Polymer, liquid repellent material containing said polymer, photosensitive composition containing said polymer, cured product obtained by curing said photosensitive composition, pattern film-equipped substrate, method for manufacturing said pattern film-equipped substrate, and image display device having said pattern film-equipped substrate

Abstract

The purpose of the present invention is to provide: a polymer that has liquid repellency to ink and exhibits lyophilicity to a resist solvent; a liquid repellent material containing said polymer; a photosensitive composition containing said polymer; a cured product obtained by curing said photosensitive composition; a pattern film-equipped substrate having a pattern film that has liquid repellency to ink and exhibits lyophilicity to a resist solvent; a method for manufacturing said pattern film-equipped substrate; and an image display device having said pattern film-equipped substrate. The present invention relates to a polymer having a specific repeating unit.

Description

A polymer, a liquid-repellent material containing the polymer, a photosensitive composition containing the polymer, a cured product obtained by curing the photosensitive composition, a substrate with a patterned film, a method for manufacturing the substrate with the patterned film, and an image display device having the substrate with the patterned film.

[0001] This disclosure relates to a polymer, a liquid-repellent material containing the polymer, a photosensitive composition containing the polymer, a cured product obtained by curing the photosensitive composition, a substrate with a patterned film, a method for manufacturing the substrate with the patterned film, and an image display device having the substrate with the patterned film.

[0002] When manufacturing display elements such as organic EL displays, micro-LED displays, and quantum dot displays, the inkjet method is known as a method for forming organic layers with functions such as light emission (light-emitting layers) and organic layers with functions such as wavelength conversion (wavelength conversion layers). There are several inkjet methods, and specifically, examples include a method in which ink is dropped from a nozzle into the recesses of a pattern film with irregularities formed on a substrate and solidified, or a method in which ink droplets are dropped onto a pattern film that has been formed on a substrate in advance, creating hydrophilic areas that are wetted by the ink and liquid-repellent areas that repel the ink, and the ink adheres only to the hydrophilic areas.

[0003] In particular, in the method of solidifying ink dropped from a nozzle into the recesses of the pattern film mentioned above, two main methods can be employed to create such a pattern film with irregularities. One is photolithography, which involves exposing the surface of a photosensitive resist film coated on a substrate in a patterned manner to form exposed and unexposed areas, and then dissolving and removing either area with a developer. The other is imprint, which uses printing technology. After forming the pattern film with irregularities, it is common to perform UV ozone treatment or oxygen plasma treatment on the entire substrate. This UV ozone treatment or oxygen plasma treatment can remove residual organic matter, especially in the recesses of the pattern film, and reduce uneven wetting of the dropped ink, thereby preventing malfunctions of the display element.

[0004] The raised parts of the formed pattern film are called banks (septaments), and when ink is dropped into the recesses of the pattern film, the banks act as barriers to prevent the inks from mixing. To enhance this barrier effect, the upper surface of the banks is required to be liquid-repellent to ink.

[0005] Table 4 of Patent Document 1 shows the results of measuring the surface free energy of compositions using fluorine-containing compounds and siloxane-containing compounds, and states that a surface free energy of 20 mN / m or less indicates that high liquid repellency is necessary for the bank.

[0006] Patent Document 2 discloses that compounds containing fluoropolyether groups exhibit high liquid repellency, and provides criteria for determining the contact angle of a bank with respect to five types of solvents. It states that a contact angle of 70 degrees or more with respect to hexanediol diacrylate (HDDA) and a contact angle of 62 degrees or more with respect to propylene glycol monomethyl ether acetate (PGMEA) are considered the highest values, meaning that the bank is required to exhibit high liquid repellency.

[0007] Japanese Patent Publication No. 2023-31448 Japanese Patent Publication No. 2023-3396

[0008] As described above, conventional technologies have required the use of fluorine-containing compounds and siloxane-containing compounds in the bank to exhibit higher liquid repellency. On the other hand, after diligent research, the inventors have found that while high liquid repellency is paramount for the bank in the conventional method of bonding two glass substrates, a method using a single glass substrate and laminating each layer is also conceivable. In this case, the bank is required to be liquid-repellent to ink, while it is required to be hydrophilic to the resist resin composition in order to coat the top surface of the bank with a resist resin composition. Here, since resist resin compositions usually contain a large amount of resist solvent to dissolve or disperse the various components blended into the composition, hydrophilicity to the resist solvent is required. Thus, the inventors realized that if the manufacturing method of the image display device is changed, the properties required of the bank may change significantly.

[0009] The present disclosure solves the newly discovered problems by the inventors, and provides a polymer having liquid repellency against ink and showing lyophilicity against a resist solvent, a liquid repellent material containing the polymer, a photosensitive composition containing the polymer, a cured product obtained by curing the photosensitive composition, a substrate with a pattern film having liquid repellency against ink and showing lyophilicity against a resist solvent, a method for manufacturing the substrate with a pattern film, and an image display device having the substrate with a pattern film.

[0010] As a result of intensive studies by the inventors, it has been found that the above problems can be solved by a specific polymer, and the present disclosure has been completed. That is, the present disclosure (1) relates to a polymer having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3). (In formula (1), R １ represents a hydrogen atom or a methyl group. R ２ represents a hydrocarbon group having 6 to 24 carbon atoms. r represents 0 or 1. When r is 0, (—C(═O)—O—) represents a single bond.) (In formula (2), R １０ represents a hydrogen atom or a methyl group. B is independently a hydrocarbon group, a hydroxyl group, a carboxyl group, —C(═O)—O—R １１ (R １１ represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cyclic alkyl group having 3 to 15 carbon atoms.), —O—C(═O)—R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms.) or —O—R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms.). m represents an integer of 0 to 5.) (In formula (3), R ５ , R ６ each independently represents a hydrogen atom or a methyl group. A represents a divalent group.)

[0011] The present disclosure (2) is the R of the above formula (1) ２However, this relates to the polymer described in (1) of this disclosure, which is an alkyl group having 6 to 24 carbon atoms.

[0012] Disclosure (3) relates to the polymer according to Disclosure (1) or (2), wherein the fluorine atom content is 1% by mass or less.

[0013] This disclosure (4) relates to a polymer according to any one of items (1) to (3) of this disclosure, wherein the silicon atom content is 1% by mass or less.

[0014] Disclosure (5) relates to a liquid-repellent material comprising the polymer described in any one of paragraphs (1) to (4) of Disclosure.

[0015] Disclosure (6) relates to a photosensitive composition comprising a polymer described in any one of Disclosures (1) to (4).

[0016] This disclosure (7) relates to a cured product obtained by curing the photosensitive composition described in this disclosure (6).

[0017] This disclosure (8) relates to a method for manufacturing a substrate with a patterned film, comprising: a film-forming step of applying the photosensitive composition described in this disclosure (6) onto a resin layer formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; and a development step of developing the film after the exposure step with an alkaline developer to obtain a patterned film.

[0018] This disclosure (9) relates to a method for manufacturing a substrate with a patterned film according to this disclosure (8), wherein the patterned film is a partition.

[0019] This disclosure (10) relates to a patterned substrate having a patterned film on which the cured product described in this disclosure (7) is patterned on a resin layer formed on a substrate.

[0020] This disclosure (11) relates to a substrate with a patterned film according to this disclosure (10), wherein the patterned film is a partition.

[0021] This disclosure (12) relates to an image display device having a patterned film substrate as described in this disclosure (10).

[0022] This disclosure (13) relates to an image display device having a patterned substrate as described in this disclosure (11).

[0023] The present disclosure (14) relates to a method for manufacturing a substrate with a patterned film, comprising: a film-forming step of applying a photosensitive composition onto a resin layer 1 formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; a developing step of developing the film after the exposure step with an alkaline developer to obtain a patterned film constituting a partition wall; a layer-forming step of providing an emissive layer or a wavelength-converting layer in a region partitioned by the partition wall; and a resin-forming step of applying a resin-containing liquid onto the partition wall and the emissive layer or the wavelength-converting layer to form a resin layer 2, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less.

[0024] The present disclosure (15) relates to a substrate with a pattern film, comprising: a pattern film constituting a partition wall provided on a resin layer 1 formed on a substrate; an emissive layer or wavelength conversion layer provided in a region partitioned by the partition wall; and a resin layer 2 provided on the partition wall and the emissive layer or wavelength conversion layer, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less.

[0025] This disclosure (16) relates to an image display device having a patterned substrate as described in this disclosure (15).

[0026] The polymer of this disclosure is a polymer having repeating units represented by formula (1), formula (2), and formula (3), and therefore exhibits liquid-repellent properties to ink and hydrophilic properties to resist solvents.

[0027] The liquid-repellent material of this disclosure contains the polymer of this disclosure and therefore has liquid-repellent properties to inks and exhibits hydrophilicity to resist solvents.

[0028] The photosensitive composition of this disclosure contains the polymer of this disclosure and therefore has liquid-repellent properties to inks and is hydrophilic to resist solvents.

[0029] The cured product of this disclosure is obtained by curing the photosensitive composition of this disclosure, and therefore has liquid-repellent properties to ink and is hydrophilic to resist solvents.

[0030] The method for manufacturing a patterned substrate according to the present disclosure includes a film-forming step of applying the photosensitive composition according to the present disclosure onto a resin layer formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; and a development step of developing the film after the exposure step with an alkaline developer to obtain a patterned film. Because the photosensitive composition according to the present disclosure is used, which is liquid-repellent to ink and hydrophilic to resist solvents, it is possible to manufacture a patterned substrate having a patterned film that is liquid-repellent to ink and hydrophilic to resist solvents.

[0031] The present disclosure provides a method for manufacturing a patterned substrate, comprising: a film-forming step of applying a photosensitive composition onto a resin layer 1 formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; a developing step of developing the film after the exposure step with an alkaline developer to obtain a patterned film constituting a partition wall; a layer-forming step of providing an emissive layer or a wavelength-converting layer in the region partitioned by the partition wall; and a resin-forming step of applying a resin-containing liquid onto the partition wall and the emissive layer or the wavelength-converting layer to form a resin layer 2, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more, and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less. The patterned film constituting the partition wall is liquid-repellent to ink and hydrophilic to resist solvents, thus enabling the manufacture of a patterned substrate having a patterned film that is liquid-repellent to ink and hydrophilic to resist solvents.

[0032] The patterned substrate of the present disclosure has a patterned film on which the cured product of the present disclosure is patterned on a resin layer formed on the substrate, and is therefore a patterned substrate having a patterned film that is liquid-repellent to ink and hydrophilic to resist solvent.

[0033] The patterned substrate of this disclosure has a patterned film that constitutes a partition wall, provided on a resin layer 1 formed on the substrate, a light-emitting layer or a wavelength conversion layer provided in the region partitioned by the partition wall, and a resin layer 2 provided on the partition wall and the light-emitting layer or the wavelength conversion layer, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less. The patterned film constituting the partition wall is liquid-repellent to ink and hydrophilic to resist solvent, thus the patterned substrate has a patterned film that is liquid-repellent to ink and hydrophilic to resist solvent.

[0034] The image display device of this disclosure has a patterned film on a substrate of this disclosure, which has a patterned film that is liquid-repellent to ink and hydrophilic to resist solvents, and is therefore expected to have a higher yield during device fabrication.

[0035] The present disclosure will be described in detail below, but the description of the constituent elements described below is an example of an embodiment of the present disclosure and is not limited to these specific contents. It can be implemented in various ways within the scope of its gist.

[0036] In this specification, the notation "X to Y" in descriptions of numerical ranges means "X or greater and Y or less" unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or greater and 5 mass% or less".

[0037] In this specification, "polymer," "resin," and "polymer" are synonymous and, unless otherwise noted, refer to high-molecular-weight compounds.

[0038] In this specification, "bank" and "partition" are synonymous, and unless otherwise noted, they refer to the raised portion of a patterned film with uneven surfaces in an inkjet process.

[0039] In this disclosure, the reason why the above-mentioned effects are obtained is not entirely clear, but it is presumed to be due to the following mechanism. The repeating unit represented by formula (1) above is a hydrocarbon group having 6 to 24 carbon atoms, R ２It is a unit having a relatively long-chain hydrocarbon group R ２ As a result, the polymer exhibits liquid repellency to ink while being hydrophilic to resist solvents. The repeating unit represented by formula (2) is a unit having a benzene ring, and this benzene ring provides liquid repellency to ink. The repeating unit represented by formula (3) is a unit having a vinyl group which is a crosslinking site, and this vinyl group allows the crosslinking reaction to proceed, enabling the formation of a suitable cured product. As described above, the polymer of this disclosure is a polymer having a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (3), and therefore exhibits liquid repellency to ink, is hydrophilic to resist solvents, and can form a suitable cured product.

[0040] (Polymers) First, the polymers of the present disclosure will be described. The polymers of the present disclosure are polymers having repeating units represented by the following formula (1), repeating units represented by the following formula (2), and repeating units represented by the following formula (3). (In formula (1), R １ R represents a hydrogen atom or a methyl group. ２ The symbol represents a hydrocarbon group with 6 to 24 carbon atoms. r represents either 0 or 1. When r is 0, (-C(=O)-O-) represents a single bond. (In formula (2), R １０ represents a hydrogen atom or a methyl group. B independently represents a hydrocarbon group, a hydroxyl group, a carboxyl group, and -C(=O)-O-R. １１ (R １１ )-O-C(=O)-R １２ (R １２ ) or -O-R represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. １２ (R １２ represents a linear alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms. m represents an integer from 0 to 5. (In formula (3), R ５ , R ６Each of these independently represents either a hydrogen atom or a methyl group. A represents a divalent group.

[0041] In the polymers of this disclosure, each unit in each repeating unit may be the same or different. Therefore, the polymers of this disclosure may be polymers in which one or more units corresponding to the repeating unit represented by formula (1), one or more units corresponding to the repeating unit represented by formula (2), and one or more units corresponding to the repeating unit represented by formula (3) are combined. In the polymers of this disclosure, it is preferable that each unit in each repeating unit is the same.

[0042] In formula (1), R １ This represents either a hydrogen atom or a methyl group, but a hydrogen atom is preferred.

[0043] In formula (1), R ２ R represents a hydrocarbon group with 6 to 24 carbon atoms. ２ The carbon number of the hydrocarbon group tends to improve liquid repellency to ink as it increases, and improve hydrophilicity to resist solvents as it decreases. Therefore, to obtain a better balance between liquid repellency to ink and hydrophilicity to resist solvents, it is preferably 8 to 22, more preferably 10 to 20, even more preferably 12 to 18, and particularly preferably 14 to 16.

[0044] In this specification, unless otherwise specified, a hydrocarbon group is a group composed of a carbon atom and a hydrogen atom.

[0045] R ２ Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. Among these, alkyl groups, alkenyl groups, and alkynyl groups are preferred, and alkyl groups are more preferred. ２ The hydrocarbon group may be linear, branched, or cyclic, but it is preferably linear.

[0046] R ２Examples of alkyl groups include linear, branched, or cyclic groups, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, cyclohexyl, norbornyl, and adamantyl groups. ２ The alkyl group is preferably linear.

[0047] R ２ Examples of alkenyl groups include linear, branched, or cyclic groups, such as 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, octadecenyl group, and cyclohexenyl group. ２ The alkenyl group is preferably in a linear form.

[0048] R ２ Examples of alkynyl groups include linear, branched, or cyclic groups, such as 1-hexynyl, 2-hexynyl, 1-octinyl, desinyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, octadecynyl, and cyclohexynyl groups. ２ The alkynyl group is preferably in a linear form.

[0049] R ２ Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl groups.

[0050] In formula (1), r represents either 0 or 1, but is preferably 1. When r is 0, (-C(=O)-O-) represents a single bond.

[0051] The following structures are examples of preferred repeating units represented by formula (1). Note that all alkyl groups in the following structures are linear.

[0052]

[0053] In formula (2), R １０This represents either a hydrogen atom or a methyl group, but a hydrogen atom is preferred.

[0054] In formula (2), B is independently a hydrocarbon group, a hydroxyl group (-OH), a carboxyl group (-COOH), and -C(=O)-O-R. １１ (R １１ )-O-C(=O)-R １２ (R １２ ) or -O-R represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. １２ (R １２ ) represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. Among these, hydrocarbon groups, -O-C(=O)-R １２ , -O-R １２ A hydrocarbon group is preferred, and a hydrocarbon group is more preferred.

[0055] The number of carbon atoms in the hydrocarbon group of B is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 2 to 6.

[0056] Examples of hydrocarbon groups in B include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. Among these, alkyl groups, alkenyl groups, and alkynyl groups are preferred, with alkyl groups being more preferred. The hydrocarbon group in B may be linear, branched, or cyclic, but it is preferably branched.

[0057] The alkyl group of B may be linear, branched, or cyclic, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, norbornyl, and adamantyl groups. The alkyl group of B is preferably branched. Since the alkyl group may be linear or branched, the propyl group means n-propyl or isopropyl, the butyl group means n-butyl, sec-butyl, or tert-butyl, and the same applies to other groups that may be linear or branched.

[0058] The alkenyl group of B may be linear, branched, or cyclic, and examples include vinyl groups, allyl groups, propenyl groups, and methylethenyl groups. The alkenyl group of B is preferably branched.

[0059] The alkynyl group of B may be linear, branched, or cyclic, and examples include ethynyl groups and propagyl groups. The alkynyl group of B is preferably branched.

[0060] Examples of the aryl group of B include phenyl, tolyl, xylyl, and naphthyl groups.

[0061] R １１ A linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, R １２ The linear alkyl group having 1 to 6 carbon atoms, the branched alkyl group having 3 to 6 carbon atoms, or the cyclic alkyl group having 3 to 6 carbon atoms is R ２ Similar to the alkyl groups of B, examples of cyclic alkyl groups include the cyclohexyl group. １１ As such, a linear alkyl group having 1 to 15 carbon atoms is preferred, with the number of carbon atoms preferably being 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. １２ Preferably, the alkyl group is a linear alkyl group having 1 to 6 carbon atoms, and the number of carbon atoms is preferably 1 to 3.

[0062] In formula (2), m represents an integer from 0 to 5, preferably an integer from 0 to 4, more preferably an integer from 0 to 3, even more preferably an integer from 0 to 2, and particularly preferably an integer from 0 to 1.

[0063] Regarding the repeating unit represented by formula (2), the following structures are examples of preferred structures. Note that C in the following structures ４ H ９ They are all linear in structure.

[0064]

[0065] In formula (3), R ５ , R ６Each of these independently represents either a hydrogen atom or a methyl group, but a hydrogen atom is preferred.

[0066] The repeating unit represented by formula (3) above is a unit having a vinyl group which is a crosslinking site, and this vinyl group allows the crosslinking reaction to proceed, and a suitable cured product to be formed. Therefore, the repeating unit represented by formula (3) above is not particularly limited as long as it is a unit having a vinyl group which is a crosslinking site, and the divalent group of A is also not particularly limited.

[0067] The number of carbon atoms in the divalent group of A is preferably 1 to 30, more preferably 1 to 25, even more preferably 2 to 20, and particularly preferably 3 to 15.

[0068] Examples of the divalent group of A include a divalent hydrocarbon group which may have a heteroatom.

[0069] The divalent hydrocarbon group may have heteroatoms. Examples of heteroatoms include nitrogen, oxygen, sulfur, fluorine, and chlorine atoms. Among these, nitrogen and oxygen atoms are preferred. The divalent hydrocarbon group may have multiple of these heteroatoms. The divalent hydrocarbon group may be linear, branched, or cyclic.

[0070] Examples of divalent hydrocarbon groups include alkylene groups, alkenylene groups, alkylylene groups, and arylene groups.

[0071] An example of a repeating unit represented by the above formula (3) is the repeating unit represented by the following formula (3-1).

[0072] In equation (3-1), R ５ , R ６ Each of these independently represents either a hydrogen atom or a methyl group.

[0073] In equation (3-1), W ２represents a divalent linking group, and can be -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH-, or C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH-, or C(=O)-NH- are preferred.

[0074] W ２ However, when the polymer is -O-C(=O)-NH-, it exhibits superior liquid repellency to ink after UV ozone treatment or oxygen plasma treatment, making it a particularly preferred embodiment.

[0075] In equation (3-1), A ２ A ３ Each of these independently represents a divalent linking group, and represents 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, wherein any number of hydrogen atoms in the alkylene group are hydroxyl groups or O-C(=O)-CH ３ It may be replaced with.

[0076] Divalent linking group A ２ A ３ When each of these is independently a linear alkylene group having 1 to 10 carbon atoms, examples include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0077] Divalent linking group A ２ A ３ Each of these can be an independent branched alkylene group having 3 to 10 carbon atoms, for example, isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, isohexalene, etc.

[0078] Divalent linking group A ２ A ３When each of these is independently a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0079] If any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, the hydroxyl-substituted alkylene group may be, for example, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH) (CH ３ )CH ２ Examples include: -)

[0080] Furthermore, any number of hydrogen atoms in these alkylene groups can be -O-C(=O)-CH ３ If substituted, the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is -O-C(=O)-CH ３ We can list the things that have been replaced.

[0081] In particular, divalent linking group A ２ A ３ These are, independently, a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, and a 1-hydroxyethylene group (-CH(OH)CH ２-), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), ethylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-) is particularly preferred.

[0082] In formula (3-1), Y ２ , Y ３ represents a divalent linking group, and each independently represents -O- or NH-, and -O- is more preferred.

[0083] In formula (3-1), n represents an integer from 1 to 3, and n being 1 is particularly preferred.

[0084] In formula (3-1), r represents 0 or 1. When r is 0 (-C(=O)-) represents a single bond.

[0085] For the repeating unit represented by formula (3-1), the following structures can be exemplified as preferred.

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] Another example of a repeating unit represented by formula (3) above is the repeating unit represented by formula (3-2) below. Preferred repeating units for formula (3) are the repeating unit represented by formula (3-1) above and the repeating unit represented by formula (3-2) below.

[0092] In equation (3-2), R ５ , R ６ Each of these independently represents either a hydrogen atom or a methyl group.

[0093] In equation (3-2), A ３ Each of these independently represents a divalent linking group, and represents 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, wherein any number of hydrogen atoms in the alkylene group are hydroxyl groups, O-C(=O)-CH ３ Or O-C (=O)-A ４ -COOH may be substituted. Here, A ４ is a divalent linking group, A ４ A ３ Similar groups can be cited, but it is preferable that they be linear alkylene groups having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms).

[0094] Divalent linking group A ３ When each of these is independently a linear alkylene group having 1 to 10 carbon atoms, examples include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0095] Divalent linking group A ３ Each of these can be an independent branched alkylene group having 3 to 10 carbon atoms, for example, isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, isohexalene, etc.

[0096] Divalent linking group A ３When each of these is independently a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0097] If any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, the hydroxyl-substituted alkylene group may be, for example, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH) (CH ３ )CH ２ Examples include: -)

[0098] Furthermore, any number of hydrogen atoms in these alkylene groups can be -O-C(=O)-CH ３ Ya-O-C(=O)-CH ２ CH ２ When substituted with -COOH, the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is -O-C(=O)-CH ３ Ya-O-C(=O)-CH ２ CH ２ - We can list the things that have been replaced by COOH.

[0099] In particular, divalent linking group A ３These are, independently, a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, and a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxyisopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), -CH ２ -CH(OC(=O)-CH ２ CH ２ -COOH)CH ２ - is preferred, and a 2-hydroxy-n-propylene group, -CH ２ -CH(OC(=O)-CH ２ CH ２ -COOH)CH ２ - is preferable.

[0100] In equation (3-2), Y ２ , Y ３ The group represents a divalent linking group, which independently represents -O- or NH-, with -O- being more preferable.

[0101] In equation (3-2), n represents an integer between 1 and 3, and it is particularly preferable that n is 1.

[0102] In equation (3-2), r represents either 0 or 1. When r is 0, (-C (=O)-) represents a single bond.

[0103] Regarding the repeating unit represented by formula (3-2), the following structures can be exemplified as preferred.

[0104]

[0105] While preferred structures of the repeating units represented by formula (1), formula (2), and formula (3) (the repeating units represented by formula (3-1) and formula (3-2)) have been illustrated, combinations of each preferred structure of the repeating unit represented by formula (1), each preferred structure of the repeating unit represented by formula (2), and each preferred structure of the repeating unit represented by formula (3) (the repeating units represented by formula (3-1) and formula (3-2)) are also preferred embodiments.

[0106] The content of the repeating unit represented by formula (1) in 100 mol% of the polymer of this disclosure is not particularly limited, but is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, and even more preferably 20 to 50 mol%. This tends to result in a more favorable outcome of the effects of this disclosure.

[0107] The content of the repeating unit represented by formula (2) in 100 mol% of the polymer of this disclosure is not particularly limited, but is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 35 mol%. This tends to result in a more favorable outcome of the effects of this disclosure.

[0108] The content of the repeating unit represented by formula (3) in 100 mol% of the polymer of this disclosure is not particularly limited, but is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, and even more preferably 20 to 50 mol%. This tends to result in a more favorable outcome of the effects of this disclosure.

[0109] The polymers of this disclosure may have repeating units other than those represented by formula (1), formula (2), and formula (3). Examples of other units include the repeating unit represented by formula (4) below. Other units may be used alone or in combination of two or more types.

[0110] The polymer of this disclosure tends to exhibit favorable solubility in alkaline developers because it has repeating units represented by the following formula (4).

[0111] In equation (4), R１３ represents a hydrogen atom or a methyl group.

[0112] In equation (4), A ４ represents a divalent linking group, and represents 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, wherein any number of hydrogen atoms in the alkylene group are hydroxyl groups or O-C(=O)-CH ３ It may be replaced with.

[0113] Divalent linking group A ４ When it is a linear alkylene group having 1 to 10 carbon atoms, examples include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.

[0114] Divalent linking group A ４ When this refers to a branched alkylene group having 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentalene, and isohexalene groups.

[0115] Divalent linking group A ４ When this refers to a cyclic alkylene group having 3 to 10 carbon atoms, examples include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

[0116] If any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, the hydroxyl-substituted alkylene group may be, for example, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH) (CH ３ )CH ２ Examples include: -)

[0117] Furthermore, any number of hydrogen atoms in these alkylene groups can be -O-C(=O)-CH ３ If substituted, the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is -O-C(=O)-CH ３ We can list the things that have been replaced.

[0118] In particular, divalent linking group A ４ These are methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxyisopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -) is preferred, and the group may be an ethylene group, a propylene group, or a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxyisopropylene group (-CH(CH ２ OH)CH ２ -) is more preferable, with an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-) is particularly preferred.

[0119] In equation (4), Y ４ represents a divalent linking group, which represents -O- or NH-, and is more preferably -O-.

[0120] In equation (4), r represents either 0 or 1. When r is 0, (-C (=O)-) represents a single bond.

[0121] In equation (4), E １ E represents a hydroxyl group, a carboxyl group, or an oxirane group. １ When the group is an oxirane group, examples include an ethylene oxide group, a 1,2-propylene oxide group, a 1,3-propylene oxide group, etc. Among these, an ethylene oxide group is preferred.

[0122] In equation (4), s represents either 0 or 1. When s is 0, (-Y ４ -A ４ -) represents a single bond. When r is 0 and s is 0, E is present in the main chain of the repeating unit. １ This results in a structure where these elements are joined together.

[0123] The following structures are examples of preferred repeating units represented by equation (4).

[0124]

[0125] In equation (4), E １ When is a hydroxyl group or a carboxyl group, the repeating unit represented by formula (4) can impart solubility to the polymer in an alkaline developer. Therefore, if you want to impart alkali developability to a film obtained from the polymer of this disclosure, add E to the polymer of this disclosure. １ It is preferable to include a repeating unit represented by formula (4) when is a hydroxyl group or a carboxyl group.

[0126] The content of the repeating unit represented by formula (4) in 100 mol% of the polymer disclosed herein is not particularly limited, but is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, and even more preferably 3 to 20 mol%. This tends to result in good alkali developability.

[0127] In 100 mol% of the polymer of this disclosure, the total content of repeating units represented by formula (1), formula (2), and formula (3) is preferably 50 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, particularly preferably 98 mol% or more, and most preferably 100 mol%. This tends to more favorably obtain the effects of this disclosure. In this specification, the content of each unit in the polymer is measured by NMR.

[0128] The weight-average molecular weight (Mw) of the polymers of this disclosure is preferably 2,000 to 200,000, more preferably 5,000 to 150,000, and even more preferably 10,000 to 100,000. This tends to result in more favorable results of the effects of this disclosure.

[0129] The degree of dispersion (Mw / Mn) of the polymers disclosed herein is preferably 1.1 to 4.0, more preferably 1.3 to 3.0, and even more preferably 1.5 to 2.5. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers are measured by the method described in the Examples.

[0130] In 100% by mass of the polymer disclosed herein, the content of fluorine atoms is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and most preferably 0% by mass. This tends to ensure good liquid repellency to inks. In this specification, the content of fluorine atoms in the polymer is, １９ It is measured by F-NMR.

[0131] In 100% by mass of the polymer of this disclosure, the content of silicon atoms is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and most preferably 0% by mass. This tends to ensure good liquid repellency to ink. In this specification, the content of silicon atoms in the polymer is, ２９ It is measured by Si-NMR.

[0132] The polymer of this disclosure may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. A random copolymer is preferred because it readily exhibits properties that are liquid-repellent to inks and hydrophilic to resist solvents.

[0133] Preferred embodiments of the polymers of this disclosure are as follows: <<Embodiment 1-1>> Polymer formula (1) having repeating units represented by the following formula (1): R of formula (1) ２ However, alkyl groups having 6 to 24 carbon atoms (preferably linear alkyl groups having 6 to 24 carbon atoms)

[0134] <<Aspect 1-2>> Polymer formula (1) having repeating units represented by the following formula (1) and formula (2): Same formula (2) as in Aspect 1-1: B is a hydrocarbon group (preferably an alkyl group) (preferably a branched hydrocarbon group (preferably a branched alkyl group))

[0135] <<Aspect 1-3>> Polymer formula (1) having repeating units represented by the following formula (1) and formula (2): Same formula (2) as in Aspect 1-1: B is a hydrocarbon group (preferably an alkyl group) (preferably a branched hydrocarbon group (preferably a branched alkyl group)), m is an integer from 0 to 1

[0136] (Liquid-repellent material) The polymer of the present disclosure can impart liquid-repellent properties to the resulting cured product, and is therefore suitable for use as a liquid-repellent material. Accordingly, the liquid-repellent material of the present disclosure includes the polymer of the present disclosure. The polymer of the present disclosure may be used alone or in combination of two or more types.

[0137] In 100% by mass of the liquid-repellent material of the present disclosure, the content of the polymer of the present disclosure is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass. This tends to result in a more favorable acquisition of the effects of the present disclosure.

[0138] (Photosensitive Composition) Next, the photosensitive composition (photosensitive resin composition) of the present disclosure will be described. The photosensitive composition of the present disclosure includes the polymer of the present disclosure. The polymer of the present disclosure may be used alone or two or more may be used in combination.

[0139] The content of the polymer of this disclosure in 100% by mass of the photosensitive composition is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, and even more preferably 1 to 40% by mass. This tends to result in a more favorable acquisition of the effects of this disclosure.

[0140] The following describes the formulations that may be included in the photosensitive composition of this disclosure.

[0141] <Solvent> The photosensitive composition of the present disclosure preferably contains a solvent. In the photosensitive composition of the present disclosure, the solvent is not particularly limited as long as the polymer of the present disclosure is soluble in it, but examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, fluorinated solvents, etc. These may be used individually or in combination of two or more.

[0142] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexisanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

[0143] Examples of polyhydric alcohols and their derivatives include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0144] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0145] Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and γ-butyrolactone. Examples of aromatic solvents include xylene and toluene.

[0146] Examples of fluorinated solvents include chlorofluorocarbons (CFCs), alternative CFCs, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0147] In addition, to improve coating properties, high-boiling point weak solvents such as turpentine-based petroleum naphtha solvents or paraffinic solvents can be used.

[0148] Among them, the solvents include methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate It is preferable that the substance is at least one selected from the group consisting of cetate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropyl alcohol. It is more preferable that the substance is methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, or γ-butyrolactone.

[0149] The amount of solvent in the photosensitive composition of this disclosure is preferably in the range of 50 to 2000 parts by mass, and more preferably 100 to 1000 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains an alkali-soluble resin as described later, the amount of the resin is included). By adjusting the amount of solvent, the thickness of the formed resin film can be adjusted, and within the above range, a resin film thickness particularly suitable for obtaining an organic EL bank can be obtained.

[0150] <Photopolymerization Initiator> The photosensitive composition of this disclosure preferably contains a photopolymerization initiator. In the photosensitive composition of this disclosure, the photopolymerization initiator is not particularly limited as long as it polymerizes monomers using high-energy rays such as electromagnetic waves or electron beams, and known photopolymerization initiators can be used. As the photopolymerization initiator, a photoradical initiator or a photoacid initiator can be used, and these may be used alone, in combination with a photoradical initiator and a photoacid initiator, or two or more photoradical initiators or photoacid initiators may be used in combination. In addition, by using an additive in combination with the photopolymerization initiator, it is possible to carry out living polymerization in some cases, and known additives can be used.

[0151] Photoradical initiators can be classified into, for example, intramolecular cleavage types that generate radicals by cleaving intramolecular bonds through absorption by electromagnetic waves or electron beams, and hydrogen abstraction types that generate radicals by using hydrogen donors such as tertiary amines or ethers in combination. Any of these may be used. Other types of photoradical initiators may also be used.

[0152] Examples of photoradical initiators include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, acyloin-based, and oxime ester-based compounds.

[0153] Examples of benzophenone derivatives include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0154] Examples of acetophenone derivatives include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0155] Examples of diketone compounds include 4,4'-dimethoxybenzyl, methyl benzoylmate, and 9,10-phenanthrenequinone. Among these, 4,4'-dimethoxybenzyl and methyl benzoylmate are preferred.

[0156] Examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0157] Examples of quinone compounds include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0158] Examples of acyloin derivatives include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

[0159] Examples of oxime esters include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone. Among these, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone is preferred.

[0160] As photoradical initiators, acylphosphine oxide systems and oxime ester systems are preferred, with acylphosphine oxide systems being more preferred.

[0161] Among commercially available photoradical initiators, preferred examples include products manufactured by BASF Co., Ltd.: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocure 1173, Lucilin TPO, Omnirad 819, etc.

[0162] The photoacid initiator is specifically an onium salt consisting of a pair of at least one cation selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxantonium, and (2,4-cyclopentadien-1-yl)(1-methylethylbenzene)iron, and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate. Among these, bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfidetetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

[0163] Examples of commercially available photoacid generators include: Sunapro Co., Ltd.'s product names: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S; Dow Chemical Japan Ltd.'s product names: Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, Cyracure Photocuring Initiator UVI-6976; and ADEKA Corporation's product names: ADEKA Optomer SP-150, ADEKA Optomer SP-152, ADEKA Optomer SP-170, ADEKA Optomer SP Examples include -172, Adeka Optomer SP-300, products manufactured by Nippon Soda Co., Ltd.: CI-5102, CI-2855, products manufactured by Sanshin Chemical Industry Co., Ltd.: Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-180, products manufactured by Lamberti: Esacure 1064, Esacure 1187, and products manufactured by Ciba Specialty Chemicals Co., Ltd.: Irgacure 250.

[0164] The content of the photopolymerization initiator in the photosensitive composition of this disclosure is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains an alkali-soluble resin as described later, the total amount of that resin is included). When the content of the photopolymerization initiator is 0.1 parts by mass or more, a sufficient crosslinking effect tends to be obtained, and when it is 30 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0165] <Crosslinking Agent> The photosensitive composition of this disclosure preferably contains a crosslinking agent. The crosslinking agent reacts with the vinyl groups of the polymer of this disclosure, allowing the polymer to adopt a crosslinked structure, which tends to improve the mechanical strength of the resulting film.

[0166] Known crosslinking agents can be used, specifically including compounds obtained by reacting amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, and glycoluryl with formaldehyde or a lower alcohol, and substituting the hydrogen atoms of the amino group with a hydroxymethyl group or a lower alkoxymethyl group; polyfunctional epoxy compounds; polyfunctional oxetane compounds; polyfunctional isocyanate compounds; and polyfunctional acrylate compounds. Here, those using melamine are called melamine-based crosslinking agents, those using urea are called urea-based crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are called alkylene urea-based crosslinking agents, and those using glycoluryl are called glycoluryl-based crosslinking agents. These crosslinking agents may be used individually or in combination of two or more.

[0167] The crosslinking agent is preferably at least one selected from these crosslinking agents, with glycoluryl-based crosslinking agents and polyfunctional acrylate compounds being particularly preferred, and polyfunctional acrylate compounds being more preferred.

[0168] Examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine, with hexamethoxymethylmelamine being the most preferred.

[0169] Examples of urea-based crosslinking agents include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, with bismethoxymethylurea being the most preferred.

[0170] Examples of alkylene urea crosslinking agents include ethylene urea crosslinking agents such as mono and / or dihydroxymethylated ethyleneurea, mono and / or dimethoxymethylated ethyleneurea, mono and / or diethoxymethylated ethyleneurea, mono and / or dipropoxymethylated ethyleneurea, and mono and / or dibutoxymethylated ethyleneurea; propylene urea crosslinking agents such as mono and / or dihydroxymethylated propyleneurea, mono and / or dimethoxymethylated propyleneurea, mono and / or diethoxymethylated propyleneurea, mono and / or dipropoxymethylated propyleneurea, and mono and / or dibutoxymethylated propyleneurea; and 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0171] Examples of glycoluryl crosslinking agents include mono, di, tri and / or tetrahydroxymethylated glycoluryl, mono, di, tri and / or tetramethoxymethylated glycoluryl, mono, di, tri and / or tetraethoxymethylated glycoluryl, mono, di, tri and / or tetrapropoxymethylated glycoluryl, and mono, di, tri and / or tetrabutoxymethylated glycoluryl.

[0172] Examples of polyfunctional acrylate compounds include polyfunctional acrylates (e.g., product names from Shin-Nakamura Chemical Industry Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP), polyethylene glycol diacrylate (e.g., product names from Shin-Nakamura Chemical Industry Co., Ltd.: A-200, A-400, A-600), urethane acrylates (e.g., product names from Shin-Nakamura Chemical Industry Co., Ltd.: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200), pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.

[0173] The following are examples of preferred polyfunctional acrylate compounds.

[0174]

[0175]

[0176]

[0177]

[0178] The crosslinking agent content in the photosensitive composition of this disclosure is preferably 10 to 400 parts by mass, and more preferably 50 to 300 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains an alkali-soluble resin as described later, the total amount of that resin is included). When the crosslinking agent content is 10 parts by mass or more, a sufficient crosslinking effect tends to be obtained, and when it is 400 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0179] <Alkali-Soluble Resin> The photosensitive composition of this disclosure preferably contains an alkali-soluble resin. When the photosensitive composition of this disclosure contains an alkali-soluble resin, the shape of the bank obtained from the photosensitive composition of this disclosure tends to be improved. The alkali-soluble resin may be used alone or two or more types may be used in combination.

[0180] The alkali-soluble resin is not particularly limited as long as it is a resin that can be dissolved in an alkali, and for example, alkali-soluble novolac resins can be given. Alkali-soluble novolac resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

[0181] Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, pyrogallol, phloroglucinol, thymol, isothymol, and the like. These phenols may be used individually or in combination of two or more types.

[0182] Examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, etc. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethyl sulfuric acid, p-toluenesulfonic acid, etc. These acid catalysts may be used individually or in combination of two or more types.

[0183] Other examples of alkali-soluble resins include epoxy (meth)acrylate adducts (acid-modified epoxy (meth)acrylate-based alkali-soluble resins) obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols (bisphenol-type epoxy compound) with (meth)acrylic acid, and then reacting the resulting compound having a hydroxyl group with a polybasic carboxylic acid or its anhydride. Commercially available acid-modified epoxy acrylate systems include, for example, products from Nippon Kayaku Co., Ltd.: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, ZCR-1569H, and ZAR-2050H.

[0184] An epoxy compound having two glycidyl ether groups derived from bisphenols refers to an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epihalohydrins, or an equivalent thereof. Since this reaction generally involves oligomerization of the diglycidyl ether compound, it includes epoxy compounds containing two or more bisphenol skeletons.

[0185] Examples of bisphenols include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl) hexafluoropropane, bis(4-hydroxyphenyl) hexafluoropropane, bis(4-hydroxyphenyl) 3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane , 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy- Examples include 3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, and the like.These can be used individually, or two or more can be used in combination.

[0186] Examples of polybasic carboxylic acids or their anhydrides include monoanhydrides of dicarboxylic acids or tricarboxylic acids, and dianhydrides of tetracarboxylic acids. These may be used individually or in combination of two or more.

[0187] Examples of acid monoanhydrides of dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. These may be used individually or in combination of two or more. Examples of acid monoanhydrides of chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and others. Furthermore, examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, trimellitic acid, and other acid monoanhydrides.

[0188] Examples of dianhydrides of tetracarboxylic acids include dianhydrides of chain-type hydrocarbon tetracarboxylic acids, dianhydrides of alicyclic tetracarboxylic acids, and dianhydrides of aromatic tetracarboxylic acids. These may be used individually or in combination of two or more. Examples of dianhydrides of chain-type hydrocarbon tetracarboxylic acids include dianhydrides of butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc. Examples of dianhydrides of alicyclic tetracarboxylic acids include dianhydrides of cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, etc. Examples of dianhydrides of aromatic tetracarboxylic acids include dianhydrides of pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, etc.

[0189] The weight-average molecular weight of the alkali-soluble resin component is preferably 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive composition.

[0190] The content of the alkali-soluble resin in the photosensitive composition of this disclosure is preferably 300 to 10,000 parts by mass, and more preferably 500 to 7,000 parts by mass, per 100 parts by mass of the polymer of this disclosure. When the content of the alkali-soluble resin is 10,000 parts by mass or less, better liquid repellency tends to be obtained.

[0191] <Naphthoquinone diazide group-containing compound> The photosensitive composition of this disclosure may contain a naphthoquinone diazide group-containing compound. When the photosensitive composition of this disclosure contains a naphthoquinone diazide group-containing compound, the shape of the bank obtained from the photosensitive composition of this disclosure tends to be improved. The naphthoquinone diazide group-containing compound is not particularly limited, and any compound commonly used as a photosensitive component in i-line resist compositions can be used.

[0192] Examples of naphthoquinone diazide group-containing compounds include naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds, naphthoquinone-1,2-diazide sulfonic acid ester compounds, orthobenzoquinone diazide sulfonic acid ester compounds, orthanthraquinone diazide sulfonic acid ester compounds, etc. Among these, naphthoquinone-1,2-diazide-4-sulfonic acid ester compounds, naphthoquinone-1,2-diazide-5-sulfonic acid ester compounds, and naphthoquinone-1,2-diazide-6-sulfonic acid ester compounds are preferred due to their excellent solubility. These may be used individually or in combination of two or more.

[0193] The content of the naphthoquinone diazide group-containing compound in the photosensitive composition of this disclosure is preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains the aforementioned alkali-soluble resin, the total amount including that resin). A content of 60 parts by mass or less tends to yield better sensitivity as a photosensitive composition.

[0194] <Basic Compounds> The photosensitive composition of this disclosure may contain basic compounds. Basic compounds have the effect of slowing down the diffusion rate when the acid generated from the photoacid generator diffuses into the film of the photosensitive composition of this disclosure. By incorporating basic compounds, the acid diffusion distance can be adjusted, and the shape of the bank tends to be improved. In addition, by incorporating basic compounds, the bank tends to be less prone to deformation even if the drying time between bank formation and exposure is long, and a bank with the desired precision can be stably formed.

[0195] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, specifically secondary or tertiary aliphatic amines and alkyl alcohol amines. These may be used individually or in combination of two or more.

[0196] Examples of aliphatic amines include ammonia (NH₄). ３ Examples include alkylamines or alkyl alcoholamines in which at least one hydrogen atom of a molecule is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, and di-n-octylamine. Examples include di-n-nonylamine, di-n-decanylamine, di-n-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decanylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, dialkylamines, trialkylamines, and alkyl alcoholamines are preferred, with alkyl alcoholamines being more preferred. Among alkyl alcoholamines, triethanolamine and triisopropanolamine are particularly preferred.

[0197] Aromatic amines and heterocyclic amines include, for example, aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, 1,5-diazabicyclo[4.3.0]nona-5-ene, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, and bis(1,2,2,6, Examples include hindered amines such as 6-pentamethyl-4-piperidyl) sevagate, 2-hydroxypyridine, aminocresol, 2,4-quinoline diol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, and other alcoholic nitrogen-containing compounds, as well as picoline, lutidine, pyrrole, piperidine, piperazine, indole, hexamethylenetetramine, and the like.

[0198] In the photosensitive composition of this disclosure, the content of the basic compound is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains the aforementioned alkali-soluble resin, the total amount of the resin). When the amount of the basic compound is 0.001 parts by mass or more, the effect as an additive is sufficiently obtained, and when it is 2 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0199] <Other Additives> The photosensitive compositions of this disclosure may contain other additives as needed. Examples of other additives include dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, defoamers, compatibilizers, adhesives, antioxidants, and chain transfer agents. These may be used individually or in combination of two or more. These other additives may be known.

[0200] Furthermore, it is preferable that the surfactant contains, for example, either a fluorine-based surfactant or a silicone-based surfactant (a surfactant containing both a fluorine atom and a silicon atom), or two or more of these.

[0201] By incorporating an adhesive, better adhesion to the substrate tends to be achieved. Examples of adhesives include silane coupling agents and phosphate esters. Examples of silane coupling agents include sulfide-based, mercapto-based, protected mercapto-based, vinyl-based, amino-based, glycidoxy-based, nitro-based, and chloro-based agents. These may be used alone or in combination of two or more. Among these, vinyl-based agents are preferred, and (meth)acrylic-based phosphate compounds are more preferred. Examples of (meth)acrylic-based phosphate compounds include KBM-503 and KBM-5103 from Shin-Etsu Chemical Co., Ltd. As for phosphate esters, those having vinyl, acrylic, or methacrylic groups in the crosslinking site are desirable, such as KAYAMER-PM21 from Nippon Kayaku Co., Ltd.

[0202] In the photosensitive composition of this disclosure, the content of the adhesive is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains the aforementioned alkali-soluble resin, the total amount of the resin is included). This tends to result in better adhesion to the substrate.

[0203] Examples of coloring agents include coloring pigments and coloring dyes. These may be used individually or in combination of two or more.

[0204] Examples of coloring pigments include inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and cold dust; organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, perylene, anthrapyrimidine, carbazole violet, anthrapyridine, azo orange, flavanthrone yellow, isoindoline yellow, azo yellow, induthrone blue, dibromanthathrone red, perylene red, azo red, and anthraquinone red; and aluminum powder, alumina powder, bronze powder, copper powder, tin powder, zinc powder, iron phosphide, and finely atomized titanium.

[0205] Examples of usable organic pigments include, but are not limited to, those with the following color index numbers: Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279 etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81 etc. Pigment Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214 etc. Pigment Green 7, 36, 58 etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80 etc. Pigment Violet 19, 23, 37 etc.

[0206] Examples of coloring dyes include monoazo, disazo, metal complex salt type monoazo, anthraquinone, methine, phthalocyanine, and triallylmethane dyes.

[0207] Colorants are typically dispersed in a solvent to form a colorant dispersion, which is then mixed with other components. A dispersant may be added in this process. The dispersant can be any known compound used for pigment (colorant) dispersion (compounds commercially available under names such as dispersants, dispersion wetting agents, or dispersion accelerators), without any particular limitations. Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). These may be used individually or in combination of two or more. The amount of dispersant is preferably 1 to 35% by mass, and more preferably 2 to 25% by mass, relative to the colorant. While high-viscosity substances such as resins generally have a dispersion-stabilizing effect, those without dispersion-promoting properties are not treated as dispersants. However, this does not restrict their use for the purpose of stabilizing dispersion.

[0208] In the photosensitive composition of this disclosure, the content of the colorant is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains the aforementioned alkali-soluble resin, the total amount of the resin is included).

[0209] Chain transfer refers to a component that receives radicals from the growing polymer chain in a radical polymerization system and generates new radicals. By using a chain transfer agent, the degree of polymerization can be adjusted, and the properties of the cured film can be modified. Examples of chain transfer agents include aromatic hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane; mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, n-dodecyl mercaptan, t-tetradecyl mercaptan, and t-dodecyl mercaptan; hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetraxthioglycolate, pentaerythritol Examples include thiol compounds such as thritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and pentaerythritol tetrakis(3-mercaptobutyrate); sulfide compounds such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; and N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-terpinene, and dipentene. These may be used individually or in combination of two or more. Thiol compounds are particularly preferred.

[0210] In the photosensitive composition of this disclosure, the content of the chain transfer agent is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer of this disclosure (however, if the photosensitive composition contains the aforementioned alkali-soluble resin, the total amount of the resin). This allows for suitable curability to be maintained and allows for adjustment of the development contrast with the unexposed areas.

[0211] (Method for manufacturing cured product, method for manufacturing substrate with patterned film) Next, a method for manufacturing a cured product using the photosensitive composition of this disclosure, and a method for manufacturing a substrate with a patterned film will be described.

[0212] The method for manufacturing a cured product according to this disclosure (method for manufacturing a substrate with a patterned film) includes (1-1) a film formation step, (1-2) an exposure step, and (1-3) a development step, and may further include (1-4) a baking step. Each step is described below.

[0213] (1-1) Film Forming Process First, in the film forming process, the photosensitive composition of the present disclosure is applied to a resin layer 1 formed on a substrate to form a film. Specifically, the photosensitive composition of the present disclosure is applied to a resin layer 1 formed on a substrate, and then heated to form a film. The heating conditions are not particularly limited, but are preferably 80 to 100°C and 60 to 200 seconds. This makes it possible to remove solvents and other substances contained in the photosensitive composition.

[0214] The substrate can be a silicon wafer, metal, glass, ITO substrate, etc. Furthermore, an organic resin layer 1 is pre-formed on the substrate. The resin layer 1 formed on the substrate may cover the entire surface or only a portion of it. The resin layer 1 is not particularly limited as long as it contains resin; examples include an anti-reflective film, a layer beneath a multilayer resist, etc., and a pattern may be formed on it. The surface of the substrate and the resin layer 1 may also be pre-cleaned. For example, cleaning can be done using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), etc.

[0215] As a method for applying the photosensitive composition of this disclosure onto a resin layer 1 formed on a substrate, a suitable coating apparatus such as a slit coater, die coater, gravure coater, dip coater, or spin coater may be used. Alternatively, methods such as immersion coating, spray coating, or roller coating can also be used.

[0216] Here, the film formed on the resin layer 1 formed on the substrate may be formed over the entire surface of the resin layer 1 formed on the substrate, or it may be formed on only a part of it.

[0217] The film thickness is preferably 1 to 500 μm. If the film is thinner than 1 μm, the mechanical strength of the film may decrease, and if the thickness exceeds 500 μm, the surface irregularities tend to increase, making it difficult to obtain a flat film.

[0218] (1-2) Exposure process Next, in the exposure process, the film after the film formation process is exposed to high-energy rays through a photomask to transfer the pattern of the photomask to the film. Specifically, a desired photomask is set in the exposure apparatus, and high-energy rays are exposed to the film after the film formation process through the photomask. The high-energy rays are preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

[0219] High-energy radiation exposure doses range from 1 to 200 mJ / cm². ２ Preferably, the concentration is 10 to 100 mJ / cm². ２ It is preferable that it be so.

[0220] (1-3) Development Process Next, in the development process, the film after the exposure process is developed with an alkaline developer to obtain a pattern film. Specifically, the film after the exposure process is developed with an alkaline aqueous solution to form a pattern film. That is, a pattern film is formed by dissolving either the exposed or unexposed parts of the film in an alkaline aqueous solution.

[0221] As the alkaline aqueous solution, for example, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, etc. can be used. When the alkaline aqueous solution is an aqueous solution of tetramethylammonium hydroxide (TMAH), its concentration is preferably 0.1 to 5% by mass, and more preferably 2 to 3% by mass.

[0222] The development method can be any known method, such as the dip method, paddle method, or spray method.

[0223] The development time (the time the developer is in contact with the film) is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0224] After development, a step may be provided to wash the pattern film using deionized water or the like, if necessary. The washing method and washing time are preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0225] (1-4) Baking process In the baking process, after the development process, the pattern film is cured by baking to obtain a cured product. Specifically, after the development process, the pattern film is cured by heating and baking to obtain a cured product. The cured product of this disclosure is obtained by curing the photosensitive composition of this disclosure. Baking can be performed on a hot plate, and the baking conditions are preferably 140°C or lower (preferably 60 to 130°C) and 10 to 120 minutes.

[0226] Furthermore, in the above manufacturing method, UV ozone treatment or oxygen plasma treatment may be performed after the baking process (1-4). Of these, UV ozone treatment is preferable. This makes it possible to remove organic matter remaining in the recesses of the pattern film and reduce uneven wetting of the dropped ink, thereby preventing malfunctions of the display element.

[0227] The cured product obtained in this manner exhibits excellent liquid repellency to ink and can therefore be used as a bank for organic EL displays, micro-LED displays, quantum dot displays, etc. In other words, the manufacturing method for the cured product of this disclosure can also be used to manufacture banks for organic EL displays, micro-LED displays, quantum dot displays, etc. Thus, the pattern film functions as a bank (separator).

[0228] Furthermore, the patterned film substrate manufactured in this manner is a patterned film having a patterned film formed on a resin layer 1 formed on the substrate, and can be used as a substrate for organic EL displays, micro-LED displays, quantum dot displays, etc. In other words, the manufacturing method of the patterned film substrate of this disclosure can also be used to manufacture substrates for organic EL displays, micro-LED displays, quantum dot displays, etc. Thus, the patterned film functions as a bank (partition).

[0229] The cured product of the present disclosure is liquid-repellent to ink and hydrophilic to resist solvent. Therefore, in the method for manufacturing a patterned substrate of the present disclosure, the development step preferably further includes a development step of developing the film after the exposure step with an alkaline developer to obtain a patterned film constituting a partition wall, a layer formation step of providing an emissive layer or a wavelength conversion layer in the region partitioned by the partition wall, and a resin layer formation step of applying a resin-containing liquid onto the partition wall and the emissive layer or the wavelength conversion layer to form a resin layer 2.

[0230] In other words, the method for manufacturing a patterned substrate according to the present disclosure preferably includes: a film-forming step of applying the photosensitive composition of the present disclosure onto a resin layer 1 formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; a developing step of developing the film after the exposure step with an alkaline developer to obtain a patterned film constituting a partition wall; a layer-forming step of providing an emissive layer or a wavelength-converting layer in the region partitioned by the partition wall; and a resin-forming step of applying a resin-containing liquid onto the partition wall and the emissive layer or the wavelength-converting layer to form a resin layer 2.

[0231] This allows the cured product of the present disclosure to exhibit more favorable performance. Specifically, since the cured product of the present disclosure is liquid-repellent to ink, it is possible to suitably provide an emissive layer or a wavelength-converting layer by an inkjet method. Furthermore, since the cured product of the present disclosure is hydrophilic to resist solvents, it has good affinity with resin-containing liquids, so a resin-containing liquid can be applied to the partition wall to suitably form a resin layer 2.

[0232] (2) Layer Formation Process In the layer formation process, a light-emitting layer or a wavelength conversion layer is provided in the region partitioned by the partition wall. Specifically, a light-emitting layer or a wavelength conversion layer is provided in the region partitioned by the partition wall by an inkjet method. More specifically, ink is dropped into the region partitioned by the partition wall to fill the space separated by the partition wall with ink, and then the filled ink is dried and / or cured as necessary to form a light-emitting layer or a wavelength conversion layer. Since the partition wall has liquid-repellent properties to ink, it is possible to suitably prevent ink from overflowing into adjacent cells due to insufficient liquid-repellent properties on the upper surface of the partition wall. This layer formation process is characterized by the use of the cured product of this disclosure as the partition wall, and the method of providing the light-emitting layer or wavelength conversion layer by an inkjet method is not particularly limited, and known methods can be applied as appropriate. In this specification, a light-emitting layer means a layer that emits light by electroluminescence, and a wavelength conversion layer means a layer that has wavelength conversion properties, which absorbs electromagnetic waves and emits electromagnetic waves with a wavelength different from the wavelength of the absorbed electromagnetic waves.

[0233] The ink is not particularly limited as long as it contains a light-emitting material or a wavelength-converting material, but it may also contain a solvent, a photocrosslinkable diluent, etc. These may be used alone or in combination of two or more. A light-emitting material means an organic material that emits light by electroluminescence, and a wavelength-converting material means a material that has wavelength-converting properties, such as absorbing electromagnetic waves and emitting electromagnetic waves of a different wavelength than the absorbed electromagnetic waves. Examples of light-emitting materials and wavelength-converting materials include inorganic phosphors and organic phosphors. These may be used alone or in combination of two or more.

[0234] Ink typically contains a solvent. The solvent contained in the ink is a solvent used as a so-called reactive diluent, and may be used alone or in combination of two or more. Specifically, the solvent contained in the ink is a compound having a (meth)acryloyl group in its molecule, which has low viscosity and high resin solubility, more specifically, R ２ - (OCOCR １ =CH ２ ) ｎ (Here, R １ is H or CH ３ , an integer n = 1 or greater, R ２Examples of compounds are those represented by an n-valent group, which has four or more carbon atoms (for example, a hydrocarbon group that may have a heteroatom). Note that (meth)acryloyl group refers to both acryloyl group and methacryloyl group. Specific examples include hexanediol diacrylate (HDDA), butyl acrylate, benzyl acrylate, nonanediol diacrylate, neopentyl glycol diacrylate, tricyclodecanediol diacrylate, 2-hydroxy-3-methacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, ethoxylated bisphenol A diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated glycerin triacrylate, tris-(2-acryloxyethyl) isocyanurate, pentaerythritol tritetraacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane Triacrylate, dipentaerythritol polyacrylate, ethoxylated dipentaerythritol polyacrylate, polypentaerythritol polyacrylate, hexanediol dimethacrylate, butyl methacrylate, benzyl methacrylate, nonanediol dimethacrylate, neopentyl glycol dimethacrylate, tricyclodecanediol dimethacrylate, 2-hydroxy-3-methacrylpropyl methacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polytetramethylene glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin trimethacrylate, tris-(2-methacryloxyethyl) isocyanurate, pentaerythritol tritetramethacrylate,Examples include pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol polymethacrylate, ethoxylated dipentaerythritol polymethacrylate, and polypentaerythritol polymethacrylate. These may be used individually or in combination of two or more. Among these, hexanediol diacrylate (HDDA) is preferred. The solvent content in 100% by mass of ink is preferably 1 to 99% by mass, more preferably 10 to 90% by mass.

[0235] The drying method is not particularly limited and includes vacuum drying, heat drying, etc., and the drying conditions are also not particularly limited. The method and conditions for curing are also not particularly limited.

[0236] (3) Resin layer formation process In the resin layer formation process, a resin-containing liquid is applied to the partition wall and the light-emitting layer or the wavelength conversion layer to form a resin layer 2. Specifically, after applying the resin-containing liquid to the partition wall and the light-emitting layer or the wavelength conversion layer, the resin-containing liquid is heated to form a resin layer 2 (film).

[0237] In the method for manufacturing a cured product (method for manufacturing a patterned substrate) of the present disclosure, the resin layer formation step includes the above-described steps of (1-1) film formation, (1-2) exposure, and (1-3) development, and may further include a (1-4) bake step, in which a resist resin composition, which is a liquid containing resin, may be used instead of the photosensitive composition of the present disclosure. Also, if the resin layer 2 is a simple film without a pattern, curing may be performed as appropriate after the above-described step (1-1) film formation. Here, the resin layer 2 formed on the partition wall and the light-emitting layer or the wavelength conversion layer may be formed on the entire surface of these layers or on only a part of them.

[0238] A liquid containing a resin (resist resin composition) contains a resist solvent for dissolving or dispersing the resin. The resist solvent can be, for example, any compound that does not have a (meth)acryloyl group in its molecule, and among the solvents described in the photosensitive composition section, compounds that do not have a (meth)acryloyl group are examples. These may be used alone or in combination of two or more. Among these, polyhydric alcohols and their derivatives (excluding compounds having a (meth)acryloyl group) are preferred. Specific examples of resist solvents include, for example, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. These may be used individually or in combination of two or more. Among these, propylene glycol monomethyl ether acetate (PGMEA) is preferred.

[0239] The content of the resist solvent in 100% by mass of the resin-containing liquid (resist resin composition) is preferably 20 to 99% by mass, more preferably 50 to 90% by mass.

[0240] Since the cured product of this disclosure exhibits hydrophilicity with respect to the resist solvent, the resin contained in the resin-containing liquid (resist resin composition) can be used without restriction as long as it is soluble or dispersible in the resist solvent, for example, novolac epoxy acrylate. These may be used alone or in combination of two or more.

[0241] The resin-containing liquid (resist resin composition) may contain various compounding agents as described in the photosensitive composition of this disclosure.

[0242] The patterned substrate of the present disclosure, manufactured by the above manufacturing method, is a patterned substrate having a patterned film constituting a partition wall, in which the cured product of the present disclosure is patterned on a resin layer 1 formed on a substrate; an emissive layer or wavelength conversion layer provided in the region partitioned by the partition wall; and a resin layer 2 provided on the partition wall and the emissive layer or wavelength conversion layer. The partition wall has liquid-repellent properties to ink and is hydrophilic to resist solvent, so it can suitably prevent ink from overflowing into adjacent cells due to insufficient liquid-repellent properties on the upper surface of the partition wall, and the emissive layer or wavelength conversion layer can be provided with precision, and it has good compatibility with resin-containing liquids, so a resin-containing liquid can be applied on the partition wall to suitably form the resin layer 2, and the resin layer 2 can be provided with precision.

[0243] Because the cured product (separator) of this disclosure is liquid-repellent to ink, the contact angle with hexanediol diacrylate is preferably 20 degrees or more, more preferably 30 degrees or more, even more preferably 40 degrees or more, particularly preferably 50 degrees or more, and most preferably 55 degrees or more. The upper limit is not particularly limited, but for example, it could be 80 degrees or less, 75 degrees or less, or 70 degrees or less. Because the cured product (separator) of this disclosure is hydrophilic to resist solvents, the contact angle with propylene glycol monomethyl ether acetate is preferably 40 degrees or less, more preferably 35 degrees or less, even more preferably 30 degrees or less, particularly preferably 20 degrees or less, and most preferably 10 degrees or less. The lower limit is not particularly limited, but for example, it could be 1 degree or more or 5 degrees or more. In this specification, the contact angle with hexanediol diacrylate and the contact angle with propylene glycol monomethyl ether acetate are measured by the method described in the examples. In this specification, all units of contact angle are degrees.

[0244] A cured product (separator) that satisfies the above characteristics (contact angle) is liquid-repellent to ink and hydrophilic to resist solvents. A cured product (separator) that satisfies the above characteristics can be obtained, for example, by curing the photosensitive composition of this disclosure. Furthermore, since fluorine atoms and silicon atoms have very strong liquid-repellent properties to resist solvents, hydrophilicity to resist solvents tends to be obtained by using polymers with low fluorine atom content and silicon atom content.

[0245] In view of the above findings, the present disclosure is a method for manufacturing a patterned substrate, comprising: a film-forming step of applying a photosensitive composition onto a resin layer 1 formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; a developing step of developing the film after the exposure step with an alkaline developer to obtain a patterned film constituting a partition wall; a layer-forming step of providing an emissive layer or a wavelength-converting layer in a region partitioned by the partition wall; and a resin-forming step of applying a resin-containing liquid onto the partition wall and the emissive layer or the wavelength-converting layer to form a resin layer 2, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less. The partition wall having a specific contact angle is liquid-repellent to ink and hydrophilic to resist solvents, so it can effectively prevent ink from overflowing into adjacent cells due to insufficient liquid-repellent properties on the upper surface of the partition wall, and it has good affinity with resin-containing liquids, so a resin-containing liquid can be applied to the partition wall to form a suitable resin layer 2.

[0246] The patterned substrate of this disclosure comprises: a patterned film constituting a partition wall provided on a resin layer 1 formed on a substrate; an emissive layer or wavelength conversion layer provided in a region partitioned by the partition wall; and a resin layer 2 provided on the partition wall and the emissive layer or wavelength conversion layer, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less. The partition wall having a specific contact angle is liquid-repellent to ink and hydrophilic to resist solvent, so it can suitably prevent ink from overflowing into adjacent cells due to insufficient liquid-repellent properties on the upper surface of the partition wall, and the emissive layer or wavelength conversion layer can be provided with precision, and it has good compatibility with resin-containing liquids, so a resin-containing liquid can be applied on the partition wall to suitably form the resin layer 2, and the resin layer 2 can be provided with precision.

[0247] Furthermore, the cured product of this disclosure can also be suitably used as a simple film without a pattern. In this case, due to its unique properties of being liquid-repellent to ink and hydrophilic to resist solvents, the cured product of this disclosure can be used as a water- and oil-repellent agent for treating fabrics (substrates) such as clothing, or as a sealing agent for protecting microfabricated semiconductor substrates (substrates), or as a film for protecting substrates in various applications.

[0248] (Image Display Device) The image display device of the present disclosure has a substrate with a patterned film of the present disclosure. Specifically, the image display device of the present disclosure has a display element using the substrate with a patterned film of the present disclosure (cured product of the present disclosure). Examples of image display devices of the present disclosure include organic EL displays, micro-LED displays, quantum dot displays, etc.

[0249] The following are examples that more specifically disclose embodiments of this disclosure. However, this disclosure is not limited to these embodiments.

[0250] 1. Synthesis of Polymers The obtained polymers were analyzed by the following method: [Measurement of the molar ratio of each constituent unit of the polymer] The molar ratio of each constituent unit in the polymer was: １ H-NMR, １９ F-NMR or １３ The molecular weight was determined from the C-NMR measurements. [Measurement of polymer molecular weight] The weight-average molecular weight (Mw) and molecular weight dispersion (ratio of number-average molecular weight Mn to weight-average molecular weight Mw; Mw / Mn) of the polymer were measured using high-speed gel permeation chromatography (hereinafter sometimes referred to as GPC; manufactured by Tosoh Corporation, model HLC-8320GPC), with one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) connected in series, tetrahydrofuran (THF) used as the developing solvent, and polystyrene used as the standard substance. A refractive index difference detector was used as the detector.

[0251] Next, we will summarize the monomers used. The monomers in Tables 1 and 2 are as follows. Note that all of the reagents used were those from Tokyo Chemical Industry Co., Ltd. Hexadecyl acrylate (hereinafter referred to as HA), t-butylstyrene (hereinafter referred to as t-BuSt), hydroxyethyl methacrylate (hereinafter referred to as HEMA), methacrylic acid (hereinafter referred to as MAA), stearyl acrylate (hereinafter referred to as SA), stearyl methacrylate (hereinafter referred to as SMA), hexadecyl methacrylate (hereinafter referred to as HMA), tetradecyl acrylate (hereinafter referred to as TeA), docosyl acrylate (hereinafter referred to as DA), octyl acrylate (hereinafter referred to as OA), lauryl acrylate (hereinafter referred to as LA), lignoceryl acrylate (hereinafter referred to as LGA), myricyl acrylate (hereinafter referred to as MLA), 1H,1H,2H,2H-nonafluorohexyl acrylate (hereinafter referred to as C4F-A) Acrylic acid 1H,1H,2H,2H-tridecafluoro-n-octyl (hereinafter referred to as C6F-A), Styrene (hereinafter referred to as St), Acetoxystyrene (hereinafter referred to as p-AcOSt), Acrylic acid (hereinafter referred to as AA)

[0252] (Manufacturing Example 1) Synthesis of HEMA-derived resin 1 First step radical polymerization In a 500 mL glass flask equipped with a stirrer, 29.7 g (0.10 mol) of HA, 16.0 g (0.10 mol) of t-BuSt, 13.0 g (0.10 mol) of HEMA, 0.86 g (0.01 mol) of MAA, and 120 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were added and mixed at room temperature (approximately 20°C). Subsequently, 7.13 g (0.031 mol) of 2,2'-azobis(methyl isobutyrate) (Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as V-601) was added to the flask and degassed while stirring. After that, the flask was purged with nitrogen gas, the internal temperature was raised to 79°C, and the reaction was carried out overnight. In this way, a precursor solution of HEMA-derived resin 1 was obtained. The structure of the HEMA-derived resin 1 precursor is shown below.

[0253] Furthermore, the composition ratio of each structural unit of the HEMA-derived resin 1 precursor was as follows (mol ratio): structural units derived from HA: structural units derived from t-Bu-St: structural units derived from HEMA: structural units derived from MAA = 32:32:33:3

[0254] Step 2: Crosslinking (Introduction of Acrylic Groups) After the reaction was complete, the flask was purged with dry air, and the reaction solution was cooled to an internal temperature of 60°C. After cooling, 0.01 g of dibutylhydroxytoluene (Tokyo Chemical Industries, Ltd., hereinafter referred to as BHT) and 14.1 g (0.10 mol) of 2-isocyanatoethyl acrylate (Showa Denko K.K., product name: Karenz AOI, hereinafter referred to as AOI) were added to the flask, and the mixture was stirred for 6 hours. The stirred solution was then cooled to room temperature (20°C). Subsequently, 175 g of PGMEA was added, and the solution was prepared to a concentration of approximately 20% polymerization, yielding 367 g of HEMA-derived resin 1 in 99% yield. Based on GPC measurement results, the Mw of HEMA-derived resin 1 was 19,300 and the Mw / Mn was 1.9. Furthermore, the composition ratio of each structural unit (each structural unit in the formula below) of HEMA-derived resin 1 remained unchanged from before the introduction of the crosslinking site, and in mol ratio, the ratio was: structural units derived from HA: structural units derived from t-Bu-St: structural units derived from the part of HEMA in which the crosslinking site was introduced: structural units derived from MAA = 32:32:33:3

[0255] (Production Examples 2-18) Synthesis of HEMA-derived resins 2-18 HEMA-derived resins 2-18 were synthesized in the same manner as in Production Example 1, except that the monomer composition and other aspects shown in Table 1 were changed.

[0256]

[0257] (Manufacturing Example 19) Synthesis of GlyMA-derived resin 1 First step of radical polymerization In a 500 mL glass flask equipped with a stirrer, at room temperature (approximately 20°C), 29.7 g (0.10 mol) of hexadecyl acrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HA), 16.0 g (0.10 mol) of t-butylstyrene (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as t-BuSt), 14.2 g (0.10 mol) of glycidyl methacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as GlyMA), and 150 g of butyl acetate were added and mixed. Then, 7.13 g (0.031 mol) of 2,2'-azobis(methyl isobutyrate) (product of Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as V-601) was added to the flask and the mixture was degassed while stirring. Furthermore, the flask was purged with nitrogen gas, the internal temperature was raised to 80°C, and the reaction was carried out overnight. In this way, a precursor solution of GlyMA-derived resin 1 was obtained. The structure of the precursor of GlyMA-derived resin 1 is shown below.

[0258] Furthermore, the composition ratio of each structural unit of the precursor of GlyMA-derived resin 1 was 33:34:33 in mole ratio, with structural units derived from HA, structural units derived from t-BuSt, and structural units derived from GlyMA.

[0259] Step 2: Crosslinking (Introduction of Acrylic Groups) After the reaction was complete, the flask was purged with dry air, and the reaction solution was cooled to an internal temperature of 60°C. After cooling, 0.01 g of dibutylhydroxytoluene (Tokyo Chemical Industries, Ltd., hereinafter referred to as BHT), 7.2 g (0.10 mol) of acrylic acid (Tokyo Chemical Industries, Ltd., hereinafter referred to as AA), and 2.62 g (0.01 mol) of triphenylphosphine (Tokyo Chemical Industries, Ltd.) were added to the flask and stirred for 6 hours. Then, 9.0 g (0.09 mol) of succinic anhydride (Tokyo Chemical Industries, Ltd.) was added, and the mixture was heated for another 6 hours, after which the solution was cooled to room temperature (20°C). Then, 170 g of PGMEA was added, and the solution was prepared to a concentration of approximately 20% by weight, yielding 399 g of solution of GlyMA derivative resin 1 in 99% yield. Based on the GPC measurement results, the Mw of GlyMA-derived resin 1 was 17,300 and the Mw / Mn ratio was 1.7. Furthermore, the composition ratio of each structural unit (each structural unit in the formula below) of GlyMA-derived resin 1 remained unchanged from before the introduction of the crosslinking site, and in mol ratio, the ratio was: structural units derived from HA: structural units derived from t-BuSt: structural units derived from the portion of GlyMA in which the crosslinking site was introduced: structural units derived from the portion in which the carboxylic acid site was further introduced = 32:34:3:30.

[0260] (Production Examples 20-24) Synthesis of GlyMA-derived resins 2-6 The GlyMA-derived resins 2-6 were synthesized in the same manner as in Production Example 19, except that the monomer composition and other aspects shown in Table 2 were changed.

[0261]

[0262] 2. Preparation of Photosensitive Resin Compositions The components used in the preparation of the photosensitive resin compositions of the examples and comparative examples are shown below. <Alkali-soluble resin> "ZAR-2050H": Manufactured by Nippon Kayaku Co., Ltd. (Special BIS-A type epoxy resin, compound of the following formula) <Crosslinking agent> RP-1040: Manufactured by Nippon Kayaku Co., Ltd. (Ethoxylated glycerin tetraacrylate, compound of the following formula) <Adhesion-enhancing agent> PM-21: Manufactured by Nippon Kayaku (phosphate ester compound, compound of the following formula) <Chain transfer agent> PEMP: Manufactured by SC Organic Chemicals Co., Ltd. (Pentaerythritol tetrakis(3-mercaptopropionate), compound of the following formula) <Initiator> IrgacureOxe01: Manufactured by BASF (1-[4-(phenylthio)phenyl]octane-1,2-dione = 2-(O-benzoyloxime), a compound of the following formula) Ominirad920: Manufactured by IGM Resins (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, compound of the following formula)

[0263] (Preparation of Colored Pigment Dispersion 1) The pigment, dispersant, alkali-soluble resin (described as alkali-soluble resin in Table 3), and solvent listed in Table 3 were mixed in the mass ratios listed in Table 3. This solution was dispersed at 25°C using 50 g of 0.5 mmφ zirconia beads in a bead mill for 12 hours. After the dispersion treatment, the beads were removed by filtration to prepare Colored Pigment Dispersion 1.

[0264] Lactam black (compound of the following formula) was synthesized according to the synthesis example of compound A1 described in

[0061] of Japanese Patent Application Publication No. 2015-121753. The obtained lactam black had a pigment content of 50% by mass relative to the total solids, and a particle size D50 of 250 nm. Here, D50 was measured using an ELSZ neoSE particle size analyzer manufactured by Otsuka Electronics Co., Ltd., after diluting the solution 10 times with PGMEA.

[0265]

[0266] [Preparation of Photosensitive Basic Composition] A jujube-shaped stirrer tip (2.5 cm) was added to a 500 ml round-bottom flask, then 75.01 g of PGMEA was added, and while stirring at 150 rpm, 25.11 g of ZAR-2050H, 25.03 g of RP-1040, 13.12 g of PEMP, 1.50 g of PM-21, 37.51 g of colored pigment dispersion 1, 0.72 g of IrgacureOxe01, 1.51 g of Omnirad920, and 100.55 g of PGMEA was added to wash away the raw materials adhering to the flask walls, and the mixture was stirred for 5 hours. After that, PGMEA was added to adjust the solution to 45% by weight. Using a PTFE membrane filter with a pore size of 3 μm, the mixture was filtered through a 1 L stainless steel pressure filter, and the prepared liquid was collected in a clean bottle to obtain 270 g of photosensitive basic composition 1 (without liquid repellent). (Recovery rate: 98%)

[0267] [Preparation of Photosensitive Compositions] Photosensitive base composition 1 was weighed out in 10g portions and divided into 24 portions. 0.6g each of HEMA-derived resins 1-18 and GlyMA-derived resins 1-6 synthesized in each production example were added to each portion, and the mixture was stirred for 2 hours to obtain evaluation photosensitive compositions 1-24.

[0268] 3. Evaluation [Contact Angle Test] Alkali-free glass (thickness 0.7 mm x 100Φ) was washed with ultrapure water, then with acetone. A UV ozone treatment device (manufactured by Sen Special Light Source Co., Ltd., model number PL17-110) was used to treat the substrate with UV ozone for 2 minutes. Next, evaluation photosensitive compositions 1 to 16 were applied to the UV ozone-treated substrate using a spin coater (manufactured by Mikasa, model number MS-B100) at a rotation speed of 500 rpm, and heated on a hot plate at 80°C for 90 seconds. The prepared resin film was then exposed to ghhi rays (wavelengths 365, 405, 436 nm) at a rate of 10 mJ / cm² using a manual exposure machine (manufactured by SCREEN Finetech Solutions, model number MA-1400). ２ (Illuminance 30mW / cm ２The film was then irradiated and exposed. Afterwards, it was shower-washed in a developing machine (Mikasa, model AD-3000) with a 0.04 wt% KOH aqueous solution for 60 seconds and then with distilled water for 10 seconds. Furthermore, the prepared resin film was exposed to ghhi rays (wavelengths 365, 405, 436 nm) at a rate of 1 J / cm² using a manual exposure machine (SCREEN Finetech Solutions, model MA-1400) across the entire surface of the coated film. ２ (Illuminance 30mW / cm ２ After irradiation and additional exposure, the film was heated on a hot plate at 90°C for 30 minutes to obtain a cured film. The obtained cured film was subjected to a contact angle measurement using a contact angle measuring device (Kyowa Interface Science Co., Ltd., DMo-702) in a clean room at 23°C. A 1 μL droplet of the measurement solvent (water, hexanediol diacrylate (HDDA), PGMEA, methyl benzoate (BzOMe)) was prepared and dropped onto the obtained cured film. The contact angle (degrees) of the droplet on the cured film was evaluated 10 seconds after dropping. The results are shown in Tables 4 and 5.

[0269]

[0270]

[0271] [Formation of evaluation partitions] Partitions (patterns) were formed on the substrate according to the following procedure. A 10 cm square ITO substrate was washed with ultrapure water, and then with acetone. After that, UV ozone treatment was performed on the substrate for 5 minutes using a UV ozone treatment device (manufactured by Sen Special Light Source Co., Ltd., model number PL17-110). A photosensitive composition was applied to the resulting UV ozone-treated substrate using a spin coater (manufactured by Mikasa, model number MS-B100) at a rotation speed of 500 rpm, and heated on a hot plate at 80°C for 90 seconds. Using a manual exposure machine (manufactured by SCREEN Finetech Solutions, model number MA-1400), the accumulated exposure amount E was determined to produce a line width of 10 ± 0.5 μm after development, through a mask with line:space = 10 μm:10 μm. ＯLight was irradiated using this method. The light source for this mask aligner is an ultra-high pressure mercury lamp, and the spectrum of light emitted from this mercury lamp includes the i-line (wavelength 365 nm) and h-line (wavelength 405 nm) emission spectrum. Spray development was performed for 40 seconds with a 0.04 mass% KOH aqueous solution. After development, it was rinsed with pure water for 10 seconds. Then, the remaining developer and / or rinse solution was N ２ It was removed by blowing. Subsequently, a manual exposure machine (SCREEN Finetech Solutions, model MA-1400) was used to expose the entire coated film with ghhi rays (wavelengths 365, 405, 436 nm) at a rate of 1 J / cm². ２ (Illuminance 30mW / cm ２ After irradiation and additional exposure, the film was heated on a hot plate at 90°C for 30 minutes to obtain a cured film. The obtained cured film, with a thickness of approximately 10 μm, was used to evaluate the partition performance.

[0272] [Optimal exposure amount] Cumulative exposure amount E in the above [Formation of evaluation partition] Ｏ In other words, the optimal exposure was defined as the exposure amount that yielded a pattern that was nearly faithful to the line width and space width of the mask.

[0273] [Pattern Shape] The cross-section of the line-and-space pattern at the optimal exposure was photographed using a scanning electron microscope. The height from the top surface of the substrate to the top of the pattern was defined as the pattern height, the maximum pattern width in the upper part of the pattern (i.e., from the top of the pattern to half the pattern height) was defined as width A, and the minimum pattern width in the lower part of the pattern (i.e., from the contact surface between the substrate and the pattern to half the pattern height) was defined as width B. The value of width A - width B was used as an indicator of the pattern shape. The closer this value is to 0, the closer the cross-sectional shape of the pattern is to a rectangle.

[0274] [Adding liquid to the openings] (suitable for inkjet printing) A 10 μm thick cured film was prepared using the same procedure as in [Formation of evaluation partitions] above, except that the mask used during exposure was changed to a pattern with a line width of 10 μm and 20 grids arranged in a 300 × 300 μm square opening. The cured film obtained above was immersed for 3 minutes in HDDA containing IrgacureOXE01 dissolved in it at a concentration of 1 wt% of the total amount of the substrate placed in the petri dish. After that, the substrate with the film attached was pulled straight up, and the entire coated film was exposed to ghhi lines (wavelengths 365, 405, 436 nm) at 1 J / cm using a manual exposure machine (SCREEN Finetech Solutions, model MA-1400). ２ (Illuminance 30mW / cm ２ After irradiation and additional exposure, the samples were heated on a hot plate at 120°C for 60 minutes. Using a laser microscope, top-view images were used to evaluate the results as follows: samples with a hardened film formed in all 20 locations within a 300 × 300 μm opening were rated as good; samples with a hardened film formed in 15 to 19 locations were rated as good (peeling in 5 to 1 locations); and samples with fewer than 14 locations were rated as unacceptable.

[0275] [Lamination after adding liquid to the openings] A photosensitive base composition 1, which does not contain liquid-repellent components, was applied to the film containing the cured HDDA film in the openings created in [adding liquid to the openings] using a spin coater (Mikasa Corporation, model MS-B100) at a rotation speed of 500 rpm, and heated on a hot plate at 80°C for 90 seconds. The prepared resin film was exposed to ghhi rays (wavelengths 365, 405, 436 nm) at a rate of 10 mJ / cm² using a manual exposure machine (SCREEN Finetech Solutions, model MA-1400) over the entire coated film. ２ (Illuminance 30mW / cm ２ The film was then irradiated and exposed. Afterwards, it was shower-washed in a developing machine (Mikasa, model AD-3000) with a 0.04 wt% KOH aqueous solution for 60 seconds and then with distilled water for 10 seconds. Furthermore, the prepared resin film was exposed to ghhi rays (wavelengths 365, 405, 436 nm) at a rate of 1 J / cm² using a manual exposure machine (SCREEN Finetech Solutions, model MA-1400) across the entire surface of the coated film. ２ (Illuminance 30mW / cm ２After irradiation and additional exposure, the film was heated on a hot plate at 90°C for 30 minutes to obtain a cured film. The entire surface of the obtained cured film was observed using a laser microscope. The best result was when the upper layer film did not peel off and remained 100% of the total surface area of ​​the cured film, good if 90% or more of the film remained, acceptable if 60% or more of the film remained, and unacceptable if less than that.

[0276]

[0277]

[0278] From Tables 4 to 7, it was found that the polymer of this disclosure is a polymer having repeating units represented by formula (1), formula (2), and formula (3), and therefore exhibits liquid repellency to ink and hydrophilicity to resist solvents.

Claims

1. A polymer having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3). (In formula (1), R １ represents a hydrogen atom or a methyl group. R ２ represents a hydrocarbon group having 6 to 24 carbon atoms. r represents 0 or 1. When r is 0, (-C(=O)-O-) represents a single bond.) (In formula (2), R １０ represents a hydrogen atom or a methyl group. Each B independently represents a hydrocarbon group, a hydroxyl group, a carboxyl group, -C(=O)-O-R １１ (R １１ represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms.), -O-C(=O)-R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.) or -O-R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.). m represents an integer from 0 to 5.) (In formula (3), R ５ , R ６ each independently represents a hydrogen atom or a methyl group. A represents a divalent group.) 2. R in formula (1) above ２ The polymer according to claim 1, wherein the alkyl group has 6 to 24 carbon atoms.

3. The polymer according to claim 1, wherein the fluorine atom content is 1% by mass or less.

4. The polymer according to claim 1, wherein the silicon atom content is 1% by mass or less.

5. A liquid-repellent material comprising the polymer according to any one of claims 1 to 4.

6. A photosensitive composition comprising the polymer according to any one of claims 1 to 4.

7. A cured product obtained by curing the photosensitive composition according to claim 6.

8. A method for manufacturing a substrate with a patterned film, comprising: a film-forming step of applying the photosensitive composition according to claim 6 onto a resin layer formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; and a development step of developing the film after the exposure step with an alkaline developer to obtain a patterned film.

9. The method for manufacturing a substrate with a patterned film according to claim 8, wherein the patterned film is a partition.

10. A substrate with a patterned film having a patterned film on which the cured product according to claim 7 is patterned on a resin layer formed on the substrate.

11. The patterned substrate according to claim 10, wherein the patterned film is a partition.

12. An image display device having a patterned substrate according to claim 10.

13. An image display device having a patterned substrate according to claim 11.

14. A method for manufacturing a substrate with a patterned film, comprising: a film-forming step of applying a photosensitive composition onto a resin layer 1 formed on a substrate to form a film; an exposure step of irradiating the film after the film-forming step with high-energy rays through a photomask to transfer the pattern of the photomask to the film; a developing step of developing the film after the exposure step with an alkaline developer to obtain a patterned film constituting a partition wall; a layer-forming step of providing an emissive layer or a wavelength-converting layer in the region partitioned by the partition wall; and a resin layer-forming step of applying a resin-containing liquid onto the partition wall and the emissive layer or the wavelength-converting layer to form a resin layer 2, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less.

15. A substrate with a patterned film, comprising: a patterned film constituting a partition wall provided on a resin layer 1 formed on a substrate; an emissive layer or wavelength conversion layer provided in a region partitioned by the partition wall; and a resin layer 2 provided on the partition wall and the emissive layer or wavelength conversion layer, wherein the contact angle of the partition wall with respect to hexanediol diacrylate is 20 degrees or more, and the contact angle with respect to propylene glycol monomethyl ether acetate is 40 degrees or less.

16. An image display device having a patterned substrate according to claim 15.

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