Resin, composition, photocrosslinked product, and electronic device comprising same

Abstract

The present invention provides a resin that has liquid repellency and that can be insolubilized with respect to a solvent by photocrosslinking with a low exposure amount. A resin according to the present invention comprises a repeating unit that is represented by formula (1) and a repeating unit that contains a silicon atom but does not contain a fluorine atom. (In formula (1), R1 represents a methyl group or the like, L1 represents a divalent linking group or the like, A represents an m-valent linking group, and R2 to R6 each represent a hydrogen atom or the like. m represents an integer of not less than 2, and n represents an integer of m-1.)

Description

Resins, compositions, photocrosslinked materials, and electronic devices comprising them

[0001] This invention relates to resins, and more specifically, to resins that can be suitably used in electronic devices.

[0002] In recent years, there has been active technological development regarding the manufacture of organic electronic devices using a low-cost, highly productive all-printing method. For example, the development of organic transistors is progressing. These organic transistors are manufactured through numerous processes, including a step where a protective film made of resin protects the organic transistor and a step in forming the pattern for the electroluminescent (EL) light-emitting portion. This pattern is, for example, provided to cover the source electrode, drain electrode, and organic semiconductor or polymer layer, and is not present on the electrodes where the EL light-emitting portion is formed.

[0003] Typically, the EL light-emitting portion is formed using photolithography, a technique that involves exposing a substrate surface coated with a photosensitive material (resist) to a pattern via a photomask or reticle, thereby forming a pattern consisting of exposed and unexposed areas. In photolithography, the EL light-emitting portion is opened up by either dry etching or wet etching.

[0004] Photoreactive polymer materials are used as pattern-forming materials. In coating methods such as all-printing, the material is dissolved in a solvent to form an ink, which is then applied. After the solvent is dried and removed, the material is photocrosslinked to make it insoluble in the solvent and form a pattern. Therefore, polymer materials used in coating methods such as all-printing are required to have excellent solubility in the solvent and to be able to undergo photocrosslinking at room temperature and with short exposure time after solvent removal.

[0005] Here, we describe a method for manufacturing organic electroluminescent elements included in organic electroluminescent displays and organic electroluminescent lighting. First, the polymer material is applied to a substrate, and the areas where a pattern is to be formed are photocrosslinked, while the areas that have not been photocrosslinked are removed. The remaining areas then form the pattern. Various functional layers are then laminated onto the areas where the polymer material has been removed (inside the pattern). While a technique using ink-like raw materials to form these functional layers is promising, the materials constituting the pattern are expected to have liquid-repellent properties to prevent ink adhesion inside the pattern and ink leakage beyond the areas where the polymer material has not been removed (outside the pattern).

[0006] Furthermore, in organic semiconductor devices, it is expected that when forming interlayer insulating films or gate insulating films on the source electrode, drain electrode, and organic semiconductor layer, patterns can be formed by photolithography without damage, and contact holes and the like can be formed in the insulating film.

[0007] As an example of such a material, Patent Document 1 mentions a negative photosensitive resin composition and a photocurable pattern produced therefrom, which have high photoreactivity, can be patterned with an alkaline solution, and can form a liquid-repellent film. However, because the fluororesin in this composition does not have photocurability, it is necessary to heat-cur it at high temperature for a long time after patterning. High temperature and long processing can degrade the performance of electronic devices and limit the selection of plastic substrates. Therefore, there has been a need to develop a photocrosslinkable fluororesin material to prevent the degradation of electronic device performance.

[0008] There is a method for forming patterns using a resin soluble in a fluorinated solvent, as disclosed in Patent Document 2 and Non-Patent Document 1. However, this resin has the problem of not being photocrosslinkable.

[0009] Examples of resins that can be photocrosslinked include those described in Non-Patent Document 2, which use anthracene crosslinking groups.

[0010] Furthermore, Patent Documents 3 and 4 propose resins having a specific structure.

[0011] Japanese Patent No. 5932512, Japanese Patent No. 6281427, Publication No. WO2022 / 210326, Publication No. WO2024 / 070915

[0012] Appl. Phys. Express 7, 101602 (2014) J Polym Sci A Polym Chem 53, 1252 (2015)

[0013] However, the resin described in Non-Patent Document 2 has low photocrosslinking properties and requires high exposure. Therefore, there is a need for a resin with high photoreactivity.

[0014] Furthermore, the resins described in Patent Documents 3 and 4 contain fluoroalkyl groups, and in recent years, due to environmental concerns, there has been a demand for resins that do not contain fluoroalkyl groups.

[0015] The present invention has been made in view of the above problems, and its purpose is to provide a resin that has liquid-repellent properties and can be made insoluble in solvents by photocrosslinking with a low exposure.

[0016] As a result of diligent research to solve the above problems, the inventors of this invention discovered that a resin having a specific structure can solve the above problems, and thus completed the present invention.

[0017] In other words, the present invention is a resin containing repeating units represented by the following formula (1) which include a photocrosslinkable group, and repeating units which include silicon atoms but do not include fluorine atoms.

[0018] In other words, the present invention has the following gist.

[0019] [1] A resin containing repeating units represented by the following formula (1) that include a photocrosslinkable group, and repeating units that contain silicon atoms but do not contain fluorine atoms.

[0020] (In formula (1), R １ L represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent linking group, A represents an mvalent linking group, and R ２ , R ３ , R ４ , R ５ and R ６is the same as or different from, and represents one kind selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group. m represents an integer of 2 or more, and n represents an integer of m - 1.)

[0021] According to the present invention, a resin that does not contain a fluoroalkyl group, has liquid repellency, and is insolubilized in a solvent by photocrosslinking with a low exposure amount can be obtained. The resin can be used for pattern formation, and by forming a pattern using the resin, it is possible to prevent a decrease in the performance of the obtained electronic device.

[0022] It is a diagram showing a cross-sectional shape of an organic transistor. It is a diagram showing a cross-sectional shape of an organic transistor, which is one form of the electronic device of the present invention.

[0023] Hereinafter, the resin according to one aspect of the present invention will be described in detail.

[0024] The resin according to this aspect is a resin containing a repeating unit represented by the following formula (1) and a repeating unit containing a silicon atom and not containing a fluorine atom.

[0025] The formula (1) in the resin according to this aspect has a photocrosslinkable group. As a result, the resin exhibits high photoreactivity, and it is possible to selectively insolubilize only the irradiated portion in the film obtained by coating the resin.

[0026] In formula (1), R １ represents a hydrogen atom or a methyl group.

[0027] In formula (1), L １ represents a single bond or a divalent linking group.

[0028] L １The divalent linking group in this is preferably a divalent linking group selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-), or a divalent linking group formed by combining at least two of these groups. This makes it possible to form a flat, crack-free film.

[0029] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0030] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-tylpropylene group.

[0031] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0032] Examples of arylene groups having 6 to 12 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0033] Of these divalent linking groups, it is more preferable that they are ester bonds (-C(=O)O-) formed by combining a carbonyl group and an ether group, or linking groups formed by combining a phenylene group and an ether group, and even more preferable that they are (-C(=O)O-).

[0034] In formula (1), A represents an m-valent linking group. m represents an integer of 2 or more, preferably an integer between 2 and 5, more preferably an integer between 3 and 4, and even more preferably 3.

[0035] A may be a C1 to C24 hydrocarbon group with an metric value, which may have substituents, as this improves the solubility of the resulting resin in organic solvents.

[0036] Examples of substituents that the m-valent hydrocarbon group A may have include alkyl groups, alkoxy groups, halogen atoms, and hydroxyl groups.

[0037] As the alkyl group, for example, linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms are preferred, more preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, and cyclohexyl groups, even more preferably alkyl groups having 1 to 4 carbon atoms, and particularly preferably methyl or ethyl groups.

[0038] Examples of alkoxy groups include linear or branched alkyl groups having 1 to 16 carbon atoms, such as methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, n-octylooxy, n-nonyloxy, n-decyloxy, n-dodecyloxy, n-tetradecyloxy, 2-ethylhexyloxy, 3-ethylheptyloxy, and 2-hexyldecyloxy. Particularly preferred are groups selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, and n-octylooxy groups.

[0039] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred. However, this excludes cases where the substituent is a fluorine atom and is substituted in a way that forms a fluoroalkyl group.

[0040] In particular, the hydrocarbon group A with an m-valence is preferably one of the linking groups consisting of the following formulas (a-1) to (a-4).

[0041] In equations (a-1) to (a-4), *L is the same as L in equation (1). １ The bond position is shown, and the asterisk (*) at the end of the carbon atom indicates the bond position with the oxygen atom constituting the ester group in formula (1) above.

[0042] The m-valent hydrocarbon group A is preferably a trivalent linking group of one of the group consisting of formulas (a-1), (a-2), and (a-3), for the sake of ease of reaction in monomer synthesis, more preferably a trivalent linking group of formula (a-1) or formula (a-2), and even more preferably a trivalent linking group of formula (a-1).

[0043] In formula (1), R ２ , R ３ , R ４ , R ５ and R ６ This represents one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, or an amino group, which are identical or distinct.

[0044] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred.

[0045] As a linear alkyl group having 1 to 20 carbon atoms, alkyl groups having 1 to 6 carbon atoms are preferred. Specifically, examples include methyl groups, ethyl groups, and n-propyl groups, with methyl groups or ethyl groups being preferred.

[0046] As branched alkyl groups having 3 to 20 carbon atoms, alkyl groups having 3 to 6 carbon atoms are preferred, and specifically, examples include isopropyl groups and tert-butyl groups.

[0047] As for cyclic alkyl groups having 3 to 20 carbon atoms, alkyl groups having 3 to 6 carbon atoms are preferred. Specifically, examples include cyclopropyl groups, cyclopentyl groups, and cyclohexyl groups, with cyclohexyl groups being preferred among them.

[0048] As for alkoxy groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms are preferred, and specifically, examples include methoxy groups, ethoxy groups, n-butoxy groups, and methoxyethoxy groups.

[0049] As for the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferred. Specifically, examples include the phenyl group, α-methylphenyl group, and naphthyl group, with the phenyl group being the most preferred.

[0050] As for the aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 12 carbon atoms is preferred. Specifically, examples include the phenyloxy group and the 2-naphthyloxy group, with the phenyloxy group being the most preferred.

[0051] Examples of amino groups include primary amino groups (-NH ２ Examples include secondary amino groups such as methylamino groups; tertiary amino groups such as dimethylamino groups, diethylamino groups, dibenzylamino groups, and groups with nitrogen atoms of nitrogen-containing heterocyclic compounds (e.g., pyrrolidine, piperidine, piperazine, etc.) as bonding sites.

[0052] R ２ , R ３ , R ４ , R ５ and R ６ For reasons of improving the solubility in organic solvents, photocurability, and liquid repellency of the resin, it is preferable that the element be a hydrogen atom, an alkyl group, or a halogen atom, and more preferably a hydrogen atom.

[0053] The repeating unit represented by formula (1) containing a photocrosslinkable group (hereinafter sometimes referred to as repeating unit B) specifically includes, for example, the repeating units B-1 to B-14 and B17 to B-26 shown below, among which B-1 to B-14 are preferred, and B-1, B-2, and B-13 are particularly preferred. In the following formula, Me represents a methyl group, Et represents an ethyl group, and Pr represents an isopropyl group.

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] A resin according to one aspect of the present invention is a resin that contains repeating units represented by formula (1) including a photocrosslinkable group, as well as repeating units that contain silicon atoms but do not contain fluorine atoms. The repeating units that contain silicon atoms but do not contain fluorine atoms do not have fluoroalkyl groups. As a result, the resin according to this aspect is a resin suitable for environmental issues.

[0060] The repeating unit that contains silicon atoms but does not contain fluorine atoms is preferably the repeating unit represented by the following formula (2).

[0061] In formula (2), R ７ represents a hydrogen atom or a methyl group.

[0062] In formula (2), L ２ represents a single bond or a divalent linking group.

[0063] L ２The divalent linking group in this is preferably a divalent linking group selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), or an imino group (-NH-), or a divalent linking group that is a combination of at least two of these groups. This enables the formation of a flat and crack-free film.

[0064] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0065] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-tylpropylene group.

[0066] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0067] Examples of arylene groups having 6 to 12 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0068] Of these divalent linking groups, it is more preferable that they are ester bonds (-C(=O)O-) formed by combining a carbonyl group and an ether group, or linking groups formed by combining a phenylene group and an ether group, and even more preferable that they are (-C(=O)O-).

[0069] In formula (2), Rf １represents a substituent having a silicon atom, and preferred substituents are those represented by the following general formulas E-1 and E-2, with E-1 being more preferred from the viewpoint of liquid repellency.

[0070] In formula (E-1), R ａ , R ｂ , R ｃ , R ｄ and R ｅ represents one of the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms, which are the same or different, with linear alkyl groups having 1 to 20 carbon atoms being preferred. N represents an integer between 1 and 10,000, preferably between 1 and 1,000, and more preferably between 1 and 500.

[0071] In formula (E-2), R ｆ , R ｇ and R ｈ Examples of these groups, which may be identical or distinct, include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aryl oxy groups having 6 to 20 carbon atoms, alkylsilyloxy groups having 1 to 20 carbon atoms in each alkyl group, and alkoxysilyloxy groups having 1 to 20 carbon atoms in each alkoxy group, with alkylsilyloxy groups having 1 to 20 carbon atoms being preferred.

[0072] In formulas (E-1) and (E-2), the linear alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms. Specifically, examples include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, with the methyl group or an n-butyl group being preferred.

[0073] In formulas (E-1) and (E-2), branched alkyl groups having 3 to 20 carbon atoms are preferred, and specifically, examples include isobutyl group, isopropyl group, and tert-butyl group.

[0074] In formulas (E-1) and (E-2), the cyclic alkyl group having 3 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms. Specifically, examples include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, with the cyclohexyl group being the most preferred.

[0075] In formulas (E-1) and (E-2), the alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 8 carbon atoms. Specifically, examples include a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group.

[0076] In formulas (E-1) and (E-2), the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms. Specifically, examples include a phenyl group, an α-methylphenyl group, and a naphthyl group, with the phenyl group being the most preferred.

[0077] In formulas (E-1) and (E-2), the aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms. Specifically, examples include a phenyloxy group and a 2-naphthyloxy group, with the phenyloxy group being the most preferred.

[0078] Examples of alkylsilyloxy groups having 1 to 20 carbon atoms include trimethylsilyloxy and triethylsilyloxy, with trimethylsilyloxy being preferred.

[0079] Examples of alkoxysilyloxy groups having 1 to 20 carbon atoms include trimethoxysilyloxy.

[0080] Specific substituents having a silica atom represented by formulas (E-1) and (E-2) include silicone residues such as polydimethylsiloxane, polymethylphenylsiloxane, polyether-modified polydimethylsiloxane, polyether ester-modified polydimethylsiloxane, hydroxyl-group-containing polyether-modified polydimethylsiloxane, acrylic-group-containing polyether-modified polydimethylsiloxane, and acrylic-group-containing polyester-modified polydimethylsiloxane, as well as silyl groups such as trimethylsilyl, trimethoxysilyl, triethylsilyl, triethoxysilyl, and tris(trimethylsilyloxy)silyl. Among these, polydimethylsiloxane, polymethylphenylsiloxane, and tris(trimethylsilyloxy)silyl are preferred, and polydimethylsiloxane is particularly preferred.

[0081] A resin according to one aspect of the present invention may contain one repeating unit represented by formula (2), or it may contain two or more repeating units. For example, Rf １ As a repeating unit having a group represented by the aforementioned formula (E-1), and Rf １ The resin may include both repeating units having the group represented by formula (E-2) described above, or it may include two or more groups represented by formula (E-1) with different numbers of carbon atoms in the repeating unit. A resin according to one aspect of the present invention preferably includes one repeating unit represented by formula (2).

[0082] In one aspect of the present invention, a repeating unit containing silicon atoms but not fluorine atoms in the resin can be specifically one of the group consisting of repeating units represented by the following formulas (C-1) to (C-29), among which one of the group consisting of repeating units represented by formulas (C-1) to (C-14) is preferred, and one of the group consisting of repeating units represented by formulas (C-1) to (C-4) or one of the group consisting of repeating units represented by formulas (C-10) to (C-12) is particularly preferred. In the following formulas, Me represents a methyl group, Et represents an ethyl group, n-Pr represents an n-propyl group, and n-Bu represents an n-butyl group. In the above formulas, l represents an integer between 1 and 10,000, preferably between 1 and 1,000, and more preferably between 1 and 500.

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] In one aspect of the present invention, the resin is preferably a copolymer comprising a repeating unit represented by formula (1) and a repeating unit represented by formula (2). That is, in one aspect of the present invention, the resin is preferably a copolymer represented by the following formula (6).

[0092] (In equation (6), R １ , R ７ L independently represents a hydrogen atom or a methyl group. １ , L ２ A independently represents a single bond or a divalent linking group, A represents an mvalent linking group, and R ２ , R ３ , R ４ , R ５ and R ６ Rf represents one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, or an amino group, either identical or distinct. m represents an integer greater than or equal to 2, and n represents an integer equal to m-1. １ R represents a substituent having a silicon atom. ) In formula (6), R １ , L １ A, R ２ , R ３ , R ４ , R ５ and R６ R in equation (1) above is １ , L １ A, R ２ , R ３ , R ４ , R ５ and R ６ It is synonymous with [the above].

[0093] In formula (6), R ９ , L ２ , Rf １ R in equation (2) above is ７ , L ２ , Rf １ It is synonymous with [the above].

[0094] The copolymer represented by formula (6) may be a random copolymer or a block copolymer.

[0095] In one aspect of the present invention, the resin preferably contains 10 mol% to 90 mol% of the repeating unit represented by formula (1), preferably 20 mol% to 80 mol%, and preferably 20 mol% to 70 mol%.

[0096] Furthermore, it is preferable to contain 0.01 mol% to 50 mol% of repeating units that contain silicon atoms but do not contain fluorine atoms, more preferably 0.1 mol% to 20 mol%, and particularly preferably 0.1 mol% to 10 mol%.

[0097] The resin of this embodiment may contain at least one of repeating units containing an acidic functional group and repeating units containing a hydrophilic functional group, from the viewpoint of exhibiting solubility in alkaline solutions.

[0098] Specifically, it is preferable that at least one of the repeating units containing an acidic functional group and the repeating unit containing a hydrophilic functional group has a repeating unit containing a functional group selected from a carboxyl group, a sulfo group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group, and a cyano group, and more preferably that the repeating unit contains a carboxyl group.

[0099] At least one of these repeating units containing acidic functional groups and repeating units containing hydrophilic functional groups may be used alone or in combination of two or more. If the repeating unit containing acidic functional groups and the repeating unit containing hydrophilic functional groups have the same chemical structure, they are counted as one unit. Furthermore, the repeating unit used may contain both acidic and hydrophilic functional groups, or it may contain both acidic, non-hydrophilic functional groups and hydrophilic, non-acidic functional groups.

[0100] It is preferable that at least one of the repeating units containing an acidic functional group and the repeating unit containing a hydrophilic functional group is a repeating unit represented by the following formula (3).

[0101] (In formula (3), R ９ L represents a hydrogen atom or a methyl group. ３ (This represents a single bond or a divalent linking group.) ３ The divalent linking group in this is preferably a divalent linking group selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-), or a divalent linking group formed by combining at least two of these groups. This makes it possible to form a flat and crack-free film.

[0102] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0103] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-methylpropylene group.

[0104] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0105] Examples of arylene groups having 6 to 12 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0106] Of these divalent linking groups, it is more preferable that they be arylene groups having 6 to 12 carbon atoms, and even more preferable that they be phenylene groups.

[0107] L ３ It is more preferable that the group is a single bond or an arylene group having 6 to 12 carbon atoms, and even more preferable that it is a single bond or a phenylene group.

[0108] In one aspect of the present invention, a repeating unit containing an acidic functional group and a repeating unit containing a hydrophilic functional group in a resin can be specifically listed as one of the group consisting of repeating units represented by the following formulas (D-1) to (D-23), among which (D-1) to (D-2) and (D-19) to (D-23) that satisfy formula (2) are preferred, (D-1) to (D-2) and (D-20) to (D-22) are more preferred, and (D-1) and (D-22) are even more preferred.

[0109] In the following formula, R ９ This is either a hydrogen atom or a methyl group.

[0110]

[0111] In one aspect of the present invention, when the resin contains one or more units selected from the group consisting of repeating units containing acidic functional groups and repeating units containing hydrophilic functional groups, it is preferable that the resin contains 5 mol% to 50 mol% of the repeating unit represented by formula (1), and more preferably 5 mol% to 40 mol% of the repeating unit, from the viewpoint of increasing solubility in alkaline solutions and enabling more efficient photocuring. Similarly, it is preferable that the resin contains 0.01 mol% to 50 mol% of repeating units containing silicon atoms but not fluorine atoms, more preferably 0.1 mol% to 20 mol%, and particularly preferable 0.1 mol% to 10 mol%. Similarly, it is preferable that the resin contains 20 mol% to 90 mol% of one or more units selected from the group consisting of repeating units containing acidic functional groups and repeating units containing hydrophilic functional groups, more preferably 30 mol% to 90 mol%, and particularly preferable 50 mol% to 80 mol%.

[0112] A resin according to one aspect of the present invention is preferably a copolymer comprising a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (3). That is, a resin according to one aspect of the present invention is preferably a copolymer represented by the following formula (7).

[0113] (In equation (7) R １ , R ７ , R ９ L independently represents a hydrogen atom or a methyl group. １ , L ２ , L ３ A independently represents a single bond or a divalent linking group, A represents an mvalent linking group, and R ２ , R ３ , R ４ , R ５ and R ６is the same or different and represents one kind selected from the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group. m represents an integer of 2 or more, and n represents an integer of m - 1. Rf １ represents a substituent having a silicon atom. In formula (7), R １ , L １ , A, R ２ , R ３ , R ４ , R ５ and R ６ are synonymous with R １ , L １ , A, R ２ , R ３ , R ４ , R ５ and R ６ in formula (1).

[0114] In formula (7), R ７ , L ２ , Rf １ are synonymous with R ７ , L ２ , Rf １ in formula (2). In formula (7), R ９ , L ３ are synonymous with R ９ , L ３ in formula (3).

[0115] The copolymer represented by formula (7) may be a random copolymer or a block copolymer.

[0116] The resin according to one aspect of the present invention may contain other monomer repeating units, to the extent that it does not depart from the purpose of the present invention. Examples of other monomer repeating units include olefin residue units such as ethylene residue units, propylene residue units, and 1-butene residue units; vinyl aromatic hydrocarbon residue units such as styrene residue units and α-methylstyrene residue units; vinyl carboxylate ester residue units such as vinyl acetate residue units, vinyl propionate residue units, and vinyl pivalate residue units; vinyl ether residue units such as methyl vinyl ether residue units, ethyl vinyl ether residue units, and butyl vinyl ether residue units; N-substituted maleimide residue units such as N-methyl maleimide residue units, N-cyclohexyl maleimide residue units, and N-phenyl maleimide residue units; acrylonitrile residue units; methacrylonitrile residue units; and other units.

[0117] In the resin according to this embodiment, there are no restrictions on the molecular weight, and for example, those with a molecular weight of 2,000 to 10,000,000 (g / mol) can be used. From the viewpoint of the solution viscosity and mechanical strength of the obtained resin, it is preferably 10,000 to 1,000,000 (g / mol).

[0118] The method for synthesizing the resin according to this embodiment is not particularly limited. For example, it can be synthesized by mixing the monomer that forms the repeating unit B described above, the monomer that forms the repeating unit containing silicon atoms but not fluorine atoms described above, and any other monomer that forms a repeating unit, and polymerizing them in an organic solvent using a radical polymerization initiator.

[0119] The resin according to this embodiment is preferably soluble in an alkaline solution. The alkaline solution will be described below.

[0120] The above-mentioned alkaline solution is preferably an aqueous solution of an alkali containing at least one of inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, and cyclic amines.

[0121] Examples of inorganic alkalis include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.

[0122] Examples of primary amines include ethylamine and n-propylamine.

[0123] Examples of secondary amines include diethylamine and di-n-butylamine.

[0124] Examples of tertiary amines include triethylamine and methyldiethylamine.

[0125] Examples of alcohol amines include dimethylethanolamine and triethanolamine.

[0126] Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.

[0127] Examples of cyclic amines include pyrrole and piperidine.

[0128] Among these, inorganic alkalis, tertiary amines, alcohol amines, and quaternary ammonium salts are preferred as alkaline solutions, with quaternary ammonium salts being particularly preferred.

[0129] The hydrogen ion concentration index of the above alkaline solution is preferably pH 8 or higher, more preferably pH 10 or higher, and even more preferably pH 12 or higher.

[0130] A composition according to one aspect of the present invention will be described below.

[0131] A composition according to one aspect of the present invention is a composition comprising the resin, one or more photocrosslinkable monomers belonging to the group represented by the following formulas (b), (c), (d), and (e), and a sensitizer and / or a photoinitiator.

[0132] The photocrosslinkable monomer is one or more photocrosslinkable monomers from the group represented by the following formulas (b), (c), (d), and (e), and among these, one or more photocrosslinkable monomers selected from the group consisting of the photocrosslinkable monomer represented by formula (b), the photocrosslinkable monomer represented by formula (d), and the photocrosslinkable monomer represented by formula (e) are preferred, and the photocrosslinkable monomer represented by formula (d) is even more preferred.

[0133] (In formula (b), R １０ L represents a hydrogen atom or a methyl group. ４ and L ５ These represent divalent linking groups, which are identical or distinct, and X １ X represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and a linear hydroxyalkyl group having 1 to 20 carbon atoms. ２ k represents an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. q is an integer from 1 to 4, p and s are integers from 0 to 3, either identical or distinct, where q + p + s = 4, and if q, p, or s is an integer of 2 or more, the structural parts whose numbers are determined by q, p, or s are either identical or distinct. k is an integer of 0 or more.

[0134] (In formula (c), R １１ L represents a hydrogen atom or a methyl group. ６ and L ７ These represent divalent linking groups, which are identical or distinct, and X ３ and X ４ t represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, either identical or distinct. t is an integer from 1 to 4, v and w are integers from 0 to 3, either identical or distinct, and t + v + w = ​​4. If t, v, or w is an integer of 2 or more, the structural parts whose numbers are determined by t, v, or w are either identical or distinct.

[0135] (In formula (d), R１２ L represents the same or different hydrogen atom or methyl group, ８ represents a divalent linking group, X ５ and X ７ X represents a divalent linking group that is the same or different from the other. ６ I represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a linear hydroxyalkyl group having 1 to 20 carbon atoms. I and II represent integers from 0 to 3, either identical or distinct, where I + II = 3. If I or II is an integer of 2 or more, the structural parts whose number is determined by I or II are either identical or distinct.

[0136] (In formula (e), R １３ (where f represents a hydrogen atom or a methyl group, and f and g each independently represent an integer of 1 or more.)

[0137] L in equation (b) ４ and L ５ The same or different groups represent a divalent linking group, and the divalent linking group is preferably a divalent linking group selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an ethenylene group (-CH=CH-), an arylene group having 6 to 15 carbon atoms, an ether group (-O-), a substituted ether group, a carbonyl group (-C(=O)-), and a single bond, or a divalent linking group that is a combination of at least two of these groups.

[0138] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0139] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-methylpropylene group.

[0140] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0141] Examples of arylene groups having 6 to 15 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0142] Of these divalent linking groups, L ４ As such, it is more preferably an ether group or a linear alkylene group having 1 to 10 carbon atoms, and even more preferably an ether group, a methylene group, an ethylene group, or a propylene group, with the ether group being particularly preferred. ５ For example, -COO-CH=CH-, -O-CO-CH=CH-, -CH ２ -O-CO-CH=CH-, linear alkylene groups having 1 to 10 carbon atoms are preferred, such as -COO-CH=CH-, -O-CO-CH=CH-, and -CH ２ It is even more preferable that the group is -O-CO-CH=CH-, a methylene group, an ethylene group, or a propylene group.

[0143] X in equation (b) １This represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a linear hydroxyalkyl group having 1 to 20 carbon atoms. Among the linear alkyl groups having 1 to 20 carbon atoms, linear alkyl groups having 1 to 6 carbon atoms are preferred, specifically including, for example, a methyl group, an ethyl group, or an n-propyl group, with the methyl group or ethyl group being preferred. Among the branched alkyl groups having 3 to 20 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms are preferred, specifically including, for example, an isopropyl group or a tert-butyl group. Among the cyclic alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms are preferred, specifically including, for example, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, with the cyclohexyl group being preferred. As the linear hydroxyalkyl group having 1 to 20 carbon atoms, linear hydroxyalkyl groups having 1 to 6 carbon atoms are preferred. Specifically, examples include hydroxymethyl group, 2-hydroxyethyl group, and 3-hydroxyn-propyl group, with hydroxymethyl group or 2-hydroxyethyl group being preferred.

[0144] X １ Preferably, the group consists of a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, and more preferably, a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group.

[0145] X in equation (b) ２This represents an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. The aryl group having 6 to 20 carbon atoms may have substituents. As the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferred, specifically, for example, a phenyl group, an α-methylphenyl group, a naphthyl group, etc., with the phenyl group being preferred among them. As the linear alkyl group having 1 to 20 carbon atoms, a linear alkyl group having 1 to 6 carbon atoms is preferred, specifically, for example, a methyl group, an ethyl group, an n-propyl group, etc., with the methyl group or an ethyl group being preferred among them. As branched alkyl groups having 3 to 20 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms are preferred, specifically, for example, isopropyl group and tert-butyl group. As cyclic alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms are preferred, specifically, for example, cyclopropyl group, cyclopentyl group and cyclohexyl group, with cyclohexyl group being preferred among them.

[0146] Furthermore, possible substituents on an aryl group having 6 to 20 carbon atoms include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, halogen groups, linear alkyl halides having 1 to 20 carbon atoms, and amino groups. Specific examples of each are the same as those described for other structural positions: linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, halogen groups, linear alkyl halides having 1 to 20 carbon atoms, and amino groups.

[0147] X ２ The preferred members are aryl groups having 6 to 20 carbon atoms and linear alkyl groups having 1 to 20 carbon atoms, and particularly preferred are phenyl groups, naphthyl groups, methyl groups, and ethyl groups.

[0148] In equation (b), q represents an integer between 1 and 4, p and s represent integers greater than or equal to 0, either identical or distinct, and q + p + s = 4. Therefore, p and s are integers between 0 and 3, inclusive. When q is an integer greater than or equal to 2, the structural parts whose numbers are determined by q may be identical or distinct from each other. Similarly, when p is an integer greater than or equal to 2, the structural parts whose numbers are determined by p may be identical or distinct from each other. Similarly, when s is an integer greater than or equal to 2, the structural parts whose numbers are determined by s may be identical or distinct from each other.

[0149] In formula (b), k is an integer greater than or equal to 0, preferably an integer between 0 and 5, and particularly preferably 0 or 1.

[0150] Examples of photocrosslinkable monomers represented by specific formula (b) include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and monomers corresponding to the repeating units B-1 to B-14 and B-17 to B-22 mentioned above.

[0151] L in equation (c) ６ and L ７ The same or different groups represent a divalent linking group, and the divalent linking group is preferably a divalent linking group selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, an ether group (-O-), a substituted ether group, a carbonyl group (-C(=O)-), and a single bond, or a divalent linking group that is a combination of at least two of these groups.

[0152] Here, the linear alkylene group having 1 to 10 carbon atoms, the branched alkylene group having 3 to 10 carbon atoms, or the cyclic alkylene group having 3 to 10 carbon atoms, and the arylene group having 6 to 15 carbon atoms are represented by L in formula (b). ４ and L ５ Examples similar to the divalent linking group in [the given text] can be given.

[0153] Substitutive ethers are groups in which a substituent is bonded to an ether group, such as groups in which an ether group and an alkylene group are bonded, for example, -O-CH ２ -, -O-C ２ H ４ Examples include -, etc., and these may be included repeatedly.

[0154] X in equation (c) ３ and X ４ X represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 3 to 20 carbon atoms is an example of X in formula (b). １ Similar examples can be given.

[0155] X ３ and X ４ Preferably, the members are hydrogen atoms and linear alkyl groups having 1 to 20 carbon atoms, and particularly preferably hydrogen atoms, methyl groups, and ethyl groups.

[0156] In equation (c), t represents an integer between 1 and 4, v and w represent integers greater than or equal to 0, either identical or distinct, and t + v + w = ​​4. Therefore, v and w are integers between 0 and 3, inclusive. When t is an integer greater than or equal to 2, the structural parts whose numbers are determined by t may be identical or distinct from one another. Similarly, when v is an integer greater than or equal to 2, the structural parts whose numbers are determined by v may be identical or distinct from one another. Similarly, when w is an integer greater than or equal to 2, the structural parts whose numbers are determined by w may be identical or distinct from one another.

[0157] Examples of photocrosslinkable monomers represented by formula (c) include bisphenol A polyethylene glycol diether di(meth)acrylate and bisphenol A polypropylene glycol diether di(meth)acrylate.

[0158] L in equation (d) ８The symbol represents a divalent linking group, and the divalent linking group is preferably a divalent linking group selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), -COO-CH=CH-, and a single bond.

[0159] Examples of linear alkylene groups having 1 to 10 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and desilene groups.

[0160] Examples of branched alkylene groups having 3 to 10 carbon atoms include, for example, dimethylmethylene group, methylethylene group, 2,2-dimethylpropylene group, and 2-ethyl-2-methylpropylene group.

[0161] Examples of cyclic alkylene groups having 3 to 10 carbon atoms include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, and exo-tetrahydrodicyclopentadiene-diyl, with cyclohexylene being the most preferred.

[0162] Examples of arylene groups having 6 to 15 carbon atoms include phenylene groups, xylylene groups, biphenylene groups, naphthylene groups, and 2,2'-methylenebisphenyl groups, with phenylene groups being preferred among them.

[0163] Of these divalent linking groups, L ８ The group is more preferably an ether group or a linear alkylene group having 1 to 10 carbon atoms, and even more preferably an ether group, a methylene group, an ethylene group, or a propylene group.

[0164] X in equation (d) ５ and X ７ L represents a divalent linking group that is the same or different from the other, and L represents a divalent linking group. ８Similar divalent linking groups can be cited, among which linear alkylene groups having 1 to 10 carbon atoms are more preferred, and methylene groups, ethylene groups, and propylene groups are even more preferred.

[0165] X in equation (d) ６ The group represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. Of the linear alkyl groups having 1 to 20 carbon atoms, linear alkyl groups having 1 to 6 carbon atoms are preferred, specifically, for example, a methyl group, an ethyl group, or an n-propyl group, with methyl or ethyl groups being preferred. Of the branched alkyl groups having 3 to 20 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms are preferred, specifically, for example, an isopropyl group or a tert-butyl group. Of the cyclic alkyl groups having 3 to 20 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms are preferred, specifically, for example, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, with cyclohexyl groups being preferred.

[0166] In equation (d), I and II represent integers greater than or equal to 0, either identical or distinct, and I + II = 3. Therefore, I and II are integers between 0 and 3, inclusive. When I is an integer greater than or equal to 2, the structural parts whose numbers are determined by I may be identical or distinct from one another. Similarly, when II is an integer greater than or equal to 2, the structural parts whose numbers are determined by II may be identical or distinct from one another.

[0167] Examples of photocrosslinkable monomers represented by formula (d) include ditrimethylolpropanetetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0168] In formula (e), f and g are each an independent integer of 1 or more, preferably an integer between 1 and 20, and particularly preferably an integer between 1 and 6.

[0169] Specific examples of photocrosslinkable monomers represented by formula (e) include butanediol diacrylate, dipropylene glycol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, and tetraethylene glycol diacrylate.

[0170] Next, we will explain sensitizers and photoinitiators. One embodiment of the present invention is a composition containing a sensitizer and / or a photoinitiator, and it is particularly preferable that it contains a photoinitiator.

[0171] The sensitizer can be any agent that promotes the crosslinking reaction of the photocrosslinkable group. Examples of sensitizers include acyloins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; carbonyl compounds such as anthraquinone, 2-methylanthraquinone, 1,2-benzanthraquinone, 1-chloroanthraquinone, and cyclohexanone; diketones such as diacetyl and benzyl; 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; and p-toluenesulfone. Examples include sulfonyl halides such as nitryl chloride, I-naphthalene 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 vicramid; coumarins such as 7-diethylamino-3-tenoylcoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); halogenated hydrocarbons such as carbon tetrachloride, hexabromoethane, and 1,1,2,2-tetrabromoethane; nitrogen derivatives such as diazomethane, abisisobutyronitrile, hydrazine, and trimethylbenzylammonium chloride; and dyes such as ethionine, thionine, and methylene blue. By including a sensitizer, the resin in this embodiment can be crosslinked (insolubilized) with a lower exposure. Furthermore, two or more types of sensitizers can be used in combination as needed.

[0172] Among these, acyloins, phenones, and coumarins are preferred as sensitizers, with phenones being particularly preferred.

[0173] As photoinitiators, known photoinitiators can be used. Specific examples include oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-benzoyl oxime)] (e.g., product name: IRGACUREOXE01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetyl oxime) (e.g., product names: IRGACUREOXE02, IRGACUREOXE03); α-aminoalkylphenone compounds such as IRGACURE369 (product name) and IRGACURE907 (product name); and acylphosphine oxide compounds such as DAROCURTPO (product name) (all manufactured by Ciba Specialty Chemicals). In terms of the reactivity of the radicals generated, IRGACUREOXE01 and IRGACUREOXE02 are preferred. The photoinitiator may be used alone or in combination of two or more.

[0174] In a composition according to one aspect of the present invention, the proportions of the resin, photocrosslinkable monomer, and sensitizer and / or photoinitiator are preferably 25% to 85% by weight of the resin, 10% to 70% by weight of the photocrosslinkable monomer, and 0.01% to 10% by weight of the sensitizer and / or photoinitiator; more preferably 40% to 80% by weight of the resin, 10% to 50% by weight of the photocrosslinkable monomer, and 4% to 10% by weight of the sensitizer and / or photoinitiator; and particularly preferably 50% to 70% by weight of the resin, 20% to 40% by weight of the photocrosslinkable monomer, and 4% to 10% by weight of the sensitizer and / or photoinitiator.

[0175] The composition according to this embodiment preferably contains an organic solvent.

[0176] The organic solvent used in the composition according to this embodiment is not limited in any way as long as it dissolves the resin according to one embodiment of the present invention, and includes 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, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, and 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, cyclohexanol 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 Ropyrus 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, 1,1,2Examples include 2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. To obtain a film with desirable properties, an organic solvent with high dissolving power for the resin is suitable, with xylene and propylene glycol monomethyl ether acetate being preferred. A mixed solvent obtained by mixing two or more of the aforementioned solvents in appropriate proportions can also be used.

[0177] When the composition according to this embodiment contains an organic solvent, it is preferable that the composition contains 1% to 50% by weight of resin and 50% to 99% by weight of the solvent relative to the entire composition. Furthermore, it is particularly preferable that the solvent content be 50% to 90% by weight relative to the entire composition.

[0178] The composition according to this embodiment may contain other components besides the resin, sensitizer and / or photoinitiator, photocrosslinkable monomer and solvent. Examples of other components include adhesion enhancers, reaction accelerators, and light-shielding materials, and among these, the inclusion of a light-shielding material is preferred.

[0179] As an adhesion enhancer, known adhesion enhancers can be used. By including an adhesion enhancer, adhesion to metals can be improved. The adhesion enhancer includes phosphoric acid-modified (meth)acrylate and / or silyl-modified (meth)acrylate. Here, "phosphoric acid-modified" means modified by ester bonding with phosphoric acid. One type of phosphoric acid-modified (meth)acrylate may be used, or two or more types may be used in combination. The phosphoric acid-modified (meth)acrylate is preferably phosphoric acid-modified methacrylate. Here, "silyl-modified" means modified by ester bonding with a silyl group. One type of silyl-modified (meth)acrylate may be used, or two or more types may be used in combination. The silyl-modified (meth)acrylate is preferably silyl-modified methacrylate.

[0180] Phosphate-modified (meth)acrylates can be produced, for example, by the following method (i), but the present invention is not limited thereto.

[0181] (i) A method for reacting a compound having a (meth)acryloyl group and a hydroxyl group with phosphoric acid.

[0182] Compounds having a (meth)acryloyl group and a hydroxyl group in one molecule that can be used in method (i) above can be produced, for example, by the following methods (ii) or (iii), but the present invention is not limited to these.

[0183] (ii) A method of reacting (meth)acrylic acid or (meth)acrylate with a polyhydric alcohol (e.g., alkylene glycol, glycerin, etc.) in a quantity ratio such that the hydroxyl group of the polyhydric alcohol remains.

[0184] (iii) A method of adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) to (meth)acrylic acid.

[0185] Commercially available phosphate-modified (meth)acrylates may be used. Examples of such commercially available products include "EBECRYL168" from Ornex Co., Ltd., "KAYAMER PM-2" and "KAYAMER PM-21" from Nippon Kayaku Co., Ltd., "Light Ester P-1M," "Light Ester P-2M," and "Light Acrylate P-1A(N)" from Kyoeisha Chemical Co., Ltd., and "JPA-514" from Johoku Chemical Industry Co., Ltd.

[0186] Commercially available silyl-modified (meth)acrylates may be used. Examples of such commercial products include 3-(trimethoxysilyl)propyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd., and KBM-502 (3-methacryloxypropylmethyldimethoxysilane), KBM-503 (3-methacryloxypropyltrimethoxysilane), KBE-502 (3-methacryloxypropylmethyldiethoxysilane), KBE-503 (3-methacryloxypropyltriethoxysilane), and KBM-5103 (3-acryloxypropyltrimethoxysilane), all manufactured by Shin-Etsu Chemical Co., Ltd.

[0187] When the composition contains an adhesion enhancer, the amount is preferably 0.05% to 10% by weight, more preferably 0.5% to 10% by weight, and particularly preferably 0.5% to 5% by weight, relative to the total composition, from the viewpoint of storage stability and curability.

[0188] As a reaction-promoting agent, known reaction-promoting agents can be used. By including a reaction-promoting agent, curability and / or adhesion can be improved. The reaction-promoting agent includes mercapto-modified (meth)acrylate. Here, "mercapto-modified" means modified by an ester bond with mercapto. Only one type of mercapto-modified (meth)acrylate may be used, or two or more types may be used in combination. The mercapto-modified (meth)acrylate is preferably mercapto-modified acrylate. Commercially available mercapto-modified (meth)acrylate may be used. Examples of such commercially available products include "ADDITOL LED 01" from Daicel Ornex Co., Ltd. and "KarenzMT PE1" from Karenz Co., Ltd.

[0189] When the composition contains a reaction-promoting agent, the amount is preferably 0.01% to 30% by weight, more preferably 0.5% to 30% by weight, and particularly preferably 0.5% to 20% by weight, based on the total composition, from the viewpoint of storage stability and curability.

[0190] As a light-shielding material, any known light-shielding material can be used. By including a light-shielding material, the optical density can be improved and it can be used as a black resist. Examples of light-shielding materials include carbon black, zirconium nitride, chromium oxide, iron oxide, titanium black, aniline black, cyanine black, and the inorganic black pigment NITRBLACK® (Night Black) UB-2 manufactured by Mitsubishi Materials Corporation. Two or more types can be appropriately selected and used. Carbon black is particularly preferred in terms of its good light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins, while the inorganic black pigment NITRBLACK® (Night Black) UB-2 (manufactured by Mitsubishi Materials Corporation) is preferred in terms of its good ultraviolet transmittance, light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins.

[0191] The light-shielding material is preferably a dispersion of water or an organic solvent because it is easily mixed with the composition.

[0192] The organic solvent is an organic solvent used in the above composition, and xylene and propylene glycol monomethyl ether acetate are preferred.

[0193] The light-shielding dispersion preferably contains 5 to 50% by weight of the light-shielding material, and more preferably 10 to 40% by weight.

[0194] When a light-shielding material is to be included in the composition, it is preferable to prepare it by mixing the composition before the light-shielding material is added with a light-shielding material dispersion. In this case, the mixing ratio by weight is preferably composition before mixing:light-shielding material dispersion = 1:0.5 to 1:1.5, and particularly preferably 1:0.8 to 1:1.2. Furthermore, the content of the light-shielding material in the entire composition after mixing (i.e., including the water or organic solvent that constituted the light-shielding material dispersion if a light-shielding material dispersion was used as the light-shielding material) is preferably 5% to 50% by weight, more preferably 5% to 30% by weight, and particularly preferably 5% to 20% by weight.

[0195] A composition according to one aspect of the present invention can be produced by mixing the resin, the compound containing the crosslinkable monomer, the sensitizer and / or the photoinitiator.

[0196] A pattern, which is one aspect of the present invention, will be described below.

[0197] A pattern can be formed using the resin according to this embodiment. More specifically, a photocrosslinked product is obtained using the resin or a composition thereof according to this embodiment, and a pattern is formed.

[0198] First, a resin coating is formed on the surface of the substrate by a known coating method. Examples of substrates include various glass plates; polyesters such as polyethylene terephthalate; polyolefins such as polypropylene and polyethylene; thermoplastic sheets such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide; epoxy resin; polyester resin; and thermosetting plastic sheets such as poly(meth)acrylic resin.

[0199] Methods for forming the coating include, for example, 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, super flexographic printing, screen printing, inkjet printing, letterpress inversion printing, inversion offset printing, and adhesion contrast printing.

[0200] Next, the coating film is dried. Drying causes the solvent to evaporate, resulting in a non-sticky coating film. Drying conditions vary depending on the boiling point and mixing ratio of the solvent used, but preferably a wide range of 50 to 150°C and 10 to 2000 seconds is possible.

[0201] When a coating film is formed using a printing method, if a coating film having a predetermined shape, i.e., the same shape as the target pattern, exposure can cause the coating film having the predetermined shape to undergo photocrosslinking, obtaining a photocrosslinked product, which is then fixed and the pattern can be formed.

[0202] On the other hand, if a coating with a predetermined shape is not formed during the coating process, a pattern can be formed from the coating using photolithography technology. When using photolithography technology, the dried coating is first exposed to light through a mask with a predetermined shape, i.e., a shape that can form the desired pattern, and then photocrosslinked.

[0203] When curing the resin according to this embodiment by photocrosslinking, radiation such as ultraviolet light and visible light is used, for example, ultraviolet light with a wavelength of 245 to 435 nm is used. The irradiation dose is appropriately changed depending on the composition of the resin, but for example, it is 10 to 5000 mJ / cm². ２ Examples include: To prevent a decrease in the degree of crosslinking and to improve economic efficiency by shortening the process time, the irradiation dose is preferably 100 to 4000 mJ / cm². 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, metal halide lamps, etc.

[0204] Ultraviolet irradiation is usually carried out in the atmosphere, but can also be carried out in an inert gas or under a constant flow of inert gas if necessary. If necessary, the photosensitizer can be added to promote the photocrosslinking reaction. After that, the material is developed with a developer to remove the unexposed areas. Any solvent that can dissolve the uncured resin can be used as the developer, for example, aromatic solvents such as benzene, toluene, and xylene; ether solvents such as dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol dimethyl ether; ketone solvents such as acetone and methyl ethyl ketone; and ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether acetate.

[0205] The development time is preferably 10 to 300 seconds. The development method can be any of the following: liquid buildup method, dipping method, etc. After development, the solvent on the substrate is removed by washing with a solvent and air-drying with compressed air or compressed nitrogen. Subsequently, the pattern is formed by heating with a heating device such as a hot plate or oven, preferably at 40 to 150°C for 5 to 90 minutes.

[0206] After forming the pixel pattern through the photolithography process described above, the substrate surface within the pixels may be cleaned. For example, this can be done by irradiating with short-wavelength ultraviolet light such as a low-pressure mercury lamp or excimer UV, or by photo-ashing. Photo-ashing is a process 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.

[0207] Thus, the resin according to this embodiment is itself soluble in organic solvents, and upon light irradiation, the photocrosslinkable groups in the side chains are crosslinked and cured, becoming insoluble in the solvent used. Utilizing this property, the resin of the present invention can be used as a negative-type resist in which the unirradiated portions are removed by the organic solvent after crosslinking by light irradiation.

[0208] After patterning using the resin according to this embodiment, the portion of the resin that remains cross-linked (outside the pattern) preferably has a contact angle of 30° or more with respect to the ink, and more preferably 40° or more, in order to avoid wetting and spreading of the ink for forming the functional layer.

[0209] The resin according to this embodiment can be used to form a protective film using the same methods as those used for coating, photocrosslinking, and development.

[0210] The resin according to this embodiment has excellent liquid-repellent properties and can be used as a pattern material when manufacturing organic transistor elements, color filters, and organic EL elements. Furthermore, the resin according to this embodiment can be used in electronic vises that include the aforementioned organic transistor elements, color filters, and organic EL elements.

[0211] An electronic device according to one aspect of the present invention will be described in detail below.

[0212] One embodiment of the present invention is a resin that can be used in electronic devices, and more specifically, an electronic device comprising a photocrosslinked product of the resin of the present invention or a composition containing the resin and an organic solvent, and an example of such an electronic device is an organic transistor.

[0213] A typical organic transistor has a gate insulating layer on a substrate, and an organic semiconductor layer is deposited on this gate insulating layer, and a source electrode, drain electrode, and gate electrode are attached. An example of the device structure of an organic transistor is shown in Figure 1 as a cross-sectional view. 1001 is a bottom gate-top contact type, 1002 is a bottom gate-bottom contact type, 1003 is a top gate-top contact type, and 1004 is a top gate-bottom contact type device structure. 1 is the organic semiconductor layer, 2 is the substrate, 3 is the gate electrode, 4 is the gate insulating layer, 5 is the source electrode, and 6 is the drain electrode.

[0214] Figure 2 shows one embodiment of an organic transistor according to one aspect of the present invention. The organic transistor 1005 shown in Figure 2 corresponds to the bottom gate-bottom contact type in Figure 1. 7 indicates a pattern, and 8 indicates a protective film layer.

[0215] In the organic transistor, the substrate that can be used is not particularly limited as long as sufficient flatness can be ensured to fabricate the device. Examples 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 made of these materials may also be used. Furthermore, the surfaces of these materials can be coated to adjust the surface tension.

[0216] Examples of plastics that can be used as substrates include polyethylene terephthalate, polyethylene naphthalate, triacetylcellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethylpentene-1, polypropylene, cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, and styrene block copolymer. Furthermore, two or more of the above plastics can be used to laminate and form a substrate.

[0217] There are no restrictions on the organic semiconductors that can be used in the organic semiconductor layer; both N-type and P-type organic semiconductors can be used, and they can also be used as bipolar transistors combining N-type and P-type semiconductors. Furthermore, both low-molecular-weight and high-molecular-weight organic semiconductors can be used, and these can also be used in mixtures. Specific examples of organic semiconductor compounds include those represented by the following formulas (F-1) to (F-11).

[0218]

[0219]

[0220]

[0221]

[0222] In this embodiment, examples of methods for forming an organic semiconductor layer include vacuum deposition of an organic semiconductor, or coating or printing by dissolving an organic semiconductor in an organic solvent. However, there are no limitations as long as a method capable of forming a thin film of the organic semiconductor layer is used. When coating or printing using a solution obtained by dissolving an organic semiconductor layer in an organic solvent, the solution concentration 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, it is preferably 0.5% to 5% by weight. The organic solvent used in this process is not limited in any way as long as it dissolves the organic semiconductor at a certain concentration that allows for film formation. Examples include 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, 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, and 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, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,Examples include 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, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and limonene. To obtain a crystalline film with desirable properties, a solvent with high dissolving power for organic semiconductors and a boiling point of 100°C or higher is suitable. Xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred. A mixed solvent obtained by mixing two or more of the aforementioned solvents in appropriate proportions can also be used.

[0223] Various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles, can be added to the organic semiconductor layer as needed, either as a solid or as a dispersion in water or an organic solvent. A polymer solution can then be applied to the insulating layer to form a protective film. Furthermore, various moisture-proof coatings, light-resistant coatings, etc., can be applied to this protective film as needed.

[0224] Examples of conductive materials that can be used as gate electrodes, source electrodes, or drain electrodes in this embodiment 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, or organic electrodes such as doped conductive polymers (e.g., PEDOT-PSS). Multiple layers of these conductive materials can also be used. Furthermore, to increase the carrier implantation efficiency, these electrodes can be surface-treated using a surface treatment agent. Examples of such surface treatment agents include benzenethiol and pentafluorobenzenethiol.

[0225] Furthermore, there are no particular limitations on the method of forming electrodes on the substrate, insulating layer, or organic semiconductor layer, and examples include vapor deposition, high-frequency sputtering, electron beam sputtering, etc. Methods such as solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, super flexographic printing, screen printing, inkjet printing, and letterpress inversion printing can also be employed using an ink obtained by dissolving nanoparticles of the conductive material in water or an organic solvent.

[0226] A resin according to one aspect of the present invention can be suitably used for patterns and protective film layers in organic transistors.

[0227] An organic transistor according to one aspect of the present invention has a mobility of 0.20 cm, from the viewpoint of the practicality of the organic transistor element. ２ It is preferable that it is greater than or equal to / Vs.

[0228] An organic transistor according to one aspect of the present invention has an on-current / off-current ratio of 10, from the viewpoint of the practicality of the organic transistor element. ５ It is preferable that the above conditions are met.

[0229] In one aspect of the present invention, it is preferable that the organic transistor has no source-drain current hysteresis, from the viewpoint of the practicality of the organic transistor element.

[0230] <Summary> As can be understood from the above description, the present invention has the following aspects: [1] A resin containing repeating units represented by the following formula (1) that include a photocrosslinkable group, and repeating units that contain silicon atoms but do not contain fluorine atoms.

[0231] (In formula (1), R １ L represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent linking group, A represents an mvalent linking group, and R ２ , R ３ , R ４ , R ５ and R ６ (1) represents one of the group consisting of a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, and an amino group, which are the same or different. (m represents an integer of 2 or more, and n represents an integer of m-1.) [2] The resin according to [1], wherein the repeating unit containing a silicon atom and not containing a fluorine atom is a repeating unit represented by the following formula (2).

[0232] (In formula (2), R ７ L represents a hydrogen atom or a methyl group. ２ Rf represents a single bond or a divalent linking group. １ (wherein represents a substituent having a silicon atom.) [3] The resin according to [1] or [2], further comprising one or more units selected from the group consisting of repeating units containing an acidic functional group and repeating units containing a hydrophilic functional group. [4] The resin according to [3], wherein at least one of the repeating units containing an acidic functional group and the repeating unit containing a hydrophilic functional group is a repeating unit containing a functional group selected from a carboxyl group, a sulfo group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group, and a cyano group. [5] The resin according to [3] or [4], wherein at least one of the repeating units containing an acidic functional group and the repeating unit containing a hydrophilic functional group is a repeating unit represented by the following formula (3).

[0233] (In formula (3), R ９ L represents a hydrogen atom or a methyl group. ３ (wherein represents a single bond or a divalent linking group.) [6] The resin according to any one of [1] to [5], wherein in formula (1), A is a linking group of the group consisting of the following formulas (a-1) to (a-4). (In equations (a-1) to (a-4), *L is the same as L in equation (1) above. １ The bond position is indicated by the * at the tip of the carbon atom, and the bond position with the oxygen atom constituting the ester group in formula (1) is indicated by the * at the tip of the carbon atom.) [7] A composition comprising the resin described in any of [1] to [6], one or more photocrosslinkable monomers from the group represented by the following formulas (b), (c), (d), and (e), and a sensitizer and / or a photoinitiator.

[0234] (In formula (b), R １０ L represents a hydrogen atom or a methyl group. ４ and L ５ These represent divalent linking groups, which are identical or distinct, and X １ X represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and a linear hydroxyalkyl group having 1 to 20 carbon atoms. ２ k represents an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. q is an integer from 1 to 4, p and s are integers from 0 to 3, either identical or distinct, where q + p + s = 4, and if q, p, or s is an integer of 2 or more, the structural parts whose numbers are determined by q, p, or s are either identical or distinct. k is an integer of 0 or more.

[0235] (In formula (c), R １１ L represents a hydrogen atom or a methyl group. ６ and L ７ These represent divalent linking groups, which are identical or distinct, and X ３ and X ４t represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, either identical or distinct. t is an integer from 1 to 4, v and w are integers from 0 to 3, either identical or distinct, and t + v + w = ​​4. If t, v, or w is an integer of 2 or more, the structural parts whose numbers are determined by t, v, or w are either identical or distinct.

[0236] (In formula (d), R １２ L represents the same or different hydrogen atom or methyl group, ８ represents a divalent linking group, X ５ and X ７ X represents a divalent linking group that is the same or different from the other. ６ I represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a linear hydroxyalkyl group having 1 to 20 carbon atoms. I and II represent integers from 0 to 3, either identical or distinct, where I + II = 3. If I or II is an integer of 2 or more, the structural parts whose number is determined by I or II are either identical or distinct.

[0237] (In formula (e), R １３ (wherein represents a hydrogen atom or a methyl group, and f and g each independently represent an integer of 1 or more.) [8] The composition according to [7], wherein the photocrosslinkable monomer is one or more crosslinkable monomers selected from the group consisting of the crosslinkable monomer represented by formula (b), the crosslinkable monomer represented by formula (d), and the crosslinkable monomer represented by formula (e). [9] The composition according to [7] or [8], further comprising one or more selected from an adhesion enhancer, a reaction accelerator, and a light shielding material.

[10] A photocrosslinked product of a resin according to any one of [1] to [6] or a composition according to any one of [7] to [9].

[11] A pattern composed of the photocrosslinked product according to

[10] .

[12] An electronic device comprising the photocrosslinked product according to

[10] .

[0238] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0239] In the examples, the following conditions and apparatus were used.

[0240] <Monomer Purity> Gas chromatography apparatus: Shimadzu Corporation, (product name) GC2014 Column: RESTEK, (product name) Rxi-1HT, 30m The purity of the monomer was analyzed using the above gas chromatography apparatus (GC).

[0241] <Composition of the resin> Using a nuclear magnetic resonance spectrometer (JEOL Ltd., product name JNM-ECZ400S), proton nuclear magnetic resonance spectroscopy ( １ It was determined by 1H-NMR spectral analysis.

[0242] <Spin Coat> Mikasa Corporation's MS-A100 was used.

[0243] <Film Thickness Measurement> Measurements were taken using a Bruker DektakXT stylus profiler.

[0244] <UV Irradiation> Using a UV mask aligner, UPE-1605MA, manufactured by Ushio Lighting Inc., with a UV intensity of 14.2 mW / cm². ２ Under these conditions, the UV irradiation time was adjusted by changing the transport speed.

[0245] <Laser Microscope> The pattern was confirmed using a Lasertec OPTELICS HYBRID laser microscope.

[0246] In the examples, the following results were obtained.

[0247] Synthesis Example 1 (Synthesis of Photocrosslinkable Monomer 1) Under a nitrogen atmosphere, 50.8 g of glycerin monomethacrylate (Bremmer GLM, NOF Corporation), 64.8 g of triethylamine, and 150 g of toluene were placed in a 1000 mL flask and thoroughly mixed. Also under a nitrogen atmosphere, 118 g of cinnamic chloride and 355 g of toluene were dissolved in a glass bottle. Then, nitrogen was passed through the flask containing glycerin monomethacrylate, triethylamine, and tetrahydrofuran and cooled to 0°C. Using a dropping funnel, the solution of dissolved cinnamic chloride was added dropwise, and the mixture was heated to room temperature and stirred for 17 hours. After that, the mixture was filtered to remove the by-product salt, and toluene was removed by aspirator and vacuum drying. Then, 300 mL of methanol was added to the product and stirred at 0°C. The precipitated powder was filtered by suction, washed with methanol, and vacuum dried. As a result, it was confirmed that the precipitated powder was the substance represented by the following formula (5) (Photocrosslinkable Monomer 1). (GC purity 96%) (Photocrosslinkable monomer 1)

[0248]

[0249] Example 1 (Polymerization of Resin 1) In a 75 mL glass ampoule, 3.41 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.71 g of Cyraprene® FM-0711 (manufactured by JNC Corporation, Mn = 1,000), 0.186 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.227 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.8 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 3.69 g of Resin 1 (yield: 72%). １¹H-NMR measurement confirmed that the composition was 87 / 13 (mol%) for photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon monomer 1 (silicon-based unit 1) [C-4], and that it is a copolymer represented by formula (8). Note that formula (8) below is intended to indicate that the ratio of repeating units [B-1] and [C-4] is 87 / 13, and does not specify their order. The same applies to formulas (9) and subsequent formulas described later.

[0250] (Resin 1)

[0251]

[0252] Example 2 (Polymerization of Resin 2) In a 75 mL glass ampoule, 4.84 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.303 g of Cyraprene® FM-0711 (manufactured by JNC Corporation, Mn = 1,000), 0.223 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.283 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.9 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.33 g of Resin 2 (yield: 84%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 1 (silicon-based unit 1) [C-4] = 98.2 / 1.8 (mol%), and that it is a copolymer represented by formula (9).

[0253] (Resin 2)

[0254]

[0255] Example 3 (Polymerization of Resin 3) In a 75 mL glass ampoule, 2.53 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 2.54 g of Cyraprene® FM-0721 (manufactured by JNC Corporation, Mn = 5,000), 0.123 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.155 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.7 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.46 g of Resin 3 (yield: 88%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 2 (silicon-based unit 2) [C-4] = 90.2 / 9.8 (mol%), and that it is a copolymer represented by formula (10).

[0256] (Resin 3)

[0257]

[0258] Example 4 (Polymerization of Resin 4) In a 75 mL glass ampoule, 4.84 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.309 g of Cyraplane® FM-0721 (manufactured by JNC Corporation, Mn = 5,000), 0.219 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.275 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.9 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.42 g of resin 4 (yield: 86%). １¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 2 (silicon-based unit 2) [C-4] = 99.4 / 0.6 (mol%), and that it is a copolymer represented by formula (11).

[0259] (Resin 4)

[0260]

[0261] Example 5 (Polymerization of Resin 5) In a 75 mL glass ampoule, 4.10 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.02 g of Cyraplane® FM-0725 (manufactured by JNC Corporation, Mn = 10,000), 0.188 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.229 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.8 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.53 g of resin 5 (yield: 89%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 3 (silicon-based unit 3) [C-4] = 99 / 1.0 (mol%), and that it is a copolymer represented by formula (12).

[0262] (Resin 5)

[0263]

[0264] Example 6 (Polymerization of Resin 6) In a 75 mL glass ampoule, 1.91 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.05 g of Cyraprene® FM-0711 (manufactured by JNC Corporation, Mn = 1,000), 2.35 g of mono-2-(methacryloyloxy)ethyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.168 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.206 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 15.3 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a constant temperature bath at 45°C and holding it there for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of hexane, and then washed with 75 mL of hexane. Furthermore, by vacuum drying at 45°C for 8 hours, 3.80 g of resin 6 was obtained (yield: 71%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 1 (silicon-based unit 1) [C-4] / acidic functional group monomer 2 (acidic functional group unit 2) [D-22] = 35 / 5.0 / 60 (mol%), and that it is a copolymer represented by formula (13).

[0265] (Resin 6)

[0266]

[0267] Example 7 (Polymerization of Resin 7) In a 75 mL glass ampoule, 2.27 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.32 g of Cyraprene® FM-0721 (manufactured by JNC Corporation, Mn = 5,000), 2.78 g of mono-2-(methacryloyloxy)ethyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.140 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.172 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 15.5 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of hexane, and then washed with 75 mL of hexane. Further vacuum drying at 45°C for 8 hours yielded 4.33 g of resin 7 (yield: 81%). １ ¹H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 2 (silicon-based unit 2) [C-4] / acidic functional group monomer 2 (acidic functional group unit 2) [D-22] = 35.8 / 0.2 / 64.0 (mol%), and that it is a copolymer represented by formula (14).

[0268] (Resin 7)

[0269]

[0270] Example 8 (Polymerization of Resin 8) In a 75 mL glass ampoule, 4.11 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.01 g of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.236 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.281 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.8 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it there for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 3.58 g of resin 8 (yield: 70%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 4 (silicon-based unit 4) [C-12] = 85 / 15 (mol%), and that it is a copolymer represented by formula (15).

[0271] (Resin 8)

[0272]

[0273] Example 9 (Polymerization of Resin 9) In a 75 mL glass ampoule, 1.83 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.21 g of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.27 g of 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.285 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.352 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 15.0 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a constant temperature bath at 45°C and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.23 g of resin 9 (yield: 79%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 4 (silicon-based unit 4) [C-12] / acidic functional group monomer 2 (acidic functional group unit 2) [D-22] = 31 / 14 / 55 (mol%), and that it is a copolymer represented by formula (16).

[0274] (Resin 9)

[0275]

[0276] Example 10 (Polymerization of Resin 10) In a 75 mL glass ampoule, 2.35 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.166 g of Cyraprene® FM-0725 (manufactured by JNC Corporation, Mn = 10,000), 2.84 g of mono-2-(methacryloyloxy)ethyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.290 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.353 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 15.5 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a constant temperature bath at 45°C and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of hexane, and then washed with 75 mL of hexane. Further vacuum drying at 45°C for 8 hours yielded 5.23 g of resin 10 (yield: 98%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 3 (silicon-based unit 3) [C-4] / acidic functional group monomer 2 (acidic functional group unit 2) [D-22] = 37.95 / 0.03 / 62.02 (mol%), and that it is a copolymer represented by formula (17).

[0277] (Resin 10)

[0278]

[0279] Example 11 (Polymerization of Resin 11) In a 75 mL glass ampoule, 2.97 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.02 g of Cyraprene® FM-0711 (manufactured by JNC Corporation, Mn=1,000), 1.11 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.264 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.323 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.8 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a constant temperature bath at 45°C and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of hexane, and then washed with 75 mL of hexane. Further vacuum drying at 45°C for 8 hours yielded 3.75 g of resin 11 (yield: 74%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 1 (silicon-based unit 1) [C-4] / acidic functional group monomer 1 (acidic functional group unit 1) [D-1] = 37.2 / 3.2 / 59.6 (mol%), confirming that it is a copolymer represented by formula (18).

[0280] (Resin 11)

[0281]

[0282] Example 12 (Polymerization of Resin 12) In a 75 mL glass ampoule, 3.32 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.581 g of Cyraprene® FM-0721 (manufactured by JNC Corporation, Mn = 5,000), 1.25 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.288 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.346 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.9 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of hexane, and then washed with 75 mL of hexane. Further vacuum drying at 45°C for 8 hours yielded 3.75 g of resin 12 (yield: 73%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 3 (silicon-based unit 3) [C-4] / acidic functional group monomer 1 (acidic functional group unit 1) [D-1] = 36.4 / 0.3 / 63.3 (mol%), confirming that it is a copolymer represented by formula (19).

[0283] (Resin 12)

[0284]

[0285] Example 13 (Polymerization of Resin 13) In a 75 mL glass ampoule, 3.77 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.49 g of Cyraprene® FM-0721 (manufactured by JNC Corporation, Mn = 5,000), 0.92 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.248 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.302 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 15.0 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of hexane, and then washed with 75 mL of hexane. Further vacuum drying at 45°C for 8 hours yielded 3.95 g of resin 13 (yield: 77%). １ ¹H-NMR measurement confirmed that the composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / silicon-based monomer 3 (silicon-based unit 3) [C-4] / acidic functional group monomer 1 (acidic functional group unit 1) [D-1] = 44.7 / 0.5 / 54.8 (mol%), and that it is a copolymer represented by formula (20).

[0286] (Resin 13)

[0287]

[0288] Synthesis Example 2 (Polymerization of Resin A) In a 75 mL glass ampoule, 4.09 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 1.06 g of dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.270 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.315 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 14.9 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it there for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.33 g of resin A (yield: 84%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / other monomer 1 (other unit 1) = 70 / 30 (mol%), and that it is a copolymer represented by formula (21).

[0289] (Resin A)

[0290]

[0291] Synthesis Example 3 (Polymerization of Resin B) In a 75 mL glass ampoule, 4.37 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 0.789 g of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.285 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.347 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 15.0 mL of 2-butanone were added. After repeated nitrogen purging and pressure release, the ampoule was fused and sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it there for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 150 mL of methanol, and then washed with 75 mL of methanol. Further vacuum drying at 45°C for 8 hours yielded 4.35 g of resin B (yield: 84%). １¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / other monomer 2 (other unit 2) = 70 / 30 (mol%), and that it is a copolymer represented by formula (22).

[0292] (Resin B)

[0293]

[0294] Synthesis Example 4 (Polymerization of Resin C) 7.26 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 8.36 g of mono-2-(methacryloyloxy)ethyl phthalate, 0.589 g of Perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 0.718 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 46.0 ml of 2-butanone were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure release, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 300 mL of hexane, and then washed twice with 150 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 13.5 g of Resin C (yield: 87%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / mono-2-(methacryloyloxy)ethyl phthalate (acidic functional group unit 2) [D-2] = 43 / 57 (mol%), and that it is a copolymer represented by formula (23).

[0295] (Resin C)

[0296]

[0297] Synthesis Example 5 (Polymerization of Resin D) 12.62 g of photocrosslinkable monomer 1 obtained in Synthesis Example 1, 3.00 g of methacrylic acid, 0.82 g of perhexyl ND (manufactured by NOF Corporation) as a polymerization initiator, 1.00 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 36.47 g of 2-butanone were placed in a 75 mL glass ampoule. After repeated nitrogen purging and pressure release, the ampoule was sealed under reduced pressure. Radical polymerization was carried out by placing this ampoule in a 45°C constant temperature bath and holding it there for 24 hours. After the polymerization reaction was complete, the polymer solution was removed from the ampoule, and this polymer solution was precipitated by dropping it into 700 mL of hexane, and then washed twice with 300 mL of hexane. Further vacuum drying at 40°C for 8 hours yielded 13.6 g of resin 8 (yield: approximately 90.8%). １ ¹H-NMR measurement confirmed that its composition was photocrosslinkable monomer 1 (photocrosslinking unit 1) [B-1] / methacrylic acid (acidic functional group unit 1) [D-1] = 46 / 54 (mol%), and that it is a copolymer represented by formula (24).

[0298] (Resin D)

[0299]

[0300] <Production of Composition Solution> [Solvent] Propylene glycol methyl ether acetate (PGMEA) "Sensitizer" 4,4'-bis(diethylamino)benzophenone "Photoinitiator" Irgacure OXE02 (manufactured by BASF Co., Ltd.) "Adhesion enhancer" 3-(trimethoxysilyl)propyl methacrylate [Photocrosslinked monomer 1] Pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Photocrosslinked monomer 2] Ditrimethylolpropane tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Photocrosslinked monomer 3] Dipentaerythritol hexaacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) "Reactivity enhancer" ADDITOL LED 01 (manufactured by Daicel Ornex Co., Ltd.) "Light-shielding dispersion 1" A 20% by weight PGMEA dispersion of the inorganic black pigment NITRBLACK (registered trademark) UB-2 (manufactured by Mitsubishi Materials Corporation) was used to prepare the composition solution in the proportions listed in Table 1.

[0301]

[0302] <Evaluation of liquid-repellent properties (water-repellent and oil-repellent), pattern formation, and blackening> Washed and dried 30 x 30 mm ２ The solution prepared in Table 1 was spin-coated onto Corning Eagle XG glass at 500 rpm for 5 seconds and 1500 rpm for 20 seconds, and then thoroughly dried. UV irradiation was performed to 70–500 mJ / cm². ２ The glass plate coated with this photocrosslinked resin film was immersed for 1 minute in acetone or alkali (aqueous solution of tetramethylammonium hydroxide (2.38%)), which is a good solvent for the resin, and then removed and dried on a hot plate at 150°C for 10 minutes. The contact angles with water, diiodomethane, anisole, and tetralin were measured using the θ / 2 method with a contact angle meter (Kyowa Interface Chemical Co., Ltd., product name DM-300). The results are shown in Table 2.

[0303] For pattern formation evaluation, a chromium-patterned mask was used as the pattern formation mask. The mask consisted of 10 squares with sides of 50 μm arranged vertically and 10 squares horizontally. (100 x 100 mm) ２ A mask is placed on a film obtained by spin-coating the solution prepared in Table 1 onto a glass substrate, and a pressure of 70-500 mJ / cm² is applied. ２ The film was irradiated with ultraviolet light. After irradiation, the uncrosslinked portions were washed off with acetone or alkali (tetramethylammonium hydroxide aqueous solution (2.38%)) for 1 minute, resulting in a 10 × 10 μm layer on the film. ２ Size: 50 x 50 μm ２ We used a laser microscope to confirm whether a pattern with 100 spaces of each size had been formed. The results are shown in Table 2.

[0304] The compositional solutions of Examples 14 to 34 were capable of forming patterns. Furthermore, they were confirmed to have large contact angles with each solvent and excellent liquid-repellent properties. On the other hand, the resins of Comparative Examples 1 to 3 had small contact angles with each solvent, low oil repellency, and did not exhibit excellent liquid repellency.

[0305] For blackening evaluation, the above composition was measured in 30 x 30 mm ２A film was deposited on a glass substrate (Corning EagleXG) using a spin coater under the conditions of 500 rpm x 5 seconds and 1500 rpm x 20 seconds, and then thoroughly dried. The film was then cured with UV irradiation at a dose that resulted in a residual film rate of 95% or more. Afterward, the optical density was measured using a UV-Vis-Near-Infrared spectrophotometer (JASCO Corporation, product name V-770). Blackening was evaluated when the optical density was 1 or higher at all wavelengths of light: 460 nm, 540 nm, and 630 nm. The result is shown in Table 2.

[0306] Examples 29-30 showed an optical density of 1 or more at light wavelengths of 460 nm, 540 nm, and 630 nm, and were blackened.

[0307]

Claims

1. A resin containing repeating units represented by the following formula (1) that include a photocrosslinkable group, and repeating units that contain silicon atoms but do not contain fluorine atoms. (In formula (1), R １ L represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent linking group, A represents an mvalent linking group, and R ２ , R ３ , R ４ , R ５ and R ６ (m represents an integer greater than or equal to 2, and n represents an integer less than or equal to m.) 2. The resin according to claim 1, wherein the repeating unit containing a silicon atom and not containing a fluorine atom is a repeating unit represented by the following formula (2). (In formula (2), R ７ represents a hydrogen atom or a methyl group. L ２ represents a single bond or a divalent linking group, and Rf １ represents a substituent having a silicon atom.) 3. The resin according to claim 1, further comprising one or more units selected from the group consisting of repeating units containing acidic functional groups and repeating units containing hydrophilic functional groups.

4. The resin according to claim 3, wherein at least one of the repeating units containing an acidic functional group and the repeating units containing a hydrophilic functional group is a repeating unit containing a functional group selected from a carboxyl group, a sulfo group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amide group, an amino group, and a cyano group.

5. The resin according to claim 3 or 4, wherein at least one of the repeating units containing an acidic functional group and the repeating units containing a hydrophilic functional group is a repeating unit represented by the following formula (3). (In formula (3), R ９ L represents a hydrogen atom or a methyl group. ３ (This represents a single bond or a divalent linking group.) 6. The resin according to claim 1 or 3, wherein in formula (1), A is one type of linking group from the group consisting of the following formulas (a-1) to (a-4). (In equations (a-1) to (a-4), *L is the same as L in equation (1) above. １ The bond position is shown, and the asterisk (*) at the end of the carbon atom indicates the bond position with the oxygen atom constituting the ester group in formula (1) above.

7. A composition comprising the resin described in claim 1, one or more photocrosslinkable monomers belonging to the group represented by the following formulas (b), (c), (d), and (e), and a sensitizer and / or photoinitiator. (In formula (b), R １０ L represents a hydrogen atom or a methyl group. ４ and L ５ These represent divalent linking groups, which are identical or distinct, and X １ X represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and a linear hydroxyalkyl group having 1 to 20 carbon atoms. ２ k represents an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. q is an integer from 1 to 4, p and s are integers from 0 to 3, either identical or distinct, where q + p + s = 4, and if q, p, or s is an integer of 2 or more, the structural parts whose numbers are determined by q, p, or s are either identical or distinct. k is an integer of 0 or more. (In formula (c), R １１ L represents a hydrogen atom or a methyl group. ６ and L ７ These represent divalent linking groups, which are identical or distinct, and X ３ and X ４ t represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, either identical or distinct. t is an integer from 1 to 4, v and w are integers from 0 to 3, either identical or distinct, and t + v + w = ​​4. If t, v, or w is an integer of 2 or more, the structural parts whose numbers are determined by t, v, or w are either identical or distinct. (In formula (d), R １２ L represents the same or different hydrogen atom or methyl group, ８ represents a divalent linking group, X ５ and X ７ X represents a divalent linking group that is the same or different from the other. ６ I represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a linear hydroxyalkyl group having 1 to 20 carbon atoms. I and II represent integers from 0 to 3, either identical or distinct, where I + II = 3. If I or II is an integer of 2 or more, the structural parts whose number is determined by I or II are either identical or distinct. (In formula (e), R １３ (where f represents a hydrogen atom or a methyl group, and f and g each independently represent an integer of 1 or more.) 8. The composition according to claim 7, wherein the photocrosslinkable monomer is one or more crosslinkable monomers selected from the group consisting of the crosslinkable monomer represented by formula (b), the crosslinkable monomer represented by formula (d), and the crosslinkable monomer represented by formula (e).

9. The composition according to claim 7, further comprising one or more selected from an adhesion enhancer, a reaction accelerator, and a light-shielding material.

10. A photocrosslinked product of the resin according to claim 1 or the composition according to claim 7.

11. A pattern composed of the photocrosslinked material according to claim 10.

12. An electronic device comprising the photocrosslinked material according to claim 10.

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