Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

• the present invention relates to a photosensitive composition, a method for producing a cured film, a partition wall, a light-emitting device, and a display device.
• One of the applications of the photosensitive composition is the use of the photosensitive composition for forming partitions (banks) in a display device.
• a method for forming an organic layer having a function such as emitting light is known in which ink is dropped, for example, by an inkjet method into the recesses of a pattern having projections and recesses formed on a substrate, and then the ink is dried and/or solidified.
• the "pattern having projections and recesses” is called a partition (bank).
• the partition acts as a barrier to prevent the inks from mixing when dropped into the recesses of the pattern.
• the partition preferably has a property of "repelling" ink to an appropriate degree. This is to prevent the ink dropped into a certain recess from “crawling" along the side of the partition and entering an adjacent recess.
• the partition wall can be formed by a photolithography method using a photosensitive composition.
• Patent Document 1 describes a negative photosensitive resin composition that contains an alkali-soluble resin or an alkali-soluble monomer having an ethylenic double bond, a photopolymerization initiator, a thiol compound having three or more mercapto groups in one molecule, and an ink repellent agent, as a composition that can be preferably used to form partition walls of optical elements.
• Patent Document 2 describes a photosensitive composition that contains at least an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and at least one compound having two or more chain-transferable substituents (specifically, a thiol compound). However, Patent Document 2 does not specifically mention the formation of partition walls in optical elements.
• photosensitive compositions are sometimes required to have good storage stability, that is, to have little change in performance over time.
• storage stability there was room for improvement in the storage stability of conventional photosensitive compositions.
• the present invention has been made in consideration of these circumstances.
• One of the objects of the present invention is to provide a photosensitive composition that has good storage stability.
• the photosensitive composition according to any one of 1. to 3. The disulfide compound (D) is a photosensitive composition containing a polymer of the thiol compound (B). 5. 1. The photosensitive composition according to any one of 1. to 4., The amount of the thiol compound (B) in the total non-volatile components of the photosensitive composition is 0.1 to 10% by mass. 6. 1. The photosensitive composition according to any one of 1. to 5., The photosensitive composition further comprises an alkali-soluble resin (E). 7. 1. The photosensitive composition according to any one of 1. to 6., The photosensitive composition further comprises a fluorine-containing resin (F). 8. 1. The photosensitive composition according to any one of 1. to 7., The photosensitive composition further comprises a colorant (G). 9. 1.
• the photosensitive composition according to any one of 1. to 8. The viscosity of the photosensitive composition measured using a Brookfield viscometer is ⁇ 0 , The photosensitive composition is stored at 40° C. for 7 days, and the viscosity of the photosensitive composition measured using a Brookfield viscometer is defined as ⁇ 1 .
• the photosensitive composition according to any one of 1. to 9. A photosensitive composition used to form a partition wall in a light-emitting device. 11.
• a partition wall formed of a cured product of the photosensitive composition according to any one of 1. to 10. 13.
• the partition wall according to claim 1 A partition wall for a light-emitting element.
• a light-emitting element comprising the partition wall according to 12. or 13., and a light-emitting layer or a wavelength conversion layer disposed in a region partitioned by the partition wall. 15.
• a display device comprising the light-emitting element according to 14.
• the present invention provides a photosensitive composition with good storage stability.
• X to Y in the description of a numerical range means from X to Y.
• 1 to 5% by mass means "1% by mass to 5% by mass.”
• an "alkyl group” includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• (meth)acrylic refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate.”
• organic group refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
• a “monovalent organic group” refers to an atomic group obtained by removing one hydrogen atom from any organic compound.
• the photosensitive composition of the present embodiment is A compound (A) having an ethylenic carbon-carbon double bond; One or more thiol compounds (B) selected from the group consisting of thiols and thiol precursors; A photoradical initiator (C); A disulfide compound (D), Includes.
• the disulfide compound (D) has been conventionally known as a chain transfer agent in radical polymerization reactions, and is generally recognized as not one that terminates the polymerization reaction itself.
• the present inventors have unexpectedly found that the disulfide compound (D) appears to enhance the storage stability of the photosensitive composition. More specifically, the mechanism behind this can be considered as follows.
• Radicals unintentionally generated in the photosensitive composition react with the thiol compound (B) to generate S radicals.
• the generated S radicals react with the disulfide compound (D) faster than they react with the compound (A) having an ethylenic carbon-carbon double bond, generating a different S radical.
• the radicals further react with the disulfide compound (D), thereby suppressing the reaction with the compound (A) having an ethylenic carbon-carbon double bond.
• the generated radicals are deactivated at a certain rate. It should be noted that the above mechanism is merely speculated, and the present invention is not limited to the description of the above mechanism.
• the photosensitive composition of the present embodiment contains a compound (A) having an ethylenic carbon-carbon double bond.
• the compound (A) having an ethylenic carbon-carbon double bond may be simply referred to as compound (A).
• any compound having an ethylenic carbon-carbon double bond can be used without any particular limitation.
• the term "ethylenic carbon-carbon double bond” means a carbon-carbon double bond that can react by the action of a radical.
• a conjugated and stabilized double bond such as a double bond in a benzene ring does not fall under the category of "ethylenic carbon-carbon double bond".
• the compound (A) has an ethylenic carbon-carbon double bond at its terminal.
• Compound (A) may be monofunctional or polyfunctional, that is, compound (A) may have only one ethylenic carbon-carbon double bond in one molecule, or may have two or more (specifically, 2 to 8, more specifically, 2 to 6) ethylenic carbon-carbon double bonds in one molecule. From the viewpoints of further improving the sensitivity and improving the physical properties of a cured film, the compound (A) is preferably polyfunctional.
• compound (A) is a (meth)acrylate compound, that is, a compound having a (meth)acryloyl group as a structure containing an ethylenic carbon-carbon double bond. More preferably, compound (A) is a (meth)acrylate compound.
• compound (A) examples include the following. Of course, compound (A) is not limited to these.
• the photosensitive composition of the present embodiment may contain only one compound (A) or may contain two or more compounds (A).
• the content of compound (A) is usually from 5 to 60% by mass, preferably from 10 to 55% by mass, and more preferably from 15 to 50% by mass, based on the total non-volatile components of the photosensitive composition.
• the content of the double bond (C ⁇ C) in the compound (A) is preferably 5 to 60 mass %, more preferably 7 to 50 mass %, and more preferably 10 to 30 mass %.
• the photosensitive composition of the present embodiment contains one or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors.
• the one or more thiol-based compounds (B) selected from the group consisting of thiols and thiol precursors may be simply referred to as thiol-based compounds (B).
• the thiol compound (B) may be monofunctional or polyfunctional, that is, the thiol compound (B) may have only one mercapto group (or latent mercapto group) in one molecule, or may have two or more (specifically, 2 to 8) mercapto groups (or latent mercapto groups) in one molecule. From the viewpoint of improving the physical properties of the cured film, the thiol compound (B) is preferably polyfunctional.
• thiol in the thiol compound (B) include those represented by the following general formula (b).
• R is a hydrogen atom, an alkyl group or a cycloalkyl group;
• X is —CO— or —CH 2 —;
• L is an n-valent linking group;
• n is an integer of 2 or more, preferably 2 to 8, and more preferably 2 to 6.
• a plurality of R's may be the same or different from each other.
• a plurality of X's may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of R's are the same from each other, and it is preferable that a plurality of X's are the same from each other.
• the alkyl group of R may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 1 to 10.
• Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. Of these, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, and a methyl group or an ethyl group is more preferred.
• L which is an n-valent linking group examples include trivalent linking groups such as a linear or branched alkylene chain (having, for example, 2 to 6 carbon atoms), a trimethylolpropane residue, an isocyanuric ring having three -(CH 2 ) p - (p is 2 to 6)), a tetravalent linking group or a pentavalent linking group such as a pentaerythritol residue, and a hexavalent linking group such as a dipentaerythritol residue.
• trivalent linking groups such as a linear or branched alkylene chain (having, for example, 2 to 6 carbon atoms), a trimethylolpropane residue, an isocyanuric ring having three -(CH 2 ) p - (p is 2 to 6)
• a tetravalent linking group or a pentavalent linking group such as a pentaerythritol residue
• thiols in the thiol-based compound (B) include, for example, the Karenz series manufactured by Showa Denko K.K.
• the thiols in this series are secondary thiols.
• Other examples include PEMP, TMMP, DPMP, and TEMPIC manufactured by SC Organic Chemical Co., Ltd.
• These thiols are primary thiols.
• primary thiols are more reactive and may be more advantageous in terms of low-temperature curing.
• secondary thiols may improve the stability of the composition by suppressing the reaction of the thiol group due to steric hindrance.
• the "thiol precursor" in the thiol compound (B) is a compound that does not have a mercapto group itself, but generates a mercapto group in the composition by physical stimulation or chemical action.
• the thiol precursor can be, for example, a thioester, a dithioester, a thiocarbamate, a dithiocarbamate, a thiocarbonate, a xanthogenate, a trithiocarbonate, etc.
• the specific structure of the thiol precursor can be, for example, one in which the -SH part in the above general formula (b) is esterified or formed into a salt.
• the thiol precursor is described, for example, in JP-A-2004-517979.
• the content ratio of mercapto groups contained in the thiol compound (B) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and more preferably 10 to 30 mass%, relative to the molecular weight of the thiol compound (B).
• this value is calculated based on the chemical structure after the thiol precursor is converted into the thiol compound.
• the photosensitive composition of this embodiment may contain only one thiol-based compound (B), or may contain two or more thiol-based compounds (B).
• the content of the thiol compound (B) is not particularly limited, but in one embodiment, it is, for example, 0.1 to 10 mass%, specifically 0.5 to 8 mass%, more specifically 1 to 5 mass%, of the total non-volatile components of the photosensitive composition.
• the content of the thiol compound (B) within the numerical range shown here is preferable because it further improves the storage stability of the photosensitive composition.
• the content of the thiol compound (B) is, for example, 0.2 to 25 mass parts, specifically 1 to 20 mass parts, more specifically 2 to 15 mass parts, relative to 100 mass parts of compound (A).
• the thiol compound (B) when used in such an amount, it is considered that the thiol compound (B) mainly functions as a chain transfer agent and is involved in adjusting the chain length of the polymer generated by the radical polymerization reaction of compound (A).
• the content of the thiol compound (B) is usually 10 to 70 mass%, preferably 15 to 60 mass%, more preferably 20 to 55 mass% of the total non-volatile components of the photosensitive composition.
• the content of the thiol compound (B) is, for example, 30 to 80 mass parts, specifically 30 to 70 mass parts, more specifically 35 to 70 mass parts, relative to 100 mass parts of the compound (A).
• the photosensitive composition is cured mainly by the thiol-ene reaction, which is known as a bond formation reaction between a thiol and an alkene.
• both the radical polymerization reaction of compound (A) and the thiol-ene reaction may occur.
• the photosensitive composition of the present embodiment contains a photoradical initiator (C).
• a photoradical initiator C
• any photoradical initiator that generates radicals when irradiated with light typically ultraviolet light such as i-line
• photoradical initiators include intramolecular cleavage types in which intramolecular bonds are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and hydrogen abstraction types in which radicals are generated by using a hydrogen donor such as a tertiary amine or ether in combination. In this embodiment, any of these may be used. Of course, other photoradical initiators may also be used.
• photoradical initiator (C) examples include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, acyloin-based, and oxime ester-based photoradical initiators.
• benzophenone-based photoradical initiators include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Of these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.
• acetophenone-based photoradical initiators include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.
• p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.
• diketone-based photoradical initiators include 4,4'-dimethoxybenzyl, methyl benzoylformate, and 9,10-phenanthrenequinone. Among these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.
• acylphosphine oxide initiators include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
• quinone initiators include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among these, camphorquinone and 1,4-naphthoquinone are preferred.
• acyloin initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Of these, benzoin and benzoin methyl ether are preferred.
• oxime ester initiators include 1-[4-(phenylthio)phenyl]-1,2-octadione-2-(o-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(o-acetyloxime)].
• preferred ones include BASF product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, Irgacure OXE-04, Darocur 1173, Lucirin TPO, and Tronly product name: TR-PBG-305.
• the photosensitive composition of the present embodiment may contain only one photoradical initiator (C), or may contain two or more photoradical initiators (C).
• the content of the photoradical initiator (C) may be appropriately adjusted in consideration of sufficient sensitivity and resolution.
• the content of the photoradical initiator (C) is usually 0.1 to 10 mass %, preferably 0.3 to 8 mass %, and more preferably 0.5 to 5 mass %, of the total non-volatile components of the photosensitive composition.
• the amount of the photoradical initiator (C) relative to 100 parts by mass of the compound (A) is usually 0.2 to 25 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass.
• the photosensitive composition of the present embodiment contains a disulfide compound (D).
• the disulfide compound (D) is considered to be particularly related to the improvement of storage stability.
• the disulfide compound (D) that can be used is not particularly limited, and any compound containing one or more disulfide bonds in one molecule can be used without particular limitation. Incidentally, when a compound has both a thiol group and a disulfide bond, the compound is classified as a disulfide compound (D).
• disulfide compound (D) examples include the following. Dialkyl disulfides such as dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-isopropyl disulfide, di-n-butyl disulfide, di-isobutyl disulfide, di-sec-butyl disulfide, di-tert-butyl disulfide, di-n-pentyl disulfide, di-tert-pentyl disulfide, diisopentyl disulfide, di-n-heptyl disulfide, di-tert-octyl disulfide, di-n-decyl disulfide, and dicyclohexyl disulfide.
• Dialkyl disulfides such as dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-isopropyl disulf
• Disulfides having an aromatic group such as dibenzyl disulfide, diphenyl disulfide, di-p-tolyl disulfide, and 5,5'-dithiobis(2-nitrobenzoic acid).
• Disulfides having a heterocyclic group such as 2,2'-dipyridyl disulfide, 4,4'-dipyridyl disulfide, 2,2'-dithiobis(5-nitropyridine), 6,6'-dithiodinicotinic acid, and 2,2'-dipyrimidinyl disulfide.
• the disulfide compound (D) a publicly known or commercially available product may be used.
• the disulfide compound (D) may be synthesized by oxidizing a thiol compound under appropriate conditions.
• the disulfide compound (D) can be synthesized by oxidizing a publicly known or commercially available thiol with an appropriate oxidizing agent.
• the synthesis of a disulfide by oxidation of a thiol is an elementary organic chemical reaction.
• the disulfide compound (D) may be a polymer (e.g., a dimer) of the thiol compound (B).
• the photosensitive composition of the present embodiment may contain a thiol compound (B) having a specific structure and a disulfide compound (D) which is a polymer of the thiol compound (B).
• the thiol compound (B) and the disulfide compound (D) are structurally similar, it is considered to be preferable in terms of the uniformity of the composition and the compatibility of the components.
• the transfer of radicals between the thiol compound (B) and the disulfide compound (D) may become smoother.
• the disulfide compound (D) does not necessarily have to contain a polymer of the thiol compound (B).
• the disulfide compound (D) is usually a low molecular weight compound.
• the disulfide compound (D) is usually not a polymer having a periodic unit structure.
• the photosensitive composition of this embodiment may contain only one disulfide compound (D), or may contain two or more disulfide compounds (D).
• the ratio of disulfide compound (D) in all non-volatile components of the photosensitive composition is preferably 1 to 30,000 ppm, more preferably 5 to 25,000 ppm, and even more preferably 10 to 20,000 ppm.
• An upper limit may be set based on the balance with other components. In that case, the upper limit mentioned here may be used.
• the amount of the disulfide compound (D) relative to 100 parts by mass of the thiol compound (B) is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 30 parts by mass, and even more preferably 0.1 to 20 parts by mass.
• this amount is 0.01 parts by mass or more, it becomes easier to obtain a sufficient effect of improving storage stability.
• this amount is 40 parts by mass or less, it is possible to obtain an effect of improving storage stability while suppressing a decrease in performance other than storage stability, such as sensitivity.
• the disulfide compound (D) receives radicals from the radicalized thiol compound (B).
• the amount of the disulfide compound (D) relative to 100 parts by mass of the thiol compound (B) described above can also be interpreted as representing the amount ratio of the thiol compound (B) to the disulfide compound (D) suitable for efficient transfer of radicals from the thiol compound (B) to the disulfide compound (D).
• the sensitivity and storage stability are in a trade-off relationship.
• the balance between the sensitivity and storage stability is good by setting the amount of the disulfide compound (D) to the above-mentioned ratio.
• the mechanism is related to the disulfide compound (D) not directly capturing the radical generated by the unintended decomposition of the photoradical initiator (C), but rather the generated radical passes through the thiol compound (B) and then propagates to the disulfide compound (D). Since the disulfide compound (D) does not directly capture the radical generated from the photoradical initiator (C), it is difficult for the radical generated during exposure to be deactivated, and the effect on sensitivity may be suppressed.
• the photosensitive composition of the present embodiment preferably contains an alkali-soluble resin (E).
• an alkali-soluble resin (E) By using the alkali-soluble resin (E), it tends to be easier to form a pattern of a desired shape, particularly when a pattern (partition wall) is formed using an alkali developer.
• the alkali-soluble resin (E) typically has an alkali-soluble group, such as a carboxy group or a phenolic hydroxy group.
• a resin which has fluorine atoms and is alkali-soluble is usually classified as a fluorine-containing resin (F) described later.
• an alkali-soluble resin (E) usually does not have fluorine atoms.
• alkali-soluble resin (E) is an alkali-soluble novolak resin, which can be obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst.
• phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol, pyrogallol, phloroglucinol, thymol, isothymol, etc.
• aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, ⁇ -phenylpropylaldehyde, ⁇ -phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.
• the acid catalyst examples include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, p-toluenesulfonic acid, etc. These acid catalysts may be used alone or in combination of two or more kinds.
• alkali-soluble resin (E) examples include alkali-soluble epoxy resins and acid-modified epoxy (meth)acrylate resins derived from epoxy resins.
• the epoxy resins or acid-modified epoxy (meth)acrylate resins may have polymerizable substituents such as hydroxyl groups or (meth)acryloyl groups in the side chains.
• examples of epoxy resins include bisphenol-type epoxy resins
• examples of acid-modified epoxy (meth)acrylate resins include those obtained by reacting bisphenol-type epoxy resins with (meth)acrylic acid.
• examples of the acid-modified epoxy (meth)acrylate resins include bisphenol-type epoxy resins or acid-modified epoxy (meth)acrylate resins having a structural unit represented by the following general formula (e).
• two R's each independently represent a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom;
• Z represents a monovalent organic group or a hydrogen atom.
• Z is a monovalent organic group having a carboxy group.
• R is a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 carbon atoms
• specific examples of R include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group is preferable from the viewpoint of availability.
• Specific examples of the linear perfluoroalkyl group having 1 to 3 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Of these, the trifluoromethyl group is preferred from the viewpoint of availability.
• Each R may have the same structure or different structures.
• Z is preferably an alkyl group having 1 to 10 carbon atoms.
• This alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic.
• At least one hydrogen atom in the monovalent organic group of Z may be substituted with a carboxy group or a hydroxy group. This enhances alkali solubility.
• the carboxyl group or hydroxyl group of the alkyl group having 1 to 10 carbon atoms represented by Z may be reacted with an esterifying agent.
• the esterifying agent include acid halides, acid anhydrides, and acids and condensing agents.
• Z is a hydrogen atom
• -O-Z may be reacted with an esterifying agent.
• the esterifying agent include the same esterifying agents as described above.
• acid anhydrides include acrylic anhydride, methacrylic anhydride, succinic anhydride, phthalic anhydride, 1,2,3,4-tetrahydrophthalic anhydride, etc.
• the amount of carboxyl groups or hydroxyl groups in the alkali-soluble resin to be reacted with the acid anhydride may be appropriately adjusted taking into consideration the solubility in alkali required for the alkali-soluble resin.
• Epoxy (meth)acrylate resins having a structural unit represented by general formula (e) are available, for example, from Nippon Kayaku Co., Ltd.
• alkali-soluble epoxy resins or acid-modified epoxy (meth)acrylate resins other than those mentioned above can also be used.
• Specific examples include alkali-soluble novolac type epoxy resins, biphenyl type epoxy resins, and acid-modified epoxy (meth)acrylate resins derived from these epoxy resins.
• examples of the acid-modified epoxy (meth)acrylate include commercially available products, such as those available from Nippon Kayaku Co., Ltd.
• the alkali-soluble resin (E) may have a polycyclic aromatic skeleton such as a fluorene skeleton.
• a polycyclic aromatic skeleton such as a fluorene skeleton.
• the heat resistance and durability of the cured pattern may be improved.
• a resin having a polycyclic aromatic skeleton may be used, or a resin having a polycyclic aromatic skeleton may be selected from a resin family different from the acid-modified epoxy (meth)acrylate resin.
• a resin having a fluorene skeleton is sometimes referred to as a "cardo resin.”
• the alkali-soluble resin (E) having a polycyclic aromatic skeleton such as a fluorene skeleton preferably has an alkali-soluble group such as a carboxy group or a hydroxy group, like other alkali-soluble resins (E).
• the alkali-soluble resin (E) may have an ethylenic carbon-carbon double bond. It is considered that the alkali-soluble resin (E) having an ethylenic carbon-carbon double bond forms a bond with the compound (A) during curing of the composition and is incorporated into the cured product. This is considered to contribute to improving the stability and heat resistance of the cured product.
• an alkali-soluble resin having an ethylenic carbon-carbon double bond is not classified as compound (A).
• the weight average molecular weight of the alkali-soluble resin (E) is preferably from 1,000 to 50,000 from the viewpoint of the developability and resolution of the photosensitive composition.
• the acid value of the alkali-soluble resin (E) (the number of milligrams of potassium hydroxide required to neutralize 1 g of a sample) can be an index of alkali solubility.
• the acid value of the alkali-soluble resin (E) is preferably 20 to 80, more preferably 30 to 70, and even more preferably 40 to 60.
• the acid value of the alkali-soluble resin used in the examples described later is about this range.
• alkali-soluble resin (E) When the alkali-soluble resin (E) is used, only one alkali-soluble resin (E) may be used, or two or more alkali-soluble resins (E) may be used. When the alkali-soluble resin (E) is used, its amount is usually from 10 to 70% by mass, preferably from 15 to 60% by mass, and more preferably from 20 to 55% by mass, based on the total non-volatile components of the photosensitive composition.
• the photosensitive composition of the present embodiment preferably contains a fluorine-containing resin (F).
• a pattern having projections and recesses (partition walls) can be formed using a photosensitive composition containing a fluorine-containing resin (F).
• the resulting pattern (partition wall) is more likely to repel ink for forming the organic layer. This means that ink dropped into one recess "crawls" along the side of the recess and reaches the adjacent recess. In other words, it is possible to prevent unintended mixing of dye between pixels.
• the fluorine-containing resin (F) that can be used is not particularly limited, but the fluorine-containing resin (F) that can be preferably used will be described below.
• the fluororesin (F) preferably has a structure represented by the following general formula (1), and more preferably has a structure represented by the following general formula (2).
• two Rf's each independently represent a linear, branched or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom
• R2 represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.
• two Rf's each independently represent a linear, branched or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom
• R 1 represents a hydrogen atom, a fluorine atom or a methyl group
• R2 represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.
• R 1 is preferably a hydrogen atom or a methyl group.
• R 2 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, a 1,1-dimethylbutyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group.
• a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
• Rf is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a n-nonafluorobutyl group, an isononafluorobutyl group, or a tert-nonafluorobutyl group, more preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group,
• Preferred specific structures of the above structural units include those described in paragraphs 0060 to 0061 of WO 2021/235541.
• the content of the structural unit represented by general formula (2) in the fluorine-containing resin (F) is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and particularly preferably 10 to 30 mass%, taking into consideration solubility in solvents and resistance to various treatments in the manufacture of light-emitting devices.
• the fluororesin (F) may contain a structure represented by the following general formula (3):
• R 3 and R 4 each independently represent a hydrogen atom or a methyl group.
• the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of the light-emitting element is more excellent, which is preferred.
• examples of the divalent linking group A1 include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.
• the divalent linking group A 1 is a branched alkylene group having 3 to 10 carbon atoms
• examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.
• divalent linking group A1 is a cyclic alkylene group having 3 to 10 carbon atoms
• examples of the divalent linking group A1 include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.
• examples of the hydroxy group-substituted alkylene group include a hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), a 1-hydroxy-n-butylene group, a 2-hydroxy-n-butylene group, a hydroxy-sec-butylene group (-CH(CH 2 OH)CH 2 CH 2 -), a hydroxy-isobutylene group (-CH 2 CH(CH 2 OH)CH 2 -), a hydroxy-tert-butylene group (-C(CH 2 OH)(CH 3 )CH 2 -), and the like.
• the divalent linking group A 1 is preferably a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), a 2-hydroxy-n-butylene group, or a hydroxy-sec-butylene group (-CH(CH 2 OH)CH 2 CH 2 -), more preferably an ethylene group, a propylene group, a 2-hydroxy-n-propylene group, or a hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), and particularly preferably an ethylene group or a 2-hydroxy-n-propylene group.
• An example of the trivalent linking group A 1 is -C(CH 2 -) 2 CH 3 , and an example of the tetra
• Y1 represents a divalent linking group and is preferably -O- or -NH-, and more preferably -O-.
• u represents an integer of 1 to 3, and u is particularly preferably 1.
• n represents an integer of 1 to 3, and is particularly preferably 1.
• the substitution positions of the aromatic rings are each independently ortho, meta, or para, and are preferably para.
• a plurality of W 1 may be the same or different from each other.
• a plurality of A 1 may be the same or different from each other.
• a plurality of Y 1 may be the same or different from each other.
• a plurality of R 4 may be the same or different from each other.
• a plurality of W 1 are the same from each other
• a plurality of A 1 are the same from each other
• a plurality of Y 1 are the same from each other
• a plurality of R 4 are the same from each other.
• the content of the structural unit represented by general formula (3) in the fluorine-containing resin (F) is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and particularly preferably 10 to 30 mass%, taking into consideration solubility in solvents and resistance to various treatments in the manufacture of light-emitting devices.
• the fluororesin (F) may contain a structure represented by the following general formula (4):
• R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
• the liquid repellency against ink after UV ozone treatment or oxygen plasma treatment in the manufacture of the light-emitting element is more excellent, which is preferred.
• divalent linking groups A 2 and A 3 are linear alkylene groups having 1 to 10 carbon atoms
• examples of the divalent linking groups include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.
• divalent linking groups A 2 and A 3 are each independently a branched alkylene group having 3 to 10 carbon atoms, examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.
• divalent linking groups A 2 and A 3 are each independently a cyclic alkylene group having 3 to 10 carbon atoms
• examples thereof include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.
• examples of the hydroxy group-substituted alkylene group include 1-hydroxyethylene group (-CH(OH)CH 2 -), 2-hydroxyethylene group (-CH 2 CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH 2 OH)CH 2 CH 2 -), hydroxy-isobutylene group (-CH 2 CH(CH 2 OH)CH 2 -), hydroxy-tert-butylene group (-C(CH 2 OH)(CH 3 )CH 2 -) and the like.
• the divalent linking groups A 2 and A 3 are each independently preferably a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH 2 -), a 2-hydroxyethylene group (-CH 2 CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), a 2-hydroxy-n-butylene group, or a hydroxy-sec-butylene group (-CH(CH 2 OH)CH 2 CH 2 -), and more preferably an ethylene group, a propylene group, a 1-hydroxyethylene group (-CH(OH)CH 2 -), a 2-hydroxyethylene group (-CH 2 CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropyl group,
• Y 2 and Y 3 each independently represent a divalent linking group, preferably —O— or —NH—, and more preferably —O—.
• n represents an integer of 1 to 3. It is particularly preferable that n is 1.
• a plurality of Y3 may be the same or different from each other.
• a plurality of R6 may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of Y3 are the same from each other, and it is preferable that a plurality of R6 are the same from each other.
• the content of the structural unit represented by general formula (4) in the fluorine-containing resin (F) is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and particularly preferably 10 to 30 mass%, taking into consideration the solubility in the solvent and the adhesion of the pattern (partition wall) to the substrate.
• the fluororesin (F) may contain a structural unit represented by general formula (5).
• R7 represents a hydrogen atom or a methyl group.
• R8 represents a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, any number of hydrogen atoms in the alkyl group being substituted with fluorine atoms, and the fluorine content in the structural unit is 30 mass% or more.
• R8 is a linear hydrocarbon group
• specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a linear alkyl group having 10 to 14 carbon atoms in which any number of hydrogen atoms have been substituted with fluorine atoms.
• R 8 is a linear hydrocarbon group
• the structural unit represented by general formula (5) is preferably a structural unit represented by the following general formula (5-1).
• R 9 has the same meaning as R 7 in formula (5).
• X is a hydrogen atom or a fluorine atom.
• X is preferably a fluorine atom.
• p is an integer from 1 to 4
• q is an integer from 1 to 14. It is particularly preferable that p is an integer from 1 to 2, and q is an integer from 2 to 8.
• the content of the structural unit represented by general formula (5) in the fluorine-containing resin (F) may be appropriately determined taking into consideration the ease with which the pattern (partition wall) repels ink and the ease with which the photosensitive composition dissolves in a solvent when the photosensitive composition is prepared.
• the content of the structural unit represented by general formula (5) in the fluorine-containing resin (F) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.
• the fluororesin may contain a structure represented by the following general formula (6):
• R 10 represents a hydrogen atom or a methyl group.
• m represents an integer of 0 to 3.
• the content of the structural unit represented by general formula (6) in the fluororesin (F) is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and particularly preferably 20 to 40 mass%, in consideration of obtaining a sufficient effect based on the structural unit represented by general formula (6) and of solvent solubility.
• the structural unit represented by the general formula (6) has solubility in an alkali developer. Therefore, when it is desired to obtain particularly good alkali developability, it is preferred that the fluorine-containing resin (F) contains a structural unit represented by the general formula (6) in which B1 is a hydroxy group or a carboxyl group.
• the fluororesin (F) may contain a structure represented by the following general formula (7):
• R 13 represents a hydrogen atom or a methyl group.
• examples of the divalent linking group A4 include a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexalene group, an n-heptalene group, an n-octalene group, an n-nonalene group, and an n-decalene group.
• the divalent linking group A4 is a branched alkylene group having 3 to 10 carbon atoms
• examples thereof include an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an isopentalene group, and an isohexalene group.
• the divalent linking group A4 is a cyclic alkylene group having 3 to 10 carbon atoms
• examples thereof include disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.
• examples of the hydroxy group-substituted alkylene group include 1-hydroxyethylene group (-CH(OH)CH 2 -), 2-hydroxyethylene group (-CH 2 CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH 2 OH)CH 2 CH 2 -), hydroxy-isobutylene group (-CH 2 CH(CH 2 OH)CH 2 -), hydroxy-tert-butylene group (-C(CH 2 OH)(CH 3 )CH 2 -) and the like.
• the divalent linking group A 4 is preferably a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, a 1-hydroxyethylene group (-CH(OH)CH 2 -), a 2-hydroxyethylene group (-CH 2 CH(OH)-), a 2-hydroxy-n-propylene group, a hydroxy-isopropylene group (-CH(CH 2 OH)CH 2 -), a 2-hydroxy-n-butylene group, or a hydroxy-sec-butylene group (-CH(CH 2 OH)CH 2 CH 2 -), and more preferably an ethylene group, a propylene group, a 1-hydroxyethylene group (-CH(OH)CH 2 -), a 2-hydroxyethylene group (-CH 2 CH(OH)-), a 2-hydroxy-n-propylene group, or a hydroxy-isopropylene group (--CH(
• Y 4 represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.
• E1 represents a hydroxyl group, a carboxyl group or an oxirane group.
• E1 is an oxirane group
• examples include an ethylene oxide group, a 1,2-propylene oxide group, a 1,3-propylene oxide group, etc.
• an ethylene oxide group is preferable.
• s represents 0 or 1.
• (-Y 4 -A 4 -) represents a single bond.
• E 1 is bonded to the main chain of the structural unit.
• the weight average molecular weight of the fluororesin (F) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000.
• GPC gel permeation chromatography
• the dispersity (Mw/Mn) of the fluororesin (F) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, and particularly preferably from 1.01 to 3.00.
• the fluororesin (F) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of dispersing the respective properties appropriately rather than locally, a random copolymer is preferable.
• the fluorine content of the fluorine-containing resin (F) is preferably 20 to 50 mass%, more preferably 25 to 40 mass%. When the fluorine content is within this range, the fluorine-containing resin (F) is easily dissolved in a solvent. Furthermore, when the fluorine content of the fluorine-containing resin (F) is within this range, a pattern (partition wall) having excellent liquid repellency is easily obtained.
• the fluorine content of the fluorine-containing resin (F) can be measured, for example, in accordance with the description in paragraph 0174 of WO 2021/235541.
• the fluorine-containing resin (F) When the fluorine-containing resin (F) is used, only one fluorine-containing resin (F) may be used, or two or more fluorine-containing resins (F) may be used.
• the amount of the fluorine-containing resin (F) used is usually from 0.1 to 10 mass %, preferably from 0.1 to 8 mass %, and more preferably from 0.5 to 5 mass %, of the total non-volatile components of the photosensitive composition.
• the photosensitive composition of the present embodiment may contain a colorant (G).
• a colorant (G) for example, by using a colorant (G) to give the resulting pattern (partition wall) a black color, unintended "light seepage” and "color mixing between adjacent pixels" in the light-emitting element can be suppressed.
• a colorant (G) to give the resulting pattern (partition wall) a white color, the reflectance of the pattern (partition wall) can be increased, and the luminance of the light emitted from the light-emitting element can be improved.
• a suitable colorant (G) may be selected so as to obtain a pattern that is neither black nor white depending on various purposes.
• the colorant (G) a pigment or a dye may be used. If necessary, a plurality of colorants may be used in combination.
• a black pigment such as carbon black may be used, or a plurality of non-black pigments may be mixed to obtain a substantially black color.
• a black pigment and a white pigment may be mixed to obtain a gray color.
• the pigment it is preferable to use an organic pigment.
• colorants (G) include known colorants such as perylene pigments, lactam pigments, azo pigments, phthalocyanine pigments, carbon pigments such as carbon black, and metal oxide pigments such as iron black and titanium oxide.
• the white pigment is preferably at least one inorganic substance selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. These inorganic substances have a high refractive index, and therefore tend to improve the light reflectivity of the partition walls that are formed. Titanium oxide is particularly preferred from the viewpoints of its high refractive index and good dispersibility in the composition.
• color pigments that can be used include various organic pigments such as yellow, orange, blue, red, green, purple, and brown. Pigment dispersions containing two or more types of organic pigments may also be used. By adjusting the types and quantitative ratios of the pigments used, it is possible to control optical properties such as solubility and light blocking properties. In particular, a combination of blue, purple, and orange is preferred from the standpoint of compatibility and uniformity of optical density.
• organic orange pigments examples include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79.
• C.I. Pigment Orange 43 is preferred from the viewpoints of dispersibility and light blocking properties.
• organic blue pigments examples include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, and 80.
• C.I. Pigment Blue 60 is preferred from the standpoint of dispersibility and light blocking properties.
• organic purple pigments examples include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
• C.I. Pigment Violet 23 is preferred from the viewpoints of dispersibility and light blocking properties.
• the pigment When a pigment is used as the colorant (G), it is preferable that the pigment has been subjected to a dispersion treatment.
• the pigment can be dispersed, for example, by treating the pigment, a dispersant, and, if necessary, a solvent, using a beads mill.
• the type of dispersant is not particularly limited, and for example, dispersants available from BYK-Chemie Corporation can be used.
• an alkali-soluble resin may be further used.
• the colorant (G) When the colorant (G) is used, only one colorant (G) may be used, or two or more colorants (G) may be used in combination.
• the amount of the colorant (G) may be appropriately adjusted in consideration of the balance between obtaining the sufficient effect of using the colorant (G) and the patterning property, developability, and strength of the pattern (partition wall) obtained.
• the amount of the colorant (G) is usually 1 to 60 mass %, preferably 3 to 55 mass %, and more preferably 5 to 50 mass % of the total non-volatile components of the photosensitive composition.
• the amount of the colorant (G) including the dispersant and the alkali-soluble resin (excluding the volatile solvent) may be within the numerical range shown here.
• the photosensitive composition of the present embodiment may contain any optional components other than those described above.
• the optional components include dissolution inhibitors, plasticizers, stabilizers, surfactants, thickeners, leveling agents, defoamers, compatibilizers, adhesion improvers, and antioxidants.
• Commercially available products can be used as these optional components.
• the "KAYAMER” series manufactured by Nippon Kayaku Co., Ltd. can be used as the adhesion improver.
• the photosensitive composition of the present embodiment is generally prepared by dissolving or dispersing the above-mentioned various components in a solvent, which generally contains an organic solvent.
• solvents that can be used. Specific examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorine-based solvents. These may be used alone or in a mixture of two or more.
• Ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.
• alcohols examples include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.
• polyhydric alcohols and their derivatives include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.
• PGME propylene glycol monomethyl ether
• PGMEA propylene glycol monomethyl ether acetate
• ethers examples include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.
• Esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and gamma-butyrolactone.
• Aromatic solvents include xylene and toluene.
• fluorine-based solvents examples include fluorocarbons, fluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.
• turpentine-based petroleum naphtha solvents and paraffin-based solvents which are high-boiling weak solvents, can be used.
• the solvent is methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate
• the carboxylic acid ester compound contains at least one selected from the group consisting of tetramethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane,
• the solvent more preferably contains methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, or ⁇ -butyrolactone.
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether
• cyclohexanone ethyl lactate
• butyl acetate butyl acetate
• ⁇ -butyrolactone ⁇ -butyrolactone
• the amount of the solvent in the photosensitive composition is preferably such that the total solids concentration is, for example, 5 to 85% by mass, specifically 10 to 60% by mass.
• the amount of the solvent By adjusting the amount of the solvent, the thickness of the film to be formed can be adjusted. If the amount of the solvent is within the above range, it is easy to obtain a film having a thickness suitable for forming a partition wall in an organic EL element.
• the photosensitive composition of this embodiment has good storage stability.
• This good storage stability can be quantified by the viscosity change rate defined by the formula: (
• ⁇ 0 is the viscosity of the photosensitive composition measured using a Brookfield viscometer
• ⁇ 1 is the viscosity of the photosensitive composition after storage at 40°C for 7 days measured using a Brookfield viscometer.
• the viscosity change rate is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less. In other words, by designing the photosensitive composition so that the viscosity change rate falls within the range shown here, the storage stability of the composition can be further improved.
• the viscosity change rate is ideally 0%.
• a cured film can be produced by using the photosensitive composition of the present embodiment, for example, through a series of steps including the following film-forming step, exposure step, development step, and heating step.
• the photosensitive composition of the present embodiment is preferably used to form partition walls in a light-emitting element.
• partition walls of a desired size and shape (specifically, partition walls having "recesses” for dropping ink) made of a cured product of the photosensitive composition of the present embodiment.
• a light emitting element can be manufactured that includes such a partition and a light emitting layer or a wavelength conversion layer that is disposed in a region (corresponding to a recess) defined by the partition.
• a display device can be manufactured using the light emitting element.
• the following describes a method for producing a cured resin film (specifically, a partition wall in a light-emitting element) using the photosensitive composition of this embodiment.
• the photosensitive composition of the present embodiment is applied onto a substrate to form a film.
• the type of substrate is not particularly limited.
• the substrate may be appropriately selected depending on the product to be manufactured.
• Examples of substrate types include silicon wafers, SiN substrates, metal substrates, glass substrates, substrates with ITO films, substrates containing metal oxides, and organic resin substrates (e.g., polyimide, polycarbonate, polyester). Any layer may be formed on at least one surface of the substrate.
• a first light-emitting layer may be disposed on at least one surface of the substrate.
• the first light-emitting layer examples include layers formed of organic EL light-emitting materials, LED light-emitting materials such as mini-LEDs, ⁇ -LEDs, and nano-LEDs, and quantum dot light-emitting materials.
• the first light-emitting layer may be a monochromatic layer or a multi-color layer, but is preferably a monochromatic layer.
• the first light-emitting layer is preferably a monochromatic light-emitting layer that emits blue light.
• an organic or inorganic film may be provided between the substrate and the first light-emitting layer.
• an anti-reflection film a lower layer of a multilayer resist, a barrier layer, etc.
• a driving circuit an electrode, a planarization layer, etc. may be formed between the substrate and the first light-emitting layer.
• a wavelength conversion layer may be provided instead of the first light emitting layer.
• the substrate may have no layer such as the first light-emitting layer formed on its surface.
• the method for applying the photosensitive composition is not particularly limited. Known methods such as spin coating, bar coating, curtain coating, etc. may be used. In some cases, the inkjet method may be applied.
• a photosensitive composition containing a solvent it is preferable to dry the solvent by heating after coating the photosensitive composition.
• the heating temperature can be, for example, 50 to 150° C., preferably 50 to 100° C., more preferably 60 to 90° C., even more preferably 70 to 90° C., and particularly preferably 80 to 90° C.
• the heating time can be 60 to 200 seconds.
• the thickness of the film (dry thickness) is usually 0.5 to 20 ⁇ m, preferably 1 to 15 ⁇ m.
• the film obtained in the film formation process is exposed to a pattern.
• the film is irradiated with light generated from a light source of an exposure device through a photomask.
• the light can be ultraviolet light, gamma rays, X-rays, etc.
• ultraviolet light especially g-rays, i-rays, etc.
• the exposure dose is not particularly limited, but is usually 1 to 200 mJ/cm 2 , preferably 10 to 100 mJ/cm 2 .
• a heat treatment may or may not be carried out.
• the film after the exposure step is typically developed using a developer, which usually dissolves the unexposed areas in the film, resulting in a pattern (partition walls).
• the developer is preferably an aqueous alkaline solution, such as an aqueous tetramethylammonium hydroxide (TMAH) solution, an aqueous tetrabutylammonium hydroxide (TBAH) solution, an aqueous sodium hydroxide solution, or an aqueous potassium hydroxide solution.
• TMAH tetramethylammonium hydroxide
• TBAH tetrabutylammonium hydroxide
• the concentration of the aqueous TMAH solution is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass.
• a developer containing an organic solvent as a main component may be used in some cases.
• the development method may be a known method. For example, the dip method, paddle method, spray method, etc. are included.
• the development time (the time during which the developer is in contact with the film) is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.
• a step of washing the pattern with deionized water or the like may be added, if necessary.
• the washing time is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 2 minutes.
• the film after development is heated, whereby the remaining reactive groups in the pattern obtained in the development step are reacted as much as possible, and the film is hardened.
• the developed film is heated, for example, at 50 to 250° C., preferably 50 to 230° C., more preferably 60 to 220° C., and even more preferably 70 to 200° C.
• the heating time is, for example, 10 minutes to 3 hours, and preferably 15 minutes to 1 hour.
• the cured film obtained in the heating step may be subjected to a UV ozone treatment or oxygen plasma treatment, which can remove organic matter remaining in the recesses of the pattern (cured film) and reduce uneven wetting of the dropped ink when the ink is dropped, as described below.
• a second light-emitting layer forming step in which a second light-emitting layer that emits light using light from the first light-emitting layer as excitation light is formed in the recesses of the pattern (cured film), i.e., in the areas partitioned by the partitions.
• the second light-emitting layer preferably contains a conventionally known material such as a quantum dot light-emitting material.
• the second light-emitting layer can be formed, for example, as described in the Background section, by dropping ink into the recesses of the pattern (cured film) by an inkjet method, and then drying and/or solidifying the ink.
• a light-emitting element may be obtained by dropping ink for forming the second light-emitting layer into the recesses of the pattern (cured film) by an inkjet method.
• ink containing red, green or blue dye may be dropped into the recesses of the pattern (cured film), i.e., into the areas defined by the partition walls, and then the ink may be dried and/or solidified.
• the structure of the precursor of fluororesin 1 is as shown below.
• the compositional ratio of the structural units of the precursor of fluororesin 1, in terms of molar ratio, (structural unit derived from BTFBE:structural unit derived from p-AcO-St:structural unit derived from MA-C6F:structural unit derived from Gly-MA) was 15:18:29:38.
• the structure of the precursor of fluororesin 2 is as shown below.
• the composition ratio of the structural units of the precursor of fluororesin 2, in terms of molar ratio, (structural units derived from BTFBE:structural units derived from HEMA:structural units derived from MA-C6F:structural units derived from MAA:structural units derived from St) was 15:25:30:10:20.
• Ethylenically unsaturated compound 1 "DPHA” (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
• Ethylenically unsaturated compound 2 "TMMT” (pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
• Thiol-based compound 1 "Karenz-MTPE1” manufactured by Showa Denko K.K.
• Thiol compound 2 "DPMP” manufactured by SC Organic Chemical Industry Co., Ltd.
• Photoradical initiator 1 "OXE-01” manufactured by BASF
• Photoradical initiator 2 "TR-PBG-305" manufactured by Tronly
• Disulfide compounds Disulfide compound 1: Disulfide compound solution 1 synthesized as described above Disulfide compound 2: Disulfide compound solution 2 synthesized as described above Disulfide compound 3: di-tert-butyl disulfide
• Alkali-soluble resin 1 Alkali-soluble resin 1: "ZAR-2050H” manufactured by Nippon Kayaku Co., Ltd. (special BIS-A type epoxy acrylate, containing the structural unit represented by the above general formula (1). Does not contain fluorine atoms.)
• Alkali-soluble resin 2 Alkali-soluble resin 2: "ZCR-1569H” (biphenyl-type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd.
• Alkali-soluble resin 3 "CCR-1171H” (cresol novolac type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd.
• Alkali-soluble resin 4 "TR-B20101" manufactured by Tronly (hereinafter referred to as a cardo resin having the structure, where the brackets represent repeating units)
• Fluorine-containing resin 1 Fluorine-containing resin 1 synthesized as described above
• Fluorine-containing resin 2 Fluorine-containing resin 2 synthesized as described above
• Fluorine-containing resin 3 DIC surface modifier "Megafac RS-72A" (fluorine-based, polyester structure)
• Black pigment dispersion 1 Black pigment dispersion 1 prepared as described above
• Black pigment dispersion 2 "NX-593" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. (dispersion of carbon black pigment, pigment content: 16% by mass)
• White pigment dispersion (“NX-501” manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. (titanium oxide pigment, rutile structure, pigment content: 73% by mass, particle size: D50 is 270 nm)
• Blue pigment dispersion Blue pigment dispersion prepared as described above
• Additive 1 Adhesion improver "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd.
• the components listed in the table below were uniformly stirred and mixed with PGMEA as a solvent to prepare a photosensitive composition.
• the amount of PGMEA was set to an amount that resulted in a non-volatile component concentration of 10% by mass or 50% by mass (two types of photosensitive compositions with different non-volatile component concentrations were prepared).
• a partition (pattern) was formed on the substrate by the following procedure. (1) A 10 cm square ITO substrate was washed with ultrapure water and then with acetone, and then subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device (manufactured by Sen Toxic Light Sources Co., Ltd., model number PL17-110). (2) After the UV ozone treatment, the photosensitive composition was applied onto the substrate using a spin coater at a rotation speed of 300 rpm. The substrate was then heated on a hot plate at 80° C. for 150 seconds. In this manner, a resin film was obtained.
• a UV ozone treatment device manufactured by Sen Toxic Light Sources Co., Ltd., model number PL17-110.
• the barrier rib pattern obtained at the optimum exposure dose E op was observed under a microscope and the resolution was evaluated according to the following criteria.
• the mask portion that blocks light i.e., the total area of the opening is 100% open (no foreign matter is found), there is no residue in the opening in the partition, and no line edge roughness is confirmed: Excellent -
• the mask portion that blocks light i.e., 99-90% of the total area of the opening is open (1-10% of the opening is filled with foreign matter), and/or line edge roughness is confirmed: Good -
• ⁇ Viscosity change rate is 5% or less: Excellent ⁇ Viscosity change rate is more than 5% and less than 10%: Good ⁇ Viscosity change rate is more than 10% and less than 15%: Acceptable ⁇ Viscosity change rate is more than 15% or solidified and cannot be measured: Unacceptable
• the mask portion that blocks light i.e., the total area of the opening is 100% open (no foreign matter is found)
• Good 99-90% of the total area of the masked portion that blocks light, i.e., the opening, is open (1-10% of the opening is filled with foreign matter)
• Passable 89-80% of the total area of the mask that blocks light, i.e., the opening, is open (11-20% of the opening is filled with foreign matter)
• Unacceptable The mask portion that blocks light, i.e., the opening area is less than 79% open.
• the ratio of the disulfide compound is shown in units of ppm based on the total non-volatile components in the composition, and the ratios of the other components are shown as mass ratios.
• the amount ratio is shown converted into the amount of non-volatile components.
• the storage stability of the photosensitive compositions of the examples containing a disulfide compound was good.
• performance other than storage stability such as sensitivity and resolution, was also good.
• the photosensitive compositions containing a disulfide compound exhibit good storage stability and also have good other performance such as sensitivity.
• the storage stability of the photosensitive compositions of the comparative examples not containing a disulfide compound was poorer than that of the examples.

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