JP2021161378A - Fluorine-based resin, composition, light crosslinkable substance, and electronic device including the same - Google Patents

Abstract

To provide a fluorine-based resin which is soluble in a fluorine solvent, and is insolubilized in a solvent by being light crosslinked at normal temperatures and a low exposure dose.SOLUTION: A fluorine-based resin has a residue unit represented by the following formula (1), and an acrylic resin residue unit having at least one group selected from the group consisting of a group represented by formula (2), a group represented by formula (3), and a group represented by formula (4), in a side chain. In the formulae, R1 represents either a hydrogen atom or a methyl group; and Rf1 is selected from the group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched chain fluoroalkyl group having 3 to 15 carbon atoms and a cyclic fluoroalkyl group having 3 to 15 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a fluororesin. More specifically, the present invention relates to a fluororesin that can be suitably used for electronic devices.

In recent years, technological development related to the manufacture of organic electronic devices by the Zeninsatsukyoku method, which is low in cost and high in productivity, has been actively carried out. As electronic devices, for example, organic transistors are being developed. This organic transistor is manufactured through a number of steps, but also includes a step in which a protective film made of resin protects the organic transistor and forms a pattern of an EL light emitting portion. This pattern is provided, for example, to cover the source electrode, the drain electrode and the organic semiconductor layer or the polymer layer, and is not present on the electrode where the EL light emitting portion is formed.

Usually, the EL light emitting part is a technique of exposing a substrate surface coated with a photosensitive substance (resist) to a pattern through a photomask, a reticle, or the like to form a pattern consisting of an exposed part and an unexposed part. Formed using photolithography. In photolithography, the EL light emitting portion is opened by a dry etching method or wet etching.

A photoreactive polymer material is used as the pattern forming material. In a coating method such as the Zeninsatsu method, the material is applied in the form of an ink in which the material is well dissolved in a solvent, the solvent is dried and removed, and then the material is photocrosslinked at room temperature for a short time. It is required to have the property of being insoluble in a solvent.

A method for manufacturing an organic electroluminescent element included in an organic field display, an organic electric field illumination, or the like is shown. First, the polymer material is applied onto the substrate, and the portion to which the pattern is to be formed is subjected to a photocrosslinking reaction, and the portion not subjected to the photocrosslinking reaction is removed. As a result, the remaining portion becomes a pattern. Various functional layers are laminated on the portion (inside the pattern) from which the polymer material has been removed. A technique for forming the functional layer using an ink-like raw material is promising, but ink adheres to the inside of the pattern and ink leaks to the outside of the region beyond the portion where the polymer material is not removed (outside the pattern). From the viewpoint of prevention, the materials constituting the pattern are expected to have liquid repellency.

Examples of such a material include a negative photosensitive resin composition which has high photoreactivity in Patent Document 1 and can be patterned, and which can form a film having high dielectric properties and excellent dielectric properties, and a photocurable pattern produced from the negative photosensitive resin composition. However, this resin is an alkali-soluble polymer and it is necessary to use water for development. In addition, it is necessary to use an organic solvent such as PGMEA (1-methoxy-2-propanol acetate) as the solvent of the composition. Both organic solvents and water cause deterioration in the performance of electronic devices. Therefore, in order to prevent deterioration of the performance of electronic devices, it has been required to develop a material that can use a fluorine-based solvent as a solvent.

As such a technique, there is a method of forming a pattern using a fluorine-based resin soluble in a fluorine solvent disclosed in Patent Document 2 and Non-Patent Document 1. However, the fluororesin has a problem that it does not photocrosslink.

Examples of the fluorine-based resin that dissolves in a fluorine solvent and photocrosslinks include a fluorine-based resin such as Non-Patent Document 2 that uses an anthracene cross-linking group. However, since the fluorine-based resin has low photocrosslinkability and requires a high irradiation amount, a fluorine-based resin having high photoreactivity has been expected.

JP-A-2017-167513 Patent No. 6281427

Apple. Phys. Express 7, 101602 (2014) J Polymer Sci A Polymer Chem 53, 1252 (2015)

The present invention has been made in view of the above problems, and an object of the present invention is to provide a pattern that is insoluble in a solvent by photocrosslinking at room temperature and a low exposure amount and has liquid repellency when photocrosslinked. An object of the present invention is to provide a fluororesin having suitable performance. Further, since the resin is soluble in a fluorine solvent and insoluble in a fluorine solvent after photocrosslinking, it can be suitably used as a protective film for protecting a functional layer in an organic device.

As a result of diligent studies, the present inventors have found that a fluororesin having a specific structure solves the above-mentioned problems, and have completed the present invention.

That is, in the present invention, the residue unit represented by the following formula (1) and
An acrylic resin residue unit having a group represented by at least one of the following formula (2), the following formula (3), and the following formula (4) in the side chain.
It is a fluorine-based resin containing.

(Here, R ₁ represents either a hydrogen atom or a methyl group. Rf ₁ is a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched chain fluoroalkyl group having 3 to 15 carbon atoms, or 3 carbon atoms. Represents one of a group consisting of ~ 15 cyclic fluorine-containing hydrocarbon groups.)

(Wherein, _{A 1} is a hydrogen atom, a hydroxyl group, an amino _group, C 1 -C alkyl group of _6, C 1 -C 1 primary or secondary alkylamino group _6, C 1 -C ₆ alkoxy group or a single Shows a bond, A ₂ is the same or different, hydrogen atom, halogen atom, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, _{alkyl group of C 1 to} C ₁₈ , fluoroalkyl group, cyclo alkyl or .B ₁ represents a single bond are the same or different and each represents a hydrogen atom or an alkyl group of C ₁ -C _6, halogen atom, a cyano group, an aryl group. However, one a ₁ and five a ₂ It is assumed that only one of them is a single bond and is bonded to another substituent.)

(Wherein, A ₃ are the same or different, a hydrogen atom, a halogen atom, a cyano group, a nitro group, carboxyalkyl group, alkyl ether group, an aryl ether group, an alkyl group of C ₁ -C _18, fluoroalkyl group, a cycloalkyl alkyl or .B ₂ represents a single bond are the same or different and each represents a hydrogen atom or an alkyl group of C ₁ -C _6, halogen atom, a cyano group, .L representing the aryl group represents a single bond or a carbonyl group. However, of the 10 a _3, only one will be assumed that indicates that it is bound to other substituents with a single bond.)

(Wherein, A ₄ are the same or different, a hydrogen atom, a halogen atom, a cyano group, a nitro group, carboxyalkyl group, alkyl ether group, an aryl ether group, an alkyl group of C ₁ -C _18, fluoroalkyl group, a cycloalkyl alkyl or .B ₃ represents a single bond are the same or different and each represents a hydrogen atom or an alkyl group of C ₁ -C _6, halogen atom, a cyano group, an aryl group. However, of the four a _4, only one of It shall indicate that it is bonded to another substituent by a single bond.)

According to the present invention, it is possible to provide a fluororesin capable of forming a liquid-repellent pattern by photocrosslinking at room temperature and a low exposure amount.

It is a figure which shows the cross-sectional shape of an organic transistor. It is a figure which shows ^{the 1} H-NMR chart of the fluororesin 2 produced in Example 2.

The fluororesin, which is one aspect of the present invention, will be described in detail below.

The fluororesin of the present invention has a residue unit represented by the formula (1), a group represented by the formula (2) in the side chain, a group represented by the formula (3), and the above formula ( It contains an acrylic resin residue unit containing a group represented by 4).

The fluororesin of the present invention contains a residue unit represented by the formula (1).

In formula (1), R ₁ represents either a hydrogen atom or a methyl group.

In the formula (1), Rf ₁ is one of a group consisting of a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched chain fluoroalkyl group having 3 to 14 carbon atoms, or a cyclic fluoroalkyl group having 3 to 13 carbon atoms. Is. Here, the fluoroalkyl group represents one in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom.

Since Rf ₁ is a fluoroalkyl group, the fluorine-based resin of the present invention exhibits affinity with a fluorine-based solvent. Further, since the formula (1) has an ester bond which is a polar group adjacent to the main chain, the fluorine-based resin film coated with the fluorine-based resin is highly flexible, flat and has no cracks. A fluorine-based resin film can be obtained.

When Rf ₁ is a linear fluoroalkyl group, the specific Rf ₁ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group substituted with a fluorine atom. , Nonyl group or alkyl group having 10 to 14 carbon atoms can be exemplified. In Rf ₁ , a hydrogen atom bonded to a carbon atom other than a carbon atom directly bonded to oxygen may be substituted with a fluorine atom.

When Rf ₁ is a linear fluoroalkyl group, it is preferably a group represented by the following formula (5).

(Here, X is either a hydrogen atom or a fluorine atom. N is an integer of 1 to 4, and m is an integer of 1 to 14.)

This makes it easier to synthesize a monomer as a raw material for each residue represented by the formula (1).

In the formula (5), n is an integer of 1 to 4, preferably 1 to 2.

In the formula (5), m is an integer of 1 to 14, preferably 2 to 10, and more preferably 4 to 8.

When Rf ₁ is a branched fluoroalkyl group, specific Rf ₁ is 1,1,1,3,3,3-hexafluoroisopropyl group, 1- (trifluoromethyl) -2,2,3. , 3,3-Pentafluoropropyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group or 1,1-bis (trifluoromethyl) ethyl group can be exemplified. ..

The residue unit represented by the formula (1) is preferably a group represented by the following formula (6).

(Here, R ₁ represents either a hydrogen atom or a methyl group. X is either a hydrogen atom or a fluorine atom. N is an integer of 1 to 4, and m is an integer of 1 to 14. .)

In formula (6), n is an integer of 1 to 4, preferably 1 to 2.

In the formula (6), m is an integer of 1 to 14, preferably 2 to 10, and more preferably 4 to 8.

The fluororesin of the present invention may contain one kind of residue unit represented by the formula (1), or may contain two or more kinds. For example, it may contain residue units of both the linear fluoroalkyl group described above and the fluoroalkyl group on the branch, or may contain residue units containing two or more linear fluoroalkyl groups having different carbon atoms. But it may be. The fluororesin of the present invention preferably contains one residue unit represented by the formula (1).

As the residue unit represented by the formula (1) in the fluororesin of the present invention, specifically, at least a group consisting of the residue units represented by the following formulas (A-1) to (A-33). One type can be mentioned.

As the residue unit represented by the formula (1), at least one of the group consisting of the residue units represented by the above formulas (A-1) to (A-33) is preferable, and the formula (A-9). At least one of the groups consisting of ~ (A-33) is more preferable, and even more preferably, the group consisting of formulas (A-14) to (A-21) or formulas (A-27) to (A-33). At least one is preferable.

The fluororesin of the present invention is an acrylic having at least one of a group consisting of a group represented by the formula (2), a group represented by the formula (3), and a group represented by the formula (4) in the side chain. Contains system resin residue units. As a result, the fluororesin of the present invention has excellent photocrosslinkability, and it is possible to selectively insolubilize only the light-irradiated portion.

The acrylic resin residue unit is preferably a residue unit represented by the following formula (7).

(Here, R ₂ represents either a hydrogen atom or a methyl group. R ₃ represents any of a single bond, a methylene group, and an ethylene group. G represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, and a carboxy group. Represents one of a group consisting of an alkyl group, an alkyl ether group, an aryl ether group, a methyl group, an ethyl group, a propyl group, a fluoroalkyl group, or a cycloalkyl group. Represents either. E is a group represented by one of the groups consisting of formulas (2), (3) or (4).)

In formula (7), R ₂ represents either a hydrogen atom or a methyl group.

In formula (7), R ₃ represents one of a group consisting of a single bond, a methylene group and an ethylene group. R ₃ is preferably a single bond or a methylene group, more preferably a single bond.

In formula (7), G represents one of a group consisting of a single bond, a methylene group, and an ethylene group. More preferably, G is one of a group consisting of a single bond and a methylene group.

In formula (7), I is a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a methyl group, an ethyl group, a propyl group, a fluoroalkyl group, or a cyclo. Represents any of the alkyl groups. The old word that I is a hydroxyl group, a halogen atom, or an aryl ether group is preferable, and I is more preferably a chlorine atom.

In formula (7), E is a group represented by one of the groups consisting of formulas (2), (3) or (4). E is preferably a group represented by either the formula (2) or (3), and more preferably a group represented by the formula (2).

Examples of the group represented by the specific formula (2) include the following. In the formula, * is the part that binds to the side chain.

Examples of the group represented by the specific formula (3) include the following.

Examples of the group represented by the specific formula (4) include the following.

The acrylic resin residue unit in the fluororesin of the present invention preferably has a group represented by the formula (2) in the side chain. Since the monomer that is the raw material of the residue unit can be more easily synthesized, the acrylic resin residue unit is the residue unit containing the side chain represented by the formula (2), and the residue unit is the following formula. It is preferably a residue unit represented by (8).

(Here, R ₂ represents either a hydrogen atom or a methyl group. B ₄ is the same or different and consists of a hydrogen atom, _{an alkyl group of C 1 to} C ₆ , a halogen atom, a cyano group, or an aryl group. D represents the same or different hydrogen atom, halogen atom, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, _{alkyl group of C 1 to} C ₁₈ , fluoroalkyl group, Alternatively, it represents one of a group consisting of cycloalkyl groups. M represents either a halogen atom or an aryl ether group.)

In formula (8), R ₂ represents either a hydrogen atom or a methyl group, preferably a methyl group.

Wherein (8), B ₄ are the same or different, a hydrogen atom, an alkyl group of C ₁ -C _6, halogen atom, represent one of the group consisting of cyano group, or an aryl group, preferably a hydrogen atom or a C _{It is any of the alkyl groups 1 to} C ₆ , and more preferably a hydrogen atom.

In formula (8), D is the same or different, hydrogen atom, halogen atom, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, _{alkyl group of C 1 to} C ₁₈ , fluoroalkyl group, Alternatively, it represents one of a group consisting of cycloalkyl groups, preferably either a hydrogen atom or _{an alkyl group of C 1 to} C ₁₈ , and more preferably a hydrogen atom.

In formula (8), M represents either a halogen atom or an aryl ether group, and is preferably a halogen atom.

Specific examples of the acrylic resin residue unit in the fluororesin of the present invention include at least one of a group consisting of residue units represented by the following formulas (B-1) to (B-22). Can be done.

As the acrylic resin residue unit, at least one of the group consisting of the residue units represented by the above formulas (B-1) to (B-15) is preferable, and the formulas (B-1) to (B-3) are preferable. ) Are more preferred.

The fluororesin of the present invention is preferably a copolymer containing a residue unit represented by the formula (1) and a residue unit represented by the formula (7). Specifically, it is preferably a copolymer represented by the following formula (9).

(Here, R ₁ and R ₂ independently represent either a hydrogen atom or a methyl group. Rf ₁ is a linear fluoroalkyl group having 1 to 15 carbon atoms and a branched chain having 3 to 15 carbon atoms. Represents one of a group consisting of a fluoroalkyl group or a cyclic fluorine-containing hydrocarbon group having 3 to 15 carbon atoms. R ₃ represents a single bond, a methylene group, or an ethylene group. G represents a hydrogen atom or a halogen. Represents one of a group consisting of an atom, a cyano group, a nitro group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a methyl group, an ethyl group, a propyl group, a fluoroalkyl group, or a cycloalkyl group. I is absent. Or represents either a halogen atom or an aryl ether group. E is a group represented by one of the group consisting of the formulas (2), (3) or (4).)

In formula (9), R ₁ and Rf ₁ are synonymous with formula (1).

In equation (9), R ₂ , R ₃ , G, I, and E are synonymous with equation (7).

The copolymer represented by the formula (9) may be a random copolymer or a block copolymer.

The fluororesin of the present invention is preferably a copolymer containing a residue unit represented by the formula (6) and a residue unit represented by the formula (8). Specifically, it is preferably a copolymer represented by the following formula (10).

(Here, R ₁ and R ₂ represent either a hydrogen atom or a methyl group. X is either a hydrogen atom or a fluorine atom. N is an integer of 1 to 4, and m is 1 to 14. It is an integer. B ₄ is the same or different _{and represents one of a group consisting of a hydrogen atom, an alkyl group of C 1 to} C ₆ , a halogen atom, a cyano group, or an aryl group. D is the same or different and represents hydrogen. .M representing atom, a halogen atom, a cyano group, a nitro group, carboxyalkyl group, alkyl ether group, an aryl ether group, an alkyl group of C ₁ -C _18, fluoroalkyl group, or one of the group consisting of cycloalkyl, Represents either a halogen atom or an aryl ether group.)

In formula (10), n is an integer of 1 to 4, preferably 1 to 2.

In the formula (10), m is an integer of 1 to 14, preferably 2 to 10, and more preferably 4 to 8.

In formula (10), R ₂ represents either a hydrogen atom or a methyl group, preferably a methyl group.

Wherein (10), B ₄ are the same or different, a hydrogen atom, an alkyl group of C ₁ -C _6, halogen atom, represent one of the group consisting of cyano group, or an aryl group, preferably a hydrogen atom or a C _{It is any of the alkyl groups 1 to} C ₆ , and more preferably a hydrogen atom.

In formula (10), D is the same or different, hydrogen atom, halogen atom, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, _{alkyl group of C 1 to} C ₁₈ , fluoroalkyl group, Alternatively, it represents one of a group consisting of cycloalkyl groups, preferably either a hydrogen atom or _{an alkyl group of C 1 to} C ₁₈ , and more preferably a hydrogen atom.

In formula (10), M represents either a halogen atom or an aryl ether group, preferably a halogen atom.

Since the fluorine-based resin of the present invention is easily dissolved by a fluorine solvent, it is preferable that the residue unit represented by the formula (1) is contained in an amount of 20 mol% or more and 95% mol% or less, and 30 mol% or more and 80% mol% or less. It is preferably contained, and 40 mol% or more and 80 mol% or less is preferable.

Further, it is preferable that the residue unit having a side chain represented by the formula (2), the formula (3) or the formula (4), that is, the acrylic resin residue unit is contained in an amount of 5 mol% or more and 80 mol% or less, preferably 20 mol% or more. It preferably contains 70 mol% or less, and preferably 20 mol% or more and 60 mol% or less. Further, a residue unit may be included in addition to the residue unit represented by the formula (1) and the residue unit represented by the formula (2), the formula (3) or the formula (4). It is preferable that the residue unit is composed only of the residue unit represented by the formula (1) and the residue unit represented by the formula (2), the formula (3) or the formula (4), and does not include any other residue units. ..

As the method for producing the fluororesin of the present invention, any production method can be used as long as a copolymer containing the residue unit represented by the formula (1) and the acrylic resin residue unit can be obtained. .. Specific production methods include (i) a method of synthesizing a monomer of the acrylic resin residue unit in advance and copolymerizing it with a monomer of the residue unit represented by the formula (1), (ii) side. After synthesizing an acrylic resin having a chain having another functional group different from the group represented by the formulas (2) to (4) and a fluororesin having a residue unit represented by the formula (1), Examples thereof include a method of converting the functional group into a photocrosslinkable group.

In the case of (i), a method of radically polymerizing the monomer for inducing the residue unit represented by the formula (1) and the monomer for inducing the acrylic resin residue unit is preferably used.

In the case of (ii), a copolymer containing a residue unit represented by the above formula (1) and a residue unit derived from an acrylic monomer having a chemically convertible functional group in the side chain. As a method for producing (hereinafter, referred to as "precursor resin"), any production method can be used as long as the precursor resin can be obtained, and among them, radical polymerization is carried out because it can be easily produced. The method is preferably used.

Examples of the monomer for inducing the specific formula (1) include compounds represented by the following formula (11).

(Here, R ₁ represents either a hydrogen atom or a methyl group. Rf ₁ is a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched chain fluoroalkyl group having 3 to 15 carbon atoms, or 3 carbon atoms. Represents one of a group consisting of ~ 15 cyclic fluoroalkyl groups.)

Specifically, when Rf ₁ is in the form of a branched chain, for example, 1,1,1,3,3,3-hexafluoropropan-2-ol (molecular formula: CF ₃ CH (OH) CF ₃ ) shown below. , 1,1,1,3,3,4,5,4-octafluorobutane-2-ol (molecular formula: CF ₃ CH (OH) CF ₂ CF ₃ ), 2-trifluoromethyl-1,1,1 , 3,3,3-hexafluoropropan-2-ol (molecular formula: (CF ₃ ) ₃ COH) or 2-trifluoromethyl-1,1,1-trifluoropropan-2-ol (molecular formula: (CF ₃₎₎ ) ₂ (CH ₃ ) COH) can be exemplified by acrylate, methacrylate, α-fluoromethacrylate or α-trifluoromethyl acrylate, respectively, which can be preferably used.

_{When Rf 1} is linear in the formula (11), as a specific example, it may be a compound represented by the following formula (12).

(In the formula, R ₁ represents either a hydrogen atom or a methyl group.
X is either a hydrogen atom or a fluorine atom. n is an integer of 1 to 4, and m is an integer of 1 to 14. )

In the formula (12), n is preferably an integer of 1 to 2 from the viewpoint of easiness of synthesizing the monomer. m is preferably an integer of 2 to 10, and more preferably an integer of 4 to 8.

As the radical polymerization, any known polymerization method, for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a precipitation polymerization method, or an emulsion polymerization method can be adopted.

Examples of the radical polymerization initiator for radical polymerization include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, and dicumylper. Organic radicals such as oxides, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperpivalate; 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azo-based radicals such as azobis (2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (cyclohexane-1-carbonitrile) An initiator and the like can be mentioned.

The solvent that can be used in the solution polymerization method, suspension polymerization method, precipitation polymerization method, and emulsion polymerization method is not particularly limited. For example, aromatic solvents such as benzene, toluene, and xylene; methanol, ethanol, propanol, butanol, etc. Alcohol-based solvent; cyclohexane; dioxane; tetrahydrofuran; acetone; methyl ethyl ketone; dimethylformamide; isopropyl acetate; water and the like, and a mixed solvent thereof is also mentioned.

Further, the polymerization temperature at the time of performing radical polymerization can be appropriately set according to the decomposition temperature of the radical polymerization initiator, and the reaction can be easily controlled. Therefore, the polymerization temperature is generally in the range of 30 to 150 ° C. It is preferable to do so.

Examples of the functional group that can be converted into the photocrossblinkable group contained in the precursor resin include a carboxyl group, a hydroxyl group, an amino group, an acid chloride group, a hydroxyl group, an epoxy group, an oxetanyl group and an azide group. Examples thereof include an aryl halide group capable of a cross-coupling reaction, an aromatic group capable of a Friedelcrafts reaction, an isocyanate group capable of reacting with an amino group and a carboxyl group, etc., which have excellent reactivity and undergo radical copolymerization. An epoxy group, an isocyanate group, a carboxyl group, and an acid chloride group are preferable because they do not inhibit the above.

Specific monomers having the above functional groups include, for example, methacrylic acid, acrylic acid, ω-carboxy-polycaprolactone monoacrylate, monosuccinate (2-acryloyloxyethyl), 6-acrylamidehexanoic acid, 4 -Vinyl benzoic acid, 3-hydroxy-1-adamantyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,4-Cyclohexanedimethanol monoacrylate, 4-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, N- (2-hydroxyethyl) acrylamide, ethylene glycol mono Vinyl ether, vinylphenol, N- (4-hydroxyphenyl) methacrylicamide, N- (hydroxymethyl) acrylamide, 3-aminostyrene, 4-aminostyrene, methacrylic acid 2,2,6,6-tetramethyl-4-piperidyl , Acrylic acid chloride, methacrylic acid chloride, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, methyl acrylate (3-ethyloxetane-3-yl) methyl, methacrylic acid (3-ethyloxetane-3-yl) ) Methyl, 3-iodostyrene, 4-iodostyrene, 3-bromostyrene, 4-bromostyrene, 3-chlorostyrene, 4-chlorostyrene, phenylacrylic acid, phenylmethacrylate, N-phenylmethacrylicamide, N-phenyl Examples thereof include acrylamide, N-benzylmaleimide, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate.

As a method for converting the functional group contained in the precursor resin into a photocrosslinkable group, any method may be used as long as the fluororesin of the present invention can be obtained. For example, a precursor having an epoxy group in the side chain. By allowing a carboxylic acid, an ester, an amine, and an acid chloride having a photocrosslinkable group (hereinafter, referred to as “photocrosslinkable compound”) to act on the resin (hereinafter, referred to as “epoxide modification reaction”), the present invention of the present invention. A fluororesin can be obtained. At this time, it is preferable to use an ester or an acid chloride, and it is particularly preferable to use an acid chloride, because gelation due to the ring-opening cross-linking reaction of the epoxy is difficult to proceed.

Specific examples of the photocrosslinkable compound include the following compounds.

The epoxy modification reaction can be carried out using a reaction catalyst. In the present invention, known catalysts such as ammonium salts, phosphonium salts, amines, and crown ether complexes can be used as reaction catalysts, and specific reaction catalysts include, for example, triethylamine, N, N-dimethyl-4. -Aminopyridine, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, 18- Examples thereof include crown 6-ether / potassium acetate complex, 18-crown 6-ether / potassium fluoride complex, 18-crown 6-ether / potassium bromide complex, 18-crown 6-ether / potassium iodide complex and the like. The amount of the catalyst added is not particularly limited, but due to the limitation of the solubility of the catalyst in the solution and the problem of economy, 0.01 to 0.7 mol with respect to 1 mol of the epoxy contained in the precursor resin. Is preferable, and 0.1 to 0.5 mol is more preferable.

The epoxy modification reaction can be carried out using a reaction solvent. The reaction solvent can be used without any limitation as long as it is stable to the epoxy modification reaction, and a sufficiently dehydrated aliphatic hydrocarbon solvent, an ether solvent, a sulfur-containing solvent, an amide solvent, etc., which are inactive to the reaction, are preferable. Used for. Cyclohexane and the like are used as the aliphatic hydrocarbon solvent, diethylene glycol dimethyl ether, tetrahydrofuran, anisole and the like are used as the ether solvent, tetrahydrothiophene 1,1-dioxide, sulfonedimethylsulfoxide and the like are used as the sulfur-containing solvent, and N is used as the amide solvent. , N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

In the epoxy modification reaction, the reaction temperature is not particularly limited, but is preferably 50 ° C. to 150 ° C. from the viewpoint of reducing the reaction time. In the epoxy modification reaction, the reaction time is not particularly limited, and examples thereof include 1 hour to 30 hours. From the viewpoint of reaction rate and economy, it is preferably 1 to 15 hours.

In the above-mentioned (ii) (a method of synthesizing a fluoropolymer having another functional group and then converting the functional group into a photocrosslinkable group), the side chain has a functional group that can be chemically converted later. Glycidyl methacrylate or glycidyl acrylate is used as the residue unit derived from the monomer, and the acid chloride of the silicate acid derivative (for example, silicate acid chloride) or aryl of the cerebral acid derivative described above is used as the photocrosslinkable compound. By carrying out the epoxy modification reaction using an ester, a resin containing an ethylenically unsaturated monomer residue unit having a photocrossblinking group represented by the formula (6) can be synthesized.

The fluororesin of the present invention may contain other monomer residue units as long as the object of the present invention is not deviated, and examples of the other monomer residue units include ethylene residue. Olefins residues such as groups, propylene residues, 1-butene residues; acrylate alkyl ester residues such as methyl acrylate residues, ethyl acrylate residues, butyl acrylate residues; methyl methacrylate residues , Ethylene methacrylate residues, butyl methacrylate residues and other methacrylate alkyl ester residues; styrene residues, α-methylstyrene residues and other vinyl aromatic hydrocarbon residues; vinyl acetate residues, propionic acid Vinyl acid vinyl ester residues such as vinyl residues and vinyl pivalate residues; Vinyl ether residues such as methyl vinyl ether residues, ethyl vinyl ether residues and butyl vinyl ether residues; N-methylmaleimide residues and N-cyclohexyl Examples thereof include N-substituted maleimide residues such as maleimide residues and N-phenylmaleimide residues; acrylonitrile residues; and methacrylonitrile residues.

In the fluororesin of the present invention, there is no limitation on the molecular weight, and for example, 2000 to 10,000,000 (g / mol) can be used. From the viewpoint of the solution viscosity of the obtained resin and the mechanical strength, it is preferably 10,000 to 1,000,000 (g / mol).

Hereinafter, a composition containing a fluorinated resin and a fluorinated solvent, which is one aspect of the present invention, will be described.

As another aspect of the present invention, the residue unit represented by the formula (1), the group represented by the formula (2) in the side chain, the group represented by the formula (3), and the formula. It is a composition of a fluorine-based resin having an acrylic resin residue unit having at least one of the group consisting of the group represented by (4), and a fluorine-based solvent. In other words, it is a solution containing a fluorine-based resin and a fluorine-based solvent (hereinafter, also referred to as "solution of the present invention"). By using the composition, it is possible to minimize damage to the device constituents mainly composed of organic substances when producing an electronic device by the Zeninsatsu method, and the performance of the electronic device is fully exhibited. It becomes possible.

The fluorinated solvent constituting the solution of the present invention may be any one that dissolves the fluorinated resin of the present invention.

Among the fluorine-based compounds contained in the fluorine-based solvent, the fluorine atom content is 50% by mass or more, 70% by mass or less, more preferably 55% by mass or more and 70% by mass or less, based on the total mass of the fluorine-based compound. .. If it exceeds 70% by mass, the above-mentioned fluororesin will not be sufficiently dissolved. If it is less than 50% by mass, the surface of the organic semiconductor film may be melted or swollen when it is applied or printed on the organic semiconductor film. As the fluorine-based solvent contained in the composition of the present invention, the following fluorine-containing hydrocarbons or fluorine-containing ethers can be preferably used.

Fluorine-containing hydrocarbons have a low ozone depletion potential and are preferable as the fluorine-based solvent contained in the composition of the present invention. In particular, linear, branched-chain or cyclic hydrocarbons having 4 to 8 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom are preferable because they are easy to apply.

Specific examples of such fluorine-containing hydrocarbons include those in which at least one hydrogen atom of butane, pentane, hexane, heptane, octane, cyclopentane or cyclohexane is replaced with a fluorine atom. Specifically, for example, CH ₃ CF ₂ CH ₂ CF ₃ , CF ₃ CHFCHFCF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ CH ₃ , Fluorine-containing hydrocarbons of hexafluorocyclopentane. Can be exemplified.

The boiling point of the fluorine-containing hydrocarbon needs to be higher than the substrate temperature at the time of coating the composition, and is preferably 20 ° C. or higher, more preferably 50 ° C. or higher than the coating temperature. If the boiling point of the fluorine-containing hydrocarbon is lower than the substrate temperature at the time of coating the composition, the fluorine-containing hydrocarbon rapidly volatilizes during the coating operation, and it is difficult to obtain sufficient flatness in the formed fluorine-based resin film. The fluorine-containing hydrocarbon used preferably has a boiling point of 200 ° C. or lower, more preferably 180 ° C. or lower. When the boiling point of the fluorine-containing hydrocarbon is 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 composition.

Among the fluorine-containing hydrocarbons, the following can be exemplified as an example having a particularly preferable boiling point.

Examples thereof include Bertrel XF (manufactured by Mitsui-Dupont Fluorochemical Co., Ltd.), Zeolara H (boiling point manufactured by Nippon Zeon Co., Ltd.), Asahiclean AC-6000, and Asahiclean AC-2000 (manufactured by Asahi Glass Co., Ltd.).

Further, since the ozone depletion potential is low, a fluorine-containing ether can be used as the fluorine-based solvent. In particular, the boiling point of the fluorine-containing ether needs to be higher than the substrate temperature at the time of coating the composition, and is preferably 20 ° C. or higher, more preferably 50 ° C. or higher than the coating temperature. If the boiling point of the fluorine-containing ether is lower than the substrate temperature at the time of coating the composition, the fluorine-containing aliphatic ether rapidly volatilizes during the coating operation, and it is difficult to obtain sufficient flatness in the formed fluorine-based resin film. The fluorine-containing ether used preferably has a boiling point of 200 ° C. or lower, more preferably 180 ° C. or lower. When the boiling point of the fluorine-containing ether is 200 ° C. or lower, the fluorine-containing ether can be easily evaporated and removed by heating from the fluorine-based resin film formed by applying the composition.

Examples of preferred fluorine-containing ethers are 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-tetrafluoro) Propoxy) propane or 2,2,3,3,3-pentafluoro-1- (1,1,2,2-tetrafluoroethoxy) propane can be exemplified.

Examples of the fluorine-containing ether having a preferable boiling point include Novec 7000, Novec 7100, Novec 7200, Novec 7300, Novec 7500, Novec 7600 (manufactured by Sumitomo 3M Ltd.), and Asahi Clean AE-3000 (manufactured by Asahi Glass Co., Ltd.). Can be done.

Further, since the coating stability is high, a fluorinated alcohol can be used as the fluorinated solvent. In particular, the boiling point of the fluorinated alcohol needs to be higher than the substrate temperature at the time of coating the composition, preferably 20 ° C. or higher, more preferably 50 ° C. or higher than the coating temperature. If the boiling point of the fluorinated alcohol is lower than the substrate temperature at the time of coating the composition, the fluorinated fatty alcohol rapidly volatilizes during the coating operation, and it is difficult to obtain sufficient flatness for the fluorinated resin film formed. The fluorinated alcohol used preferably has a boiling point of 200 ° C. or lower, more preferably 180 ° C. or lower. When the boiling point of the fluorinated alcohol is 200 ° C. or lower, the fluorinated alcohol can be easily evaporated and removed by heating from the fluorinated resin film formed by applying the composition.

Examples of preferred fluoroalcohols 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, 1H, 1H, 3H-hexafluorobutanol can be exemplified.

Further, two or more kinds of fluorine solvents may be contained in order to flatten the applied film.

The composition of the fluorine-based resin and the fluorine-based solvent of the present invention preferably contains 1 wt% or more and 50 wt% or less of the fluorine-based resin and 50 wt% or more and 99 wt% or less of the above-mentioned fluorine-based solvent, and more preferably fluorine. It is a composition containing 1 wt% or more and 30 wt% or less of a based resin and 70 wt% or more and 99 wt% or less of the above-mentioned fluorine-based solvent.

The composition of the fluororesin and the photosensitizer, which is one aspect of the present invention, will be described below.

The fluororesin of the present invention may contain a photosensitizer. Here, any one that promotes the cross-linking reaction of the photocrosslinkable group may be used. When the photosensitizer is contained, the composition of the fluororesin of the present invention and the photosensitizer may be used, or the above-mentioned solution of the present invention may further contain the photosensitizer.

Photosensitizers include, for example, hydrocarbons such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloro. Carbonyls such as anthraquinone and cyclohexanone; diketones such as diacetyl and benzyl; organic sulfides such as diphenylmonosulfide, diphenyldisulfide and tetramethylthiuram disulfide; acetophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone , 4,4'-Bis (diethylamino) benzophenone, o-methoxybenzophenone, 2,4,6-trimethoxybenzophenone and other phenones; p-toluenesulfonyl chloride, 1-naphthalenesulfonyl chloride, 1,3-benzene Hydrocarbons such as sulfonyl chloride, 2,4-dinitrobenzenesulfonyl bromide, p-acetamidebenzenesulfonyl chloride; 5-nitrofluorene, 5-nitroacenaften, N-acetyl-4-nitro-1-naphthylamine, biclamide and the like. Aromatic nitro compounds; coumarins such as 7-diethylamino-3-tenoyl coumarin, 3,3'-carbonylbis (7-diethylamino coumarin); carbon tetrachloride, hexabromoethane, 1,1,2,2- Halogenated hydrocarbons such as tetrabromoethane; nitrogen derivatives such as diazomethane, abbisisobutyronitrile, hydrazine and trimethylbenzylammonium chloride; pigments such as ethionine, thionin and methylenebul. By adding a photosensitizer, the fluororesin of the present invention can be crosslinked (insolubilized) with a lower exposure amount. In addition, two or more kinds of the sensitizer can be used in combination as needed.

The composition of the fluorine-based resin and the photosensitizer of the present invention preferably contains 70 wt% or more and 99.99 wt% or less of the fluorine-based resin and 0.01 wt% or more and 30 wt% or less of the photosensitizer. More preferably, it is a composition containing 80 wt% or more and 99.9 wt% or less of a fluororesin and 0.1 wt% or more and 15 wt% or less of a photosensitizer.

When the solution of the present invention further contains a photosensitizer, it contains 1 wt% or more and 50 wt% or less of a fluorine-based resin, 50 wt% or more and 99 wt% or less of a fluorine-based solvent, and 0.001 wt% or more and 5 wt% or less of a sensitizer. It is preferable that the fluorine-based resin is 1 wt% or more and 30 wt% or less, the fluorine-based solvent is 70 wt% or more and 99 wt% or less, and the sensitizer is 0.01 wt% or more and 3 wt% or less.

Hereinafter, a pattern composed of a fluororesin, which is one aspect of the present invention, will be described.

The fluororesin of the present invention can form a pattern.

First, a pattern forming method using the fluororesin of the present invention or a composition thereof will be described.

First, a coating film of a fluororesin is formed on the surface of the base material by a known coating film forming method.
Examples of the base material include various glass plates; polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene; thermoplastic sheets of polycarbonate, polymethylmethacrylate, polysulfone, and polyimide; epoxy resin; polyester resin; poly (meth) acrylic. Examples thereof include a heat-curable plastic sheet such as a resin.

Examples of the coating film forming method 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, and flexography. Printing, super flexographic printing, screen printing, inkjet printing, letterpress reversal printing, reversal offset printing, adhesive force contrast printing and the like can be used.

The coating is then dried. By drying, the solvent is volatilized and a non-adhesive coating film is obtained. The drying conditions vary depending on the boiling point of the solvent used, the mixing ratio, and the like, but preferably, it can be used in a wide range of about 50 to 150 ° C. and 10 to 2000 seconds.

When a predetermined pattern is formed by using a printing method at the time of forming a coating film, the pattern can be photocrosslinked and fixed by exposure to form the pattern.

On the other hand, when the pattern is not formed at the time of forming the coating film, a predetermined pattern can be formed on the coating film by using the photolithography technique. When the photolithography technique is used, first, the dried coating film is exposed through a mask having a predetermined pattern and photocrosslinked.

When the fluororesin of the present invention is cured by photocrosslinking, radiation such as ultraviolet rays and visible light is used, and examples thereof include ultraviolet rays having a wavelength of 245 to 435 nm. The irradiation amount is appropriately changed depending on the composition of the resin, and examples ^{thereof include 10 to 5000 mJ / cm 2, which} is preferable in order to prevent a decrease in the degree of cross-linking and to improve economic efficiency by shortening the process. It is 100 to 4000 mJ / cm ² . Specific light irradiation devices or light sources include, for example, germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and the like. Can be mentioned.

The irradiation of ultraviolet rays is usually carried out in the atmosphere, but can also be carried out in an inert gas or in a constant amount of an inert gas stream, if necessary. If necessary, the above-mentioned photosensitizer can be added to promote the photocrosslinking reaction. Then, it is developed with a developing solution to remove an unexposed portion. The developing solution may be any solvent as long as it dissolves an uncured fluororesin, for example, an aromatic solvent such as benzene, toluene or xylene; an ether solvent such as dioxane, diethyl ether, tetrahydrofuran or diethylene glycol dimethyl ether; Ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and propylene glycol monomethyl ether acetate can be used.

The development time is preferably 30 to 300 seconds. Further, the developing method may be any of a liquid filling method, a dipping method and the like. After development, the solvent on the substrate is removed by washing with a solvent and air-drying with compressed air or compressed nitrogen. Subsequently, a pattern is formed by heat-treating with a heating device such as a hot plate or an oven at preferably 40 to 150 ° C. for 5 to 90 minutes.

After forming the pixel pattern through the above photolithography step, dirt on the surface of the base material in the pixel may be removed. For example, the surface of the base material may be cleaned by irradiation with short-wavelength ultraviolet rays such as a low-pressure mercury lamp or excimer UV, or by light ashing treatment. The optical ashing process is a process of irradiating short-wavelength ultraviolet rays 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.

As described above, the fluorine-based resin of the present invention is itself soluble in a fluorine-based solvent or an organic solvent, and by light irradiation, the photocrosslinkable groups in the side chains are crosslinked and cured, and the fluorine-based solvent or organic is obtained. Insoluble in solvent. Utilizing this property, when the fluorine-based resin of the present invention is crosslinked by light irradiation, it can be used as a negative resist in which a portion not irradiated with light by a fluorine-based solvent or an organic solvent is removed.

After patterning the fluororesin of the present invention, the contact angle with respect to the ink is preferably 50 ° or more in order to prevent the ink from spreading in the portion (outside the pattern) where the fluororesin is crosslinked and remains.

The fluorine-based resin of the present invention has excellent liquid-repellent properties and can be used as a pattern material for manufacturing organic transistor elements, color filters, and organic EL elements. Further, the fluororesin of the present invention can be used for an electronic device including the above-mentioned organic transistor element, color filter, and organic EL element.

The electronic device according to one aspect of the present invention will be described in detail below.

The fluororesin of the present invention can be used as a member constituting an electronic device. An organic transistor can be mentioned as an electronic device.

When the fluororesin of the present invention is used for an organic transistor, the organic transistor has a gate insulating layer on a substrate, and an organic semiconductor layer is further formed on the gate insulating layer to form a source electrode, a drain electrode, and a drain electrode. It can be obtained by attaching a gate electrode.

The organic transistor of the present invention is of the 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 FIG. Any element structure may be used. Here, 1 is an organic semiconductor layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

In the organic transistor, the base material that can be used is not particularly limited as long as sufficient flatness that can fabricate the element can be ensured. , Inorganic material substrate such as indium tin oxide; Plastic; Metal such as gold, copper, chromium, titanium, aluminum; Ceramics; Coated paper; Surface coated non-woven fabric, etc. May be a multi-layered material. It is also possible to coat the surfaces of these materials in order to adjust the surface tension.

The plastics used as the base material include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene / vinyl acetate copolymer, polymethylpentene-1, and polypropylene. , Cyclic polyolefin, Fluorinated cyclic polyolefin, Polyester, Polyester, Polypolyphenol, Polyvinyl alcohol, Poly (diisopropyl fumarate), Poly (diethyl fumarate), Poly (diisopropyl maleate), Polyether sulfone, Polyphenylene sulfide, Polyphenylene ether, Examples thereof include polyester elastomers, polyurethane elastomers, polyolefin elastomers, polyamide elastomers, and styrene block copolymers. In addition, two or more of the above plastics can be laminated and used as a base material.

The organic semiconductor that can be used in the present invention is not limited in any way, and either N-type or P-type organic semiconductor can be used, and it can also be used as a bipolar transistor that combines N-type and P-type. Further, both small molecule and high molecular weight organic semiconductors can be used, and these can be mixed and used. Specific examples of the compounds include formulas (F-1) to (F-11).

In the present invention, examples of the method for forming the organic semiconductor layer include a method of vacuum-depositing an organic semiconductor, a method of dissolving an organic semiconductor in an organic solvent, coating and printing, and the like. There are no restrictions as long as it can be formed. The solution concentration when coating or printing with a solution of an organic semiconductor layer in an organic solvent 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 thickness of the layer. Therefore, it is preferably 0.5% to 5% by weight. The organic solvent at this time is not limited as long as the organic semiconductor is dissolved at a constant concentration capable of forming a film, and is hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, decalin, indan, 1-methylnaphthalene, 2 -Ethylnaphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mecitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetraline, 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-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, ethylacetate, phenylacetate, 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, isophorontriacetindecahydro-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, tet Examples thereof include lahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N, N-dimethylformamide, N-methyl-2-pyrrolidone, limonene and the like. A solvent having a high dissolving power of an organic semiconductor and a boiling point of 100 ° C. or higher is suitable for obtaining the crystal film of, xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-. Dimethylanisole, pentylbenzene, tetraline, cyclohexanbenzene and decahydro-2-naphthol are preferred. Further, a mixed solvent in which two or more of the above-mentioned solvents are mixed at an appropriate ratio can also be used.

Various organic / inorganic polymers or oligomers, or organic / inorganic nanoparticles can be added to the organic semiconductor layer as a solid or as a dispersion liquid in which the nanoparticles are dispersed in water or an organic solvent, if necessary, on the insulating layer. A protective film can be formed by applying a polymer solution to the solvent. Further, various moisture-proof coatings, light-resistant coatings and the like can be applied on the protective film as needed.

Examples of the gate electrode, source electrode, or drain electrode that can be used in the present invention include aluminum, gold, silver, copper, high-doped silicon, polysilicon, VDD, tin oxide, indium oxide, indium tin oxide, and chromium. Examples of conductive materials such as inorganic electrodes such as platinum, titanium, tantalum, graphene, and carbon nanotubes, or organic electrodes such as a doped conductive polymer (for example, PEDOT-PSS) are exemplified, and a plurality of these conductive materials are used. , Can also be used in layers. Further, in order to increase the injection efficiency of carriers, it is also possible to carry out surface treatment using a surface treatment agent on these electrodes. Examples of such a surface treatment agent include benzenethiol, pentafluorobenzenethiol and the like.

Further, the method of forming an electrode on the base material, the insulating layer or the organic semiconductor layer is not particularly limited, and examples thereof include thin film deposition, high frequency sputtering, electron beam sputtering, etc., and the nanoparticles of the conductive material are water-based or Solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexo printing, super flexo printing, screen printing, inkjet printing, letterpress inversion using ink dissolved in an organic solvent. A method such as printing can also be adopted.

From the viewpoint of practicality of the organic transistor element, the organic transistor of the present invention ^{preferably has a mobility of 0.20 cm 2} / Vs or more.

Organic transistor of the present invention, from the viewpoint of practicality of the organic transistor device, it is preferable on current / off current ratio of 10 ⁵ or more.

From the viewpoint of practicality of the organic transistor element, the organic transistor of the present invention preferably has no hysteresis of the source-drain current.

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, the molecular weight, the solubility in a fluorosolvent, the spin coating, the film thickness measurement, the UV irradiation, the evaluation method of the photocrosslinking (curing) property, the pattern formation, and the liquid repellent property are shown below. It was carried out under the conditions and equipment.

<Composition of fluororesin>
^{It was obtained by proton nuclear magnetic resonance spectroscopy (1} H-NMR) spectral analysis using a nuclear magnetic resonance measuring device (manufactured by JEOL Ltd., trade name JNM-ECZ400S).
<Solubility in fluorine-based solvent>
The fluorine-based resin and the resin for the comparative example were added to each fluorine solvent in an amount of 3 wt% or 10 wt% and mixed at room temperature, and it was visually confirmed whether or not there was an insoluble component.
<Spin coating>
MS-A100 manufactured by Mikasa Co., Ltd. was used.
<Film thickness measurement>
The measurement was performed using a Bruker Dectak XT stylus profiler.
<UV irradiation>
Using a UV mask aligner manufactured by Ushio Lighting Co., Ltd., UPE-1605MA, the UV irradiation time was adjusted by changing the transport speed under the condition of ^{UV intensity of 13.0 mW / cm 2.}
<Evaluation method of photocrosslinking (curing) property>
A fluororesin solution was spin-coated on a washed and dried 30 × 30 mm ² glass substrate (EagleXG manufactured by Corning Inc.) using a spin coater, and the film was sufficiently dried. The fluorine-based resin film was ^{irradiated with ultraviolet rays of 100 to 4000 mJ / cm 2} to photocrosslink the fluorine-based resin film. The thickness of the fluororesin film after photocrosslinking was T _0. Next, the glass substrate coated with the photocrosslinked fluororesin film was immersed in xylene or AE-3000 (manufactured by AGC), which is a good solvent for the fluororesin, for 1 minute. The removed base material was dried at 100 ° C. for 1 minute using a hot plate. The thickness of the fluororesin film after drying was defined as T ₁ . Using these film thickness measurement values, the residual film ratio (R) was calculated by the following formula.
R = T ₁ / T ₀ x 100 (%)
The photocrosslinking (curing) property was evaluated using a residual film ratio of 95% or more as a criterion for crosslinking. Hereinafter referred to as "photocrosslinkability evaluation"). Further, it is shown that the lower the irradiation with ultraviolet rays having a residual film ratio of 95% or more, the higher (faster) the photocrosslinkability.
<Pattern formation>
A mask (pattern forming mask) in which 10 squares having a side of 10 microns were arranged vertically and 10 horizontally were patterned with chrome on a 10 cm × 10 cm quartz glass was used. A mask is placed on a film of a fluororesin or composition having a thickness of 500 nm formed on a substrate and irradiated with ultraviolet rays, and then the uncrosslinked portion is washed and removed with Asahiclean AE-3000 (manufactured by AGC) or acetone. As a result, a pattern having 100 holes of 50 × 50 μm ^{2 size was formed on the film.}
<Evaluation method of liquid repellency (water repellency / oil repellency)>
A solution of a fluororesin (3 wt%) was spin-coated on a washed and dried 30 × 30 mm ² glass (Eagle XG manufactured by Corning Inc.) under the conditions of 500 rpm × 5 seconds and 1000 rpm × 20 seconds. When UV irradiation was performed, ultraviolet rays of ^{500 mJ / cm 2 were irradiated.} The substrate was immersed in a solvent similar to that used for the fluorine-based resin solution for 1 minute, taken out, rinsed with acetone, blown with nitrogen gas, and dried. The contact angle with respect to water, diiodomethane, and tetralin was measured by the θ / 2 method using a contact angle meter (manufactured by Kyowa Surface Chemistry Co., Ltd., trade name DM-300) (hereinafter referred to as “liquid repellent property evaluation”).

<Synthesis of fluororesin>
Example 1
(Manufacturing of Fluorine Resin Precursor 1)
13.45 g (25.3 mmol) of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 1.54 g (10.8 mmol) of glycidyl methacrylate, 2,4 as a chain transfer agent in a glass ampol with a capacity of 75 mL. Add 0.10 g (0.41 mmol) of -diphenyl-4-methyl-1-pentene and 0.14 g (0.36 mmol as peroxide molecule) of perhexyl ND (manufactured by Nichiyu) as a polymerization initiator, and replace with nitrogen. After repeating depressurization, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 8 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 30 g of Zeolola H (manufactured by ZEON CORPORATION). This polymer solution was added dropwise to 300 mL of methanol to precipitate, and then washed 3 times with 300 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 7.5 g of the fluororesin precursor 1 (yield: 50%). In addition, by ¹ H-NMR measurement, the copolymer composition was 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate residue unit / glycidyl methacrylate residue unit = 69.2 / 30.8 (mol%). ) Was confirmed.
(Manufacturing of Fluorine Resin 1)
After heating and drying a Schlenk tube with a capacity of 20 mL, add 1 g of fluororesin precursor 1 and 0.37 g of fluorinated resin precursor, 0.1 g of tetraethylammonium chloride as a catalyst, and 6 mL of dehydrated hexafluorobenzene under a nitrogen atmosphere, and seal with a stopcock. bottom. After stirring at room temperature until the fluororesin precursor 1 was dissolved, the mixture was stirred in an oil bath at 80 ° C. for 8 hours. The obtained resin solution was added dropwise to 100 mL of hexane to precipitate, and then washed twice with 50 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 4 hours to obtain 1.5 g of a fluororesin 1. Further, by ^{1 1} H-NMR measurement, it was confirmed that the glycidyl methacrylate residue unit of the raw material was reduced and converted to the residue unit represented by the following formula (13). As a result, the ^{copolymerization composition of the fluororesin 1 by} 1H-NMR measurement is represented by methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl residue unit (fluorine-based unit 1) / formula (13). It was confirmed that the formula (14) of the residue unit (photocrosslinking group unit) = 72.5 / 27.5 (mol%).

Example 2
(Manufacturing of Fluorine Resin Precursor 2)
1.94 g (7.4 mmol) of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 1.05 g (7.4 mmol) of glycidyl methacrylate, 2,4 as a chain transfer agent in a glass ampoule having a capacity of 15 mL. Add 0.04 g (0.17 mmol) of -diphenyl-4-methyl-1-pentene and 0.06 g (0.15 mmol as peroxide molecule) of perhexyl ND (manufactured by Nichiyu) as a polymerization initiator, and substitute with nitrogen. After repeating depressurization, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 8 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 8 g of Zeolola H (manufactured by ZEON CORPORATION). This polymer solution was added dropwise to 100 mL of methanol to precipitate, and then washed 3 times with 100 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 1.6 g of a fluororesin precursor 2. (Yield: 32%). In addition, by ¹ H-NMR measurement, the copolymer composition was 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate residue unit / glycidyl methacrylate residue unit = 50.1 / 49.9 (mol%). ) Was confirmed.
(Manufacturing of Fluorine Resin 2)
After heating and drying a Schlenk tube with a capacity of 20 mL, add 1 g of fluororesin precursor 2 and 0.74 g of fluorinated resin precursor, 0.2 g of tetraethylammonium chloride as a catalyst, and 6 mL of dehydrated hexafluorobenzene under a nitrogen atmosphere, and seal with a stopcock. bottom. After stirring at room temperature until the fluororesin precursor 2 was dissolved, the mixture was stirred in an oil bath at 80 ° C. for 8 hours. The obtained resin solution was added dropwise to 100 mL of hexane to precipitate, and then washed twice with 50 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 4 hours to obtain 1.5 g of a fluororesin 2. In addition, ^{1 1} H-NMR measurement confirmed that the glycidyl methacrylate residue unit of the raw material was reduced and converted to the residue unit represented by the formula (12). As a ^result, 1 copolymer composition of the fluorine-based resin 2 by H-NMR measurement is represented in methacrylate IH, IH, 2H, 2H-heptadecafluorodecyl residue unit (fluorine-based unit 1) / (13) It was confirmed that the formula (15) of the residue unit (photocrosslinking group unit) = 53.3 / 46.7 (mol%). ^{The 1} H-NMR chart of the obtained fluororesin 2 is shown in FIG.

Example 3
(Manufacturing of Fluorine Resin Precursor 3)
13,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 13.14 g (30.4 mmol), methacrylic acid in a glass ampoule having a capacity of 75 mL. 1.85 g (13.0 mmol) of glycidyl, 0.12 g (0.50 mmol) of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and perhexyl ND (manufactured by Nichiyu) 0 as a polymerization initiator. .17 g (0.43 mmol as peroxide molecule) was added, and after repeating nitrogen substitution and depressurization, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 8 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 30 g of Zeolola H (manufactured by ZEON CORPORATION). This polymer solution was added dropwise to 300 mL of methanol to precipitate, and then washed 3 times with 300 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 7 g of a fluororesin precursor 3. (Yield: 46.7%). In addition, ¹ H-NMR measurement revealed that the copolymer composition was methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl residue unit. It was confirmed that (fluorine-based unit 2) / glycidyl methacrylate residue unit (photocrosslinking group unit) = 71.2 / 28.8 (mol%).
(Manufacturing of Fluorine Resin 3)
After heating and drying a Schlenk tube with a capacity of 20 mL, add 1 g of fluororesin precursor 3 and 0.37 g of fluorinated resin precursor, 0.1 g of tetraethylammonium chloride as a catalyst, and 6 mL of dehydrated hexafluorobenzene under a nitrogen atmosphere, and seal with a stopcock. bottom. After stirring at room temperature until the fluororesin precursor 3 was dissolved, the mixture was stirred in an oil bath at 80 ° C. for 8 hours. The obtained resin solution was added dropwise to 100 mL of hexane to precipitate, and then washed twice with 50 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 4 hours to obtain 1.5 g of a fluororesin 3. In addition, ^{1 1} H-NMR measurement confirmed that the glycidyl methacrylate residue unit of the raw material was reduced and converted to the residue unit represented by the formula (12). As a result, ¹ H-NMR measurement revealed that the copolymer composition of the fluororesin 3 was 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoromethacrylate. Confirm that the octyl residue unit (fluorine-based unit 2) / residue unit (photocrosslinking group unit) represented by the formula (13) = 73.7 / 26.3 (mol%) formula (16). bottom.

Example 4
(Manufacturing of Fluorine Resin Precursor 4)
20.70 g (38.9 mmol) of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 5.45 g (54.5 mmol) methyl methacrylate, 8.84 g (62) of glycidyl methacrylate in a glass ampol with a capacity of 75 mL. .2 mmol), 0.42 g (1.7 mmol) of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 0.61 g (peroxide) of perhexyl ND (manufactured by Nichiyu) as a polymerization initiator. 2.2 mmol) was added as a molecule, and after repeating nitrogen substitution and depressurization, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 8 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 50 g of 2-butanone. This polymer solution was added dropwise to 500 mL of methanol to precipitate, and then washed 3 times with 500 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 20 g of the fluororesin precursor 4. (Yield: 57.1%). Further, by ¹ H-NMR measurement, the copolymer composition was determined to be methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl residue unit / methyl methacrylate / glycidyl methacrylate residue unit = 23.9 / 33. It was confirmed that it was 0 / 43.1 (mol%).
(Manufacturing of Fluorine Resin 4)
After heating and drying a Schlenk tube having a capacity of 20 mL, 15 g of a fluororesin precursor 4 and 9.0 g of silicic acid chloride, 2.4 g of tetraethylammonium chloride as a catalyst and 150 mL of dehydrated butyl acetate were added under a nitrogen atmosphere, and the mixture was sealed with a stopcock. .. After stirring at room temperature until the fluororesin precursor 4 was dissolved, the mixture was stirred in an oil bath at 80 ° C. for 8 hours. The obtained resin solution was added dropwise to 500 mL of methanol to precipitate, and then washed twice with 500 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 4 hours to obtain 20 g of a fluororesin 4. In addition, ^{1 1} H-NMR measurement confirmed that the glycidyl methacrylate residue unit of the raw material was reduced and converted to the residue unit represented by the formula (12). As a ^result, 1 copolymer composition of the fluorine-based resin 4 by H-NMR measurement, methacrylic acid IH, IH, 2H, 2H-heptadecafluorodecyl residue unit (fluorine-based unit 1) / methyl methacrylate (MMA units) / It was confirmed that the residue unit (photocrosslinking group unit) represented by the formula (13) was the formula (17) of 26.7 / 38.3 / 35.0 (mol%).

Example 5
(Manufacturing of Fluorine Resin Precursor 5)
1H, 1H, 2H, 2H-heptadecafluorodecyl 15.6 g (29.3 mmol), methyl methacrylate 5.43 g (54.3 mmol), glycidyl methacrylate 8.96 g (54.3 mmol) in a glass ampol with a capacity of 75 mL (1H, 1H, 2H, 2H-heptadecafluorodecyl) 63.0 mmol), 0.51 g (2.19 mmol) of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 0.57 g (peroxide) of perhexyl ND (manufactured by Nichiyu) as a polymerization initiator. 1.46 mmol (1.46 mmol) was added as a polymer molecule, and after repeating nitrogen substitution and depressurization, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 8 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 50 g of 2-butanone. This polymer solution was added dropwise to 500 mL of methanol to precipitate, and then washed 3 times with 500 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 17 g of the fluororesin precursor 5 (yield: 56.7%). Further, by ¹ H-NMR measurement, the copolymer composition of the fluororesin precursor 5 was determined to be methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl residue unit / methyl methacrylate residue unit / glycidyl methacrylate. It was confirmed that the residue unit = 18.0 / 34.5 / 47.6 (mol%).
(Manufacturing of Fluorine Resin 5)
After heating and drying a Schlenk tube having a capacity of 50 mL, 15 g of a fluororesin precursor 5 and 9.02 g of fluorinated resin precursor, 2.39 g of tetraethylammonium chloride as a catalyst, and 150 mL of dehydrated butyl acetate were added under a nitrogen atmosphere, and the mixture was sealed with a stopcock. .. After stirring at room temperature until the fluororesin precursor 5 was dissolved, the mixture was stirred in an oil bath at 100 ° C. for 8 hours. The obtained resin solution was added dropwise to 500 mL of methanol to precipitate, and then washed 3 times with 300 mL of methanol. Further, the mixture was vacuum dried at 45 ° C. for 4 hours to obtain 17 g of a fluororesin 5. ¹ It was confirmed by 1 H-NMR measurement that the glycidyl methacrylate residue unit of the raw material disappeared and was converted to the residue unit represented by the formula (13). As a ^result, 1 copolymer composition of the fluorine-based resin 5 by H-NMR measurement, methacrylic acid IH, IH, 2H, 2H-heptadecafluorodecyl residue unit (fluorine-based unit 1) / methyl methacrylate residue unit ( It was confirmed that the residue unit (photocrosslinking group unit) represented by the MMA unit) / formula (13) = 19.1 / 40.8 / 40.1 (mol%) formula (18).

Comparative Example 1
(Manufacturing of Fluorine Resin 6)
1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate 5.0 g (9.4 mmol) in a glass ampoule with a capacity of 15 mL Perhexyl ND (manufactured by Nichiyu) 0.04 g (0 as peroxide molecule) .09 mmol) was added, and after repeating nitrogen substitution and depressurization, the mixture was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 6 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 10 g of Novec 7200 (manufactured by 3M). This polymer solution was added dropwise to 100 mL of hexane to precipitate, and then washed 3 times with 100 mL of hexane. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 4.0 g of a fluororesin 6 (yield: 80.0%).
In addition, ^{it was confirmed by 1} H-NMR measurement that the composition was methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl residue unit (fluorine-based unit 1) = 100.0 (mol%).

Comparative Example 2
(Manufacturing of non-fluorine resin precursor 1)
17.9 g (179.6 mmol) of methyl methacrylate, 17.0 g (119.7 mmol) of glycidyl methacrylate, and 2,4-diphenyl-4-methyl-1-pentene 0 as a chain transfer agent in a glass ampol having a capacity of 75 mL. Add .81 g (3.4 mmol) and 1.16 g (4.3 mmol as peroxide molecule) of perhexyl ND (manufactured by Nichiyu) as a polymerization initiator, repeat nitrogen substitution and depressurization, and then melt under reduced pressure. I sealed it. This ampoule was placed in a constant temperature bath at 45 ° C. and held for 8 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved in 50 g of 2-butanone. This polymer solution was added dropwise to 500 mL of methanol to precipitate, and then washed 3 times with 500 mL of methanol. Further, the mixture was vacuum dried at 30 ° C. for 8 hours to obtain 20 g of the non-fluorinated resin precursor 1 (yield: 71.4%).
Further, ^{it was confirmed by 1 1} H-NMR measurement that the copolymer composition was methyl methacrylate residue unit / glycidyl methacrylate residue unit = 62.7 / 37.3 (mol%).
(Manufacturing of non-fluorine resin 1)
After heating and drying a Schlenk tube with a capacity of 50 mL, add 15 g of non-fluorine resin precursor 1 and 9.02 g of silicic acid chloride, 2.39 g of tetraethylammonium chloride as a catalyst, and 150 mL of dehydrated butyl acetate under a nitrogen atmosphere, and seal with a stopcock. bottom. After stirring at room temperature until the non-fluorinated resin precursor 1 was dissolved, the mixture was stirred in an oil bath at 100 ° C. for 8 hours. The obtained resin solution was added dropwise to 500 mL of methanol to precipitate, and then washed 3 times with 300 mL of methanol. Further, the mixture was vacuum dried at 45 ° C. for 4 hours to obtain 17 g of the non-fluorinated resin 1. ¹ It was confirmed by 1 H-NMR measurement that the glycidyl methacrylate residue unit of the raw material disappeared and was converted to the residue unit represented by the formula (13). As a result, the ^{copolymer composition of the non-fluorinated resin 1 was determined by 1} H-NMR measurement as a methyl methacrylate residue unit (MMA unit) / residue unit represented by the formula (13) (photocrosslinking group unit) = 61. It was confirmed that the formula (19) was .1 / 38.9 (mol%).

<Evaluation of liquid repellent characteristics>
Table 1 shows the evaluation results of the liquid repellency of the photocrosslinked product of the fluororesin 4, the fluororesin 6, and the non-fluorine resin 1.

Example 6
A 3 wt% solution of the fluororesin 4 in a xylene solvent was spin-coated on glass and irradiated with ultraviolet rays of ^{500 mJ / cm 2.} Further, the substrate was immersed in xylene for 1 minute, taken out, subsequently rinsed with acetone, blown with nitrogen gas, dried and evaluated. As a result, the contact angle of water was 109.3 °, the contact angle of diiodomethane was 84.3 °, and tetralin. The contact angle was 66.0 ° and it showed excellent liquid repellency.

Example 7
Fluorine resin 4 and 4,4'-bis (diethylamino) benzophenone (sensitizer 1) dissolved in a xylene solvent at 3 wt% and 0.1 wt%, respectively, were spin-coated on glass at 500 mJ / Irradiated with cm ² of ultraviolet light. Further, the substrate was immersed in xylene for 1 minute, taken out, subsequently rinsed with acetone, blown with nitrogen gas, dried and evaluated. As a result, the contact angle of water was 108.1 ° and the contact angle of diiodomethane was 83.8 ° tetralin contact. The angle was 65.5 ° and it showed excellent liquid repellency.

Comparative Example 3
A non-fluorinated resin 1 dissolved in a xylene solvent at 3 wt% was spin-coated on glass and irradiated with ultraviolet rays of ^{500 mJ / cm 2.} Further, the substrate was immersed in xylene for 1 minute, taken out, subsequently rinsed with acetone, blown with nitrogen gas, dried and evaluated. As a result, the contact angle of water was 62.1 °, the contact angle of diiodomethane was 40.8 °, and tetralin. The contact angle was 7.1 ° and it did not show excellent liquid repellency.

Comparative Example 4
A 3 wt% solution of the fluororesin 6 in a 9: 1 mixed solvent of Zeolola H and Novec 7300 was spin-coated on glass and irradiated with ultraviolet rays of ^{500 mJ / cm 2.} Further, the substrate was immersed in a 9: 1 mixed solvent of Zeolola H and Novec 7300 for 1 minute, taken out, subsequently rinsed with acetone, blown with nitrogen gas, dried and evaluated. As a result, the contact angle of water was 64.5. °, Diiodomethane contact angle 54.3 °, Tetralin contact angle 15.4 °, and did not show excellent liquid repellency.

<Evaluation of photocrosslinkability, evaluation of pattern formation>
Example 8
Fluorine-based resins 1 to 3 were dissolved in a solvent in which Zeolola H and Novec 7300 were mixed at a ratio of 9: 1, respectively, to prepare a 3 wt% solution. Photocrosslinking (curing) property was evaluated using each solution. The UV irradiation dose was set to the level of 100, 250, 500, 2000, 4000 mJ / cm ² , and after curing, it was immersed in AE-3000 for 1 minute, and the test was conducted under each condition. It was confirmed that the fluororesins 1 to 3 were crosslinked.
In addition, a pattern formation test was conducted using the same solution. The UV irradiation amount was an irradiation amount having a residual film ratio of 95% or more. Then, it was immersed in AE-3000 for 1 minute. It was confirmed that pattern formation was possible by using the solution. The results are shown in Table 2.

Comparative Example 5
The fluororesin 6 was dissolved in a solvent in which Zeolola H and Novec 7300 were mixed at a ratio of 9: 1 to prepare a 3 wt% solution. The photocrosslinking (curing) property was evaluated using the solution. The UV irradiation dose was set to the level of 100, 250, 500, 2000, 4000 mJ / cm ² , and after curing, it was immersed in AE-3000 for 1 minute, and the test was conducted under each condition. It was confirmed that the fluororesin 6 was not crosslinked.
In addition, a pattern formation test was conducted using the same solution. The UV irradiation amount was the same. Then, it was immersed in AE-3000 for 1 minute. No pattern was formed. The results are shown in Table 2.

Example 9
The fluororesin 4 was dissolved in xylene to prepare a 3 wt% solution. Photocrosslinking (curing) property was evaluated using each solution. The UV irradiation dose was set to the level of 100, 250, 500, 2000, 4000 mJ / cm ² , and after curing, it was immersed in xylene for 1 minute, and the test was conducted under each condition. It was confirmed that the fluororesins 1 to 3 were crosslinked.
In addition, a pattern formation test was conducted using the same solution. The UV irradiation amount was an irradiation amount having a residual film ratio of 95% or more. Then, it was immersed in acetone for 1 minute. It was confirmed that pattern formation was possible by using the solution. The results are shown in Table 3.

Example 10
The photocrosslinkability and pattern formation when a sensitizer was added to the fluororesins 2 and 3 were evaluated. The following sensitizers were used.
Sensitizer 1: 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry)
Sensitizer 2: 5-Nitro Asenaphthenic Acid (manufactured by Tokyo Chemical Industry)
Sensitizer 3: 3,3'-carbonylbis (7-diethylaminocoumarin) (manufactured by Tokyo Chemical Industry)
As the fluorine solvent, a solvent obtained by mixing Zeolola H and Novec 7300 at a ratio of 9: 1 or 1H, 1H, 5H-octafluoropentanol was used. Other conditions were the same as in Example 8. The results are shown in Table 4.

Comparative Example 6
Photocrosslinkability and pattern formation were evaluated under the same conditions as in Example 9 except that the fluororesin 6 was used as the fluororesin. The results are shown in Table 4.

Example 11
When a fluororesin 4 was used as the fluororesin and a sensitizer was added in the same manner as in Example 9, the photocrosslinkability and pattern formation were evaluated. The results are shown in Table 5.

<Evaluation of solubility in fluorine-based solvent>
Example 12
The solubility of the fluorine-based resins 1 to 3 and 5 in each fluorine solvent was evaluated. The results are shown in Table 6. The following fluorine solvents were used.
Fluorine solvent 1: Novec 7200
Fluorine-based solvent 2: Zeolara H
Fluorine-based solvent 3: 1: 1 mixed solution of Zeolola H and Novec 7300 Fluorine-based solvent 4: Asahiclean AE-3000
Fluorine Solvent 5: 1H, 1H, 5H-Octafluoropentanol Fluorine Solvent 6: 1H, 1H, 7H-DodecafluoroHeptanol Fluorine Solvent 7: 1H, 1H-Heptafluorobutanol Fluorine Solvent 8: 2-( Perfluorobutyl) Ethanol A non-alcoholic fluorine solvent 1-4 was prepared so that the resin content was 3 wt%.
The solution of the alcohol-based fluorine solvent 5-8 was prepared so that the resin content was 10 wt%.

Comparative Example 7
The solubility of the non-fluorine resin 1 in each fluorine solvent was evaluated. The conditions were the same as in Example 12. The results are shown in Table 6.

Claims (11)

The residue unit represented by the following formula (1) and
Acrylic resin residue unit having at least one group consisting of a group represented by the following formula (2), a group represented by the following formula (3), and a group represented by the following formula (4) in the side chain. ,
Fluorine-based resin having.

(Here, R ₁ represents either a hydrogen atom or a methyl group. Rf ₁ is a linear fluoroalkyl group having 1 to 15 carbon atoms, a branched chain fluoroalkyl group having 3 to 15 carbon atoms, or 3 carbon atoms. Represents one of a group consisting of ~ 15 cyclic fluoroalkyl groups.)

(Wherein, _{A 1} is a hydrogen atom, a hydroxyl group, an amino _group, C 1 -C alkyl group of _6, C 1 -C 1 primary or secondary alkylamino group _6, C 1 -C ₆ alkoxy group or a single Shows a bond, A ₂ is the same or different, hydrogen, halogen, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, C _{1 to} C ₁₈ alkyl group, fluoroalkyl group, cycloalkyl group. Or represents a single bond. B ₁ represents the same or different hydrogen or an alkyl group, halogen, cyano group, or aryl group of _{hydrogen or C 1 to} C _{6 , except that only one of one A 1} and five A ₂ is used. It shall indicate that one is a single bond and is bonded to another substituent.)

(Wherein, A ₃ are the same or different, hydrogen, halogen, a cyano group, a nitro group, carboxyalkyl group, alkyl ether group, an aryl ether group, an alkyl group of C ₁ -C _18, fluoroalkyl group, a cycloalkyl group Or represents a single bond. B ₂ represents the same or different hydrogen or C _{1 to} C ₆ alkyl group, halogen, cyano group, aryl group. L represents a single bond or carbonyl group, except for 10 groups. of a _3, only one will be assumed that indicates that it is bound to other substituents with a single bond.)

(Wherein, A ₄ are the same or different, hydrogen, halogen, a cyano group, a nitro group, carboxyalkyl group, alkyl ether group, an aryl ether group, an alkyl group of C ₁ -C _18, fluoroalkyl group, a cycloalkyl group or .B ₃ represents a single bond the same or different and each is hydrogen or an alkyl group of C ₁ -C _6, halogen, a cyano group, an aryl group. However, of the four a _4, only one is another single bond It shall indicate that it is bonded to the substituent of.) The fluororesin according to claim 1, which contains 20 mol% or more and 95% mol% or less of the residue unit represented by the formula (1). The fluororesin according to claim 1 or 2, which has an acrylic resin residue unit having at least a group represented by the formula (2) in the side chain. The fluororesin according to claim 3, wherein the group represented by the formula (2) is a group represented by the following formula (5).

(Here, R ₂ represents either a hydrogen atom or a methyl group.
B ₄ are the same or different and each represents a hydrogen atom, an alkyl group of C ₁ -C _6, halogen atom, one of the group consisting of cyano group, or an aryl group. D is the same or different from hydrogen atom, halogen atom, cyano group, nitro group, carboxyalkyl group, alkyl ether group, aryl ether group, C _{1 to} C ₁₈ alkyl group, fluoroalkyl group, or cycloalkyl group. Represents one of the groups. M represents either a halogen atom or an aryl ether group. ) A composition containing the fluorinated resin according to any one of claims 1 to 4 and a fluorinated solvent. The composition according to claim 5, which contains 1 wt% or more and 50 wt% or less of a fluorinated resin and 50 wt% or more and 99 wt% or less of a fluorinated solvent. The composition according to claim 5, further comprising a photosensitizer in a fluorine-based resin and a fluorine-based solvent. The composition according to claim 7, which contains 1 wt% or more and 50 wt% or less of a fluorine-based resin, 50 wt% or more and 99 wt% or less of a fluorine-based solvent, and 0.001 wt% or more and 5 wt% or less of a sensitizer. The photocrosslinked product of the fluororesin according to any one of claims 1 to 4. The pattern composed of the photocrosslinked product according to claim 9. An electronic device comprising the photocrosslinked product according to claim 9.

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