Polymer, liquid repellent material containing the same, photosensitive composition containing the same, cured product of the photosensitive composition, substrate with patterned film using the photosensitive composition, method for manufacturing the substrate with patterned film, and image display device having the substrate with patterned film

Abstract

This application provides a polymer that improves photocurability, a liquid-repellent material comprising the polymer, a photosensitive composition comprising the polymer, a cured product formed 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. This application relates to a photosensitive composition comprising a specific polymer having thiol groups.

Description

Technical Field

[0001] This application relates to polymers, liquid-repellent materials containing the polymers, photosensitive compositions containing the polymers, cured products formed by curing the photosensitive compositions, substrates with patterned films using the photosensitive compositions, methods for manufacturing the substrates with patterned films, and image display devices having the substrates with patterned films. Background Technology

[0002] In the manufacture of display elements such as organic EL displays, micro LED displays, and quantum dot displays, inkjet printing is known as a method for forming organic layers with functions such as light emission. There are several methods of inkjet printing, including: a method of curing ink that drips from a nozzle onto the recesses of a patterned film with uneven surfaces formed on a substrate; or a method of dripping ink onto a patterned film pre-formed on a substrate, where the ink consists of a hydrophilic portion (wetting part) and a hydrophobic portion (ink-repelling part), allowing the ink to adhere only to the hydrophilic portion; and so on.

[0003] In particular, regarding the method mentioned earlier for curing ink that drips from a nozzle onto the recesses of a patterned film, two main methods can be used to create such a patterned film with raised and recessed areas. One is photolithography, which forms exposed and unexposed areas by exposing the surface of a photosensitive photoresist film coated on a substrate to a pattern, and then dissolving and removing either area with a developer. The other is imprinting, which uses printing technology. Generally, after forming the patterned film with raised and recessed areas, the entire substrate is subjected to UV ozone treatment or oxygen plasma treatment. This UV ozone treatment or oxygen plasma treatment effectively removes residual organic matter from the recesses of the patterned film, reducing uneven wetting of the dripping ink and thus preventing defects in the display element.

[0004] The raised portions of the patterned film are called septa, which act as barriers to prevent ink from mixing when it drips onto the recessed portions of the film. To improve the effectiveness of this barrier, the top surface of the septa must be ink-repellent.

[0005] Patent Document 1 discloses a photosensitive resin composition containing a specific fluorinated resin that exhibits good liquid repellency. Furthermore, Patent Document 2 discloses a photosensitive resin composition containing a polysiloxane. It should be noted that Patent Document 3 discloses a photosensitive resin composition containing a polysiloxane having crosslinking groups and composed of formulas (d1-2).

[0006] “R 61 R 62 R 63 Si-O-(SiR 64 R 65 -O)n―SiR 66 R67 R 68 (d1-2)

[0007] In equation (d1-2), R 61 R 62 R 63 R 64 R 65 R 66 R 67 R 68 Each can be represented independently as a monovalent organic group or a hydrogen atom.

[0008] Furthermore, the aforementioned crosslinking groups disclosed include epoxy groups, olefinic unsaturated groups, and active groups that generate free radicals through irradiation with active energy rays. On the other hand, Patent Document 4 discloses that a polydimethylsiloxane resin layer containing a polydimethylsiloxane resin with one or more crosslinking groups has oil-repellent properties.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: International Patent Publication No. 2020 / 110793

[0012] Patent Document 2: International Patent Publication No. 2022 / 181350

[0013] Patent Document 3: International Patent Publication No. 2022 / 264909

[0014] Patent Document 4: Japanese Patent Publication No. 2022-169741 Summary of the Invention

[0015] The inventors, focusing on the liquid-repellent properties of polysiloxanes, have conducted in-depth research on photosensitive resin compositions containing polysiloxane resins. This is because, although photosensitive resin compositions containing polysiloxanes with crosslinking groups are known, specific research within the scope of current knowledge is insufficient.

[0016] The purpose of this application is to provide a polymer that can improve photocurability, a liquid-repellent material containing the polymer, a photosensitive composition containing the polymer, a cured product formed 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.

[0017] The inventors discovered through in-depth research that the polymer containing poly(dimethylsiloxane) units described in Patent Document 2 has poor photocurability and alkaline developability because the crosslinking groups are acrylate groups or vinyl groups; and that by setting the crosslinking groups to thiol groups, the photocurability and alkaline developability are excellent, thus completing the present invention. That is, this application (1) relates to a photosensitive composition comprising: a polymer having repeating units shown in formula (A) and repeating units shown in formula (B) and / or repeating units shown in formula (C).

[0018]

[0019] (In formula (A), R) 1 R 2 Each is an alkyl group, individually.

[0020]

[0021] (In formula (B), R) 3 It is a monovalent group. R 4 (It is a divalent group.)

[0022]

[0023] (In formula (C), R) 5 (It is a divalent group.)

[0024] This application (2) is based on the photosensitive composition of this application (1), wherein R of formula (B) 3 It is an alkyl group.

[0025] This application (3) is a photosensitive composition according to this application (1) or (2), wherein the polymer has repeating units represented by the formula (C).

[0026] This application (4) is a photosensitive composition comprising: a polymer having repeating units as shown in formula (B-1) below.

[0027]

[0028] (In formula (B-1), R) 4 (It is a divalent group.)

[0029] This application (5) is a photosensitive composition according to any one of the claims (1) to (4), further comprising: a photopolymerization initiator; and a compound having a group capable of reacting with a thiol group.

[0030] This application (6) is a photosensitive composition according to this application (5), wherein the photopolymerization initiator is an acylphosphine oxide photopolymerization initiator or an oxime ester photopolymerization initiator.

[0031] This application (7) is a photosensitive composition according to this application (5), wherein the photopolymerization initiator is an acylphosphine oxide-based photopolymerization initiator.

[0032] This application (8) is a cured product, which is formed by curing the photosensitive composition described in any one of (1) to (7) of this application.

[0033] This application (9) is a method for manufacturing a substrate with a patterned film, comprising:

[0034] In the film-forming process, the photosensitive composition described in any one of (1) to (7) of this application is coated onto a substrate to form a film;

[0035] The exposure process involves exposing the film, after the film-forming process, to high-energy rays through a photomask, thereby transferring the pattern of the photomask onto the film; and

[0036] The developing process involves developing the film after the exposure process with an alkaline developing solution to obtain a patterned film.

[0037] This application (10) is a method for manufacturing a substrate with a patterned film according to the method described in this application (9), wherein the patterned film is a partition.

[0038] This application (11) is a method for manufacturing a substrate with a patterned film according to the present application (9) or (10), wherein the substrate with the patterned film is a substrate for forming display elements by inkjet printing.

[0039] This application (12) is a substrate with a patterned film, which has a patterned film formed by patterning the cured material described in this application (8) on the substrate.

[0040] This application (13) is a substrate with a patterned film according to this application (12), wherein the patterned film is a partition.

[0041] This application (14) is an image display device having a substrate with a patterned film as described in this application (12).

[0042] This application (15) is an image display device having a substrate with a patterned film as described in this application (13).

[0043] This application (16) is a polymer having repeating units as shown in formula (A), repeating units as shown in formula (B), and / or repeating units as shown in formula (C).

[0044]

[0045] (In formula (A), R) 1 R 2 Each is an alkyl group, individually.

[0046]

[0047] (In formula (B), R) 3 It is a monovalent group. R 4 (It is a divalent group.)

[0048]

[0049] (In formula (C), R) 5 (It is a divalent group.)

[0050] This application (17) is based on the polymer described in this application (16), wherein R of formula (B) 3 It is an alkyl group.

[0051] This application (18) is a polymer according to this application (16) or (17) having repeating units represented by the formula (C).

[0052] This application (19) is a polymer having repeating units as shown in formula (B-1).

[0053]

[0054] (In formula (B-1), R) 4 (It is a divalent group.)

[0055] This application (20) is a liquid-repellent material comprising any one of the polymers described in any one of (16) to (19) of this application.

[0056] The effects of the invention

[0057] The polymer of this application has excellent photocurability because it is a polymer (1) having repeating units shown in the aforementioned formula (A), repeating units shown in the aforementioned formula (B), and / or repeating units shown in the aforementioned formula (C), or a polymer (2) having repeating units shown in the aforementioned formula (B-1).

[0058] The liquid-repellent material of this application has excellent photocurability because it contains the polymer of this application.

[0059] The photosensitive composition of this application has excellent photocurability because it contains the polymer of this application.

[0060] The cured product of this application is formed by curing the photosensitive composition of this application, and therefore has excellent alkaline developability (resolution after development) and liquid repellency.

[0061] The method for manufacturing a substrate with a patterned film according to this application includes: a film-forming step, in which the photosensitive composition of this application, which has excellent photocurability, is coated onto a substrate to form a film; an exposure step, in which the film after the aforementioned film-forming step is exposed to high-energy rays through a photomask to transfer the pattern of the photomask to the film; and a development step, in which the film after the aforementioned exposure step is developed with an alkaline developer to obtain the patterned film. Because the photosensitive composition of this application, which has excellent photocurability, is used, substrates with patterned films can be manufactured with high productivity. Furthermore, the patterned film on the substrate has excellent resolution because it is liquid-repellent and formed from a photosensitive composition that imparts good alkaline developability to the obtained cured material.

[0062] The substrate with patterned film of this application has a patterned film formed by patterning the cured material of this application on the substrate, and therefore is a substrate with liquid repellency and excellent resolution patterned film.

[0063] The image display device of this application has a "patterned film substrate of this application with a patterned film having liquid repellency and excellent resolution", so the color purity of the light-emitting layer is high and it is expected to have high brightness. Detailed Implementation

[0064] The present application is described in detail below, but the description of the constituent elements described below is only one example of the implementation of the present application and is not limited to these specific contents. Various modifications can be made within the scope of its spirit.

[0065] In this specification, the designation of "X to Y" in the description of numerical ranges, unless otherwise specified, means X or more and Y or less. For example, "1 to 5% by mass" means "1% or more and 5% or less by mass".

[0066] In this specification, “polymer,” “resin,” and “polymer” are synonyms and, unless otherwise noted, refer to high molecular weight compounds.

[0067] In this specification, "dike" and "wall" are synonyms, and unless otherwise noted, they refer to the raised portion of a patterned film with raised and recessed surfaces in an inkjet process.

[0068] While the reasons for achieving the aforementioned effects may not be clear in this application, it can be inferred that they are caused by the following mechanism.

[0069] The polymer (1) having repeating units as shown in the aforementioned formula (A), repeating units as shown in the aforementioned formula (B), and / or repeating units as shown in the aforementioned formula (C) can impart liquid repellency to the obtained cured product due to having repeating units as shown in the aforementioned formula (A), and has excellent photocurability due to having repeating units as shown in the aforementioned formula (B) and / or repeating units as shown in the aforementioned formula (C), and can impart good alkali developability to the obtained cured product.

[0070] Furthermore, the polymer (2) having the repeating unit shown in the aforementioned formula (B-1) has a methyl group bonded to silicon atoms in the repeating unit shown in the aforementioned formula (B-1), thus imparting liquid repellency to the obtained cured product. It also has excellent photocurability due to the presence of thiol groups in the repeating unit shown in the aforementioned formula (B-1), thus imparting good alkali developability to the obtained cured product.

[0071] Furthermore, since polymers (1) and (2) contain siloxane structures and are flexible skeletons, they become polymer chains suitable for coating the substrate surface, thus achieving a good recoil contact angle.

[0072] (polymer)

[0073] First, polymer (1) and polymer (2) which are polymers in this application will be described.

[0074] <Polymer (1)>

[0075] Polymer (1) is a polymer having repeating units as shown in formula (A) and repeating units as shown in formula (B) and / or repeating units as shown in formula (C). That is, polymer (1) is a polymer having repeating units as shown in formula (A) and simultaneously having repeating units as shown in formula (B) and / or repeating units as shown in formula (C). Since polymer (1) is a polymer having repeating units as shown in formula (A) and simultaneously having at least repeating units as shown in formula (B) or repeating units as shown in formula (C), it can be presumed that it can exert the aforementioned effects.

[0076] In polymer (1), the units in each repeating unit may be the same or different. Therefore, polymer (1) may also be a polymer composed of one or more units conforming to the repeating unit shown in formula (A) and one or more units conforming to the repeating unit shown in formula (B). Alternatively, polymer (1) may also be a polymer composed of one or more units conforming to the repeating unit shown in formula (A) and one or more units conforming to the repeating unit shown in formula (C). Alternatively, polymer (1) may also be a polymer composed of one or more units conforming to the repeating unit shown in formula (A), one or more units conforming to the repeating unit shown in formula (B), and one or more units conforming to the repeating unit shown in formula (C). In polymer (1), the units in each repeating unit are preferably the same.

[0077]

[0078] (In formula (A), R) 1 R 2 Each is an alkyl group, individually.

[0079]

[0080] (In formula (B), R) 3 It is a monovalent group. R 4 (It is a divalent group.)

[0081]

[0082] (In formula (C), R) 5 (It is a divalent group.)

[0083] In formula (A), R 1 R 2 Each is an alkyl group independently, but R 1 R 2 Preferably, the same functional groups are used. Thus, there is a tendency to form a symmetrical structure, which is easy to arrange on the surface of the film and can better achieve the effects of this application.

[0084] R 1 R 2 The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, further preferably 1 to 4, and particularly preferably 1. R 1 R 2 The fewer carbon atoms in an alkyl group, the more likely it is to impart better liquid repellency to the resulting cured product.

[0085] As R 1 R 2The alkyl group, for example, can be linear or branched, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among them, methyl, ethyl, and propyl are preferred for the reason that they tend to impart better liquid repellency to the obtained cured product, and methyl and ethyl are more preferred, and methyl is even more preferred.

[0086] It should be noted that since alkyl groups can be straight-chain or branched, propyl refers to n-propyl and isopropyl, and butyl refers to n-butyl, sec-butyl, and tert-butyl. The same applies to other groups that can be straight-chain or branched.

[0087] In equation (B), R 3 It is a monovalent group.

[0088] R 3 The number of carbon atoms in the monovalent group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1. R 3 The fewer carbon atoms in a monovalent group, the more likely it is to impart better liquid repellency to the resulting cured product.

[0089] As R 3 The monovalent group is not particularly limited, but examples include hydrogen atoms and monovalent hydrocarbon groups. Among them, monovalent hydrocarbon groups are preferred.

[0090] A monovalent hydrocarbon group may also have heteroatoms, but it is preferable not to have heteroatoms. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, fluorine atoms, chlorine atoms, etc. A monovalent hydrocarbon group may also have multiple such heteroatoms.

[0091] Examples of monovalent hydrocarbon groups include alkyl, alkenyl, alkynyl, and aryl groups. Among these, alkyl and aryl groups are preferred, and alkyl groups are more preferred.

[0092] As R 3 Alkyl groups, for example, with R 1 R 2 The alkyl groups are the same, and their preferred methods are also the same.

[0093] As R 3 The alkenyl group can be linear or branched, and examples include vinyl, allyl, propenyl, methyl vinyl, etc.

[0094] As R 3 The alkynyl group can be either linear or branched, and examples include ethynyl and propynyl.

[0095] As R 3The aryl group can be exemplified by, for example, phenyl, tolyl, xylyl, naphthyl, etc. Among them, phenyl is preferred.

[0096] In equation (B), R 4 It is a divalent group. R 4 Since the divalent group can be detached from the chain in a manner that allows the thiol group to react readily, there are no particular restrictions.

[0097] R 4 The number of carbon atoms in the divalent group is preferably 1 to 10, more preferably 1 to 7, further preferably 2 to 5, and particularly preferably 2 to 4.

[0098] As R 4 The divalent group can be exemplified by, for example, a divalent hydrocarbon group. Among these, a divalent hydrocarbon group is preferred.

[0099] A divalent hydrocarbon group may also have heteroatoms, but it is preferable not to have heteroatoms. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, fluorine atoms, chlorine atoms, etc. A divalent hydrocarbon group may also have multiple such heteroatoms.

[0100] Examples of divalent hydrocarbon groups include alkylene, alkenylene, ynylene, and arylene. Among these, alkylene and arylene are preferred, and alkylene is more preferred.

[0101] As R 4 The alkylene groups, for example, can be linear or branched, and examples include: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, decadecylene, hexadecylene, heptadecanyl, and octadecylene. Among these, ethylene, propylene, and butylene are preferred for the reason that the distance from the Si bond should not be too far or too close, and propylene is more preferred. Furthermore, the alkylene groups are preferably linear.

[0102] As R 4 The alkenyl group can be linear or branched, and examples include: vinylidene, propenylidene, butenylidene, pentenylidene, hexenylidene, octeneyl, etc.

[0103] As R 4 The ynyl group can be linear or branched, and examples include: ynylene, propynylene, butynylene, pentynoylene, hexynylene, heptynoylene, octynoylene, etc.

[0104] As R 4 Examples of arylene groups include: phenylene, naphthylene, biphenylene, etc.

[0105] In equation (C), R5 It is a divalent group. R 5 divalent groups and R 4 The divalent groups are the same, and since there are no particular limitations as long as the thiol group can be allowed to leave the chain autonomously in a manner that facilitates its reaction, R is acceptable. 5 divalent groups and R 4 The divalent groups are the same, and their preferred methods are also the same, but R 5 The divalent group also preferably has an oxygen atom.

[0106] For the repeating unit shown in equation (A), the following structure can be cited as a preferred approach.

[0107]

[0108] For the repeating unit shown in equation (B), the following structure can be cited as a preferred structure.

[0109]

[0110] For the repeating unit shown in equation (C), the following structure can be cited as a preferred structure.

[0111]

[0112] Although preferred structures of the repeating unit shown in Equation (A), Equation (B), and Equation (C) have been exemplified, combinations of the preferred structures of the repeating unit shown in Equation (A) and the preferred structures of the repeating unit shown in Equation (B); combinations of the preferred structures of the repeating unit shown in Equation (A) and the preferred structures of the repeating unit shown in Equation (C); and combinations of the preferred structures of the repeating unit shown in Equation (A), the preferred structures of the repeating unit shown in Equation (B), and the preferred structures of the repeating unit shown in Equation (C) are also preferred methods.

[0113] Polymer (1) is a polymer having the repeating unit shown in formula (A), the repeating unit shown in formula (B), and / or the repeating unit shown in formula (C) as described above, but preferably having both the repeating unit shown in formula (A) and the repeating unit shown in formula (C). This tends to better achieve the effects of this application (especially liquid repellency) and heat resistance. It can be inferred that because the polymer has a branched structure through the repeating unit shown in formula (C), the polymer is more likely to adopt a three-dimensional structure, resulting in less movement within the cured film. Furthermore, polymer (1) preferably has the repeating unit shown in formula (A), the repeating unit shown in formula (B), and the repeating unit shown in formula (C). This polymer (1) tends to have a lower molecular weight, and even with a lower molecular weight, it tends to impart better liquid repellency to the obtained cured product. Moreover, due to its low molecular weight, it tends to be readily compatible with photosensitive compositions.

[0114] The content of the repeating unit shown in formula (A) in 100 mol% of polymer (1) is preferably 30 to 99 mol%, more preferably 40 to 95 mol%, and even more preferably 50 to 90 mol%. As a result, there is a tendency to impart better liquid repellency to the obtained cured product.

[0115] The content of the repeating unit shown in formula (B) and the repeating unit shown in formula (C) (in the case of having both the repeating unit shown in formula (B) and the repeating unit shown in formula (C), the total content of the repeating unit shown in formula (B) and the repeating unit shown in formula (C)) in 100 mol% of polymer (1) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 50 mol%. This results in superior photocurability and a tendency to impart better alkali developability to the obtained cured product.

[0116] In addition to the repeating units shown in formula (A), formula (B), and formula (C), polymer (1) may also have other units (other units). Examples of other units include the structures described below. Other units may be used individually or in combination of two or more.

[0117]

[0118] The total content of the repeating unit shown in formula (A), the repeating unit shown in formula (B), and the repeating unit shown in formula (C) in 100 mol% of polymer (1) is preferably 50 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, more preferably 98 mol% or more, and most preferably 100 mol%. Therefore, there is a tendency to obtain the effects of this application more appropriately.

[0119] In this specification, the content of each unit in the polymer can be determined by... 29 The determination was performed using Si-NMR.

[0120] The weight-average molecular weight (Mw) of 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 effectively achieve the effects of this application, including reduced liquid drop (receding contact angle). This is presumably because movement within the polysiloxane-structured film is suppressed.

[0121] The dispersion (Mw / Mn) of 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.

[0122] In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer can be determined by the methods described in the examples.

[0123] The developing speed (DR) of 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.

[0124] In this specification, the development rate (DR) of the polymer can be determined by the method described in the examples.

[0125] Polymer (1) can be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. Block copolymers are preferred for the reason that the liquid drop (receding contact angle) of the same unit joint increases, while random copolymers are preferred for the reason that they impart solubility in solvents. To obtain the advantages of both block copolymers and random copolymers, it is preferable that the polymer has a random structure at both ends and a block structure in the center. More preferably, the random structure is composed of repeating units "shown by formula (A), repeating units "shown by formula (B), and / or repeating units "shown by formula (C)"; and the block structure is composed of "repeating units "shown by formula (A)".

[0126] The preferred manner of polymer (1) is as follows.

[0127] Method 1-1

[0128] Polymers having repeating units as shown in formula (A) and repeating units as shown in formula (B)

[0129] Formula (A): R 1 and R 2 methyl

[0130] Formula (B): R 3 It is an alkyl group (preferably methyl). R 4 It is an alkylene group (preferably a straight-chain alkylene group).

[0131] Methods 1-2

[0132] Polymers having repeating units as shown in formula (A) and repeating units as shown in formula (C)

[0133] Formula (A): Same as Method 1-1

[0134] Formula (C): R 5 It is an alkylene group (preferably a straight-chain alkylene group).

[0135] Methods 1-3

[0136] Polymers having repeating units as shown in formula (A), repeating units as shown in formula (B), and repeating units as shown in formula (C)

[0137] Formula (A): Same as Method 1-1

[0138] Formula (B): Same as Method 1-1

[0139] Formula (C): Same as method 1-2

[0140] Next, the monomers used in the polymerization of polymer (1) will be explained. The repeating units shown in formula (A), formula (B), and formula (C) can be synthesized, for example, using compounds shown in formula (a-1), difunctional compounds shown in formula (b), and trifunctional compounds shown in formula (c) as monomers, respectively. Alternatively, the repeating unit shown in formula (A) can also be synthesized using cyclic compounds as monomers, whereby the cyclic compounds are formed from repeating units of formula (A) such as those shown in formula (a-2). In this case, there is a tendency to synthesize polymers with relatively large weight-average molecular weights while also forming block structures.

[0141]

[0142] (In equation (a-1), R) 1 R 2 With R in equation (A) 1 R 2 Same. R 11 R 12 Each is an alkyl group, individually.

[0143]

[0144] (In formula (b), R) 3 R 4 With R in equation (B) 3 R 4 Same. R 13 R 14 Each is an alkyl group, individually.

[0145]

[0146] (In equation (c), R) 5 With R in equation (C) 5 Same. R 15 R 16 R 17 Each is an alkyl group, individually.

[0147]

[0148] R in equations (a-1), (b), and (c) 11 ~R 17 The alkyl group is usually methyl or ethyl.

[0149] The polymerization method of polymer (1) is not particularly limited, and a conventional polymerization reaction can be used. Polymer (1) can be suitably manufactured by a person skilled in the art using the monomers described above and a known polymerization method, for example, by referring to the method described in International Patent Publication No. 2022 / 181350. In addition, for polymer (1) with random structure at both ends and block structure in the middle, a cyclic siloxane (a-2) is first ring-opened polymerized under alkaline conditions to synthesize a polydimethylsiloxane homopolymer. Then, it is obtained by reacting (polymerizing) (b) or (c) at both ends. As an example of a method for manufacturing a polymer having such a structure, “Synthesis 2: Ring-opening polymerization of cyclic siloxane” in the manufacturing example of this application specification can be cited.

[0150] <Polymer (2)>

[0151] Polymer (2) is a polymer having repeating units as shown in formula (B-1). In polymer (2), the units in each repeating unit may be the same or different, but are preferably the same.

[0152]

[0153] (In formula (B-1), R) 4 (It is a divalent group.)

[0154] The repeating unit shown in equation (B-1) is equivalent to R of the repeating unit shown in equation (B). 3The unit is methyl, and apart from this, it also includes a preferred embodiment that is the same as the repeating unit shown in formula (B). This can be presumed because the R of the repeating unit shown in formula (B) 3 Since it is methyl, the obtained cured material can be imparted with liquid repellency even without the repeating unit shown by formula (A). It should be noted that since the matters already described for polymer (1) are basically the same for polymer (2), the following description will focus on the specific points in polymer (2). For matters not described for polymer (2), preferred embodiments are also included, which are basically the same as those for polymer (1).

[0155] The content of the repeating unit shown in formula (B-1) in 100 mol% of polymer (2) can also be 100 mol%, but is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 50 mol%. Thus, there is a tendency to obtain the effects of this application more appropriately.

[0156] In addition to the repeating unit shown in formula (B-1), polymer (2) may also have repeating units shown in formula (A), repeating units shown in formula (B) other than those shown in formula (B-1), repeating units shown in formula (C), and other units mentioned above. These units may be used individually or in combination of two or more. When polymer (2) has repeating units shown in formula (A) in addition to the repeating units shown in formula (B-1), polymer (2) becomes polymer (1) having repeating units shown in formula (B-1), and also includes the preferred embodiment, which is the same as polymer (1).

[0157] The preferred ranges for the weight-average molecular weight (Mw), dispersity (Mw / Mn), and development speed (DR) of polymer (2) are the same as those for polymer (1).

[0158] The preferred manner of polymer (2) is as follows.

[0159] Method 2-1

[0160] Polymers having the following repeating units as shown in formula (B-1)

[0161] Equation (B-1): R 4 It is an alkylene group (preferably a straight-chain alkylene group).

[0162] Method 2-2

[0163] Polymers having repeating units as shown in formula (A) and repeating units as shown in formula (B-1)

[0164] Formula (A): R 1and R 2 methyl

[0165] Formula (B-1): Same as Method 2-1

[0166] Methods 2-3

[0167] Polymers having repeating units as shown in formula (B-1) and repeating units as shown in formula (C)

[0168] Formula (B-1): Same as Method 2-1

[0169] Formula (C): R 5 It is an alkylene group (preferably a straight-chain alkylene group).

[0170] Methods 2-4

[0171] Polymers having repeating units as shown in formula (A), repeating units as shown in formula (B-1), and repeating units as shown in formula (C)

[0172] Formula (A): Same as Method 2-2

[0173] Formula (B-1): Same as Method 2-1

[0174] Formula (C): Same as method 2-3

[0175] The repeating unit shown in formula (B-1), for example, can be the R of a difunctional compound shown in formula (b). 3 The polymer (2) is synthesized by using a methyl compound as a monomer. The polymerization method of polymer (2) is not particularly limited and is the same as that of polymer (1).

[0176] (Liquid-repellent material)

[0177] The polymer of this application is suitable for use as a liquid-repellent material because it imparts liquid repellency to the resulting cured product. Accordingly, the liquid-repellent material of this application includes the polymer of this application. The polymer of this application can be used alone or in combination of two or more.

[0178] In the liquid-repellent material of this application, the content of the polymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, more preferably 98% by mass or more, and most preferably 100% by mass. Therefore, it is likely that the effects of this application can be more effectively obtained.

[0179] (Photosensitive composition)

[0180] Next, the photosensitive composition (photosensitive resin composition) of this application will be described. The photosensitive composition of this application comprises the polymer of this application. Specifically, the photosensitive composition of this application comprises: a polymer (1) having repeating units shown in formula (A) and repeating units shown in formula (B) and / or repeating units shown in formula (C); and / or a polymer (2) having repeating units shown in formula (B-1). The polymers of this application may be used alone or in combination of two or more.

[0181] The content of the polymer of this application 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. Therefore, it is likely that the effects of this application can be more readily obtained.

[0182] The following describes the compounding agents contained in the photosensitive composition of this application.

[0183] Solvent

[0184] The photosensitive composition of this application preferably contains a solvent. In the photosensitive composition of this application, the solvent is not particularly limited as long as it is soluble in the polymer of this application, but examples include: ketones, alcohols, polyols and their derivatives, ethers, esters, aromatic solvents, fluorinated solvents, etc. These can be used alone or in combination of two or more.

[0185] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isopentyl ketone, 2-heptylcyclopentanone, methyl isobutyl ketone, and 2-heptanone.

[0186] 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, sec-pentanol, 2-ethyl-1-butanol, dodecanol, hexadecyl alcohol, oleyl alcohol, etc.

[0187] Examples of polyols and their derivatives include: ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0188] Examples of ethers include: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0189] 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.

[0190] Examples of aromatic solvents include xylene and toluene.

[0191] Examples of fluorinated solvents include: Freon, Freon substitutes, perfluorinated compounds, and hexafluoroisopropanol.

[0192] In addition, to improve coatability, turpentine-based petroleum naphtha solvents or paraffin-based solvents, which are high-boiling-point weak solvents, can be used.

[0193] The solvent is preferably selected from at least one of the following groups: methyl ethyl ketone, cyclohexanone, methyl isopentyl 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 monomethyl ether monoacetate, dipropylene glycol monoethyl ether monoacetate, dipropylene glycol monopropyl ether monoacetate, dipropylene glycol monobutyl ether monoacetate, dipropylene glycol monophenyl ether monoacetate, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropanol. More preferably, methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

[0194] The amount of solvent in the photosensitive composition of this application is preferably in the range of 50 to 2000 parts by mass relative to 100 parts by mass of the polymer of this application (wherein, in the case where the photosensitive composition contains an alkali-soluble resin described later, this is the amount of the added resin). More preferably, it is in the range of 100 to 1000 parts by mass. By adjusting the amount of solvent, the film thickness of the formed resin film can be adjusted. If it is within the aforementioned range, a film thickness suitable for obtaining a resin film for obtaining a barrier for organic EL can be obtained.

[0195] Photopolymerization initiators

[0196] The photosensitive composition of this application preferably contains a photopolymerization initiator. In the photosensitive composition of this application, the photopolymerization initiator is not particularly limited to any substance that polymerizes monomers using high-energy rays such as electromagnetic waves or electron beams; well-known photopolymerization initiators can be used.

[0197] Photoradical initiators or photoacid generators can be used as photopolymerization initiators. These can be used alone, in combination, or in a mixture of two or more photoradical initiators or photoacid generators. Furthermore, by using additives in conjunction with photopolymerization initiators, living polymerization can also be achieved, depending on the circumstances. These additives can be well-known substances.

[0198] Photoradical initiators can be classified as, for example, intramolecularly cleaving type, where intramolecular bonds break due to absorption by electromagnetic waves or electron beams to generate free radicals, and hydrogen abstraction type, where free radicals are generated by combining hydrogen donors such as tertiary amines or ethers. Either type can be used. Photoradical initiators other than those listed above can also be used.

[0199] Specifically, photoradical initiators include: benzophenone-based, acetylphenylone-based, diketone-based, acylphosphine oxide-based, quinone-based, azobin-based, and oxime ester-based, etc.

[0200] Examples of benzophenone-based compounds include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4′-bis(dimethylamino)benzophenone, and 4,4′-bis(diethylamino)benzophenone. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4′-bis(diethylamino)benzophenone are preferred.

[0201] Examples of acetylphenyl ketones include: acetylphenyl ketone, 2-(4-toluenesulfonyloxy)-2-phenylacetylphenyl ketone, p-dimethylaminoacetylphenyl ketone, 2,2′-dimethoxy-2-phenylacetylphenyl ketone, p-methoxyacetylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]butane-1-one, etc. Among these, p-dimethylaminoacetylphenyl ketone and p-methoxyacetylphenyl ketone are preferred.

[0202] Examples of diketone compounds include 4,4′-dimethoxybenzoiloyl, methyl benzoylformate, and 9,10-phenanthroquinone. 4,4′-dimethoxybenzoiloyl and methyl benzoylformate are preferred.

[0203] Examples of acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0204] Examples of quinone compounds include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Camphorquinone and 1,4-naphthoquinone are preferred.

[0205] Examples of benzoin systems include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

[0206] Examples of oxime esters include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone. Among them, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone is preferred.

[0207] As a photoradical initiator, acylphosphine oxide-based or oxime ester-based initiators are preferred, and acylphosphine oxide-based initiators are more preferred.

[0208] Among commercially available photoradical initiators, preferred substances include those manufactured by BASF: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Darocur 1173, Lucirin TPO, Omnirad 819, etc.

[0209] Photoacid-generating agents, specifically, are onium salts formed by at least one cation selected from the group consisting of aromatic sulfonic acids, aromatic monium, aromatic diazonium, aromatic ammonium, thiaanthraium, thiaoxaneonium, 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.

[0210] Among them, bis(4-(diphenylsulfonium)phenyl)sulfide-bis(hexafluorophosphate), bis(4-(diphenylsulfonium)phenyl)sulfide-tetra(pentafluorophenyl)borate, and diphenylsulfonium hexafluorophosphate are preferred.

[0211] Commercially available photoacid generators include, for example: San-Apro Ltd.'s products: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S; Dow Chemical Japan Ltd.'s products: CYRACURE photocuring initiator UVI-6990, CYRACURE photocuring initiator UVI-6992, CYRACURE photocuring initiator UVI-6976; ADEKA Co., Ltd.'s products: ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER SP-172, ADEKA OPTOMER SP-300; Nippon Soda Co., Ltd.'s products: CI-5102, CI-2855; and 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; ESACURE 1064 and ESACURE 1187 manufactured by LAMBERTI SpA; Irgacure 250 manufactured by CibaSpecialty Chemicals, Inc., etc.

[0212] The content of the photopolymerization initiator in the photosensitive composition of this application is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the polymer of this application (wherein, in the case where the photosensitive composition contains an alkali-soluble resin described later). If the content of the photopolymerization initiator is 0.1 parts by weight or more, there is a tendency to obtain a sufficient crosslinking effect; if it is 30 parts by weight or less, there is a tendency to obtain better resolution and sensitivity.

[0213] <Compounds containing groups capable of reacting with thiol groups>

[0214] The photosensitive composition of this application preferably comprises a compound having a group capable of reacting with a thiol group.

[0215] As for the aforementioned groups capable of reacting with thiol groups, there is no particular limitation as long as the groups are capable of reacting with the thiol groups present in the polymer of this application, but examples include: olefinic carbon-carbon double bonds, epoxy groups, NCH2OR groups (where R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), oxetyl groups, and isocyanate groups. For example, olefinic carbon-carbon double bonds and epoxy groups are preferred, and olefinic carbon-carbon double bonds are more preferred. In other words, monomers having groups capable of reacting with thiol groups are preferably compounds having olefinic carbon-carbon double bonds and / or epoxy groups, and more preferably compounds having olefinic carbon-carbon double bonds (olefinic unsaturated compounds). Compounds having olefinic carbon-carbon double bonds and / or epoxy groups can undergo polymerization reactions on their own and are monomers that become the matrix in photosensitive compositions or substances that can become polymers.

[0216] "Alkene carbon-carbon double bond" refers to a carbon-carbon double bond that can react due to the action of free radicals. For example, the double bond of the benzene ring, which is stabilized by conjugation, does not meet the definition of "alkene carbon-carbon double bond".

[0217] From the viewpoint of enhanced reactivity, compounds having the aforementioned olefinic carbon-carbon double bonds are preferably those having olefinic carbon-carbon double bonds at their ends.

[0218] Furthermore, compounds having the aforementioned olefinic carbon-carbon double bond are preferably compounds having a (meth)acryloyl group. In short, a (meth)acryloyl group is preferred as the structure containing an olefinic carbon-carbon double bond. It should be noted that (meth)acryloyl group refers to either acryloyl or methacryloyl.

[0219] The compounds described above that have groups capable of reacting with thiol groups can be monofunctional or polyfunctional. In short, the compound may have only one group capable of reacting with thiol groups (preferably an alkene carbon-carbon double bond) in one molecule, or it may have two or more (preferably 2 to 8, more preferably 2 to 6) groups capable of reacting with thiol groups (preferably alkene carbon-carbon double bonds) in one molecule.

[0220] From the viewpoint of further improving sensitivity or enhancing physical properties during curing, the aforementioned compound having a group capable of reacting with a thiol group is preferably multifunctional. In other words, the aforementioned compound having a group capable of reacting with a thiol group is preferably a crosslinking agent having multiple groups capable of reacting with thiol groups.

[0221] By reacting with the thiol groups of the polymer in this application, the crosslinking agent can enable the polymer to adopt a crosslinked structure, which tends to increase the mechanical strength of the formed film.

[0222] Crosslinking agents can be well-known substances, specifically including: compounds that react formaldehyde or formaldehyde and lower alcohols with amino-containing compounds such as melamine, guanidineamine, phenylguanidineamine, urea, ethionide, propionide, and acetylenide, so that the hydrogen atoms of the amino group are replaced by hydroxymethyl or lower alkoxymethyl groups; polyfunctional epoxy compounds; polyfunctional oxobutane compounds; polyfunctional isocyanate compounds; polyfunctional acrylate compounds; and other polyfunctional olefinic unsaturated compounds. Here, substances using melamine are referred to as melamine-based crosslinking agents, substances using urea are referred to as urea-based crosslinking agents, substances using alkylurea such as ethionide and propionide are referred to as alkylurea-based crosslinking agents, and substances using acetylenide are referred to as acetylenide-based crosslinking agents. These crosslinking agents can be used alone or in combination of two or more.

[0223] As a crosslinking agent, it is preferred to select at least one of these crosslinking agents, particularly preferably acetylenoid crosslinking agents, polyfunctional epoxy compounds, polyfunctional olefin unsaturated compounds, more preferably polyfunctional olefin unsaturated compounds, and even more preferably polyfunctional acrylate compounds.

[0224] Examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine, with hexamethoxymethyl melamine being the preferred choice.

[0225] Examples of urea-based crosslinking agents include dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutyloxymethylurea, with dimethoxymethylurea being the preferred choice.

[0226] Examples of alkylene urea crosslinking agents include: mono- and / or dihydroxymethylated ethylene, mono- and / or dimethoxymethylated ethylene, mono- and / or diethoxymethylated ethylene, mono- and / or dipropoxymethylated ethylene, mono- and / or dibutoxymethylated ethylene, etc.; mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, mono- and / or dibutoxymethylated propylene urea, etc.; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

[0227] Examples of acetylenurea crosslinking agents include: mono-, di-, tri- and / or tetra-hydroxymethylated acetylenurea, mono-, di-, tri- and / or tetra-methoxymethylated acetylenurea, mono-, di-, tri- and / or tetra-ethoxymethylated acetylenurea, mono-, di-, tri- and / or tetra-propoxymethylated acetylenurea, and mono-, di-, tri- and / or tetra-butoxymethylated acetylenurea.

[0228] Examples of multifunctional epoxy compounds include aliphatic glycidyl ether polyepoxides and aliphatic glycidyl ether epoxides.

[0229] As a polyfunctional olefinic unsaturated compound, compounds having two or more olefinic carbon-carbon double bonds can be used without particular limitation. From the viewpoint of improved reactivity, polyfunctional olefinic unsaturated compounds preferably have olefinic carbon-carbon double bonds at their ends.

[0230] As a polyfunctional olefinic unsaturated compound, a polyfunctional (meth)acrylate compound is preferred. Examples of polyfunctional (meth)acrylate compounds include: ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, di(trimethylolpropane)tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, and other polyacrylate polyol esters; acrylate epoxy esters such as dimethacrylate of bisphenol A diglycidyl ether and dimethacrylate of hexanediol diglycidyl ether; and urethane (meth)acrylates obtained by reacting polyisocyanates with hydroxyl-containing (meth)acrylates such as hydroxyethyl (meth)acrylate.

[0231] Commercially available polyfunctional (meth)acrylate compounds include, for example: polyfunctional (meth)acrylates (e.g., products manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP), polyethylene glycol diacrylates (e.g., products manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: A-200, A-400, A-600), and urethane acrylates (e.g., products manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200).

[0232] Preferred substances are exemplified below as multifunctional acrylate compounds.

[0233]

[0234]

[0235]

[0236]

[0237] The content of the compound (preferably a crosslinking agent) having a group capable of reacting with a thiol group in the photosensitive composition of this application is preferably 10 to 400 parts by mass relative to 100 parts by mass of the polymer of this application (wherein, in the case where the photosensitive composition contains an alkali-soluble resin described later, this is the amount of the resin added). Wherein, if the content of the compound (preferably a crosslinking agent) having a group capable of reacting with a thiol group is 10 parts by mass or more, there is a tendency to obtain a sufficient crosslinking effect; if it is 400 parts by mass or less, there is a tendency to obtain better resolution and sensitivity.

[0238] Alkali-soluble resins

[0239] The photosensitive composition of this application preferably contains an alkali-soluble resin. If the photosensitive composition of this application contains an alkali-soluble resin, there is a tendency to obtain a better shape of the septum obtained from the photosensitive composition of this application. The alkali-soluble resin can be used alone or in combination of two or more types.

[0240] As an alkali-soluble resin, there are no particular limitations as long as the resin can be dissolved in alkali. Examples include alkali-soluble phenolic varnish resin.

[0241] Alkali-soluble phenolic varnish resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

[0242] Examples of phenols include: phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylcresol, 3,4,5-trimethylcresol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, 1,2,3-phenylpyrogallol, 1,3,5-phenylpyrogallol, thymol, isothymol, etc. These phenols can be used alone or in combination of two or more.

[0243] Examples of aldehydes include: formaldehyde, trioxane, polyoxymethylene, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, p-phthalaldehyde, isophthalaldehyde, etc.

[0244] 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 can be used alone or in combination of two or more.

[0245] In addition, examples of alkali-soluble resins include: acid adducts of (meth)acrylate epoxy esters obtained by reacting (meth)acrylate with an epoxy compound having two glycidyl ether groups derived from bisphenols (bisphenol-type epoxy compounds), and reacting a polycarboxylic acid or its anhydride with the obtained compound having hydroxyl groups (acid-modified (meth)acrylate epoxy ester-based alkali-soluble resins). Commercially available acid-modified epoxy acrylate systems include, for example, products manufactured by Nippon Kayaku Co., Ltd., under the following 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.

[0246] Epoxides derived from bisphenols and having two glycidyl ether groups refer to epoxy compounds or equivalent substances obtained by reacting bisphenols with epihaloalcohols and having two glycidyl ether groups. During this reaction, oligomerization of the diglycidyl ether compound is generally present, resulting in epoxy compounds containing more than two bisphenol backbones.

[0247] Examples of bisphenols include: bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, 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-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichloro ... Dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) Propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene Fluorene, 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′-biphenyl, 3,3′-biphenyl, etc. These can be used alone or in combination of two or more.

[0248] Examples of polycarboxylic acids or their anhydrides include monocarboxylic or tricarboxylic acid anhydrides, diacarboxylic acid anhydrides, etc. These can be used alone or in combination of two or more.

[0249] Examples of monoacid anhydrides that are dicarboxylic or tricarboxylic acids include: monoacid anhydrides of alicyclic dicarboxylic or tricarboxylic acids, monoacid anhydrides of alicyclic dicarboxylic or tricarboxylic acids, and monoacid anhydrides of aromatic dicarboxylic or tricarboxylic acids. These can be used alone or in combination of two or more. Examples of monoacid anhydrides that are alicyclic dicarboxylic or tricarboxylic acids include: succinic acid, acetosuccinic acid, maleic acid, adipic acid, itconic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, α-ketoglutaric acid, pimelic acid, sebacic acid, octanoic acid, and diethylene glycol. Examples of monoacid anhydrides that are alicyclic dicarboxylic or tricarboxylic acids include: cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornane dicarboxylic acid. In addition, examples of monoanhydrides that are aromatic dicarboxylic or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, 1,2,4-benzenetricarboxylic acid, etc.

[0250] Examples of dianhydrides that are tetracarboxylic acids include: dianhydrides of alicyclic tetracarboxylic acids, dianhydrides of alicyclic tetracarboxylic acids, and dianhydrides of aromatic tetracarboxylic acids. These can be used alone or in combination of two or more. Examples of dianhydrides that are alicyclic tetracarboxylic acids include: butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc. Examples of dianhydrides that are alicyclic tetracarboxylic acids include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, etc. Furthermore, examples of dianhydrides that are aromatic tetracarboxylic acids include: dianhydrides of 1,2,4,5-phenyltetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, etc.

[0251] From the viewpoint of the developability and resolution of the photosensitive composition, the weight-average molecular weight of the alkali-soluble resin component is preferably 1,000 to 50,000.

[0252] The content of alkali-soluble resin in the photosensitive composition of this application is preferably 300 to 10,000 parts by weight, more preferably 500 to 7,000 parts by weight, relative to 100 parts by weight of the polymer of this application. If the content of alkali-soluble resin is less than 10,000 parts by weight, there is a tendency to obtain better liquid repellency.

[0253] <Naphthoquinone diazido group compounds>

[0254] The photosensitive composition of this application may also contain a naphthoquinone diazide compound. If the photosensitive composition of this application contains a naphthoquinone diazide compound, there is a tendency to obtain a better septum shape from the photosensitive composition of this application.

[0255] There are no particular limitations on the use of naphthoquinone diazido compounds as photosensitive components commonly used in photoresist compositions for i-line applications.

[0256] Examples of naphthoquinone-containing diazidoyl compounds include: naphthoquinone-1,2-diazido-4-sulfonate compounds, naphthoquinone-1,2-diazido-5-sulfonate compounds, naphthoquinone-1,2-diazido-6-sulfonate compounds, naphthoquinone-1,2-diazido-sulfonate compounds, o-benzoquinone diazido-sulfonate compounds, and o-anthraquinone diazido-sulfonate compounds. Among these, naphthoquinone-1,2-diazido-4-sulfonate compounds, naphthoquinone-1,2-diazido-5-sulfonate compounds, and naphthoquinone-1,2-diazido-6-sulfonate compounds are preferred for their excellent solubility. These compounds can be used alone or in combination of two or more.

[0257] The content of the naphthoquinone diazido group compound in the photosensitive composition of this application is preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the polymer of this application (wherein, in the case where the photosensitive composition contains the aforementioned alkali-soluble resin). If it is 60 parts by weight or less, there is a tendency to obtain better sensitivity as a photosensitive composition.

[0258] <Alkaline compounds>

[0259] The photosensitive composition of this application may also contain a basic compound. The basic compound has the effect of slowing down the diffusion rate of the acid generated by the aforementioned photoacid-generating agent within the film of the photosensitive composition of this application.

[0260] By mixing alkaline compounds, the acid diffusion distance can be adjusted, which tends to improve the shape of the dike.

[0261] Furthermore, by mixing alkaline compounds, even if the time from the formation of the barrier to exposure is long, the barrier is not easily deformed, and there is a tendency to stably form a barrier with the desired accuracy.

[0262] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Aliphatic amines are preferred, specifically secondary or tertiary aliphatic amines and alkanolamines. These can be used alone or in combination of two or more.

[0263] Examples of aliphatic amines include alkylamines or alkanolamines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-nonylamine, di-n-decylamine, di-dodecylamine, dicyclohexylamine, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-octanolamine, etc.

[0264] The preferred amines are dialkylamines, trialkylamines, and alkanolamines, with alkanolamines being more preferred. Among the alkanolamines, triethanolamine and triisopropanolamine are preferred.

[0265] Examples of aromatic 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, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, and other aniline derivatives; 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, 4,4 Heterocyclic amines such as dimethylimidazoline; hindered amines such as bis(1,2,2,6,6-pentamethyl-4-piperidinyl ester) sebacate; nitrogen-containing alcohols such as 2-hydroxypyridine, carbamophenol, 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, and 1-[2-(2-hydroxyethoxy)ethyl]piperazine; methylpyridine, dimethylpyridine, pyrrole, piperidine, piperazine, indole, and hexamethylenetetramine.

[0266] The content of the alkaline compound in the photosensitive composition of this application is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the polymer of this application (wherein, in the case where the photosensitive composition contains the aforementioned alkali-soluble resin). If the amount of alkaline compound is 0.001 parts by mass or more, the effect as an additive can be sufficiently obtained; if it is 2 parts by mass or less, there is a tendency to obtain better resolution and sensitivity.

[0267] <Other Additives>

[0268] The photosensitive composition of this application may also contain other additives as needed. Examples of other additives include: dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, defoamers, compatibilizers, sealing agents, antioxidants, chain transfer agents, and various other additives. These can be used alone or in combination of two or more.

[0269] These other additives can also be well-known substances.

[0270] It should be noted that, as a surfactant, it is preferably either a fluorinated or a silicone surfactant (fluorinated surfactant and silicone surfactant, surfactant containing both fluorine and silicon atoms), or contains two or more of them.

[0271] By compounding adhesives, there is a tendency to achieve better adhesion to the substrate. Examples of adhesives include silane coupling agents and phosphate esters. Examples of silane coupling agents include sulfide-based, mercapto-based, capped mercapto-based, vinyl-based, amino-based, epoxypropoxy-based, nitro-based, and chlorine-based agents. These can be used alone or in combination of two or more. Vinyl-based agents are preferred, and (meth)acryloyl-based phosphorus compounds are more preferred. Examples of (meth)acryloyl-based phosphorus compounds include KBM-503 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

[0272] As phosphate esters, phosphate esters having vinyl, acryloyl, or methacryloyl groups at the crosslinking site are preferred, and examples include KAYAMER-PM21 manufactured by Nippon Kayaku Co., Ltd.

[0273] The content of the adhesive in the photosensitive composition of this application is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the polymer of this application (wherein, in the case where the photosensitive composition contains the aforementioned alkali-soluble resin). This tends to result in better adhesion to the substrate.

[0274] Examples of coloring agents include pigments and dyes. These can be used alone or in combination of two or more.

[0275] Examples of coloring pigments include: titanium dioxide, carbon black, graphite, iron oxide, and coal powder; inorganic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, perylene, anthraquinone, carbazole violet, anthraquinone, azo orange, styroquinone yellow, isoindoline yellow, azo yellow, indanthrin blue, dibromoanthanthrone red, perylene red, azo red, and anthraquinone red; and aluminum powder, alumina powder, bronze powder, copper powder, tin powder, zinc powder, iron phosphide, and micronized titanium dioxide.

[0276] It should be noted that, among the examples of usable organic pigments, those whose color index names include the following numbers are not limited to these.

[0277] 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.

[0278] Pigment Orange: 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

[0279] 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.

[0280] Pigment Green 7, 36, 58, etc.

[0281] Pigment Blue in 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.

[0282] Pigment purple 19, 23, 37, etc.

[0283] Examples of coloring dyes include: monoazo dyes, diazo dyes, metal salt monoazo dyes, anthraquinone dyes, methylene dyes, phthalocyanine dyes, and triarylmethane dyes.

[0284] Colorants are typically mixed with other formulation components in the form of a colorant dispersion dispersed in a solvent, at which point a dispersant may be added. The dispersant can be any well-known compound used for pigment (colorant) dispersion (compounds commercially available under names such as dispersant, dispersing wetting agent, dispersion accelerator, etc.). Examples of dispersants include, for example, cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative-type dispersants (dispersion aids). These can be used alone or in combination of two or more. The amount of dispersant in the formulation is preferably 1 to 35% by mass relative to the colorant, more preferably 2 to 25% by mass. It should be noted that high-viscosity substances such as resins generally have a stabilizing effect on dispersion, but those without dispersion-promoting ability are not considered dispersants. However, the use of substances intended for stabilizing dispersion is not limited to these substances.

[0285] The content of colorant in the photosensitive composition of this application is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the polymer of this application (wherein, in the case where the photosensitive composition contains the aforementioned alkali-soluble resin).

[0286] Chain transfer agents are components that, in a free radical polymerization system, absorb free radicals in a self-growing polymer chain, thereby generating new free radicals. By using chain transfer agents, the degree of polymerization can be adjusted, and the properties of the cured film can be modified. Examples of chain transfer agents include: aromatic hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and chloroform; thiols such as octylthiol, n-butylthiol, n-pentylthiol, n-hexadecylthiol, n-tetradecylthiol, n-dodecylthiol, tert-tetradecylthiol, and tert-dodecylthiol; hexanedithiol, decanedithiol, 1,4-butanediol dimercaptopropionate, 1,4-butanediol dimercaptoacetic acid, ethylene glycol dimercaptoacetic acid, ethylene glycol dimercaptopropionate, trimethylolpropane tri(mercaptoacetic acid), trimethylolpropane trimercaptopropionic acid, trimethylolpropane tri(3-mercaptobutyric acid), pentaerythritol tetramercaptoacetic acid, pentaerythritol tetramercaptopropionate, and tri(2- Thiol compounds such as hydroxyethyl ester (hydroxyethyl ester) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and pentaerythritol tetrakis(3-mercaptobutyric acid) ester; sulfides such as methyl dixanthranilate disulfide, ethyl dixanthranilate disulfide, isopropyl dixanthranilate disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinene, α-terpinene, γ-terpinene, and dipentene. These can be used alone or in combination of two or more. Thiol compounds are preferred.

[0287] In the photosensitive composition of this application, the content of the chain transfer agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the polymer of this application (wherein, in the case where the photosensitive composition contains the aforementioned alkali-soluble resin). This maintains suitable curability and allows for adjustment of the development contrast with the unexposed portion.

[0288] (Method for manufacturing cured material, method for manufacturing substrate with patterned film)

[0289] Next, a method for manufacturing a cured product using the photosensitive composition of this application and a method for manufacturing a substrate with a patterned film will be described.

[0290] The method for manufacturing a cured product (a method for manufacturing a substrate with a patterned film) of this application includes (1-1) a film-forming process, (1-2) an exposure process and (1-3) a development process, and may further include (1-4) a baking process.

[0291] The following describes each process.

[0292] (1-1) Film-making process

[0293] First, in the film-forming process, the photosensitive composition of this application is coated onto a substrate to form a film.

[0294] Specifically, after coating the photosensitive composition of this application onto a substrate, the photosensitive composition is formed into a film by heating.

[0295] There are no particular limitations on the heating conditions, but 80–100°C and 60–200 seconds are preferred.

[0296] Therefore, solvents and other substances contained in the photosensitive composition can be removed.

[0297] The substrate can be made of silicon wafers, metal, glass, ITO substrates, etc.

[0298] Alternatively, organic or inorganic films can be pre-formed on the substrate. For example, it can be an anti-reflective film, a lower layer of a multilayer photoresist, or a pattern formed thereon. Furthermore, the substrate can be pre-cleaned. For example, ultrapure water, acetone, or alcohols (methanol, ethanol, isopropanol) can be used for cleaning.

[0299] As a method for coating the photosensitive composition of this application onto a substrate, for example, any suitable coating apparatus such as a slot coater, die coater, rotary gravure coater, dip coater, or spin coater can be used. Alternatively, dip coating, spray coating, or roll coating can also be performed.

[0300] Here, the film formed on the substrate can be formed on the entire surface of the substrate or on a portion thereof.

[0301] The thickness of the membrane is preferably 1 to 500 μm. If the membrane becomes thinner than 1 μm, the mechanical strength of the membrane may decrease. If the thickness exceeds 500 μm, the surface unevenness tends to increase, making it difficult to obtain a flat membrane.

[0302] (1-2) Exposure process

[0303] Next, in the exposure process, the film after the aforementioned film-making process is exposed to high-energy rays through a photomask to transfer the pattern of the photomask onto the film.

[0304] Specifically, the desired photomask is placed on the exposure device, and the film after the aforementioned film-making process is exposed to high-energy rays through the photomask.

[0305] The high-energy rays are preferably selected from at least one of the group consisting of ultraviolet rays, gamma rays, X-rays and alpha rays.

[0306] The preferred exposure dose for high-energy rays is 1–200 mJ / cm². 2 More preferably 10–100 mJ / cm 2 .

[0307] (1-3) Developing process

[0308] Next, in the developing process, the film after the aforementioned exposure process is developed with an alkaline developing solution to obtain a patterned film.

[0309] Specifically, the film after the exposure process is developed with an alkaline aqueous solution to create a patterned film.

[0310] That is, a patterned film is made by dissolving either the exposed portion or the unexposed portion of the film in an alkaline aqueous solution.

[0311] As an alkaline aqueous solution, for example, tetramethylammonium hydroxide (TMAH) aqueous solution, tetrabutylammonium hydroxide (TBAH) aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, etc. can be used.

[0312] When the alkaline aqueous solution is a tetramethylammonium hydroxide (TMAH) aqueous solution, its concentration is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass.

[0313] The development method can be any well-known method, such as dip coating, puddle method, spray coating, etc.

[0314] The developing time (the time the developing solution contacts the film) is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.

[0315] After development, a step of cleaning the pattern film with deionized water can be added as needed. For the cleaning method and time, 10 seconds to 3 minutes is preferred, and 30 seconds to 2 minutes is more preferable.

[0316] (1-4) Baking process

[0317] In the baking process, after the aforementioned developing process, the aforementioned patterned film is baked to cure it and obtain a cured product.

[0318] Specifically, after the aforementioned developing process, the aforementioned patterned film is cured by heating and baking to produce a cured product. The cured product of this application is obtained by curing the photosensitive composition of this application.

[0319] Baking can be carried out on a heating plate, and the baking conditions are preferably below 140°C (preferably 60-130°C) for 10-120 minutes.

[0320] It should be noted that in the aforementioned manufacturing method, UV ozone treatment or oxygen plasma treatment can also be performed after the baking process (1-4). Among these, UV ozone treatment is preferred.

[0321] This removes organic matter remaining in the recesses of the aforementioned pattern film, reduces uneven wetting of dripping ink, and thus prevents malfunctions of the display element.

[0322] The cured product obtained by this operation has excellent liquid repellency and can therefore be used as a barrier for organic EL displays, micro LED displays and quantum dot displays.

[0323] In short, the curing method of this application can also be used to manufacture dams for organic EL displays, micro LED displays, and quantum dot displays. In this way, the aforementioned patterned film functions as a dam (partition).

[0324] Furthermore, the substrate with patterned film of this application manufactured in this manner is a substrate with patterned film formed by patterning the cured material of this application on the substrate, and can be used as a substrate for organic EL displays, micro LED displays, and quantum dot displays, etc.

[0325] In short, the method for manufacturing a substrate with a patterned film according to this application can also be used to manufacture substrates for organic EL displays, micro LED displays, and quantum dot displays. In this way, the aforementioned patterned film functions as a partition. Accordingly, the substrate with a patterned film according to this application can be suitably used as a substrate for forming display elements using an inkjet printing method.

[0326] In the method for manufacturing the cured product of this application, the photosensitive composition can be cured at low temperatures (e.g., below 140°C). Therefore, when manufacturing barrier materials for organic EL displays, micro-LED displays, and quantum dot displays using the method for manufacturing the cured product of this application, barrier materials can be formed without causing significant thermal damage to the light-emitting layer.

[0327] In the method for manufacturing a substrate with a patterned film according to this application, the photosensitive composition can be cured at a low temperature. Therefore, when manufacturing substrates for organic EL displays, micro LED displays, and quantum dot displays using the method for manufacturing a substrate with a patterned film according to this application, the substrate can be formed without causing significant thermal damage to the light-emitting layer.

[0328] In addition, the cured product of this application can also be used appropriately as a simple film without a pattern.

[0329] In this case, the cured product of this application has excellent water / oil repellency due to its low surface free energy. For example, it can be used as a film to protect the substrate in various applications such as water and oil repellent agents for treating fabrics (substrates) such as clothing or sealants for protecting substrates (substrates) of precision-machined semiconductors.

[0330] (Image display device)

[0331] The image display device of this application has a substrate with a patterned film as described in this application. Specifically, the image display device of this application has a display element using a substrate with a patterned film as described in this application (a cured product of this application).

[0332] Examples of image display devices for this application include organic EL displays, micro LED displays, and quantum dot displays.

[0333] Example

[0334] The following examples illustrate more specific embodiments of the present application. However, the present application is not limited to these examples.

[0335] 1. Polymer Synthesis

[0336] The analysis of the obtained polymers was performed using the following methods.

[0337] [Determination of the molar ratio of each structural unit of the polymer]

[0338] The molar ratio of each structural unit in the polymer is determined by... 1 H-NMR, 29 Si-NMR or 13 The value is determined by the C-NMR measurement.

[0339] [Determination of polymer molecular weight] GPC

[0340] The weight-average molecular weight (Mw) and molecular weight dispersion (the ratio of number-average molecular weight Mn to weight-average molecular weight Mw; Mw / Mn) of the polymer were determined using high-performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, model HLC-8320GPC). One ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) were connected in series. Tetrahydrofuran (THF) was used as the developing solvent, and polystyrene was used as the standard. A refractive index difference detector was used.

[0341] [Determination of polymer development speed (DR)]

[0342] The polymer was coated onto a glass substrate using a spin coater at 1000 rpm, and then heated on a hot plate at 80°C for 150 seconds to form a resin film with a thickness of 1 μm. The film thickness was then measured.

[0343] The formed film was immersed in a 2.38% TMAH aqueous solution, and the film thickness was measured after 10 s, 20 s, and 30 s to confirm the degree of film development.

[0344] The film thickness was determined by scribing a line on the substrate where the film was formed, marking that point as 0, and then confirming the difference using a laser microscope.

[0345] Next, a summary of the monomers used will be provided. The monomers listed in Tables 1A and 1B are as follows. It should be noted that reagents from Tokyo Chemical Industries, Ltd. were used for all of them.

[0346] DEDMS: Compounds represented by the following formula (diethoxydimethylsilane)

[0347]

[0348] SH (2-functional): Compounds represented by the following formula (3-mercaptopropylmethyldimethoxysilane (MrPMDMS))

[0349]

[0350] SH (3-functional): Compounds represented by the following formula (3-mercaptopropyltrimethoxysilane (MrPTMS))

[0351]

[0352] Acryloyl group (2-functional): 3-Acryloyloxypropylmethyldimethoxysilane (APMDMS)

[0353] Acryloyl group (3-functional): 3-Acryloyloxypropyltrimethoxysilane (APTMS)

[0354] Vinyl (3-functional): Vinyltrimethoxysilane (VTMS)

[0355] Epoxy group (3-functional): 3-Epoxypropoxypropyltrimethoxysilane (GPTMS)

[0356] The polymer was synthesized using the two methods disclosed below. It should be noted that, when using method 2, the amount of DEDMS in the table is derived from the amount of hexamethylcyclotrisiloxane.

[0357] Synthesis 1: Polycondensation of alkoxysilanes under acid catalyst

[0358] Synthesis 2: Ring-opening polymerization of cyclic siloxanes

[0359] (Production Example 1) Synthesis of Polymer 1

[0360] Use of Synthesis Method 1

[0361] In a 100 mL glass flask equipped with a magnetic stirrer, 33.4 g of DEDMS (0.23 mol), 4.61 g of MrPMDMS (0.03 mol), 9.93 g of ultrapure water (0.55 mol), and 0.63 g of acetic acid (product of Tokyo Chemical Industry Co., Ltd.) (0.11 mol) were added at room temperature (about 20 °C), and the temperature was raised to an internal temperature of 75 °C and allowed to react overnight. 70 mL of isopropyl ether (product of FUJIFILM Wako Pure Chemical Corporation) was added to the reaction solution. After transferring to a 200 mL glass flask equipped with a magnetic stirrer, 50 mL of ultrapure water was added while stirring, and the liquid separation operation was performed again. The product was obtained as a colorless and transparent solution from the organic layer. 48.73 g of 2-acetoxy-1-methoxypropyl glycol ester (product of Kanto Chemical Co., Inc.; hereinafter designated as PGMEA) was added to this solution, and water and ethanol were removed by distillation under reduced pressure. 54.75 g (10.15 g of solid component) of liquid-repellent polysiloxane 1 was obtained as a colorless and transparent solution with a yield of 54%.

[0362] <NMR Measurement Results> The composition ratio of each structural unit of liquid-repellent polysiloxane 1 is expressed in mol ratio. Structural unit based on DEDMS: Structural unit based on MrPMDMS = 9:1.

[0363]

[0364] (Production Example 2) Synthesis of Polymer 2

[0365] Use of Synthesis Method 2

[0366] In a 200 mL glass flask equipped with a magnetic stirrer, 0.05 L (0.62 mol) of tetrahydrofuran (product of Kanto Chemical Co., Inc.) was used as a reaction solvent at room temperature (about 20 °C), and 20.0 g of HMCTS (0.09 mol), 0.16 g of ultrapure water (9.00×10 -3 mol), and 0.13 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter designated as TBD.) (9.34×10 -4 mol) were added, and the temperature was raised to an internal temperature of 30 °C and allowed to react for 1 hour. 1.8 g of MrPMDMS (0.01 mol) and 0.02 g of ultrapure water (1.11×10-3 (in mol), and the reaction was further carried out at an internal temperature of 30 °C for 20 minutes. 0.05 g of acetic acid (product of Tokyo Chemical Industry Co., Ltd.) (9.34×10 -4 (in mol) was added to the reaction system for neutralization, and then the product was concentrated by distillation under reduced pressure. Next, after adding heptane (30 mL) to the product to form a solution, methanol (50 mL) was added, stirred and allowed to stand, and the supernatant was removed. After repeating the washing with this methanol again, 51.44 g of PGMEA (0.39 mol) was added, and water, methanol, and heptane were removed by distillation under reduced pressure, and 71.63 g (solid component 17.93 g) of liquid-repellent polysiloxane 2 was obtained as a colorless transparent solution with a yield of 87%.

[0367] <NMR measurement results> The composition ratio of each structural unit of the liquid-repellent polysiloxane 2 is expressed in mol ratio, and the structural unit based on hexamethylcyclotrisiloxane: the structural unit based on MrPMDMS = 9:1.

[0368]

[0369] (Production Example 3) Synthesis of Polymer 3

[0370] Use of Synthesis Method 1

[0371] In a 100 mL glass flask equipped with a stir bar, 33.4 g of DEDMS (0.23 mol), 4.91 g of MrPTMS (0.03 mol), 9.93 g of ultrapure water (0.55 mol), and 0.63 g of acetic acid (product of Tokyo Chemical Industry Co., Ltd.) (0.11 mol) were added at room temperature (about 20 °C), and the temperature was raised to an internal temperature of 75 °C and the reaction was carried out overnight. 70 mL of isopropyl ether (product of FUJIFILM Wako Pure Chemical Corporation) was added to the reaction solution, and after transferring it to a 200 mL glass flask equipped with a stir bar, 50 mL of ultrapure water was added while stirring, and the liquid separation operation was carried out again, and the product was obtained as a colorless transparent solution from the organic layer. 48.73 g of 2-acetoxy-1-methoxypropyl glycol ester (product of Kanto Chemical Co., Inc.; hereinafter referred to as PGMEA) was added to this solution, and water and ethanol were removed by distillation under reduced pressure, and 54.75 g (solid component 10.95 g) of liquid-repellent polysiloxane 3 was obtained as a colorless transparent solution with a yield of 55%.

[0372] <NMR measurement results> The composition ratio of each structural unit of the liquid-repellent polysiloxane 3 is expressed in mol ratio, and the structural unit based on DEDMS: the structural unit based on MrPTMS = 9:1.

[0373]

[0374] (Production Example 4) Synthesis of Polymer 4

[0375] Use of Synthesis Method 2

[0376] In a 200 mL glass flask equipped with a stir bar, at room temperature (about 20 °C), using 0.05 L (0.62 mol) of tetrahydrofuran (product of Kanto Chemical Co., Inc.) as the reaction solvent, 20.0 g of hexamethylcyclotrisiloxane (product of Tokyo Chemical Industry Co., Ltd.) (0.09 mol), 0.16 g of ultrapure water (9.00×10 -3 mol), 0.13 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (product of Tokyo Chemical Industry Co., Ltd. hereinafter designated as TBD) (9.34×10 -4 mol) were added, and the temperature was raised to an internal temperature of 30 °C and the mixture was reacted for 1 hour. 1.96 g of MrPTMS (0.01 mol), 0.02 g of ultrapure water (1.11×10 -3 mol) were added, and the mixture was further reacted at an internal temperature of 30 °C for 20 minutes. 0.05 g of acetic acid (product of Tokyo Chemical Industry Co., Ltd.) (9.34×10 -4 mol) was added to the reaction system for neutralization, and then the product was concentrated by distillation under reduced pressure. Next, after adding heptane (30 mL) to the product to form a solution, methanol (50 mL) was added, stirred, and allowed to stand, and the supernatant was removed. After repeating the washing with this methanol again, 51.44 g of PGMEA (0.39 mol) was added, and water, methanol, and heptane were removed by distillation under reduced pressure, and 71.63 g (18.14 g of solid content) of liquid-repellent polysiloxane 4 was obtained as a colorless transparent solution with a yield of 85%.

[0377] <NMR Measurement Results> The composition ratio of each structural unit of liquid-repellent polysiloxane 4 is expressed as a molar ratio, and the structural unit based on hexamethylcyclotrisiloxane: the structural unit based on MrPTMS = 9:1.

[0378]

[0379] (Production Examples 5 to 32) Synthesis of Polymers 5 to 32

[0380] The monomer composition and polymerization method shown in Table 1A and Table 1B were changed, and except for this point, the same procedures as in Production Examples 1 to 4 were carried out to synthesize Polymers 5 to 32.

[0381] The monomer composition and weight-average molecular weight of each polymer are shown in Tables 1A and 1B. It should be noted that Table 1A shows polymers of this application with thiol groups as crosslinking sites, and Table 1B shows polymers of comparative examples with acrylate groups, vinyl groups, or epoxy groups as crosslinking sites.

[0382] [Table 1A]

[0383]

[0384] [Table 1B]

[0385]

[0386]

[0387] Polymer structures of polymers 1, 2, 5, and 6

[0388]

[0389] Polymer structures of polymers 3, 4, 7, 8, 9, and 10

[0390]

[0391] Polymer structures of polymers 11, 12, 15, and 16

[0392]

[0393] Polymer structures of polymers 13, 14, 17, 18, and 19

[0394]

[0395] Polymer structures of polymers 20 and 21

[0396]

[0397] Polymer structures of polymers 22, 23, and 24

[0398]

[0399] Polymer structures of polymers 25, 26, and 27

[0400]

[0401] Polymer structures of polymers 28 and 29

[0402]

[0403] Polymer structures of polymers 30, 31, and 32

[0404] 2. Preparation of photosensitive resin composition

[0405] The following shows the components used in the preparation of the photosensitive resin compositions in the examples and comparative examples.

[0406] <Alkene Unsaturated Compound (A)>

[0407] Alkene unsaturated compounds: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.

[0408] <Photopolymerization Initiator (B)>

[0409] Photopolymerization initiator 1: BASF's "Irgacure OXE-01" (oxime ester initiator (2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone))

[0410] Photopolymerization initiator 2: BASF's "Omnirad 920" (acylphosphine oxide initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide)).

[0411] <Alkali-soluble resin (C)>

[0412] Alkali-soluble resin: "ZAR-2050H" (BIS-A type epoxy resin (acid-modified (meth)acrylate epoxy ester alkali-soluble resin)) manufactured by Nippon Kayaku Co., Ltd.

[0413] <Additives>

[0414] Sealing agent: "KAYAMER PM-21" (a compound with the following formula) manufactured by Nippon Kayaku Co., Ltd.

[0415]

[0416] <Chain transfer agent>

[0417] Chain transfer agent: "Karenz MT-PE1" (pentaerythritol tetrakis(3-mercaptobutyrate) ester) manufactured by Showa Denko Co., Ltd.

[0418] (Preparation of coloring pigment dispersion 1)

[0419] The pigment, dispersant, alkali-soluble resin (described as alkali-soluble resin in Table 2), and solvent listed in Table 2 were mixed in the mass ratios described in Table 2. The solution was dispersed at 25°C using 0.5 mm φ zirconia beads in a bead mill for 12 hours. After dispersion, the beads were removed by filtration to prepare pigment dispersion 1.

[0420] [Table 2]

[0421]

[0422] [Preparation of the base solution for photosensitive resin]

[0423] A photosensitive resin base solution was prepared by mixing 1.7 parts by weight of Karenz MT-PE1 as a chain transfer agent, 43.1 parts by weight of DPHA as an olefinic unsaturated compound (A), 43.1 parts by weight of ZAR-2050H as an alkali-soluble resin (C), 1.7 parts by weight of PM-21 as a binding agent, 8.6 parts by weight of coloring pigment dispersion 1, and 100 parts by weight of PGMEA as a solvent. The resulting solution was filtered through a 3.0 μm membrane filter.

[0424] One part by mass of a photoradical initiator (Irgacure Oxe-01 in Tables 3A and 3B; Omnirad 920 in Tables 4A and 4B) and one part by mass of a synthetic silicone-type liquid repellent material (polymer) 1-32 (not mixed in Comparative Examples 1-0 and 2-0) were added to the photosensitive resin base composition liquid, stirred and dissolved, and the obtained photosensitive resin composition was evaluated using the method described later.

[0425] 3. Evaluation of the dike

[0426] [The formation of the dike]

[0427] A 10 cm square alkali-free glass substrate was cleaned with ultrapure water, followed by acetone cleaning, and then subjected to UV ozone treatment for 5 minutes. Subsequently, a photosensitive resin composition was applied to the UV-ozone-treated substrate using a spin coater at 200 rpm, followed by heating at 80°C for 150 seconds on a heated plate to form a 10 μm thick resin film. The resin film was then exposed to i-lines (wavelength 365 nm) through a mask with a linewidth and spacing of 10 μm using a mask alignment device (Hughes Microtechnology, Inc.).

[0428] The obtained cured film after exposure was evaluated for its solubility in the developer, its barrier performance (sensitivity, resolution), and the contact angle of the barrier portion and the opening portion.

[0429] [Developer solubility]

[0430] The cured film on the exposed ITO substrate was immersed in an alkaline developer for 80 seconds at room temperature, and the solubility of the alkaline developer was evaluated. 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 barrier was evaluated by measuring the thickness of the barrier after immersion using a contact thickness gauge. Complete dissolution of the barrier was defined as "soluble," while the presence of undissolved photoresist film was defined as "insoluble."

[0431] [Dike performance (sensitivity, resolution)]

[0432] When forming the barrier as described above with the aforementioned line width and spacing, the optimal exposure value Eop (mJ / cm²) is determined by finding the point where the liquid repellency of the barrier portion is maintained at a high level, based on the composition of the added silicon-type liquid-repellent material. 2 Sensitivity (mJ / cm²) is defined as an indicator of sensitivity. 2 The smaller the value of ), the better the photocurability.

[0433] In addition, the obtained dike patterns were observed using a laser microscope (Kines, VX-1100) (3000x) to evaluate the resolution. Those where the line width edge roughness could not be identified were classified as "excellent", those where the line width edge roughness was slightly identified were classified as "good", and those where the line width edge roughness was significant were classified as "unacceptable".

[0434] [Contact Angle]

[0435] Spray development was performed for 40 seconds using a 2.38% (w / w) TMAH aqueous solution. After development, the film was rinsed with pure water for 10 seconds. Residual developer and / or rinse solution were then removed using N2 spray. The substrate with the obtained cured film was heated at 230°C for 20 minutes. The contact angles of water and propylene glycol monomethyl ether acetate (PGMEA) on the surface of the cured film were measured at five points on the coating using a contact angle meter (DMs-601, Kyowa Interface Science Co., Ltd.). A higher contact angle in the exposed area indicates greater curing of the liquid-repellent component, which is desirable. A lower contact angle in the unexposed area is preferable, as the liquid-repellent component will remain after development if the contact angle is high.

[0436] [Table 3A]

[0437]

[0438] [Table 3B]

[0439]

[0440] [Table 4A]

[0441]

[0442] [Table 4B]

[0443]

[0444] As shown in Tables 3A, 3B, 4A, and 4B, the polymer of this application exhibits excellent photocurability and can impart good alkali developability and liquid repellency to the obtained cured product. The obtained cured product has excellent alkali developability (resolution after development) and liquid repellency.

[0445] It should be noted that polymers 30 to 32 in this application, as shown in Table 1A, have relatively low molecular weights. However, even so, Examples 1-14 to 1-16 and 2-14 to 2-16 using these polymers exhibit relatively high contact angles with the exposed portion of the PGMEA, resulting in excellent liquid repellency in the cured products. Furthermore, due to their low molecular weight, these polymers are readily compatible with photosensitive compositions.

[0446] The polymer of this application, which has thiol groups as crosslinking sites, tends to exhibit higher sensitivity and superior photocurability compared to the polymers of comparative examples that have acrylate or vinyl groups as crosslinking sites. It should be noted that the polymers of the comparative examples, which only have epoxy groups as crosslinking sites, did not cure. This is because epoxy groups do not contribute to free radical reactions.

[0447] If the contact angle of the unexposed portion (opening) is confirmed, "Comparative Examples 1-1 to 1-16" and "Comparative Examples 2-1 to 2-16" exhibit higher liquid repellency compared to Comparative Examples 1-0 and 2-0. This can be presumed to be because the liquid-repellent material remained and was not completely removed during the developing process. On the other hand, in the examples, each exhibited a contact angle of the same degree as Comparative Examples 1-0 and 2-0, indicating that the liquid-repellent material did not (and was not easily) remain. This difference can be presumed to be due to alkaline developability.

[0448] This application is based on Japanese Patent Application No. 2023-202128, filed on November 29, 2023, and claims priority under the Paris Convention and the regulations of the countries in which it is applied. The contents of that application are incorporated herein by reference in their entirety.

Claims

1. A photosensitizing composition comprising: a polymer having repeating units of formula (A), formula (B), and / or formula (C), In formula (A), R 1 R 2 Each is an alkyl group independently; In equation (B), R 3 A group with a monovalent charge; R 4 It is a divalent group; In equation (C), R 5 It is a divalent group.

2. The photosensitizing composition according to claim 1, wherein, R in equation (B) 3 It is an alkyl group.

3. The photosensitizing composition according to claim 1, wherein, The polymer has repeating units as shown in formula (C).

4. A photosensitizing composition comprising: a polymer having repeating units as shown in formula (B-1); In equation (B-1), R 4 It is a divalent group.

5. The photosensitizing composition according to any one of claims 1 to 4, further comprising: Photopolymerization initiators; and Compounds that have groups that can react with thiol groups.

6. The photosensitizing 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 photosensitizing composition according to claim 5, wherein, The photopolymerization initiator is an acylphosphine oxide-based photopolymerization initiator.

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

9. A method for manufacturing a substrate with a patterned film, comprising: The film-forming process involves coating the photosensitive composition according to any one of claims 1 to 4 onto a substrate to form a film; In the exposure process, the film after the film-making process is exposed to high-energy rays through a photomask to transfer the pattern of the photomask onto the film. as well as The developing process involves developing the film after the exposure process with an alkaline developing solution to obtain a patterned film.

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

11. The method for manufacturing a substrate with a patterned film according to claim 9, wherein, The substrate with the patterned film is a substrate used to form display elements by inkjet printing.

12. A substrate with a patterned film, wherein the substrate has a patterned film obtained by patterning the cured material as described in claim 8.

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

14. An image display device having a substrate with a patterned film as described in claim 12.

15. An image display device having a substrate with a patterned film as described in claim 13.

16. A polymer having repeating units represented by formula (A), repeating units represented by formula (B), and / or repeating units represented by formula (C), In formula (A), R 1 R 2 Each is an alkyl group independently; In equation (B), R 3 A group with a monovalent charge; R 4 It is a divalent group; In equation (C), R 5 It is a divalent group.

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

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

19. A polymer having repeating units as shown in formula (B-1), In equation (B-1), R 4 It 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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