective film-forming composition of the present invention is used in an organic transistor, the organic transistor has a gate insulating layer on a substrate, and is obtained by further forming an organic semiconductor layer on this gate insulating layer, and providing a source electrode, a drain electrode, and a gate electrode.

[0110] The organic transistor of the present invention may have any of the following device structures: bottom gate-top contact type (A), bottom gate-bottom contact type (B), top gate-top contact type (C), and top gate-bottom contact type (D) shown in Figure 1. Here, 1 represents an organic semiconductor layer, 2 represents a substrate, 3 represents a gate electrode, 4 represents a gate insulating layer, 5 represents a source electrode, and 6 represents a drain electrode.

[0111] The substrate that can be used in the organic transistor is not particularly limited as long as it can ensure sufficient flatness for fabricating an element, and examples thereof include inorganic material substrates such as glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; plastics; metals such as gold, copper, chromium, titanium, and aluminum; ceramics; coated paper; and surface-coated nonwoven fabrics. Composite materials made of these materials or multilayer materials of these materials may also be used. Furthermore, the surfaces of these materials can be coated to adjust the surface tension.

[0112] Examples of plastics that can be used as the substrate include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethylpentene-1, polypropylene, cyclic polyolefins, fluorinated cyclic polyolefins, polystyrene, polyimide, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomers, polyurethane elastomers, polyolefin elastomers, polyamide elastomers, and styrene block copolymers. Furthermore, two or more of the above plastics can be laminated together and used as the substrate.

[0113] When the protective film-forming composition of the present invention is applied to an organic semiconductor, it does not dissolve or swell the organic semiconductor film, so that a coating film can be formed by wet deposition on the organic semiconductor film. Furthermore, when the fluororesin film is patterned using photolithography, printing, or imprinting, and then the organic semiconductor film is wet-etched, the organic semiconductor film can be patterned without being immersed in an etchant such as a hydrocarbon solvent or an aromatic solvent.

[0114] The protective film-forming composition of the present invention can be applied to organic semiconductor or organic light-emitting materials that are sensitive to water and organic solvents, and can therefore be used as a protective layer that protects these materials from water and organic solvents.

[0115] There are no limitations on the organic semiconductors that can be used in the present invention, and both N-type and P-type organic semiconductors can be used, and a bipolar transistor combining N-type and P-type can also be used. Also, both low-molecular-weight and high-molecular-weight organic semiconductors can be used, and they can also be used in combination. Specific examples of compounds include those represented by formulas (F-1) to (F-11).

[0116]

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[0117]

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[0118]

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[0119]

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[0120] In the present invention, examples of methods for forming an organic semiconductor layer include a method of vacuum vapor deposition of an organic semiconductor, or a method of dissolving an organic semiconductor in an organic solvent and coating or printing the solution, but there are no limitations as long as the method can form a thin film of an organic semiconductor layer. When coating or printing using a solution in which the organic semiconductor layer is dissolved in an organic solvent, the concentration of the solution varies depending on the structure of the organic semiconductor and the solvent used, but from the viewpoint of forming a more uniform semiconductor layer and reducing the layer thickness, it is preferably 0.5% to 5% by weight. The organic solvent used in this case is not limited as long as it dissolves the organic semiconductor at a certain concentration that allows film formation, and examples thereof include hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, a mixture of dimethylnaphthalene isomers, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butylene glycol, ethylene glycol, benzyl alcohol, glycerin, cyclohexanol acetate, 3-methyl-4-phenylpropanol, 2-methyl-1, ... -Methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-tetrahydro-1-naphthol, α-terpineol, isophorone triacetin decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, Examples of suitable solvents include dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. However, to obtain a crystal film with desirable properties, a solvent with a high dissolving power for organic semiconductors and a boiling point of 100°C or higher is suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred. Mixed solvents containing two or more of the above solvents in appropriate ratios can also be used.

[0121] Various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles can be added to the organic semiconductor layer as needed, either as solids or as dispersions of nanoparticles in water or organic solvents, and a protective film can be formed by coating the insulating layer with the polymer solution. Furthermore, various moisture-proof coatings, light-resistant coatings, etc. can be applied to this protective film as needed.

[0122] Examples of gate electrodes, source electrodes, or drain electrodes that can be used in the present invention include inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, polysilicon, silicide, tin oxide, indium oxide, indium tin oxide, chromium, platinum, titanium, tantalum, graphene, and carbon nanotubes, as well as organic electrodes such as doped conductive polymers (e.g., PEDOT-PSS). Multiple layers of these conductive materials can also be used. Furthermore, to improve carrier injection efficiency, these electrodes can be surface-treated using a surface treatment agent. Examples of such surface treatment agents include benzenethiol and pentafluorobenzenethiol.

[0123] Furthermore, there are no particular limitations on the method for forming an electrode on the substrate, insulating layer, or organic semiconductor layer, and examples thereof include vapor deposition, high-frequency sputtering, and electron beam sputtering. It is also possible to employ methods such as solution spin coating, drop casting, dip coating, doctor blade coating, die coating, pad printing, roll coating, gravure printing, flexographic printing, superflexographic printing, screen printing, inkjet printing, and letterpress reverse printing using an ink in which nanoparticles of the conductive material are dissolved in water or an organic solvent.

[0124] From the viewpoint of practicality of the organic transistor element, the organic transistor of the present invention has a mobility of 0.20 cm 2 It is preferable that the value is equal to or greater than / Vs.

[0125] From the viewpoint of practicality of the organic transistor element, the organic transistor of the present invention has an on-current / off-current ratio of 10 5 It is preferable that this is equal to or greater than this.

[0126] From the viewpoint of practicality of the organic transistor element, it is preferable that the organic transistor of the present invention has no hysteresis in the source-drain current. [Example]

[0127] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, the composition of the resin, spin coating, film thickness measurement, UV irradiation, evaluation method of photocrosslinking (curing) properties, and pattern formation were carried out under the following conditions and using the following equipment.

[0128] <Composition of fluororesin> It was determined by proton nuclear magnetic resonance spectroscopy ( 1 1H-NMR) spectrum analysis using a nuclear magnetic resonance measuring device (manufactured by JEOL Ltd., trade name JNM-ECZ400S). <Solubility in fluorosolvent> The fluororesin and the resin for comparative examples were added to each fluorosolvent to a concentration of 10 wt%, mixed while heating to 100 °C, and then cooled to room temperature. The presence of insoluble matter or precipitates was visually confirmed. Hereinafter, this is referred to as "solubility evaluation". <Spin coating> MS-A100 manufactured by Mikasa Co., Ltd. was used. <Flatness> The fluororesin described below was adjusted to 10 wt% in each fluorosolvent, washed, and dried on a 30 × 30 mm 2 glass substrate (Eagle XG manufactured by Corning) under the conditions of 500 rpm for 5 seconds → 1000 rpm for 20 seconds. After drying at 90 °C for 1 minute, the surface of the spin-coated film was observed using a laser microscope, OPTELICS (registered trademark) HYBRID, manufactured by Lasertec Corporation. Hereinafter, this is referred to as "flatness evaluation". <Film thickness measurement> Measurement was performed using a DektakXT stylus profiler manufactured by Bruker. <UV irradiation> Using a UV mask aligner, UPE-1605MA, manufactured by USHIO Lighting Co., Ltd., the UV irradiation time was adjusted by changing the conveyance speed under the condition of a UV intensity of 13.0 mW / cm 2 . <Evaluation method of photocrosslinking (curing) properties> Washed and dried 30 × 30 mm 2A solution of a fluorine-based resin or a protective film-forming composition was spin-coated onto a glass substrate (Corning Eagle XG) using a spin coater so that the film thickness after drying would be 2000 nm or more, and the resulting film was thoroughly dried. 2 The protective film-forming composition film was photocrosslinked by irradiating it with ultraviolet light of 1000 nm. The thickness of this film was measured using a DektakXT stylus profiler manufactured by Bruker and designated as T0. Next, the glass plate coated with this photocrosslinked protective film-forming composition film was immersed in AE-3000 (manufactured by AGC), a good solvent for the protective film-forming composition, for 1 minute, then removed and dried at 100°C using a hot plate for 1 minute, after which the film thickness was measured and designated as T1. Using these measured film thickness values, the remaining film ratio (R) was calculated using the following formula. R = T1 / T0 × 100(%) Photocrosslinking (curing) was evaluated using a residual film rate of 95% or more as the criterion for crosslinking. (Hereinafter referred to as "photocrosslinking evaluation"). The lower the UV irradiation intensity required to achieve a residual film rate of 95% or more, the higher (faster) the photocrosslinking.

[0129] In the examples, the synthesis of fluorine-based resins, evaluation of solubility in fluorine-based solvents, evaluation of solvent resistance and pattern formation were carried out under the following conditions, and the results were obtained.

[0130] Example 1 A 75 mL glass ampoule was charged with 25.3 g of the compound represented by general formula (10), 4.7 g of glycidyl methacrylate, 1.3 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 70 g of 1,1,2,2,3,3,4-heptafluorocyclopentane (ZEON Corp.). The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, dropped into 300 mL of methanol, and precipitated. The polymer solution was then washed twice with 200 mL of methanol. The resulting mixture was then vacuum dried at 30°C for 8 hours, yielding 27 g of fluororesin precursor 1 (yield: 90%). 1It was confirmed by 1 H-NMR measurement that the copolymer composition was: residue units represented by general formula (11) / glycidyl methacrylate residue units=48 / 52 (mol %).

[0131] [ka]

[0132] [ka]

[0133] After heating and drying a 200 mL Schlenk flask, 8 g of fluororesin precursor 1, 4.73 g of cinnamic acid chloride, 1.25 g of tetraethylammonium chloride as a catalyst, and 72 g of 1,1,2,2,3,3,4-heptafluorocyclopentane were added under a nitrogen atmosphere and sealed with a stopcock. The flask was stirred at room temperature until fluororesin precursor 1 was dissolved, and then stirred in an oil bath at 80°C for 8 hours. The resulting resin solution was dropped into 500 mL of hexane to precipitate, and then washed twice with 300 mL of methanol. This was further vacuum dried at 40°C for 6 hours to obtain 9.75 g of fluororesin 1. 1 H-NMR measurement confirmed that the glycidyl methacrylate residue units in the raw material had decreased and were converted to residue units represented by formula (12). 1 H-NMR measurement confirmed that the copolymer composition of fluororesin 1 was formula (13), where the residue unit (fluorine-based unit) represented by general formula (11) / residue unit (photocurable group unit) represented by formula (12)=52 / 48 (mol %).

[0134] [ka]

[0135] [ka]

[0136] The synthesized fluorine-based resin 1 was subjected to a solubility evaluation using the following fluorine-based solvents. Solvent 1: Methoxyperfluoroheptene Solvent 2: 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane Solvent 3: 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane

[0137] Fluorine-based resin 1 showed excellent solubility, dissolving in fluorine-based solvents 1 to 3. The results are shown in Table 1.

[0138] <Flatness evaluation> The synthesized fluorine-based resin 1 was subjected to a flatness evaluation using the following fluorine-based solvents. Solvent 1: Methoxyperfluoroheptene Solvent 4: 1H,1H,5H-octafluoropentanol Solvent 5: methoxyperfluoroheptene and 1H,1H,5H-octafluoropentanol mixed in a volume ratio of 7:3 Solvent 6: 5:5 volume mixture of methoxyperfluoroheptene and 1H,1H,5H-octafluoropentanol

[0139] For Fluorine-based resin 1, undulations occurred on the surface of the fluororesin film when Fluorine-based solvent 1 was used, and the film was not flat. It was confirmed that the surfaces of the fluororesin films obtained using solutions of Fluorine-based solvents 4 to 6 were flat and free of undulations.

[0140] <Photocuring evaluation> The synthesized fluororesin 1 was mixed with 4,4'-bis(diethylamino)benzophenone as a sensitizer and dissolved in 1H,1H,5H-octafluoropentanol solvent to prepare a solution. The photocuring properties of the prepared solution (fluororesin 1: 15 wt%, sensitizer: 0.2 wt%) were evaluated, and the remaining film rate was 95% or more, confirming photocuring.

[0141] <Pattern formation> For pattern formation, 4,4'-bis(diethylamino)benzophenone was added as a sensitizer to fluororesin 1, and the mixture was dissolved in methoxyperfluoroheptane solvent to prepare a solution (fluororesin 2: 3 wt%, sensitizer: 0.1 wt%).

[0142] A mask (patterning mask) was used, which was patterned with chrome to form a shape of 10 squares with 50 microns on a 10cm x 10cm glass substrate. The solution was spin-coated onto the substrate, the mask was placed on the film, and ultraviolet light was applied. After that, the uncrosslinked portions were washed and removed with Asahiklin AE-3000 (manufactured by AGC), leaving a 50 x 50 μm pattern on the film. 2 A pattern with 100 holes of the same size was formed.

[0143] <Damage evaluation of organic semiconductors> Washed and dried 100 x 100 mm 2 Aluminum was vacuum-deposited onto glass (Corning Eagle XG) to form a 50 nm thick gate electrode, and then Parylene C was deposited as an insulating film using chemical vapor deposition. Silver was then sputter-deposited to form source and drain electrodes with a 50 nm thick channel length of 10 μm and an electrode width of 500 μm. The substrate was then immersed in a 30 mmol / L solution of pentafluorobenzenethiol in 2-propanol for 5 minutes, removed, washed with 2-propanol, and blow-dried.

[0144] A 0.8 wt% solution of organic semiconductor (di-n-hexyldithienobenzodithiophene) in tetralin was inkjet printed onto the channel area, the solvent was evaporated, and the device was dried at 90°C for 20 minutes. After that, the organic transistor device characteristics were evaluated, and the mobility was found to be 0.30 cm. 2 / V·s. Next, 4,4'-bis(diethylamino)benzophenone was added as a sensitizer to fluororesin 1, and the mixture was dissolved in methoxyperfluoroheptene solvent. The solution (fluororesin 1: 3 wt%, sensitizer: 0.1 wt%) was spin-coated onto the organic transistor at 500 rpm for 5 seconds and 1000 rpm for 20 seconds, and then dried at 50°C. After that, the organic transistor device characteristics were evaluated, and the mobility was found to be 0.30 cm. 2 / V·s, and no degradation in mobility was confirmed.

[0145] Comparative Example 1 A 75 mL glass ampoule was charged with 5.71 g of the compound represented by general formula (10), 4.28 g of glycidyl methacrylate, 0.29 g of Perhexyl ND (NOF Corp.) as a polymerization initiator, and 23.3 g of dehydrated butyl acetate. The ampoule was repeatedly purged with nitrogen and depressurized, and then sealed under reduced pressure. The ampoule was placed in a thermostatic chamber at 45°C and held there for 24 hours to allow radical polymerization. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and the polymer solution was precipitated by dropping it into 300 mL of methanol. The precipitate was then washed twice with 200 mL of methanol. The resulting mixture was vacuum dried at 30°C for 8 hours, yielding 9.4 g of fluororesin precursor 3 (yield: 94%). 1 It was confirmed by 1 H-NMR measurement that the copolymer composition was such that the residue unit represented by the general formula (11) / glycidyl methacrylate residue unit=20 / 80 (mol %).

[0146] After heating and drying a 200 mL Schlenk flask, 8 g of fluororesin precursor 3, 6.02 g of cinnamic acid chloride, 1.60 g of tetraethylammonium chloride as a catalyst, and 72 g of butyl acetate were added under a nitrogen atmosphere and sealed with a stopcock. The mixture was stirred at room temperature until fluororesin precursor 1 was dissolved, and then stirred in an oil bath at 100°C for 8 hours. The resulting resin solution was dropped into 500 mL of hexane to precipitate, and then washed twice with 300 mL of methanol. This was further vacuum dried at 40°C for 6 hours to obtain 9.5 g of fluororesin 3. 1H-NMR measurement confirmed that the glycidyl methacrylate residue units in the raw material had decreased and were converted to residue units represented by formula (12). 1 H-NMR measurement confirmed that the copolymer composition of fluororesin 2 was formula (15), where the residue unit (fluorine-based unit) represented by general formula (11) / residue unit represented by formula (12)=21 / 79 (mol %).

[0147] [ka]

[0148] The solubility of the synthesized fluororesin 2 was evaluated in the same manner as in Example 1. Fluororesin 1 was insoluble in all fluorine-based solvents. The results are shown in Table 1.

[0149] [Table 1]

Claims

1. A residue unit represented by formula (1): At least one of the group consisting of residue units represented by formula (2) and residue units represented by formula (3) accounts for 30 mol % or more of the total residue units of the fluororesin, and A fluorine-based resin containing an ethylenically unsaturated monomer residue unit having a photocrosslinkable group in the side chain, represented by the following formula (4): and a fluorine-based solvent. 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 (In formulas (1) to (3), R １ represents one of the group consisting of a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. １ is terminated with CF ３ a linear perfluoroalkyl group having 1 to 6 carbon atoms, the terminal of which is CF ３ or a branched perfluoroalkyl group having 3 to 6 carbon atoms, ３ Rf represents one kind of a group consisting of cyclic perfluoroalkyl groups having 3 to 6 carbon atoms. ２ Rf represents one of the group consisting of a linear perfluoroalkylene group having 1 to 6 carbon atoms, a branched perfluoroalkylene group having 3 to 6 carbon atoms, or a cyclic perfluoroalkylene group having 3 to 6 carbon atoms. ３ is terminated with CF ３ a linear perfluoroalkyl group having 1 to 5 carbon atoms, the terminal of which is CF ３ or a branched perfluoroalkyl group having 3 to 5 carbon atoms, ３ Rf represents a cyclic perfluoroalkyl group having 3 to 5 carbon atoms. ４ represents a linear perfluoroalkylene group having 1 to 5 carbon atoms, a branched perfluoroalkylene group having 3 to 5 carbon atoms, or a cyclic perfluoroalkylene group having 3 to 5 carbon atoms. ２ ~R ５ each independently represents a hydrogen atom or a fluorine atom, n represents an integer of 1 to 5, X represents a single bond, CH ２ , an oxygen atom, or a sulfur atom. L is represented by the following general formula (a): 【Chemistry 4】 (where R ２ represents either a hydrogen atom or a methyl group. ４ are the same or different and represent a hydrogen atom, C １ ~C ６ D's may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, C １ ~C １８ M represents one of the group consisting of an alkyl group, a fluoroalkyl group, or a cycloalkyl group, and M represents either a halogen atom or an aryl ether group. 【Transformation 5】 (Here, in formula (a), the sum of l and m is an integer of 2 to 6, and when l and / or m is 2 or more, a —CH═CH— structure may be included instead of —CHCH—. Q is a single bond, —OCONH—, —CONH—, —O—, —NH—, —CO—O—, —O—CO—, —NHCONH—, or —CH—.)

2. 2. The composition for forming a protective film according to claim 1, wherein the fluorine-containing solvent is at least one member selected from the group consisting of fluorine-containing hydrocarbons, fluorine-containing ethers and fluorine-containing alcohols.

3. The composition for forming a protective film according to claim 1 , further comprising a photosensitizer.

4. A method for manufacturing an organic semiconductor device, comprising forming a fluorine-based resin film on an organic semiconductor film using the composition for forming a protective film according to claim 1 .

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