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

Abstract

Provided are: a polymer that can improve photocurability; 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 using said photosensitive composition; a method for manufacturing said pattern film-equipped substrate; and an image display device having said pattern film-equipped substrate. The present disclosure relates to a photosensitive composition containing a specific polymer having a thiol group.

Description

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

[0001] The present 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 using the photosensitive composition, a method for manufacturing the substrate with the patterned film, and an image display device having the substrate with the patterned film.

[0002] Inkjet printing is known as a method for forming organic layers having functions such as light emission when manufacturing display elements such as organic EL displays, micro LED displays, and quantum dot displays. There are several inkjet printing methods, including a method in which ink is dropped from a nozzle onto recesses of a patterned film having projections and recesses formed on a substrate and then solidified, and a method in which ink droplets are dropped onto a patterned film previously formed on a substrate, with lyophilic portions that are ink-wettable and lyophobic portions that repel ink, and the ink is deposited only on the lyophilic portions.

[0003] In particular, in the former method of solidifying ink dropped from a nozzle into recesses in a patterned film, two main methods can be used to produce a patterned film having such irregularities. One is a photolithography method in which the surface of a photosensitive resist film applied to a substrate is exposed to light in a pattern to form exposed and unexposed areas, and one of the areas is dissolved and removed with a developer. The other is an imprinting method using printing technology. After forming a patterned film having irregularities, the entire substrate is typically subjected to UV ozone treatment or oxygen plasma treatment. This UV ozone treatment or oxygen plasma treatment can remove residual organic matter, particularly in the recesses of the patterned film, and reduce uneven wetting of the dropped ink, thereby preventing display element defects.

[0004] The convex portions of the patterned film with the resulting unevenness are called banks (partition walls), and act as barriers to prevent the inks from mixing when droplets of ink are dropped into the concave portions of the patterned film. To enhance this barrier effect, the top surface of the bank must be liquid-repellent to ink.

[0005] Patent Document 1 discloses that a photosensitive resin composition containing a specific fluorine-containing resin has good liquid repellency. Patent Document 2 discloses a photosensitive resin composition containing polysiloxane. Furthermore, Patent Document 3 discloses a photosensitive resin composition containing a crosslinking group, "R ６１ R ６２ R ６３ Si—O—(SiR ６４ R ６５ —O)n-SiR ６６ R ６７ R ６８　　 (d1-2) In formula (d1-2), R ６１ , R ６２ , R ６３ , R ６４ , R ６５ , R ６６ , R ６７ , R ６８ each independently represent a monovalent organic group or a hydrogen atom." The document discloses a photosensitive resin composition containing a polysiloxane consisting of the following: The crosslinking groups disclosed include epoxy groups, ethylenically unsaturated groups, and active groups that generate radicals upon irradiation with active energy rays. Meanwhile, Patent Document 4 discloses that a polydimethylsiloxane resin layer containing a polydimethylsiloxane resin containing one or more crosslinkable groups has oil repellency.

[0006] International Publication No. 2020 / 110793 International Publication No. 2022 / 181350 International Publication No. 2022 / 264909 Japanese Patent Application Laid-Open No. 2022-169741

[0007] The present inventors have focused on the liquid repellency of polysiloxane and have conducted extensive research on photosensitive resin compositions containing polysiloxane resins, because although photosensitive resin compositions containing polysiloxanes having crosslinking groups are known, they believe that specific research into these compositions has been insufficient within the scope of conventional knowledge.

[0008] The present disclosure aims to provide a polymer capable of improving photocurability, 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 using the photosensitive composition, a method for manufacturing the substrate with a pattern film, and an image display device having the substrate with a pattern film.

[0009] As a result of extensive investigations, the present inventors have found that the polymer containing poly(dimethylsiloxane) units described in Patent Document 2 has poor photocurability and alkaline developability because the crosslinkable groups are acrylate groups or vinyl groups, but that by using thiol groups as the crosslinkable groups, the photocurability and alkaline developability are excellent, leading to the completion of the present disclosure. Specifically, the present disclosure (1) relates to a photosensitive composition containing a polymer having a repeating unit represented by the following formula (A), and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C): (In formula (A), R １ , R ２ are each independently an alkyl group. (In formula (B), R ３ is a monovalent group. ４ is a divalent group. (In formula (C), R ５ is a divalent group.

[0010] The present disclosure (2) relates to R in the formula (B). ３ is an alkyl group.

[0011] The present disclosure (3) relates to the photosensitive composition according to the present disclosure (1) or (2), wherein the polymer has a repeating unit represented by the formula (C).

[0012] The present disclosure (4) relates to a photosensitive composition containing a polymer having a repeating unit represented by the following formula (B-1): (In formula (B-1), R ４ is a divalent group.

[0013] The present disclosure (5) relates to the photosensitive composition according to any one of the present disclosures (1) to (4), further comprising a photopolymerization initiator and a compound having a group capable of reacting with a thiol group.

[0014] The present disclosure (6) relates to the photosensitive composition according to the present disclosure (5), in which the photopolymerization initiator is an acylphosphine oxide-based photopolymerization initiator or an oxime ester-based photopolymerization initiator.

[0015] The present disclosure (7) relates to the photosensitive composition according to the present disclosure (5), in which the photopolymerization initiator is an acylphosphine oxide-based photopolymerization initiator.

[0016] The present disclosure (8) relates to a cured product obtained by curing the photosensitive composition according to any one of the present disclosures (1) to (7).

[0017] The present disclosure (9) relates to a method for producing a substrate with a patterned film, the method including: a film-forming step of applying the photosensitive composition according to any one of the present disclosures (1) to (7) onto a substrate to form a film; an exposure step of irradiating and exposing the film after the film-forming step with high-energy rays through a photomask to transfer a 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] The present disclosure (10) relates to the method for producing a substrate with a patterned film according to the present disclosure (9), wherein the patterned film is a partition wall.

[0019] The present disclosure (11) relates to the method for producing a substrate with a patterned film according to the present disclosure (9) or (10), wherein the substrate with a patterned film is a substrate for forming a display element by an inkjet method.

[0020] The present disclosure (12) relates to a substrate with a patterned film, which has a patterned film on a substrate, the cured product according to the present disclosure (8) being formed in a pattern.

[0021] The present disclosure (13) relates to the substrate with a patterned film according to the present disclosure (12), wherein the patterned film is a partition wall.

[0022] The present disclosure (14) relates to an image display device having the substrate with the patterned film according to the present disclosure (12).

[0023] The present disclosure (15) relates to an image display device having the substrate with the patterned film according to the present disclosure (13).

[0024] The present disclosure (16) relates to a polymer having a repeating unit represented by the following formula (A), and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C): (In formula (A), R １ , R ２ are each independently an alkyl group. (In formula (B), R ３ is a monovalent group. ４ is a divalent group. (In formula (C), R ５ is a divalent group.

[0025] The present disclosure (17) relates to R in the formula (B). ３ is an alkyl group.

[0026] The present disclosure (18) relates to the polymer according to the present disclosure (16) or (17), which has a repeating unit represented by the formula (C).

[0027] The present disclosure (19) relates to a polymer having a repeating unit represented by the following formula (B-1): (In formula (B-1), R ４ is a divalent group.

[0028] The present disclosure (20) relates to a liquid-repellent material containing the polymer according to any one of the present disclosures (16) to (19).

[0029] The polymer of the present disclosure is a polymer (1) having a repeating unit represented by formula (A), and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C), or a polymer (2) having a repeating unit represented by formula (B-1), and therefore has excellent photocurability.

[0030] The liquid repellent material of the present disclosure contains the polymer of the present disclosure and therefore has excellent photocurability.

[0031] The photosensitive composition of the present disclosure has excellent photocurability because it contains the polymer of the present disclosure.

[0032] The cured product of the present disclosure is obtained by curing the photosensitive composition of the present disclosure, and therefore has excellent alkaline developability (resolution after development) and liquid repellency.

[0033] The method for producing a substrate with a patterned film of the present disclosure includes a film-forming step of applying the photosensitive composition of the present disclosure, which has excellent photocurability, onto a substrate to form a film; an exposure step of irradiating and exposing the film after the film-forming step to 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. The use of the photosensitive composition of the present disclosure, which has excellent photocurability, allows for the production of substrates with a patterned film with high productivity. Furthermore, the patterned film on the substrate has excellent resolution because it is formed from a photosensitive composition that has liquid repellency and can impart good alkaline developability to the resulting cured product.

[0034] The substrate with a pattern film of the present disclosure has a pattern film on which the cured product of the present disclosure is patterned, and therefore is a substrate with a pattern film that has excellent liquid repellency and resolution.

[0035] The image display device of the present disclosure has a patterned film-formed substrate of the present disclosure having a patterned film with excellent liquid repellency and resolution, and is therefore expected to have a light-emitting layer with high color purity and high brightness.

[0036] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0037] In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means at least X and at most Y. For example, "1 to 5% by mass" means "at least 1% by mass and at most 5% by mass."

[0038] In this specification, the terms "polymer," "resin," and "polymeric substance" are synonymous and mean a polymeric compound unless otherwise noted.

[0039] In this specification, the terms "bank" and "partition wall" are synonymous and mean the convex portions of a pattern film having concaves and convexes in an inkjet method, unless otherwise noted.

[0040] In the present disclosure, the reason why the above-mentioned effects are obtained is not entirely clear, but it is presumed that the following mechanism is involved. Polymer (1) having a repeating unit represented by formula (A) and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C) can impart liquid repellency to the resulting cured product due to the repeating unit represented by formula (A). Polymer (2) having a repeating unit represented by formula (B-1) can impart liquid repellency to the resulting cured product due to the repeating unit represented by formula (B-1) containing a methyl group bonded to a silicon atom. Polymer (2) having a repeating unit represented by formula (B-1) can impart liquid repellency to the resulting cured product due to the repeating unit represented by formula (B-1) containing a thiol group. Polymer (1) and (2) can impart excellent photocurability and good alkaline developability to the resulting cured product due to the repeating unit represented by formula (B-1) containing a siloxane structure and a flexible backbone. This allows the polymer chains to favorably cover the substrate surface, resulting in a favorable receding contact angle.

[0041] (Polymer) First, polymer (1) and polymer (2), which are polymers of the present disclosure, will be described.

[0042] <Polymer (1)> Polymer (1) is a polymer having a repeating unit represented by the following formula (A), and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C). That is, polymer (1) is a polymer having a repeating unit represented by the following formula (A), as well as a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C). Since polymer (1) is a polymer having a repeating unit represented by the following formula (A), as well as at least a repeating unit represented by formula (B) or a repeating unit represented by formula (C), it is presumed that the above-mentioned effects are exhibited.

[0043] In polymer (1), the units in each repeating unit may be the same or different. Thus, polymer (1) may be a polymer in which one or more units corresponding to the repeating unit represented by formula (A) are combined with one or more units corresponding to the repeating unit represented by formula (B). Polymer (1) may also be a polymer in which one or more units corresponding to the repeating unit represented by formula (A) are combined with one or more units corresponding to the repeating unit represented by formula (C). Polymer (1) may also be a polymer in which one or more units corresponding to the repeating unit represented by formula (A), one or more units corresponding to the repeating unit represented by formula (B), and one or more units corresponding to the repeating unit represented by formula (C). In polymer (1), it is preferable that the units in each repeating unit are the same. (In formula (A), R １ , R ２ are each independently an alkyl group. (In formula (B), R ３ is a monovalent group. ４ is a divalent group. (In formula (C), R ５ is a divalent group.

[0044] In formula (A), R １ , R ２ are each independently an alkyl group, but R １ , R ２ are also preferably the same group. This results in a symmetrical structure, which is easily aligned on the surface of the formed film, and the effects of the present disclosure tend to be more favorably obtained.

[0045] R １ , R ２ The number of carbon atoms in the alkyl group of R is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1. １ , R ２ The fewer the number of carbon atoms in the alkyl group, the better the liquid repellency tends to be imparted to the resulting cured product.

[0046] R １, R ２ Examples of the alkyl group may be linear or branched, and include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Among these, methyl, ethyl, and propyl groups are preferred, more preferably methyl and ethyl groups, and even more preferably methyl groups, because they tend to impart better liquid repellency to the resulting cured product. Note that the alkyl group may be linear or branched, so a propyl group refers to an n-propyl group or an isopropyl group, and a butyl group refers to an n-butyl group, a sec-butyl group, or a tert-butyl group, and the same applies to other groups that may be linear or branched.

[0047] In formula (B), R ３ is a monovalent group.

[0048] R ３ The number of carbon atoms in the monovalent group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1. ３ The fewer the number of carbon atoms in the monovalent group, the better the liquid repellency tends to be imparted to the resulting cured product.

[0049] R ３ The monovalent group is not particularly limited, but examples thereof include a hydrogen atom and a monovalent hydrocarbon group, among which a monovalent hydrocarbon group is preferred.

[0050] The monovalent hydrocarbon group may contain a heteroatom, but preferably does not contain a heteroatom. Examples of heteroatoms include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, and a chlorine atom. The monovalent hydrocarbon group may contain a plurality of these heteroatoms.

[0051] Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. Among these, an alkyl group and an aryl group are preferred, and an alkyl group is more preferred.

[0052] R ３ Examples of the alkyl group include R １ , R ２The same applies to the alkyl group of the above, including preferred embodiments.

[0053] R ３ The alkenyl group may be, for example, linear or branched, and includes a vinyl group, an allyl group, a propenyl group, a methylethenyl group, and the like.

[0054] R ３ The alkynyl group may be, for example, linear or branched, and includes an ethynyl group, a propargyl group, and the like.

[0055] R ３ Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. Of these, a phenyl group is preferred.

[0056] In formula (B), R ４ is a divalent group. ４ The divalent group is not particularly limited as long as it can separate the thiol group from the main chain so that the thiol group can easily react.

[0057] R ４ The divalent group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, even more preferably 2 to 5 carbon atoms, and particularly preferably 2 to 4 carbon atoms.

[0058] R ４ Examples of the divalent group include divalent hydrocarbon groups, and among these, divalent hydrocarbon groups are preferred.

[0059] The divalent hydrocarbon group may have a heteroatom, but preferably does not have a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, and a chlorine atom. The divalent hydrocarbon group may have a plurality of these heteroatoms.

[0060] Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, etc. Among these, an alkylene group and an arylene group are preferred, and an alkylene group is more preferred.

[0061] R ４The alkylene group may be, for example, linear or branched, and includes methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, and octadecylene. Among these, ethylene, propylene, and butylene groups are preferred, with propylene being more preferred, because they are neither too far from nor too close to the Si bond. Furthermore, the alkylene group is preferably linear.

[0062] R ４ The alkenylene group may be, for example, linear or branched, and includes a vinylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, an octenylene group, and the like.

[0063] R ４ The alkynylene group may be, for example, linear or branched, and includes an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, and the like.

[0064] R ４ Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group.

[0065] In formula (C), R ５ is a divalent group. ５ is a divalent group represented by R ４ As with the divalent group R, there are no particular limitations as long as it is possible to separate the thiol group from the main chain so that the thiol group can easily react. ５ is a divalent group represented by R ４ The same applies to the divalent group R, including preferred embodiments thereof. ５ It is also preferred that the divalent group has an oxygen atom.

[0066] The repeating unit represented by formula (A) may preferably have the following structure.

[0067] The repeating unit represented by formula (B) may preferably have the following structure.

[0068] As the repeating unit represented by formula (C), the following structures can be exemplified as preferred ones.

[0069] Preferred structures of the repeating unit represented by formula (A), the repeating unit represented by formula (B), and the repeating unit represented by formula (C) have been exemplified, but combinations of preferred structures of the repeating unit represented by formula (A) with preferred structures of the repeating unit represented by formula (B), combinations of preferred structures of the repeating unit represented by formula (A) with preferred structures of the repeating unit represented by formula (C), and combinations of preferred structures of the repeating unit represented by formula (A), preferred structures of the repeating unit represented by formula (B), and preferred structures of the repeating unit represented by formula (C) are also preferred embodiments.

[0070] The polymer (1) is a polymer having a repeating unit represented by the above formula (A), as well as a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C). It is preferable that the repeating unit represented by formula (A) and the repeating unit represented by formula (C) are present. This tends to more favorably achieve the effects of the present disclosure (particularly, liquid repellency) and heat resistance. This is presumably because the repeating unit represented by formula (C) gives the polymer a branched structure, making it more likely to adopt a three-dimensional structure and resulting in less movement within the cured film. It is also preferable that the polymer (1) has a repeating unit represented by formula (A), a repeating unit represented by formula (B), and a repeating unit represented by formula (C). Such a polymer (1) tends to have a low molecular weight, and despite its low molecular weight, it tends to be able to impart better liquid repellency to the resulting cured product. Furthermore, due to its low molecular weight, it tends to be more compatible with the photosensitive composition.

[0071] The content of the repeating unit represented by formula (A) is preferably 30 to 99 mol %, more preferably 40 to 95 mol %, and even more preferably 50 to 90 mol %, based on 100 mol % of polymer (1). This tends to impart better liquid repellency to the resulting cured product.

[0072] The content of the repeating unit represented by formula (B) and the repeating unit represented by formula (C) (when both the repeating unit represented by formula (B) and the repeating unit represented by formula (C) are present, the total content of the repeating unit represented by formula (B) and the repeating unit represented by formula (C)) is preferably 1 to 70 mol %, more preferably 5 to 60 mol %, and even more preferably 10 to 50 mol %, based on 100 mol % of polymer (1). This tends to provide better photocurability and impart better alkali developability to the resulting cured product.

[0073] The polymer (1) may have a repeating unit represented by formula (A), a repeating unit represented by formula (B), and a repeating unit represented by formula (C) as well as other units (other units). Examples of the other units include the following structures. The other units may be used alone or in combination of two or more.

[0074] The total content of the repeating unit represented by formula (A), the repeating unit represented by formula (B), and the repeating unit represented by formula (C) 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% in 100 mol% of the polymer (1). This tends to more suitably achieve the effects of the present disclosure. In this specification, the content of each unit in the polymer is ２９ It is measured by Si-NMR.

[0075] The weight-average molecular weight (Mw) of the polymer (1) is preferably 1,000 to 50,000, more preferably 1,500 to 30,000, and even more preferably 8,000 to 13,000. This tends to more favorably achieve the effects of the present disclosure, such as the liquid sliding properties (receding contact angle). This is presumably because the movement of the polysiloxane structure in the film is suppressed.

[0076] The dispersity (Mw / Mn) of the polymer (1) is preferably 1.0 to 3.0, more preferably 1.1 to 2.5, and even more preferably 1.2 to 2.0. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are measured by the method described in the examples.

[0077] The development rate (DR) of the polymer (1) is preferably 5 to 200 nm / s, more preferably 10 to 150 nm / s, and even more preferably 15 to 100 nm / s. In this specification, the development rate (DR) of the polymer is measured by the method described in the examples.

[0078] Polymer (1) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. A block copolymer is preferred because a series of identical units improves the liquid rolling property (receding contact angle), while a random copolymer is preferred because it provides solubility in solvents. To obtain the advantages of both block and random copolymers, it is more preferred that both ends of the polymer have a random structure and the center of the polymer has a block structure. Here, it is even more preferred that the random structure is composed of a repeating unit represented by formula (A) and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C), and that the block structure is composed of a repeating unit represented by formula (A).

[0079] A preferred embodiment of the polymer (1) is as follows: <<Embodiment 1-1>> A polymer having a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B): Formula (A): R １ and R ２ is a methyl group Formula (B): R ３ is an alkyl group (preferably a methyl group). ４ represents an alkylene group (preferably a linear alkylene group)

[0080] <<Embodiment 1-2>> A polymer having a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (C): Formula (A): Same as embodiment 1-1 Formula (C): R ５represents an alkylene group (preferably a linear alkylene group)

[0081] <<Embodiment 1-3>> A polymer having a repeating unit represented by the following formula (A), a repeating unit represented by formula (B), and a repeating unit represented by formula (C): Formula (A): Same as embodiment 1-1 Formula (B): Same as embodiment 1-1 Formula (C): Same as embodiment 1-2

[0082] Next, the monomers used in the polymerization of polymer (1) will be described. The repeating unit represented by formula (A), the repeating unit represented by formula (B), and the repeating unit represented by formula (C) are each formed, for example, by synthesis using, as a monomer, a compound represented by formula (a-1), a bifunctional compound represented by formula (b), and a trifunctional compound represented by formula (c). The repeating unit represented by formula (A) can also be formed by synthesis using, as a monomer, a cyclic compound formed from the repeating unit represented by formula (A), such as a compound represented by formula (a-2). In this case, a block structure can be suitably formed, and a polymer having a relatively large weight-average molecular weight tends to be synthesized.

[0083] (In formula (a-1), R １ , R ２ is R in formula (A). １ , R ２ It is the same as R １１ , R １２ are each independently an alkyl group. (In formula (b), R ３ , R ４ is R in formula (B). ３ , R ４ It is the same as R １３ , R １４ are each independently an alkyl group. (In formula (c), R ５ is R in formula (C) ５ It is the same as R １５ , R １６ , R １７ are each independently an alkyl group.

[0084] R in formula (a-1), formula (b), and formula (c)１１ ~R １７ The alkyl group is usually a methyl group or an ethyl group.

[0085] The polymerization method for polymer (1) is not particularly limited, and a conventional polymerization reaction can be used. Those skilled in the art can appropriately produce polymer (1) by known polymerization methods using the above-mentioned monomers, for example, with reference to the method described in International Publication No. 2022 / 181350. Furthermore, polymer (1) having a random structure at both ends and a block structure in the center of the polymer can be obtained by first synthesizing a polydimethylsiloxane homopolymer by ring-opening polymerization of cyclic siloxane (a-2) under basic conditions. Then, both ends are reacted (polymerized) with (b) or (c). An example of a method for producing a polymer having such a structure is Synthesis 2: Ring-opening polymerization of cyclic siloxane in the Production Examples of the present specification.

[0086] <Polymer (2)> Polymer (2) is a polymer having a repeating unit represented by the following formula (B-1): In polymer (2), the units in each repeating unit may be the same or different, but are preferably the same. (In formula (B-1), R ４ is a divalent group.

[0087] The repeating unit represented by formula (B-1) is a repeating unit represented by formula (B) ３ is a methyl group, and other than this, it is the same as the repeating unit represented by formula (B), including preferred embodiments. ３ is a methyl group, it is presumed that even if the repeating unit represented by formula (A) is not present, liquid repellency can be imparted to the resulting cured product. Note that the matters explained for polymer (1) are basically the same for polymer (2), so the following explanation will focus on the characteristic features of polymer (2). The matters not explained for polymer (2) are basically the same as those for polymer (1), including preferred embodiments.

[0088] The content of the repeating unit represented by formula (B-1) in 100 mol % of the polymer (2) may be 100 mol %, but is preferably 1 to 70 mol %, more preferably 5 to 60 mol %, and even more preferably 10 to 50 mol %, which tends to more suitably achieve the effects of the present disclosure.

[0089] In addition to the repeating unit represented by formula (B-1), polymer (2) may have a repeating unit represented by formula (A), a repeating unit represented by formula (B) other than the repeating unit represented by formula (B-1), a repeating unit represented by formula (C), or the other units described above. These units may be used alone or in combination of two or more. When polymer (2) has a repeating unit represented by formula (A) in addition to the repeating unit represented by formula (B-1), polymer (2) becomes polymer (1) having a repeating unit represented by formula (B-1), and is similar to polymer (1) including preferred aspects.

[0090] The preferred ranges of the weight average molecular weight (Mw), the dispersity (Mw / Mn) and the development rate (DR) of the polymer (2) are the same as those of the polymer (1).

[0091] A preferred embodiment of the polymer (2) is as follows: <<Embodiment 2-1>> A polymer having a repeating unit represented by the following formula (B-1): Formula (B-1): R ４ represents an alkylene group (preferably a linear alkylene group)

[0092] <<Embodiment 2-2>> Polymer having a repeating unit represented by the following formula (A) and a repeating unit represented by formula (B-1): Formula (A): R １ and R ２ is a methyl group Formula (B-1): same as embodiment 2-1

[0093] <<Embodiment 2-3>> Polymer having a repeating unit represented by the following formula (B-1) and a repeating unit represented by formula (C): Formula (B-1): Same as embodiment 2-1 Formula (C): R ５ represents an alkylene group (preferably a linear alkylene group)

[0094] <<Embodiment 2-4>> A polymer having a repeating unit represented by the following formula (A), a repeating unit represented by formula (B-1), and a repeating unit represented by formula (C): Formula (A): Same as embodiment 2-2 Formula (B-1): Same as embodiment 2-1 Formula (C): Same as embodiment 2-3

[0095] The repeating unit represented by formula (B-1) can be, for example, a monomer containing R ３ The polymer (2) can be prepared by synthesizing the polymer (2) using a compound in which R is a methyl group. The polymerization method for the polymer (2) is not particularly limited, and can be the same as that for the polymer (1).

[0096] (Liquid-repellent material) The polymer of the present disclosure can impart liquid-repellency to the resulting cured product, and therefore can be suitably used as a liquid-repellent material. Therefore, 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.

[0097] The content of the polymer of the present disclosure in 100% by mass of the liquid repellent material 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, which tends to more suitably obtain the effects of the present disclosure.

[0098] (Photosensitive Composition) Next, the photosensitive composition (photosensitive resin composition) of the present disclosure will be described. The photosensitive composition of the present disclosure contains the polymer of the present disclosure. Specifically, the photosensitive composition of the present disclosure contains a polymer (1) having a repeating unit represented by formula (A), and a repeating unit represented by formula (B) and / or a repeating unit represented by formula (C), and / or a polymer (2) having a repeating unit represented by formula (B-1). The polymer of the present disclosure may be used alone, or two or more types may be used in combination.

[0099] The content of the polymer of the present disclosure in 100% by mass of the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, and even more preferably 0.5 to 10% by mass, which tends to more suitably achieve the effects of the present disclosure.

[0100] The ingredients that may be included in the photosensitive composition of the present disclosure will be described below.

[0101] <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 it dissolves the polymer of the present disclosure, and examples thereof include ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatic solvents, and fluorine-based solvents. These may be used alone or in combination of two or more.

[0102] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, methyl isobutyl ketone, methyl isopentyl ketone, 2-heptanone, etc. 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-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, oleyl alcohol, etc.

[0103] Examples of polyhydric alcohols and derivatives thereof 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, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0104] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0105] Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, etc. Examples of aromatic solvents include xylene, toluene, etc.

[0106] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0107] In addition, for the purpose of improving the coating property, turpentine-based petroleum naphtha solvents and paraffin-based solvents, which are high-boiling weak solvents, can be used.

[0108] Among these, 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 monoa The solvent is preferably at least one selected from the group consisting of dipropylene glycol monoacetate 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. Methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone are more preferred.

[0109] The amount of solvent in the photosensitive composition of the present 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 the present disclosure (however, if the photosensitive composition contains an alkali-soluble resin described below, this is the total amount of the resin). By adjusting the amount of solvent, the thickness of the resin film to be formed can be adjusted, and within this range, a resin film thickness particularly suitable for obtaining a bank for organic EL can be obtained.

[0110] <Photopolymerization Initiator> The photosensitive composition of the present disclosure preferably contains a photopolymerization initiator. In the photosensitive composition of the present disclosure, the photopolymerization initiator is not particularly limited as long as it polymerizes a monomer by 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. These may be used alone, or a photoradical initiator and a photoacid initiator may be used in combination, or two or more types of photoradical initiators or photoacid initiators may be mixed and used. Furthermore, by using an additive together with the photopolymerization initiator, it is also possible to perform living polymerization in some cases, and known additives can be used as the additive.

[0111] Photoradical initiators can be classified into, for example, intramolecular cleavage types in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and hydrogen abstraction types in which radicals are generated in combination with a hydrogen donor such as a tertiary amine or ether, and any of these may be used. Photoradical initiators other than those types listed above may also be used.

[0112] Specific examples of the photoradical initiator include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, acyloin-based, and oxime ester-based initiators.

[0113] Examples of benzophenone-based compounds include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Of these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0114] Examples of acetophenone-based compounds 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, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. Of these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0115] Examples of diketones include 4,4'-dimethoxybenzyl, methyl benzoylformate, 9,10-phenanthrenequinone, etc. Among these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

[0116] Examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0117] Examples of quinones include anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone, etc. Among these, camphorquinone and 1,4-naphthoquinone are preferred.

[0118] Examples of acyloin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Of these, benzoin and benzoin methyl ether are preferred.

[0119] Examples of oxime esters include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, and among these, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone is preferred.

[0120] As the photoradical initiator, acylphosphine oxides and oxime esters are preferred, and acylphosphine oxides are more preferred.

[0121] Among commercially available photoradical initiators, preferred ones include those manufactured by BASF under the following product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocur 1173, Lucirin TPO, and Omnirad 819.

[0122] Specifically, the photoacid initiator is an onium salt formed by a pair of at least one cation selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, 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]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

[0123] Examples of commercially available photoacid initiators include those manufactured by San-Apro Co., Ltd. under the product names CPI-100P, CPI-110P, CPI-101A, CPI-200K, and CPI-210S; those manufactured by Dow Chemical Japan under the product names Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, and Cyracure Photocuring Initiator UVI-6976; and those manufactured by ADEKA Corporation under the product names Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, and Adekaoptomer SP-170. -172, Adekaoptomer SP-300, Nippon Soda Co., Ltd. product names: CI-5102, CI-2855, Sanshin Chemical Industry Co., Ltd. product names: San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110, San-Aid SI-180, Lamberti Co., Ltd. product names: Esacure 1064, Esacure 1187, and Ciba Specialty Chemicals Co., Ltd. product name: Irgacure 250.

[0124] The content of the photopolymerization initiator in the photosensitive composition of the present disclosure is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure (however, when the photosensitive composition contains an alkali-soluble resin described below, this is the total amount of the resin). When the content of the photopolymerization initiator is 0.1 part 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.

[0125] <Compound Having a Group Reactive with a Thiol Group> The photosensitive composition of the present disclosure preferably contains a compound having a group reactive with a thiol group. The group reactive with a thiol group is not particularly limited as long as it is a group reactive with the thiol group contained in the polymer of the present disclosure, but may be an ethylenic carbon-carbon double bond, an epoxy group, an NCH ２Examples of such a group include an OR group (where R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), an oxetane group, and an isocyanate group. For example, an ethylenic carbon-carbon double bond or an epoxy group is preferred, and an ethylenic carbon-carbon double bond is more preferred. In other words, the monomer having a group capable of reacting with a thiol is preferably a compound having an ethylenic carbon-carbon double bond and / or an epoxy group, and more preferably a compound having an ethylenic carbon-carbon double bond (ethylenically unsaturated compound). A compound having an ethylenic carbon-carbon double bond and / or an epoxy group is capable of undergoing a polymerization reaction by itself, and can serve as a base monomer or polymer in a photosensitive composition.

[0126] An "ethylenic carbon-carbon double bond" means a carbon-carbon double bond that can react by the action of a radical. Conjugated and stabilized double bonds such as the double bond of a benzene ring do not fall under the category of "ethylenic carbon-carbon double bond." From the viewpoint of improving reactivity, it is preferable that the compound having the ethylenic carbon-carbon double bond has an ethylenic carbon-carbon double bond at its terminal. Furthermore, it is preferable that the compound having the ethylenic carbon-carbon double bond is a compound having a (meth)acryloyl group. In other words, a (meth)acryloyl group is preferred as the structure containing an ethylenic carbon-carbon double bond. It should be noted that a (meth)acryloyl group refers to an acryloyl group or a methacryloyl group.

[0127] The compound having a group reactive with a thiol group may be monofunctional or polyfunctional. That is, the compound may have only one group reactive with a thiol group (preferably an ethylenic carbon-carbon double bond) per molecule, or may have two or more (preferably 2 to 8, more preferably 2 to 6) groups reactive with a thiol group (preferably an ethylenic carbon-carbon double bond) per molecule. From the viewpoint of further improving sensitivity and improving physical properties after curing, the compound having a group reactive with a thiol group is preferably polyfunctional. In other words, the compound having a group reactive with a thiol is preferably a crosslinking agent having multiple groups reactive with thiols.

[0128] The crosslinking agent reacts with the thiol group of the polymer of the present disclosure, allowing the polymer to adopt a crosslinked structure, which tends to improve the mechanical strength of the film formed.

[0129] Known crosslinking agents can be used, and specific examples include compounds in which an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethyleneurea, propyleneurea, or glycoluril is reacted with formaldehyde or formaldehyde and a lower alcohol, and the hydrogen atom of the amino group is substituted with a hydroxymethyl group or a lower alkoxymethyl group, and polyfunctional ethylenically unsaturated compounds such as 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 ethyleneurea and propyleneurea are called alkylene urea-based crosslinking agents, and those using glycoluril are called glycoluril-based crosslinking agents. These crosslinking agents may be used alone or in combination of two or more.

[0130] The crosslinking agent is preferably at least one selected from these crosslinking agents, and in particular, glycoluril crosslinking agents, polyfunctional epoxy compounds, and polyfunctional ethylenically unsaturated compounds are preferred, polyfunctional ethylenically unsaturated compounds are more preferred, and polyfunctional acrylate compounds are even more preferred.

[0131] Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine, with hexamethoxymethylmelamine being particularly preferred.

[0132] Examples of urea-based crosslinking agents include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among these, bismethoxymethylurea is preferred.

[0133] Examples of the alkylene urea crosslinking agent include ethylene urea crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, and mono- and / or dibutoxymethylated ethylene urea; propylene urea crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, and mono- and / or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0134] Examples of glycoluril crosslinking agents include mono-, di-, tri-, and / or tetrahydroxymethylated glycoluril, mono-, di-, tri-, and / or tetramethoxymethylated glycoluril, mono-, di-, tri-, and / or tetraethoxymethylated glycoluril, mono-, di-, tri-, and / or tetrapropoxymethylated glycoluril, and mono-, di-, tri-, and / or tetrabutoxymethylated glycoluril.

[0135] Examples of polyfunctional epoxy compounds include aliphatic glycidyl ether polyepoxides and aliphatic glycidyl ether epoxides.

[0136] As the polyfunctional ethylenically unsaturated compound, a compound having two or more ethylenic carbon-carbon double bonds can be used without any particular limitation. From the viewpoint of improving reactivity, it is preferable that the polyfunctional ethylenically unsaturated compound has an ethylenic carbon-carbon double bond at its terminal.

[0137] As the polyfunctional ethylenically unsaturated compound, polyfunctional (meth)acrylate compound is preferred.As the polyfunctional (meth)acrylate compound, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other polyol polyacrylates, bisphenol A diglycidyl ether di(meth)acrylate, hexanediol diglycidyl ether di(meth)acrylate and other epoxy acrylates, polyincinate and hydroxyl group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate are obtained by reaction and the urethane (meth)acrylate etc.

[0138] Examples of commercially available polyfunctional (meth)acrylate compounds include polyfunctional (meth)acrylates (e.g., product names A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol diacrylates (e.g., product names A-200, A-400, A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.), and urethane acrylates (e.g., product names UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0139] Preferred examples of the polyfunctional acrylate compound are shown below.

[0140]

[0141]

[0142]

[0143]

[0144] The content of the compound having a group reactive with a thiol (preferably a crosslinking agent) in the photosensitive composition of the present disclosure is preferably 10 to 400 parts by mass, and more preferably 50 to 300 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure (however, if the photosensitive composition contains an alkali-soluble resin described below, this includes the total amount of the resin). In particular, when the content of the compound having a group reactive with a thiol (preferably a crosslinking agent) 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.

[0145] <Alkali-soluble resin> The photosensitive composition of the present disclosure preferably contains an alkali-soluble resin. When the photosensitive composition of the present disclosure contains an alkali-soluble resin, the shape of the bank obtained from the photosensitive composition of the present disclosure tends to be better. The alkali-soluble resin may be used alone or in combination of two or more.

[0146] The alkali-soluble resin is not particularly limited as long as it is a resin that is soluble in alkali, and examples thereof include alkali-soluble novolak resins, which can be obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

[0147] 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-methyl-catechol, pyrogallol, phloroglucinol, thymol, isothymol, etc. These phenols may be used alone or in combination of two or more.

[0148] 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, and isophthalaldehyde. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

[0149] Other examples of alkali-soluble resins include epoxy (meth)acrylate acid adducts (acid-modified epoxy (meth)acrylate alkali-soluble resins) obtained by reacting an epoxy compound (bisphenol-type epoxy compound) having two glycidyl ether groups derived from a bisphenol with (meth)acrylic acid, and then reacting the resulting compound having a hydroxy group with a polybasic carboxylic acid or its anhydride. Commercially available acid-modified epoxy acrylates include those manufactured by Nippon Kayaku Co., Ltd. under the product names: 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.

[0150] The epoxy compound having two glycidyl ether groups derived from a bisphenol refers to an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with an epihalohydrin, or an equivalent thereof. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds having two or more bisphenol skeletons.

[0151] 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-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)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- 9,9-bis(4-hydroxy-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 may be used alone or in combination of two or more.

[0152] Examples of polybasic carboxylic acids or anhydrides thereof include monoanhydrides of dicarboxylic acids or tricarboxylic acids, dianhydrides of tetracarboxylic acids, etc. These may be used alone or in combination of two or more.

[0153] Examples of dicarboxylic or tricarboxylic acid monoanhydrides include acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic or tricarboxylic acids. These may be used alone or in combination of two or more. Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids include acid monoanhydrides of 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 or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. Examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like.

[0154] Examples of tetracarboxylic acid dianhydrides include acid dianhydrides of chain hydrocarbon tetracarboxylic acids, acid dianhydrides of alicyclic tetracarboxylic acids, and acid dianhydrides of aromatic tetracarboxylic acids. These may be used alone or in combination of two or more. Examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include acid dianhydrides such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid. Examples of acid dianhydrides of alicyclic tetracarboxylic acids include acid dianhydrides such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. Examples of acid dianhydrides of aromatic tetracarboxylic acids include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid.

[0155] The weight average molecular weight of the alkali-soluble resin component is preferably from 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive composition.

[0156] The content of the alkali-soluble resin in the photosensitive composition of the present disclosure is preferably 300 to 10,000 parts by mass, and more preferably 500 to 7,000 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure. When the content of the alkali-soluble resin is 10,000 parts by mass or less, better liquid repellency tends to be obtained.

[0157] <Naphthoquinone diazide group-containing compound> The photosensitive composition of the present disclosure may contain a naphthoquinone diazide group-containing compound. When the photosensitive composition of the present disclosure contains a naphthoquinone diazide group-containing compound, the shape of the bank obtained from the photosensitive composition of the present disclosure tends to be more favorable. The naphthoquinone diazide group-containing compound is not particularly limited, and any compound that is typically used as a photosensitive component in i-line resist compositions can be used.

[0158] Specific 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, and orthoanthraquinone diazide sulfonic acid ester compounds. 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 compounds may be used alone or in combination of two or more.

[0159] The content of the naphthoquinone diazide group-containing compound in the photosensitive composition of the present disclosure is preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure (provided that, when the photosensitive composition contains the above-mentioned alkali-soluble resin, the amount of the resin is also included). When the content is 60 parts by weight or less, better sensitivity as a photosensitive composition tends to be obtained.

[0160] <Basic Compound> The photosensitive composition of the present disclosure may contain a basic compound. The basic compound has the function of slowing down the diffusion rate of the acid generated from the photoacid generator when it diffuses into the film of the photosensitive composition of the present disclosure. By incorporating a basic compound, it is possible to adjust the acid diffusion distance, and it tends to be possible to improve the shape of the bank. Furthermore, by incorporating a basic compound, it tends to be possible to make the bank less likely to deform, even if the waiting time before exposure after bank formation is long, and it tends to be possible to stably form a bank with the desired precision.

[0161] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among these, aliphatic amines are preferred, and specific examples include secondary or tertiary aliphatic amines, alkyl alcohol amines, and the like. These may be used alone or in combination of two or more.

[0162] Examples of aliphatic amines include ammonia (NH ３ ) in which at least one hydrogen atom has been substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof 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. , 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, tri-n-octanolamine, etc. Among these, dialkylamines, trialkylamines, and alkyl alcoholamines are preferred, and alkyl alcoholamines are more preferred. Of the alkyl alcoholamines, triethanolamine and triisopropanolamine are particularly preferred.

[0163] Examples of aromatic amines and heterocyclic amines include 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, and 2,6-dinitroaniline. aniline derivatives such as 3,5-dinitroaniline and N,N-dimethyltoluidine; heterocyclic amines such as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine and 4,4-dimethylimidazoline; bis(1,2,2,6 , 6-pentamethyl-4-piperidyl) sebagate and other hindered amines; 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 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; picoline, lutidine, pyrrole, piperidine, piperazine, indole, hexamethylenetetramine and other.

[0164] In the photosensitive composition of the present 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, relative to 100 parts by mass of the polymer of the present disclosure (however, if the photosensitive composition contains the above-mentioned alkali-soluble resin, the total amount of the resin). When the blending amount of the basic compound is 0.001 part by mass or more, a sufficient effect as an additive is obtained, and when it is 2 parts by mass or less, better resolution and sensitivity tend to be obtained.

[0165] <Other Additives> The photosensitive composition of the present disclosure may contain other additives as needed. Examples of other additives include various additives such as dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizers, adhesion agents, antioxidants, and chain transfer agents. These may be used alone or in combination of two or more. These other additives may be known additives.

[0166] As the surfactant, it is preferable to contain, for example, one or more of a fluorine-based or silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom).

[0167] The incorporation of an adhesive agent tends to exhibit better adhesion to the substrate. Examples of adhesive agents 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. Of these, vinyl-based agents are preferred, and (meth)acrylic phosphorus-containing compounds are more preferred. Examples of (meth)acrylic phosphorus-containing compounds include KBM-503 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd. As phosphate esters, those having vinyl, acrylic, or methacrylic groups at the crosslinking site are desirable, such as KAYAMER-PM21 manufactured by Nippon Kayaku Co., Ltd.

[0168] The content of the adhesive in the photosensitive composition of the present 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 the present disclosure (however, if the photosensitive composition contains the alkali-soluble resin, the total amount of the resin), which tends to exhibit better adhesion to the substrate.

[0169] Examples of the colorant include color pigments, color dyes, etc. These may be used alone or in combination of two or more.

[0170] Examples of color pigments include color inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and coal dust; color organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, perylene, anthrapyrimidine, carbazole violet, anthrapyridine, azo orange, flavanthrone yellow, isoindoline yellow, azo yellow, industhrone blue, dibromoanzathrone 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 divided titanium.

[0171] Examples of organic pigments that can be used 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 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.

[0172] Examples of coloring dyes include monoazo dyes, disazo dyes, metal complex monoazo dyes, anthraquinone dyes, methine dyes, phthalocyanine dyes, and triarylmethane dyes.

[0173] Colorants are typically dispersed in a solvent and mixed with other ingredients as a colorant dispersion, and a dispersant may be added in this case. The dispersant may be any known compound used in pigment (colorant) dispersion (e.g., compounds commercially available under the names dispersant, dispersing wetting agent, dispersion promoter, etc.), and the like, without any particular restrictions. Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). These may be used alone or in combination of two or more. The amount of dispersant added is preferably 1 to 35% by mass, and more preferably 2 to 25% by mass, of the colorant. High-viscosity substances such as resins generally have the effect of stabilizing dispersion, but those without dispersion-promoting properties are not considered dispersants. However, this does not limit their use for the purpose of stabilizing dispersion.

[0174] The content of the colorant in the photosensitive composition of the present disclosure is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure (however, when the photosensitive composition contains the alkali-soluble resin, the total amount of the resin is included).

[0175] A chain transfer agent is a component that receives a radical from a growing polymer chain in a radical polymerization system and generates a new radical. By using a chain transfer agent, the degree of polymerization can be adjusted, and the properties of the cured film can be adjusted. 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 tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, pentaerythritol Examples of suitable thiol compounds include tetrakis(3-mercaptobutyrate); sulfide compounds such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-terpinene, and dipentene. These may be used alone or in combination of two or more. Of these, thiol compounds are preferred.

[0176] The content of the chain transfer agent in the photosensitive composition of the present disclosure is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the polymer of the present disclosure (however, if the photosensitive composition contains the alkali-soluble resin, the total amount of the resin). This makes it possible to maintain appropriate curability and adjust the development contrast with the unexposed area.

[0177] (Methods for Producing a Cured Product and a Substrate with a Patterned Film) Next, methods for producing a cured product using the photosensitive composition of the present disclosure and a substrate with a patterned film will be described.

[0178] The method for producing a cured product (method for producing a substrate with a patterned film) of the present disclosure includes (1-1) a film-forming 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.

[0179] (1-1) Film Forming Step First, in the film forming step, the photosensitive composition of the present disclosure is applied to a substrate to form a film. Specifically, the photosensitive composition of the present disclosure is applied to a substrate and then heated to form the photosensitive composition into a film. The heating conditions are not particularly limited, but are preferably 80 to 100°C and 60 to 200 seconds. This allows the solvent and other components contained in the photosensitive composition to be removed.

[0180] The substrate may be a silicon wafer, metal, glass, ITO substrate, or the like. An organic or inorganic film may be pre-formed on the substrate. For example, an anti-reflective film or a lower layer of a multilayer resist may be provided, and a pattern may be formed on the lower layer. The substrate may also be pre-washed. For example, it may be washed using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), or the like.

[0181] The photosensitive composition of the present disclosure can be applied to a substrate using a suitable coating device such as a slit coater, a die coater, a gravure coater, a dip coater, a spin coater, etc. Dip coating, spray coating, roller coating, and other methods can also be used.

[0182] Here, the film formed on the substrate may be formed on the entire surface of the substrate, or may be formed on only a part of the substrate.

[0183] The thickness of the film 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 film is thicker than 500 μm, the surface irregularities tend to increase, making it difficult to obtain a flat film.

[0184] (1-2) Exposure Step Next, in the exposure step, the film after the film-forming step is exposed to high-energy rays through a photomask, and the pattern of the photomask is transferred to the film. Specifically, a desired photomask is set in an exposure device, and the film after the film-forming step is exposed to high-energy rays through the photomask. The high-energy rays are preferably at least one type selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

[0185] The exposure dose of high energy rays is 1 to 200 mJ / cm ２ is preferably 10 to 100 mJ / cm ２ It is more preferable that:

[0186] (1-3) Development Step Next, in the development step, the film after the exposure step is developed with an alkaline developer to obtain a patterned film. Specifically, the film after the exposure step is developed with an alkaline aqueous solution to obtain a patterned film. That is, either the exposed portion of the film or the unexposed portion of the film is dissolved in the alkaline aqueous solution to obtain a patterned film.

[0187] Examples of the alkaline aqueous solution that can be used include an aqueous tetramethylammonium hydroxide (TMAH) solution, an aqueous tetrabutylammonium hydroxide (TBAH) solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, etc. When the alkaline aqueous solution is an aqueous tetramethylammonium hydroxide (TMAH) solution, its concentration is preferably 0.1 to 5 mass %, and more preferably 2 to 3 mass %.

[0188] As the developing method, a known method can be used, for example, a dipping method, a puddle method, a spray method, or the like.

[0189] The development time (the time during which the developer is in contact with the film) is preferably from 10 seconds to 3 minutes, and more preferably from 30 seconds to 2 minutes.

[0190] After development, a step of washing the pattern film with deionized water, etc. may be performed as needed. The washing method and washing time are preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.

[0191] (1-4) Baking Step In the baking step, after the developing step, the patterned film is baked to cure it, thereby obtaining a cured product. Specifically, after the developing step, the patterned film is heated and baked to cure it, thereby obtaining a cured product. The cured product of the present disclosure is obtained by curing the photosensitive composition of the present disclosure. Baking can be performed on a hot plate, and the baking conditions are preferably 140°C or less (preferably 60 to 130°C) and 10 to 120 minutes.

[0192] In the manufacturing method, after the baking step (1-4), a UV ozone treatment or an oxygen plasma treatment may be performed. Among these, a UV ozone treatment is preferable. This can remove organic matter remaining in the recesses of the pattern film and reduce uneven wetting of the dropped ink, thereby preventing defects in the display element.

[0193] The cured product of the present disclosure obtained in this manner has excellent liquid repellency and can be used as a bank for organic EL displays, micro LED displays, quantum dot displays, etc. In other words, the method for producing a cured product of the present disclosure can also be used to produce banks for organic EL displays, micro LED displays, quantum dot displays, etc. In this way, the patterned film functions as a bank (partition wall).

[0194] Furthermore, the patterned film-bearing substrate of the present disclosure produced in this manner has a patterned film on a substrate, on which the cured product of the present disclosure is patterned, and can be used as a substrate for organic EL displays, micro LED displays, quantum dot displays, etc. In other words, the method for producing a patterned film-bearing substrate of the present disclosure can also be used to produce substrates for organic EL displays, micro LED displays, quantum dot displays, etc. In this way, the patterned film functions as a bank (partition). Therefore, the patterned film-bearing substrate of the present disclosure can be suitably used as a substrate for forming display elements by an inkjet method.

[0195] In the method for producing a cured product according to the present disclosure, the photosensitive composition can be cured at a low temperature (for example, at 140°C or lower). Therefore, when using the method for producing a cured product according to the present disclosure to produce a bank for an organic electroluminescent display, a micro LED display, a quantum dot display, or the like, the bank can be formed without causing significant thermal damage to the light-emitting layer. In the method for producing a substrate with a patterned film according to the present disclosure, the photosensitive composition can be cured at a low temperature. Therefore, when using the method for producing a substrate with a patterned film according to the present disclosure to produce a substrate for an organic electroluminescent display, a micro LED display, a quantum dot display, or the like, the substrate can be formed without causing significant thermal damage to the light-emitting layer.

[0196] The cured product of the present disclosure can also be suitably used as a simple film without a pattern. In this case, the cured product of the present disclosure has excellent water and oil repellency due to its low surface free energy, and can be used, for example, 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.

[0197] (Image display device) The image display device of the present disclosure has the patterned film-formed substrate of the present disclosure. Specifically, the image display device of the present disclosure has a display element using the patterned film-formed substrate of the present disclosure (the cured product of the present disclosure). Examples of the image display device of the present disclosure include an organic EL display, a micro LED display, and a quantum dot display.

[0198] Examples that more specifically disclose embodiments of the present disclosure are given below, but the present disclosure is not limited to these examples.

[0199] 1. Polymer Synthesis The polymer obtained was analyzed by the following method. [Measurement of the molar ratio of each structural unit in the polymer] The molar ratio of each structural unit in the polymer was measured by the following method. １ H-NMR, ２９ Si-NMR or １３ The molecular weight was determined from the C-NMR measurement value. [Measurement of molecular weight of polymer] GPC The weight average molecular weight (Mw) and molecular weight dispersity (ratio of number average molecular weight Mn to weight average molecular weight Mw; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, Model HLC-8320GPC) with an ALPHA-M column and an ALPHA-2500 column (both manufactured by Tosoh Corporation) connected in series, using tetrahydrofuran (THF) as the developing solvent and polystyrene as the standard substance. A refractive index difference detector was used as the detector. [Measurement of development rate (DR) of polymer] The polymer was applied to a glass substrate using a spin coater at a rotation speed of 1000 rpm, and heated on a hot plate at 80°C for 150 seconds to form a resin film with a thickness of 1 μm, and the film thickness was measured. The formed film was immersed in a 2.38% TMAH aqueous solution, and the film thickness was measured after 10 seconds, 20 seconds, and 30 seconds to confirm the degree of film thickness reduction. The film thickness was measured by drawing a line on the substrate with a needle, setting that point as 0, and then measuring the difference using a laser microscope.

[0200] Next, the monomers used will be summarized. The monomers in Tables 1A and 1B are as follows. All of the monomers used were reagents manufactured by Tokyo Chemical Industry Co., Ltd. DEDMS: A compound represented by the following formula (diethoxydimethylsilane) SH (bifunctional): a compound represented by the following formula (3-mercaptopropylmethyldimethoxysilane (MrPMDMS)) SH (trifunctional): a compound represented by the following formula (3-mercaptopropyltrimethoxysilane (MrPTMS)) Acrylic (bifunctional): 3-acryloxypropylmethyldimethoxysilane (APMDMS) Acrylic (trifunctional): 3-acryloxypropyltrimethoxysilane (APTMS) Vinyl (trifunctional): vinyltrimethoxysilane (VTMS) Epoxy (trifunctional): 3-glycidoxypropyltrimethoxysilane (GPTMS)

[0201] The polymers were synthesized using the following two methods. When Synthesis 2 was used, the amount of DEDMS in the table is the amount derived from hexamethylcyclotrisiloxane. Synthesis 1: Acid-catalyzed condensation polymerization of alkoxysilane. Synthesis 2: Ring-opening polymerization of cyclic siloxane.

[0202] (Production Example 1) Synthesis of Polymer 1 Using Synthesis Method 1 Into a 100 mL glass flask containing a stirrer, 33.4 g (0.23 mol) of DEDMS, 4.61 g (0.03 mol) of MrPMDMS, 9.93 g (0.55 mol) of ultrapure water, and 0.63 g (0.11 mol) of acetic acid (Tokyo Chemical Industry Co., Ltd.) were added at room temperature (approximately 20 ° C.), and the internal temperature was raised to 75 ° C., allowing the reaction to proceed overnight. 70 mL of isopropyl ether (Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added to the reaction solution, which was then transferred to a 200 mL glass flask containing a stirrer, followed by the addition of 50 mL of ultrapure water while stirring. Separation was performed twice, and the product was obtained from the organic layer as a colorless, transparent solution. To this solution was added 48.73 g of propylene glycol 1-monomethyl ether 2-acetate (a product of Kanto Chemical Co., Ltd.; hereinafter referred to as PGMEA), and the mixture was evaporated under reduced pressure to remove water and ethanol, yielding 54.75 g (solid content 10.15 g) of liquid-repellent polysiloxane 1 in the form of a colorless, transparent solution in a yield of 54%.

[0203] <NMR Measurement Results> The composition ratio of the constituent units of the liquid-repellent polysiloxane 1, expressed as a molar ratio, was DEDMS constituent unit: MrPMDMS constituent unit=9:1.

[0204]

[0205] (Production Example 2) Synthesis of Polymer 2 Using Synthesis Method 2 In a 200 mL glass flask containing a stirrer, 0.05 L (0.62 mol) of tetrahydrofuran (Kanto Chemical Co., Ltd. product) was added as a reaction solvent at room temperature (approximately 20° C.), 20.0 g (0.09 mol) of HMCTS, and 0.16 g (9.00×10 ―３ mol), 0.13 g (9.34 × 10 ―４ mol) was added, the internal temperature was raised to 30°C, and the reaction was carried out for 1 hour. ―３ mol) was added, and the mixture was further reacted at an internal temperature of 30° C. for 20 minutes. 0.05 g (9.34×10 mol) of acetic acid (Tokyo Chemical Industry Co., Ltd.) was added to the reaction system. ―４ After neutralization, the product was concentrated by evaporation under reduced pressure. Subsequently, heptane (30 mL) was added to the product to form a solution, and then methanol (50 mL) was added, stirred, allowed to stand, and the supernatant was removed. After repeating this methanol washing once more, 51.44 g (0.39 mol) of PGMEA was added, and the mixture was evaporated under reduced pressure to remove water, methanol, and heptane, yielding 71.63 g (solids content 17.93 g) of liquid-repellent polysiloxane 2 as a colorless, transparent solution in an 87% yield.

[0206] <NMR Measurement Results> The composition ratio of the constituent units of the liquid-repellent polysiloxane 2, expressed as a molar ratio, was hexamethylcyclotrisiloxane constituent unit:MrPMDMS constituent unit=9:1.

[0207]

[0208] (Production Example 3) Synthesis of Polymer 3 Using Synthesis Method 1 Into a 100 mL glass flask containing a stirrer, 33.4 g (0.23 mol) of DEDMS, 4.91 g (0.03 mol) of MrPTMS, 9.93 g (0.55 mol) of ultrapure water, and 0.63 g (0.11 mol) of acetic acid (Tokyo Chemical Industry Co., Ltd.) were added at room temperature (approximately 20 ° C.), and the internal temperature was raised to 75 ° C., allowing the reaction to proceed overnight. 70 mL of isopropyl ether (Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added to the reaction solution, which was then transferred to a 200 mL glass flask containing a stirrer, followed by the addition of 50 mL of ultrapure water while stirring. Separation was performed twice, and the product was obtained from the organic layer as a colorless, transparent solution. To this solution was added 48.73 g of propylene glycol 1-monomethyl ether 2-acetate (a product of Kanto Chemical Co., Ltd.; hereinafter referred to as PGMEA), and the mixture was evaporated under reduced pressure to remove water and ethanol, yielding 54.75 g (solid content 10.95 g) of liquid-repellent polysiloxane 3 in the form of a colorless, transparent solution in a yield of 55%.

[0209] <NMR Measurement Results> The composition ratio of the constituent units of the liquid-repellent polysiloxane 3, expressed as a molar ratio, was DEDMS constituent unit: MrPTMS constituent unit=9:1.

[0210]

[0211] (Production Example 4) Synthesis of Polymer 4 Using Synthesis Method 2 In a 200 mL glass flask containing a stirrer, 0.05 L (0.62 mol) of tetrahydrofuran (Kanto Chemical Co., Ltd.) was added as a reaction solvent at room temperature (approximately 20° C.), 20.0 g (0.09 mol) of hexamethylcyclotrisiloxane (Tokyo Chemical Industry Co., Ltd.) and 0.16 g (9.00×10 ―３ mol), 0.13 g (9.34 × 10 ―４ mol) was added, the internal temperature was raised to 30°C, and the reaction was carried out for 1 hour. ―３ mol) was added, and the mixture was further reacted at an internal temperature of 30° C. for 20 minutes. 0.05 g (9.34×10 mol) of acetic acid (Tokyo Chemical Industry Co., Ltd.) was added to the reaction system. ―４After neutralization, the product was concentrated by evaporation under reduced pressure. Subsequently, heptane (30 mL) was added to the product to form a solution, and then methanol (50 mL) was added, stirred, allowed to stand, and the supernatant was removed. After repeating this methanol washing once more, 51.44 g (0.39 mol) of PGMEA was added, and the mixture was evaporated under reduced pressure to remove water, methanol, and heptane, yielding 71.63 g (solid content 18.14 g) of liquid-repellent polysiloxane 4 as a colorless, transparent solution in an 85% yield.

[0212] <NMR Measurement Results> The composition ratio of the constituent units of liquid-repellent polysiloxane 4, expressed as a molar ratio, was hexamethylcyclotrisiloxane constituent unit:MrPTMS constituent unit=9:1.

[0213]

[0214] (Production Examples 5 to 32) Synthesis of Polymers 5 to 32 Polymers 5 to 32 were synthesized in the same manner as in Production Examples 1 to 4, except that the monomer compositions and polymerization methods were changed as shown in Tables 1A and 1B.

[0215] The monomer composition and weight average molecular weight of each polymer are shown in Tables 1A and 1B. Table 1A shows polymers of the present disclosure having thiol groups as crosslinking moieties, while Table 1B shows comparative polymers having acrylate groups, vinyl groups, or epoxy groups as crosslinking moieties.

[0216] Polymer structures of polymers 1, 2, 5, and 6 Polymer structures of polymers 3, 4, 7, 8, 9, and 10 Polymer structures of polymers 11, 12, 15, and 16 Polymer structures of polymers 13, 14, 17, 18, and 19 Polymer structures of polymers 20 and 21 Polymer structures of polymers 22, 23, and 24 Polymer structures of polymers 25, 26, and 27 Polymer structures of polymers 28 and 29 Polymer structures of polymers 30, 31, and 32

[0217] 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. <Ethylenically unsaturated compound (A)> Ethylenically unsaturated compound: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. <Photopolymerization initiator (B)> Photopolymerization initiator 1: "Irgacure OXE-01" (oxime ester initiator (2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone)) manufactured by BASF Corporation Photopolymerization initiator 2: "Omnirad 920" (acylphosphine oxide initiator (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide)) manufactured by BASF Corporation <Alkali-soluble resin (C)> Alkali-soluble resin: "ZAR-2050H" (BIS-A type epoxy resin (acid-modified epoxy (meth)acrylate alkali-soluble resin)) manufactured by Nippon Kayaku Co., Ltd. <Additives> Adhesion agent: "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd. (compound of the following formula) <Chain transfer agent> Chain transfer agent: "Karenz MT-PE1" (pentaerythritol tetrakis(3-mercaptobutyrate)) manufactured by Showa Denko K.K.

[0218] (Preparation of Color Pigment Dispersion 1) The pigment, dispersant, alkali-soluble resin (referred to as alkali-soluble resin in Table 2), and solvent shown in Table 2 were mixed to obtain the mass ratio shown in Table 2. This solution was subjected to a dispersion treatment in a bead mill using 0.5 mmφ zirconia beads at 25°C for 12 hours. After completion of the dispersion treatment, the beads were removed by filtration, and Color Pigment Dispersion 1 was prepared.

[0219]

[0220] [Preparation of Photosensitive Resin Basic Composition Liquid] 1.7 parts by mass of Karenz MT-PE1 as a chain transfer agent, 43.1 parts by mass of DPHA as the ethylenically unsaturated compound (A), 43.1 parts by mass of ZAR-2050H as the alkali-soluble resin (C), 1.7 parts by mass of PM-21 as an adhesive agent, 8.6 parts by mass of Color Pigment Dispersion 1, and 100 parts by mass of PGMEA as a solvent were blended, and the resulting solution was filtered through a 3.0 μm membrane filter to prepare a photosensitive resin basic composition liquid.

[0221] A photosensitive resin basic composition liquid, 1 part by mass of a photoradical initiator (Irgacure Oxe-01 for the examples in Tables 3A and 3B, and Omnirad 920 for the examples in Tables 4A and 4B), and 1 part by mass of synthesized silyl-type liquid repellent materials (polymers) 1 to 32 (not blended in Comparative Examples 1-0 and 2-0) were added to the photosensitive resin basic composition liquid, stirred, and dissolved. The resulting photosensitive resin compositions were used for evaluation by the methods described below.

[0222] 3. Bank Evaluation [Bank Formation] A 10 cm square alkali-free glass substrate was washed with ultrapure water and then with acetone, and then subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device. Next, a photosensitive resin composition was applied to the resulting UV ozone-treated substrate using a spin coater at a rotation speed of 200 rpm, and the substrate was heated on a hot plate at 80°C for 150 seconds to form a resin film with a thickness of 10 μm. Using a mask aligner (product of SUSS MicroTec KK), the resulting resin film was exposed to i-line light (wavelength 365 nm) through a mask with a line and space of 10 μm. The resulting cured film after exposure was evaluated for developer solubility and bank performance (sensitivity, resolution), and the contact angle of the bank portion and opening was measured.

[0223] [Developer Solubility] The cured film on the ITO substrate after exposure was immersed in an alkaline developer at room temperature for 80 seconds to evaluate its solubility in the alkaline developer. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) was used as the alkaline developer. The solubility of the bank was evaluated by measuring the film thickness of the bank after immersion using a contact film thickness meter. The case where the bank was completely dissolved was rated as "soluble," and the case where the resist film remained undissolved was rated as "insoluble."

[0224] [Bank Performance (Sensitivity, Resolution)] When forming the bank having the line and space pattern, the liquid repellency of the bank portion remained high in the composition to which the silyl-type liquid repellent material was added. This was determined by the optimum exposure dose Eop (mJ / cm ２ ) was calculated and used as an index of sensitivity. ２) indicates that the smaller the numerical value, the better the photocurability. The obtained bank pattern was also observed with a laser microscope (Keyence Corporation, VX-1100) (3000x magnification) to evaluate the resolution. Those with no visible line edge roughness were rated "excellent," those with slight visible line edge roughness were rated "good," and those with significant line edge roughness were rated "poor."

[0225] [Contact angle] Spray development was performed using a 2.38% by mass aqueous solution of TMAH for 40 seconds. After development, the substrate was rinsed with pure water for 10 seconds. The remaining developer and / or rinse solution was then removed by N ２ The resulting cured film was removed by blowing. The substrate having the cured film was heated at 230°C for 20 minutes, and then the contact angles of the cured film surface with water and propylene glycol monomethyl ether acetate (PGMEA) were measured at five points on the coating film using a contact angle meter (GMs-601 manufactured by Kyowa Interface Science Co., Ltd.). The higher the contact angle of the exposed area, the better, since this indicates that the liquid-repellent component has also cured. The lower the contact angle of the unexposed area, the better, since a high contact angle indicates that the liquid-repellent component remains even after development.

[0226]

[0227]

[0228] Tables 3A, 3B, 4A, and 4B show that the polymers of the present disclosure have excellent photocurability and can impart good alkaline developability and liquid repellency to the resulting cured product, and the resulting cured product has excellent alkaline developability (resolution after development) and liquid repellency. Polymers 30 to 32 of the present disclosure had relatively low molecular weights as shown in Table 1A. Nevertheless, Examples 1-14 to 1-16 and 2-14 to 2-16, which used these polymers, had relatively high contact angles of the exposed area with PGMEA, and the resulting cured product had excellent liquid repellency. Furthermore, because these polymers have low molecular weights, they are easily compatible with photosensitive compositions.

[0229] The polymer of the present disclosure having thiol groups as cross-linking moieties tends to have higher sensitivity and superior photocurability than the polymer of the comparative example having acrylate groups or vinyl groups as cross-linking moieties. The polymer of the comparative example having only epoxy groups as cross-linking moieties did not cure. This is because the epoxy groups do not contribute to the radical reaction.

[0230] When the contact angle of the unexposed area (opening) was checked, "Comparative Examples 1-1 to 1-16" and "Comparative Examples 2-1 to 2-16" showed higher liquid repellency than Comparative Example 1-0 and Comparative Example 2-0, respectively. This is presumed to be because the liquid repellent material was not completely removed during the development process and remained. On the other hand, all of the Examples showed contact angles similar to those of Comparative Example 1-0 and Comparative Example 2-0, resulting in no (or less likely to remain) liquid repellent material. This difference is presumed to be due to alkaline developability.

[0231] This application claims priority under the Paris Convention or the laws of countries that have adopted it, based on Japanese Patent Application No. 2023-202128 filed on November 29, 2023. The contents of that application are incorporated herein by reference in their entirety.

Claims

1. A photosensitive composition comprising a polymer having a repeating unit represented by the following formula (A), and a repeating unit represented by the following formula (B) and / or a repeating unit represented by the following formula (C): (In formula (A), R １ , R ２ are each independently an alkyl group. (In formula (B), R ３ is a monovalent group. ４ is a divalent group. (In formula (C), R ５ is a divalent group.

2. R in the above formula (B) ３ 2. The photosensitive composition of claim 1, wherein is an alkyl group.

3. The photosensitive composition according to claim 1, wherein the polymer has a repeating unit represented by formula (C).

4. A photosensitive composition comprising a polymer having a repeating unit represented by the following formula (B-1): (In formula (B-1), R ４ is a divalent group.

5. The photosensitive composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator and a compound having a group capable of reacting with a thiol group.

6. The photosensitive composition according to claim 5, wherein the photopolymerization initiator is an acylphosphine oxide-based photopolymerization initiator or an oxime ester-based photopolymerization initiator.

7. The photosensitive composition according to claim 5, wherein the photopolymerization initiator is an acylphosphine oxide-based photopolymerization initiator.

8. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 4.

9. A method for producing a substrate with a patterned film, comprising: a film-forming step of applying the photosensitive composition according to any one of claims 1 to 4 onto a substrate to form a film; an exposure step of exposing the film obtained after the film-forming step to high-energy rays through a photomask to transfer the pattern of the photomask to the film; and a development step of developing the film obtained after the exposure step with an alkaline developer to obtain a patterned film.

10. The method for producing a substrate with a patterned film according to claim 9, wherein the patterned film is a partition wall.

11. The method for producing a substrate with a patterned film according to claim 9, wherein the substrate with the patterned film is a substrate for forming a display element by an ink-jet method.

12. A substrate having a patterned film, the patterned film being formed on the substrate in a pattern of the cured product according to claim 8.

13. The substrate with a patterned film according to claim 12, wherein the patterned film is a partition wall.

14. An image display device comprising the substrate with the patterned film according to claim 12.

15. An image display device having a substrate with a patterned film according to claim 13.

16. A polymer having a repeating unit represented by the following formula (A), and a repeating unit represented by the following formula (B) and / or a repeating unit represented by the following formula (C): (In formula (A), R １ , R ２ are each independently an alkyl group. (In formula (B), R ３ is a monovalent group. ４ is a divalent group. (In formula (C), R ５ is a divalent group.

17. R in the above formula (B) ３ The polymer according to claim 16, wherein is an alkyl group.

18. The polymer according to claim 16, having a repeating unit represented by formula (C).

19. A polymer having a repeating unit represented by the following formula (B-1): (In formula (B-1), R ４ is a divalent group.

20. A liquid repellent material comprising the polymer according to any one of claims 16 to 19.

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