Method for producing black pattern-bearing substrate, black pattern-bearing substrate, light-emitting element, and negative-type photosensitive composition

Abstract

This method for producing a black pattern-bearing substrate comprises: a film formation step for forming an unexposed film on a substrate using a negative-type photosensitive composition; an exposure step for obtaining an exposed film by selectively irradiating the unexposed film with light having maximums in the spectrum at least in the 350-380 nm wavelength range and the 390-420 nm wavelength range; and a development step for developing the exposed film to form a pattern. The negative-type photosensitive composition in this production method comprises: a black colorant having an absorbance minimum within a wavelength range of 380-420 nm; an oxime ester photoinitiator; an acylphosphine oxide photoinitiator; and a curable component that is cured by an active species generated from the oxime ester photoinitiator or acylphosphine oxide photoinitiator.

Description

Method for manufacturing a substrate having a black pattern, substrate having a black pattern, light-emitting element, and negative photosensitive composition

[0001] The present invention relates to a method for producing a substrate having a black pattern, a substrate having a black pattern, a light-emitting device, and a negative photosensitive composition.

[0002] Various methods for producing a substrate having a pattern using a negative-type photosensitive composition and methods for producing various final products using a substrate having a pattern have been investigated. As a specific example, a method for forming partition walls (banks) in a display device using a negative-type photosensitive composition has been investigated.

[0003] When manufacturing light-emitting elements in display devices such as organic electroluminescent (EL) displays, micro LED displays, and quantum dot displays, a known method for forming an organic layer having a function such as light emission involves, for example, dropping ink into recesses of a textured pattern formed on a substrate using an inkjet method, followed by drying and / or solidifying the ink. Here, the "textured pattern" is referred to as a partition wall (bank). The partition wall acts as a barrier to prevent ink droplets from mixing when dropped into the recesses of the pattern. The partition wall preferably has a moderate ink-repelling property. This is to prevent ink dropped into one recess from "creeping" up the side of the partition wall and seeping into an adjacent recess. From the viewpoint of light-blocking properties, the partition wall is often black. The partition wall is preferably formed by photolithography using a negative-tone photosensitive composition.

[0004] 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 for forming partition walls of optical elements.

[0005] Patent Document 2 describes a curable resin composition containing an alkali-soluble resin, a radically polymerizable monomer, and a photopolymerization initiator. In this composition, the alkali-soluble resin is a resin containing a tetrahydrofuran ring, and the maximum absorption wavelength of the photopolymerization initiator is in the range of 230 nm to 360 nm. According to the description in Patent Document 2, the shape of a patterned cured film obtained using such a composition is tapered. However, Patent Document 2 does not describe using the curable resin composition to form partition walls in a display device.

[0006] International Publication No. 2014 / 084279 Japanese Patent Application Laid-Open No. 2015-22175

[0007] When attempting to form a black pattern such as a partition wall by irradiating a film formed from a negative photosensitive composition containing a black dye with light, the cross-sectional shape of the pattern tends to be inverted tapered or undercut, i.e., (width at the top of the pattern) tends to be greater than (width at the bottom of the pattern). This is because the black dye absorbs light, preventing sufficient light from reaching the bottom of the film. Considering the aforementioned use of partition walls in display devices (dropping ink into recesses in a pattern having projections and recesses), the cross-sectional shape of the pattern is preferably rectangular or tapered.

[0008] The present invention has been made in view of the above circumstances, and one of the objects of the present invention is to improve the cross-sectional shape of a pattern when a black pattern is formed by photolithography.

[0009] The present inventors have completed the invention provided below and solved the above problems.

[0010] 1. A method for manufacturing a substrate having a black pattern, comprising: a film formation step of forming an unexposed film on a substrate from a negative photosensitive composition, an exposure step of selectively irradiating the unexposed film with light having spectral maxima at least in the wavelength range of 350 to 380 nm and in the wavelength range of 390 to 420 nm to obtain an exposed film, and a development step of developing the exposed film to form a pattern, wherein the negative photosensitive composition comprises: a black colorant having an absorbance minimum in the wavelength range of 380 to 420 nm, an oxime ester photoinitiator, an acylphosphine oxide photoinitiator, and a curable component that is cured by active species generated from the oxime ester photoinitiator or the acylphosphine oxide photoinitiator. 2. The method for manufacturing a substrate described in 1., wherein the absorbance of the black colorant at a wavelength of 365 nm is greater than the minimum absorbance value of the black colorant in the wavelength range of 380 to 420 nm. 3. The method for manufacturing a substrate according to 1. or 2., wherein the content of the oxime ester photoinitiator in all non-volatile components in the negative photosensitive composition is m １ , the content of the acylphosphine oxide photoinitiator is m ２ Then, {m ２ / (m １ +m ２)}×100(%) is 45 to 95 mass % of the acylphosphine oxide-based photoinitiator. 4. A method for producing a substrate according to any one of 1. to 3., in which the black colorant is a mixture of two or more non-black colorants. 5. A method for producing a substrate according to any one of 1. to 4., in which the black colorant includes a blue pigment, a purple pigment, and an orange pigment. 6. A method for producing a substrate according to any one of 1. to 5., in which the proportion of the black colorant in all non-volatile components of the negative photosensitive composition is 5 to 15 mass %. 7. A method for producing a substrate according to any one of 1. to 6., in which the curable component includes a compound having an ethylenic carbon-carbon double bond. 8. A method for producing a substrate according to any one of 1. to 7., in which the negative photosensitive composition further includes an alkali-soluble resin. 9. A method for producing a substrate according to any one of 1. to 8. 10. A method for manufacturing a substrate according to any one of 1. to 9., wherein the negative photosensitive composition further comprises a fluorine-containing resin. 11. A substrate having a black pattern, manufactured by the method for manufacturing a substrate according to any one of 1. to 10.. 12. The substrate according to 11., wherein the optical density of the black pattern portion is 0.5 to 5. 13. A light-emitting element comprising a light-emitting layer or a wavelength conversion layer arranged in a region defined by the black pattern on the substrate according to 11. or 12.. 14. A negative photosensitive composition comprising: a black colorant having a minimum absorbance within a wavelength range of 380 to 420 nm; an oxime ester photoinitiator; an acylphosphine oxide photoinitiator; and a curable component that is cured by active species generated from the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.15. The negative photosensitive composition according to 14., wherein the absorbance of the black colorant in a wavelength range of 355 to 375 nm is greater than the minimum value of the absorbance of the black colorant in a wavelength range of 380 to 420 nm. 16. The negative photosensitive composition according to 14. or 15., wherein the content of the oxime ester photoinitiator in all nonvolatile components is m. １ , the content of the acylphosphine oxide photoinitiator is m ２ Then, {m ２ / (m １ +m ２ )}×100(%) is 45% by mass or more of the acylphosphine oxide photoinitiator. 17. The negative photosensitive composition according to any one of 14. to 16., wherein the black colorant is a mixture of two or more non-black colorants. 18. The negative photosensitive composition according to any one of 14. to 17., wherein the black colorant comprises a blue pigment, a purple pigment, and an orange pigment. 19. The negative photosensitive composition according to any one of 14. to 18., wherein the proportion of the black colorant in all non-volatile components is 5 to 15% by mass. 20. The negative photosensitive composition according to any one of 14. to 19., wherein the curable component comprises a compound having an ethylenic carbon-carbon double bond. 21. The negative photosensitive composition according to any one of 14. to 20., further comprising an alkali-soluble resin. 22. The negative photosensitive composition according to any one of 14. to 21., further comprising a fluorine-containing resin. 23. The negative photosensitive composition according to any one of 14. to 22., further comprising a chain transfer agent.

[0011] According to the present invention, the cross-sectional shape of a black pattern formed by photolithography is improved.

[0012] 1 shows the light absorption spectrum of black colorant dispersion 1 used in the examples. 2 shows the spectrum of light emitted from a light source (mercury lamp) used in the examples.

[0013] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The drawings are for illustrative purposes only, and the present invention should not be interpreted as being limited by the drawings.

[0014] In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means at least X and at most Y. For example, "1 to 5% by mass" means "at least 1% by mass and at most 5% by mass."

[0015] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both those that have no substituents and those that have a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). The term "(meth)acrylic" in this specification represents a concept that encompasses both acrylic and methacrylic. The same applies to similar notations such as "(meth)acrylate." In this specification, the term "organic group" refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

[0016] Hereinafter, the method for producing a substrate having a black pattern may be abbreviated to "substrate production method." Furthermore, in this specification, "total non-volatile components" means all components other than the solvent in the negative photosensitive composition, unless otherwise specified.

[0017] <Method for manufacturing a substrate having a black pattern> The method for manufacturing a substrate of this embodiment includes the following steps: A step of forming an unexposed film from a negative photosensitive composition on a substrate; An exposure step of selectively irradiating the unexposed film with light having a spectral maximum at least in the wavelength range of 350 to 380 nm and in the wavelength range of 390 to 420 nm to obtain an exposed film; A development step of developing the exposed film to form a pattern.

[0018] The above three steps are preferably carried out in the order listed.

[0019] The negative photosensitive composition used in the method for producing a substrate of this embodiment contains the following components.

[0020] - A black colorant having a minimum absorbance in the wavelength range of 380 to 420 nm - An oxime ester photoinitiator - An acylphosphine oxide photoinitiator - A curable component that is cured by active species generated from an oxime ester photoinitiator or an acylphosphine oxide photoinitiator

[0021] The reason why such a method for manufacturing a substrate can improve the cross-sectional shape of the black pattern can be explained as follows. Please note that the following explanation includes speculation. Furthermore, the present invention is not limited to the following explanation.

[0022] The black colorant contained in the negative-tone photosensitive composition has a minimum absorbance within the wavelength range of 380 to 420 nm. As a result, a film formed using the negative-tone photosensitive composition does not significantly absorb light with wavelengths of 380 to 420 nm. Therefore, when a film formed on a substrate using the negative-tone photosensitive composition is irradiated with light with wavelengths of 390 to 420 nm, much of the light reaches the lower part of the film. The inventors have discovered that acylphosphine oxide photoinitiators are prone to generate active species by absorbing light with wavelengths of 390 to 420 nm, such as H-rays (wavelength 405 nm) emitted from a mercury lamp (it can also be said that they have relatively high sensitivity to light with wavelengths of 390 to 420 nm). The presence of such initiators in the film generates active species in the lower part of the film. These active species promote the curing of the curable component, thereby promoting the curing reaction in the lower part of the film. This results in a more thorough curing of the lower part of the film compared to conventional methods. The negative photosensitive composition also contains an oxime ester photoinitiator. The inventors have discovered that oxime ester photoinitiators are prone to generate active species by absorbing light with a wavelength of 350 to 380 nm, such as i-line (wavelength 365 nm) emitted from a mercury lamp (it can also be said that they have relatively high sensitivity to light with a wavelength of 350 to 380 nm). Because light with a wavelength of 350 to 380 nm is less likely to reach the lower part of the film due to the influence of the black colorant, active species are generated from the oxime ester photoinitiator primarily in the upper part of the film by light with a wavelength of 350 to 380 nm, and these active species promote the curing of the curable component. This promotes the curing reaction in the upper part of the film. In this embodiment, the curing reaction proceeds in the lower part of the film mainly due to active species generated from the acylphosphine oxide photoinitiator, which is highly sensitive to light with a wavelength of 390 to 420 nm, while the curing reaction proceeds in the upper part of the film mainly due to active species generated from the oxime ester photoinitiator, which is highly sensitive to light with a wavelength of 350 to 380 nm. The former curing reaction in particular contributes to improving the conventional problem of poor cross-sectional shape of the pattern due to insufficient light reaching the bottom of the film.

[0023] The components contained in the negative photosensitive composition used in the method for producing a substrate of this embodiment, other characteristics, and specific conditions for each step will be described below.

[0024] [Negative Photosensitive Composition] (Black Colorant (or Dispersion thereof)) The black colorant has a minimum absorbance within a wavelength range of 380 to 420 nm. In other words, the black colorant has a "window" of light absorption within a wavelength range of 380 to 420 nm. By using such a black colorant, a film formed from the negative photosensitive composition is more likely to transmit light with a wavelength of 390 to 420 nm (such as H-line). The black colorant preferably has a minimum absorbance within a wavelength range of 390 to 420 nm, and more preferably has a minimum absorbance within a wavelength range of 395 to 415 nm. The black colorant exhibits a black color sufficient to obtain a black pattern that will later be provided on the substrate, and it is sufficient if the black colorant has a blackness sufficient to achieve the black color required for, for example, a partition wall in a display device. Therefore, the black colorant does not need to be jet black, and may have a slight tint when observed with the naked eye, such as a black that appears gray or a bluish black (black with a bluish tinge).

[0025] The black colorant preferably has the ability to block light with a wavelength of around 365 nm. By suppressing the arrival of light with a wavelength of around 365 nm at the lower part of the film, the pattern shape tends to be more precisely controllable. Specifically, the absorbance value of the black colorant at a wavelength of 365 nm is preferably greater than the minimum value of the absorbance of the black colorant in the wavelength range of 380 to 420 nm. More specifically, the minimum value of the absorbance of the black colorant in the wavelength range of 380 to 420 nm is set as A. ｍｉｎ The absorbance value of the black colorant for light with a wavelength of 365 nm is A ３６５ When this is done, A ３６５ / A ｍｉｎ is preferably 1.05 or more, more preferably 1.05 to 2, even more preferably 1.1 to 1.75, and particularly preferably 1.1 to 1.5.

[0026] The black colorant preferably contains one or more selected from black pigments, black dyes, and non-black colorants, and more preferably contains one or more selected from black pigments and non-black pigments. Examples of black pigments include carbon black, titanium black, perylene black, aniline black, cyanine black, and lactam black. Examples of non-black pigments include two or more organic pigments selected from the group consisting of red organic pigments, orange organic pigments, yellow organic pigments, green organic pigments, blue organic pigments, and violet organic pigments. A black colorant having a minimum absorbance in the wavelength range of 380 to 420 nm can typically be obtained by mixing two or more non-black colorants. For example, a black colorant can be obtained by mixing a blue pigment, a violet pigment, and an orange pigment. Another example is a combination of a blue pigment, a violet pigment, a green pigment, a red pigment, and an orange pigment. In this case, the red pigment and the orange pigment are preferably used in smaller amounts than the blue pigment, the violet pigment, and the green pigment. As yet another example, a relatively small amount of a black pigment such as carbon black or titanium black may be combined with a non-black pigment to produce a black colorant having a minimum absorbance in the wavelength range of 380 to 420 nm.

[0027] Examples of blue pigments 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. Among these, C.I. Pigment Blue 60 is preferred from the viewpoint of dispersibility and light-blocking properties. Examples of purple pigments 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. Among these, C.I. Pigment Violet 23 is preferred from the viewpoint of dispersibility and light-blocking properties. Examples of orange pigments include C.I. Examples of the green pigment 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. Among these, C.I. Pigment Orange 43 is preferred from the viewpoint of dispersibility and light-shielding properties. Examples of the green pigment include C.I. Examples of suitable red pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 16, 17, 17 Black, 18, 19, 20, 21, 22, 23, 24, 26, 36, 38, 39, 41, 42, 45, 48, 50, 51, 55, and 56. Examples of suitable red pigments include C.I. Pigment 5, 9, 10, 17, 48, 48:1, 48:2, 48:3, 48:4, 52:2, 119, 166, 177, 207, 209, 216, 224, 226, 242, and 254. In addition, known pigments not exemplified above can also be used, 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. From the viewpoints of solubility or dispersibility in a solvent and compatibility with other components, it is preferable that the black colorant contains an organic pigment.

[0028] For many commercially available pigments, the absorption spectra are available in literature, or manufacturers and distributors have spectral data. Furthermore, when multiple pigments are mixed, the resulting light absorption spectrum is, in principle, a superposition of the light absorption spectra of each pigment. Therefore, even without actually mixing two or more pigments, it is possible to determine, through simulation or paper studies, whether a pigment mixture has a minimum absorbance in the wavelength range of 380 to 420 nm, and to design an appropriate black colorant.

[0029] The black colorant is preferably subjected to a dispersion treatment. The dispersion can be obtained, for example, by treating the pigment, dispersant, and, if necessary, solvent using a bead mill. The type of dispersant is not particularly limited, and dispersants available from BYK-Chemie can be used, for example. Furthermore, when dispersing the pigment to produce a pigment dispersion in which the pigment is dispersed in a solvent (usually an organic solvent), an alkali-soluble resin may also be used. Since pigments are difficult to remove with an alkaline developer and tend to remain as development residues, the inclusion of an alkali-soluble resin in the pigment dispersion can be expected to reduce development residues. Specific alkali-soluble resins that can be used include those specifically listed above as alkali-soluble resins. Incidentally, when the black colorant is a black colorant dispersion, it is preferable that the black colorant dispersion satisfy the various light absorption indexes described above.

[0030] The proportion of the black colorant in the total nonvolatile components of the negative photosensitive composition is preferably 5 to 15% by mass, more preferably 7 to 13% by mass. Using a relatively large amount of black colorant can increase the degree of blackness of the resulting pattern. Furthermore, by not using too much black colorant, the proportions of other components become relatively high, making it easier to improve the balance of various performances such as photocurability and cured film properties. When the black colorant is a black colorant dispersion, the proportion of the black colorant dispersion in the total nonvolatile components of the negative photosensitive composition is preferably within the above-mentioned range.

[0031] (Oxime ester photoinitiators and acylphosphine oxide photoinitiators) Oxime ester photoinitiators and acylphosphine oxide photoinitiators are generally both compounds that generate radicals when irradiated with light, that is, photoradical initiators.

[0032] The oxime ester photoinitiator is not particularly limited as long as it has an oxime ester structure and generates active species such as radicals upon irradiation with ultraviolet light (preferably light with a wavelength of 350 to 380 nm).

[0033] Examples of the oxime ester photoinitiator include those having a structure represented by the following general formula (8).

[0034]

[0035] In general formula (8), R １４ is a hydrogen atom or a monovalent organic group, R １５ and R １６ are each independently a monovalent organic group, and preferably are each independently an alkyl group or an aromatic hydrocarbon group.

[0036] R １４ The monovalent organic group can be an alkyl group. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may have a substituent. 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.

[0037] R １５The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 1 to 10. The alkyl group may have a substituent. 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, a 2-ethylhexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Of these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group are preferred, and a hexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group are more preferred. R １５ The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. The aromatic hydrocarbon group may have a substituent. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group.

[0038] R １６ The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 1 to 10. The alkyl group may have a substituent. 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, a 2-ethylhexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Of these, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred, and a methyl group and an ethyl group are more preferred. R １５ The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. The aromatic hydrocarbon group may have a substituent. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group. Of these, a phenyl group is preferred.

[0039] The oxime ester photoinitiator may also include those having a structure represented by the following general formula (9).

[0040]

[0041] In general formula (9), R １７ is R in general formula (8) １４ is synonymous with R １８ and R １９ are each independently a hydrogen atom or a monovalent organic group, and the monovalent organic group is preferably an alkyl group; R ２０ is R in general formula (8) １６ is synonymous with R ２１ is R in general formula (8) １５ is synonymous with.

[0042] R １８ and R １９ The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may have a substituent. 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, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Of these, a butyl group is preferred.

[0043] The oxime ester photoinitiator may also include those having a structure represented by the following general formula (10).

[0044]

[0045] In general formula (10), R ２２ and R ２３ are each independently a monovalent organic group, R ２４ is R in general formula (8) １６ is synonymous with R ２５ is R in general formula (8) １５ is synonymous with.

[0046] R ２２ and R ２３The monovalent organic group can be an alkyl group or an aromatic hydrocarbon group. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group or aromatic hydrocarbon group may have a substituent. 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, a 2-ethylhexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. The aromatic hydrocarbon group may have a substituent. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group.

[0047] The oxime ester photoinitiator may also include those having a structure represented by the following general formula (11).

[0048]

[0049] In general formula (11), R ２７ is R in general formula (10) ２３ is synonymous with R ２６ and R ２８ are each independently R in general formula (8) １６ is synonymous with R ２９ and R ３０ are each independently R in general formula (8) １５ is synonymous with.

[0050] The oxime ester photoinitiator may also include those having a structure represented by the following general formula (12).

[0051]

[0052] In general formula (12), R ３１ is R in general formula (10) ２３ It is synonymous with R ３２ is R in general formula (8) １６ It is synonymous with R ３３ is R in general formula (8) １５ It is synonymous with R３４ is R in general formula (10) ２２ is synonymous with.

[0053] The oxime ester photoinitiator may also include those having a structure represented by the following general formula (13):

[0054]

[0055] In general formula (13), R ３５ is R in general formula (10) ２３ It is synonymous with R ３６ and R ３９ are each independently R in general formula (8) １６ It is synonymous with R ３７ and R ３８ are each independently R in general formula (8) １５ is synonymous with.

[0056] The acylphosphine oxide photoinitiator is not particularly limited as long as it has an acylphosphine oxide structure and generates active species such as radicals upon irradiation with ultraviolet light (preferably light with a wavelength of 390 to 420 nm).

[0057] Examples of the acylphosphine oxide photoinitiator include those having a structure represented by the following general formula (14).

[0058]

[0059] In general formula (14), R ４０ is a monovalent organic group, R ４１ ~R ５０ are each independently a hydrogen atom or a monovalent organic group.

[0060] R ４０ Examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an alkylcarbonyl group having 6 to 15 carbon atoms, and an arylcarbonyl group having 7 to 15 carbon atoms. ４０The monovalent organic group may have a substituent. Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, and 2-ethylhexyl groups. Specific examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy groups. Specific examples of aryl groups having 6 to 14 carbon atoms include phenyl, naphthyl, and anthryl groups. Specific examples of aryloxy groups having 6 to 14 carbon atoms include phenyloxy, tolyloxy, and naphthyloxy groups. Specific examples of alkylcarbonyl groups having 6 to 15 carbon atoms include acetyl, propionyl, n-butanoyl, iso-butanoyl, n-pentanoyl, and n-hexanoyl groups. Specific examples of the arylcarbonyl group having 7 to 15 carbon atoms include a benzoyl group, a 2-methylbenzoyl group, a 4-methylbenzoyl group, a 3,5-dimethylbenzoyl group, a 2,4,6-trimethylbenzoyl group, and a naphthoyl group.

[0061] R ４１ ~R ５０ Examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. ４１ ~R ５０ The monovalent organic group may have a substituent. Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, and 2-ethylhexyl groups. Specific examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy groups. Specific examples of aryl groups having 6 to 14 carbon atoms include phenyl, naphthyl, and anthryl groups.

[0062] Specific examples of oxime ester photoinitiators include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF, and N-1919 manufactured by ADEKA Corp. Specific examples of acylphosphine oxide photoinitiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0063] For the purpose of fine-tuning performance, a photoinitiator other than those described above may or may not be used. Usable photoinitiators include benzophenone-based, acetophenone-based, diketone-based, quinone-based, and acyloin-based photoradical initiators. Specific examples of 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. Specific examples of 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Of these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred. Specific examples of diketone-based photoradical initiators include 4,4'-dimethoxybenzyl, methyl benzoylformate, and 9,10-phenanthrenequinone. Of these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred. Specific examples of quinone-based initiators include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Of these, camphorquinone and 1,4-naphthoquinone are preferred. Specific examples of the acyloin initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Of these, benzoin and benzoin methyl ether are preferred.

[0064] The negative-acting photosensitive composition may contain only one oxime ester photoinitiator or two or more oxime ester photoinitiators.The negative-acting photosensitive composition may contain only one acylphosphine oxide photoinitiator or two or more acylphosphine oxide photoinitiators.

[0065] By adjusting the ratio of the oxime ester photoinitiator to the acylphosphine oxide photoinitiator, the shape of the resulting pattern can be further improved. Specifically, the content ratio of the oxime ester photoinitiator in the total nonvolatile components of the negative photosensitive composition is adjusted to m １ The content ratio of the acylphosphine oxide photoinitiator is m ２ Then, {m ２ / (m １ +m ２ )} × 100(%), the proportion of the acylphosphine oxide photoinitiator is preferably 45 to 95 mass%, more preferably 45 to 90 mass%, even more preferably 50 to 85 mass%, and particularly preferably 60 to 80 mass%. Optimizing the ratio of the two photoinitiators is believed to optimize the balance of curing in the lower and upper parts of the film, further improving the pattern shape. The negative-type photosensitive composition may further contain a known photoinitiator other than the oxime ester photoinitiator and the acylphosphine oxide photoinitiator. Examples of photoinitiators other than the oxime ester photoinitiator and the acylphosphine oxide photoinitiator include a hydroxyalkylphenone photoinitiator and a thioxanthone photoinitiator.

[0066] (Curable Component) The curable component is not particularly limited as long as it is cured (polymerized or crosslinked) by the active species generated from the oxime ester photoinitiator and / or the acylphosphine oxide photoinitiator. The curable component preferably cures by reacting with both the active species generated from the oxime ester photoinitiator and the active species generated from the acylphosphine oxide photoinitiator.

[0067] The curable component typically contains a compound having an ethylenic carbon-carbon double bond. The compound having an ethylenic carbon-carbon double bond is polymerized and cured by the action of an active radical. Hereinafter, the compound having an ethylenic carbon-carbon double bond as the curable component will be specifically described.

[0068] The term "ethylenic carbon-carbon double bond" refers to a carbon-carbon double bond that can react by the action of a radical. Conjugated double bonds such as the double bond of a benzene ring do not fall under the category of "ethylenic carbon-carbon double bond." From the viewpoint of improving reactivity, it is preferable that a compound having an ethylenic carbon-carbon double bond has an ethylenic carbon-carbon double bond at its terminal.

[0069] The compound having an ethylenic carbon-carbon double bond may be monofunctional or polyfunctional. That is, the compound having an ethylenic carbon-carbon double bond may have only one ethylenic carbon-carbon double bond per molecule, or may have two or more (specifically, 2 to 8, more specifically, 2 to 6) ethylenic carbon-carbon double bonds per molecule. From the viewpoints of further improving sensitivity and improving the physical properties of a cured film, the compound having an ethylenic carbon-carbon double bond is preferably polyfunctional.

[0070] The compound having an ethylenic carbon-carbon double bond is preferably a (meth)acrylate compound, i.e., a compound having a (meth)acryloyl group as a structure containing an ethylenic carbon-carbon double bond. The compound having an ethylenic carbon-carbon double bond is more preferably a (meth)acrylate compound.

[0071] Specific examples of compounds having an ethylenic carbon-carbon double bond include the following: Of course, compounds having an ethylenic carbon-carbon double bond are not limited to these.

[0072] Polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy acrylates such as di(meth)acrylate of bisphenol A diglycidyl ether and di(meth)acrylate of hexanediol diglycidyl ether; and urethane (meth)acrylates obtained by the reaction of polyisocyanate with a hydroxy group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate.

[0073] The negative photosensitive composition may contain only one curable component or may contain two or more curable components. The content of the curable components is usually 5 to 60 mass %, preferably 10 to 55 mass %, and more preferably 15 to 50 mass %, of the total non-volatile components of the negative photosensitive composition.

[0074] (Alkali-Soluble Resin) The negative photosensitive composition preferably contains an alkali-soluble resin. Use of an alkali-soluble resin tends to facilitate the formation of a pattern of a desired shape, particularly when forming a pattern (partition wall) using an alkali developer. The alkali-soluble resin typically has an alkali-soluble group. Examples of the alkali-soluble group include a carboxy group and a phenolic hydroxy group. Incidentally, in this specification, a resin that has a fluorine atom and is alkali-soluble is generally classified as a fluorine-containing resin, which will be described later. In other words, the alkali-soluble resin generally does not have a fluorine atom.

[0075] Examples of alkali-soluble resins include alkali-soluble novolac resins. Alkali-soluble novolac resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst. Specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methylcatechol, pyrogallol, phloroglucinol, thymol, and isothymol. These phenols may be used alone or in combination of two or more. Specific examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

[0076] Examples of alkali-soluble resins 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 their side chains. Examples of epoxy resins include bisphenol-type epoxy resins, and examples of acid-modified epoxy (meth)acrylate resins include those obtained by reacting bisphenol-type epoxy resins with (meth)acrylic acid. Specifically, examples of bisphenol-type epoxy resins or acid-modified epoxy (meth)acrylate resins having a structural unit represented by the following general formula (e) include:

[0077]

[0078] In general formula (e), two R's each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, a linear perfluoroalkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and Z represents a monovalent organic group or a hydrogen atom, provided that in at least some of the structural units represented by general formula (e) in the alkali-soluble resin (E), Z is a monovalent organic group having a carboxy group.

[0079] When 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 preferred from the viewpoint of availability. Specific examples of linear perfluoroalkyl groups having 1 to 3 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Of these, a trifluoromethyl group is preferred from the viewpoint of availability. Each R may have the same structure or different structures.

[0080] When Z is a monovalent organic group, 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 increases alkali solubility.

[0081] 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. Examples of esterifying agents include acid halides, acid anhydrides, and condensing agents. When Z is a hydrogen atom, -O-Z may be reacted with an esterifying agent. Examples of esterifying agents include the same esterifying agents described above. Examples of acid anhydrides include acrylic anhydride, methacrylic anhydride, succinic anhydride, phthalic anhydride, and 1,2,3,4-tetrahydrophthalic anhydride. Reacting these acid anhydrides with a resin can introduce ethylenically unsaturated bonds and carboxyl groups into the resin. 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 account the solubility in alkali required for the alkali-soluble resin.

[0082] Epoxy (meth)acrylate resins having a structural unit represented by general formula (e) are available from, for example, Nippon Kayaku Co., Ltd.

[0083] In addition, 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. Commercially available acid-modified epoxy (meth)acrylates can also be used. Examples of commercially available acid-modified epoxy acrylates that can be used include those manufactured by Nippon Kayaku Co., Ltd. under the product names: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H.

[0084] The alkali-soluble resin may have a polycyclic aromatic skeleton such as a fluorene skeleton. The use of such an alkali-soluble resin may improve the heat resistance and durability of the cured pattern. Specific examples of the acid-modified epoxy (meth)acrylate resin include those having a polycyclic aromatic skeleton, or resins having a polycyclic aromatic skeleton may be selected from a different family of resins than the acid-modified epoxy (meth)acrylate resin. Incidentally, resins having a fluorene skeleton are sometimes referred to as "cardo resins." Like other alkali-soluble resins, alkali-soluble resins having a polycyclic aromatic skeleton such as a fluorene skeleton preferably have an alkali-soluble group such as a carboxy group or a hydroxy group.

[0085] The alkali-soluble resin may have an ethylenic carbon-carbon double bond. It is believed that the alkali-soluble resin having an ethylenic carbon-carbon double bond forms a bond with the above-mentioned curable component during curing of the composition and is incorporated into the cured product. This is believed to contribute to improving the stability and heat resistance of the cured product. Just to be clear, the alkali-soluble resin having an ethylenic carbon-carbon double bond is not classified as the above-mentioned curable component.

[0086] The weight-average molecular weight of the alkali-soluble resin is preferably 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 (the number of milligrams of potassium hydroxide required to neutralize 1 g of sample) can be an indicator of alkali solubility. In this embodiment, the acid value of the alkali-soluble resin is preferably 20 to 80, more preferably 30 to 70, and even more preferably 40 to 60. The acid values ​​of the alkali-soluble resins used in the examples described below are on this order.

[0087] When an alkali-soluble resin is used, only one alkali-soluble resin may be used, or two or more alkali-soluble resins may be used. When an alkali-soluble resin is used, the amount thereof is usually 10 to 70% by mass, preferably 15 to 60% by mass, and more preferably 20 to 55% by mass, of the total nonvolatile components of the negative-type photosensitive composition.

[0088] (Fluorine-Containing Resin) The negative photosensitive composition preferably contains a fluorine-containing resin. By forming a pattern (partition wall) having concaves and convexes using a photosensitive composition containing a fluorine-containing resin, the resulting pattern (partition wall) is more likely to repel ink for forming an organic layer. This contributes to preventing ink dropped into a recess from "crawling" along the side of the recess and entering an adjacent recess. In other words, unintended mixing of dye between pixels can be prevented.

[0089] There are no particular restrictions on the fluorine-containing resin that can be used. Preferred fluorine-containing resins that can be used are described below. The fluorine-containing resin preferably has a structure represented by the following general formula (1), and more preferably has a structure represented by the following general formula (2).

[0090]

[0091] In the general formula (1), two Rf's each independently represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched perfluoroalkyl group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, or a fluorine atom; ２ 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.

[0092]

[0093] In the general formula (2), two Rf's each independently represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched perfluoroalkyl group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, or a fluorine atom; １ represents a hydrogen atom, a fluorine atom or a methyl group; R ２ 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.

[0094] In general formula (2), R １ is preferably a hydrogen atom or a methyl group. ２ Examples of the alkyl group 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, and an isopropyl group are preferred, and a hydrogen atom and a methyl group are more preferred.

[0095] Rf in general formula (1) or general formula (2) is preferably a fluorine atom, a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, an 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, an n-heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, or a hexafluoroisopropyl group, and particularly preferably a fluorine atom, a difluoromethyl group, or a trifluoromethyl group.

[0096] Preferred specific structures of the structural units include the structures described in paragraphs 0060 to 0061 of WO 2021 / 235541.

[0097] The content of the structural unit represented by general formula (2) in the fluorine-containing resin is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration solubility in solvents, resistance to various treatments in the production of light-emitting devices, and the like.

[0098] The fluorine-containing resin may contain a structure represented by the following general formula (3).

[0099]

[0100] In general formula (3), R ３ , R ４ each independently represents a hydrogen atom or a methyl group.

[0101] In the general formula (3), W １ represents a divalent linking group. Preferably represents -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH- is preferred. In particular, W １ However, the group —O—C(═O)—NH— is preferable because it provides better liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of a light-emitting element.

[0102] In general formula (3), A １ represents a divalent to tetravalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0103] Divalent Linking Group A １When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof 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.

[0104] Divalent Linking Group A １ When 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.

[0105] Divalent Linking Group A １ When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0106] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a hydroxyethylene group, a 1-hydroxy-n-propylene group, a 2-hydroxy-n-propylene group, and a 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 -) etc.

[0107] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３When the hydroxy group of the hydroxy group-substituted alkylene group exemplified above is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0108] Among them, the divalent linking group A １ is 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 -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group and a 2-hydroxy-n-propylene group are particularly preferred. １ As for -C(CH ２ -) ２ CH ３ and the like, and the tetravalent linking group A １ As for C(CH ２ -) ４ Examples include:

[0109] In the general formula (3), Y １ represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.

[0110] In general formula (3), u represents an integer of 1 to 3, and u is particularly preferably 1. In general formula (3), n represents an integer of 1 to 3, and n is particularly preferably 1. The substitution positions of the aromatic rings are each independently ortho-, meta-, or para-positions, and preferably para-positions. １ may be the same or different. １ may be the same or different.１ may be the same or different. ４ may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of W １ are preferably the same as each other, and a plurality of A １ are preferably the same, and a plurality of Y １ are preferably the same, and a plurality of R ４ are preferably the same as each other.

[0111] Specific preferred examples of the structure represented by general formula (3) include the structures described in paragraphs 0081 to 0084 of WO 2021 / 235541.

[0112] The content of the structural unit represented by general formula (3) in the fluorine-containing resin is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration solubility in solvents, resistance to various treatments in the production of light-emitting elements, and the like.

[0113] The fluorine-containing resin may contain a structure represented by the following general formula (4).

[0114]

[0115] In general formula (4), R ５ , R ６ each independently represents a hydrogen atom or a methyl group.

[0116] In formula (4), W ２ represents a divalent linking group, preferably -O-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH-. Among these, -O-C(=O)-NH-, -C(=O)-O-C(=O)-NH- or -C(=O)-NH- is preferred. In particular, W ２ is preferably —O—C(═O)—NH—, since the liquid repellency to ink after UV ozone treatment or oxygen plasma treatment in the manufacture of a light-emitting element is superior.

[0117] In general formula (4), A ２ represents a divalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ In the general formula (4), A ３ represents a divalent to tetravalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group can be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0118] Divalent Linking Group A ２ , A ３ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof 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.

[0119] Divalent Linking Group A ２ , A ３ When each of the groups independently represents 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.

[0120] Divalent Linking Group A ２ , A ３ When each of the groups independently represents a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0121] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a 1-hydroxyethylene group (—CH(OH)CH ２-), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0122] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３ When the hydroxy group of the hydroxy group-substituted alkylene group is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0123] Among them, the divalent linking group A ２ , A ３ each independently represents 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 -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ The trivalent linking group A3 is particularly preferably —C(CH ２ -) ２ CH ３ The tetravalent linking group A3 can be C(CH ２ -) ４ Examples include:

[0124] In the general formula (4), Y ２ , Y ３ each independently represents a divalent linking group, and is preferably —O— or —NH—, and more preferably —O—.

[0125] In the general formula (4), n represents an integer of 1 to 3. It is particularly preferable that n is 1. ３ may be the same or different. ６ may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that a plurality of Y ３ are preferably the same, and a plurality of R ６ are preferably the same as each other.

[0126] In the general formula (4), r represents 0 or 1. When r is 0, it is represented by "(-C(=O)-)". ｒ represents a single bond.

[0127] Specific preferred examples of the structure represented by general formula (4) include the structures described in paragraphs 1005 to 0109 of WO 2021 / 235541.

[0128] The content of the structural unit represented by general formula (4) in the fluorine-containing resin is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 10 to 30 mass%, taking into consideration the solubility in a solvent and the adhesion of the pattern (partition wall) to a substrate.

[0129] The fluorine-containing resin may contain a structural unit represented by general formula (5).

[0130]

[0131] In general formula (5), R ７ represents a hydrogen atom or a methyl group.

[0132] In general formula (5), R ８ 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, in which any number of hydrogen atoms are substituted with fluorine atoms, and the fluorine content in the structural unit is 30 mass% or more.

[0133] R ８ When 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.

[0134] R ８ When 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):

[0135]

[0136] In general formula (5-1), R ９ is R in general formula (5) ７ is synonymous with.

[0137] In the general formula (5-1), X is a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

[0138] In the general formula (5-1), p is an integer of 1 to 4, and q is an integer of 1 to 14. It is particularly preferable that p is an integer of 1 or 2, and q is an integer of 2 to 8.

[0139] Specific preferred examples of the structural unit represented by general formula (5) include the structures described in paragraphs 0125 to 0128 of WO 2021 / 235541.

[0140] The content of the structural unit represented by general formula (5) in the fluorine-containing resin may be appropriately determined taking into consideration the ease with which the resin repels ink when formed into a pattern (partition wall), the ease with which the resin dissolves in a solvent when the photosensitive composition is prepared, etc. Specifically, the content of the structural unit represented by general formula (5) in the fluorine-containing resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0141] The fluorine-containing resin may contain a structure represented by the following general formula (6).

[0142]

[0143] In general formula (6), R １０ represents a hydrogen atom or a methyl group.

[0144] In the general formula (6), each B independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or —C(═O)—O—R １１ (R １１ represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, in which any number of hydrogen atoms are substituted with fluorine atoms, and R １１ the fluorine content in the compound is 30% by mass or more) or —O—C(═O)—R １２ (R １２ represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.) In addition, m represents an integer of 0 to 3.

[0145] Specific preferred examples of the structure represented by general formula (6) include the structures described in paragraphs 0137 to 0138 of WO 2021 / 235541.

[0146] The content of the structural unit represented by general formula (6) in the fluorine-containing resin is preferably from 5 to 70 mass%, more preferably from 10 to 50 mass%, particularly preferably from 20 to 40 mass%, in consideration of sufficiently obtaining the effects based on the structural unit represented by general formula (6) and of solvent solubility.

[0147] In general formula (6), B １ When is a hydroxy group or a carboxyl group, the structural unit represented by general formula (6) has solubility in an alkaline developer. Therefore, when particularly good alkaline developability is desired, the fluorine-containing resin is １ It is preferable that the structural unit contains a structural unit represented by general formula (6) in which is a hydroxy group or a carboxyl group.

[0148] The fluorine-containing resin may contain a structure represented by the following general formula (7).

[0149]

[0150] In general formula (7), R １３ represents a hydrogen atom or a methyl group.

[0151] In general formula (7), A ４ represents a divalent linking group, preferably a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be substituted with hydroxy groups or -O-C(=O)-CH ３ may be substituted with

[0152] Divalent Linking Group A ４ When is a linear alkylene group having 1 to 10 carbon atoms, examples thereof 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.

[0153] Divalent Linking Group A ４ When 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.

[0154] Divalent Linking Group A ４ When is a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted cycloheptane, di-substituted cyclooctane, di-substituted cyclodecane, and di-substituted 4-tert-butylcyclohexane.

[0155] When any number of hydrogen atoms in these alkylene groups are substituted with hydroxy groups, examples of the hydroxy group-substituted alkylene group include a 1-hydroxyethylene group (—CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), hydroxy-isobutylene group (-CH ２ CH (CH ２ OH)CH ２ -), hydroxy-tert-butylene group (-C(CH ２ OH)(CH ３ ) CH ２ -) etc.

[0156] In addition, any number of hydrogen atoms in these alkylene groups may be replaced by —O—C(═O)—CH ３ When the hydroxy group of the hydroxy group-substituted alkylene group is substituted with —O—C(═O)—CH ３ Examples of what has been replaced by include:

[0157] Among them, the divalent linking group A ４is 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 -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ２ OH)CH ２ CH ２ -), and ethylene group, propylene group, 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ２ OH)CH ２ -) is more preferred, and an ethylene group, a 1-hydroxyethylene group (-CH(OH)CH ２ -), 2-hydroxyethylene group (-CH ２ CH(OH)—) is particularly preferred.

[0158] In the general formula (7), Y ４ represents a divalent linking group, preferably —O— or —NH—, and more preferably —O—.

[0159] In general formula (7), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0160] In general formula (7), E １ represents a hydroxy group, a carboxyl group, or an oxirane group. １ When is an oxirane group, examples include an ethylene oxide group, a 1,2-propylene oxide group, a 1,3-propylene oxide group, etc. Among these, an ethylene oxide group is preferred.

[0161] In the general formula (7), s represents 0 or 1. When s is 0, (-Y ４ -A ４When r is 0 and s is 0, the main chain of the structural unit does not contain E １ The resulting structure is a bonded structure.

[0162] Specific preferred examples of the structure represented by general formula (7) include the structure described in paragraph 0156 of WO 2021 / 235541.

[0163] The weight average molecular weight of the fluororesin, 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. Adjusting the molecular weight of the fluororesin may increase the strength of the pattern (partition walls) to be formed or may increase the solubility in solvents and thereby improve coatability.

[0164] The dispersity (Mw / Mn) of the fluorine-containing resin 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.

[0165] The fluorine-containing resin 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 preferred.

[0166] The fluorine content of the fluorine-containing resin is preferably 20 to 50% by mass, more preferably 25 to 40% by mass. When the fluorine content is within this range, the fluorine-containing resin is easily dissolved in a solvent. Furthermore, when the fluorine content of the fluorine-containing resin is within this range, a pattern (partition wall) having excellent liquid repellency is easily obtained. The fluorine content of the fluorine-containing resin can be measured, for example, in accordance with the description in paragraph 0174 of WO 2021 / 235541.

[0167] When a fluorine-containing resin is used, only one fluorine-containing resin may be used, or two or more fluorine-containing resins may be used. In order to achieve a balance between sufficient liquid repellency of the resulting pattern (partition wall) and good alkaline developability, the amount of the fluorine-containing resin used is usually 0.1 to 10 mass %, preferably 0.1 to 8 mass %, and more preferably 0.2 to 5 mass %, of the total non-volatile components of the photosensitive composition.

[0168] In addition, with regard to fluorine-containing resins, for example, the description in WO 2021 / 235541 can be referred to.

[0169] (Chain Transfer Agent) The negative photosensitive composition preferably contains a chain transfer agent. As is known in the field of polymer synthesis, a chain transfer agent is a component that receives a radical from a growing polymer chain in a radical polymerization system and generates a new radical. By using a chain transfer agent, the degree of polymerization can be adjusted, and the properties of the cured film can be adjusted in some cases.

[0170] Any known chain transfer agent can be used without any particular limitation. Preferably, the chain transfer agent contains a thiol compound. The thiol compound may have only one mercapto group per molecule, or may have two or more (specifically, 2 to 8) mercapto groups per molecule.

[0171] Specific examples of thiol compounds include those represented by the following general formula (b).

[0172]

[0173] In the general formula (b), R is a hydrogen atom, an alkyl group, or a cycloalkyl group, and X is —CO— or —CH ２ -, L is an n-valent linking group, and n is an integer of 2 or more, preferably 2 to 8, more preferably 2 to 6. Multiple Rs may be the same or different from each other. Furthermore, multiple Xs may be the same or different from each other. However, from the viewpoint of ease of synthesis, it is preferable that multiple Rs are the same as each other, and it is preferable that multiple Xs are the same as each other.

[0174] The alkyl group for R may be linear or branched. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms. 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.

[0175] Examples of L, which is an n-valent linking group, include a linear or branched alkylene chain (having, for example, 2 to 6 carbon atoms), a trimethylolpropane residue, -(CH ２ ) ｐ Examples of such linking groups include trivalent linking groups such as an isocyanuric ring having three - (p is 2 to 6), tetravalent linking groups or pentavalent linking groups such as a pentaerythritol residue, and hexavalent linking groups such as a dipentaerythritol residue.

[0176] Commercially available thiol compounds include, for example, the "Karends" 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.

[0177] The content of mercapto groups contained in the thiol compound is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and even more preferably 10 to 30% by mass, based on the molecular weight of the thiol compound.

[0178] When a chain transfer agent is used, only one chain transfer agent may be used, or two or more chain transfer agents may be used. When a chain transfer agent is used, the amount thereof 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 nonvolatile components of the negative photosensitive composition. Furthermore, when a chain transfer agent is used, the amount thereof 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 the curable component.

[0179] (Other Optional Components) The negative photosensitive composition may contain optional components other than those described above. Examples of optional components include dissolution inhibitors, plasticizers, stabilizers, surfactants, thickeners, leveling agents, antifoaming agents, compatibilizers, adhesion improvers, and antioxidants. Commercially available products can be used as these optional components. For example, the "KAYAMER" series manufactured by Nippon Kayaku Co., Ltd. can be used as an adhesion improver.

[0180] (Solvent) The negative photosensitive composition typically contains the above components dissolved or dispersed in a solvent, which usually contains an organic solvent.

[0181] Usable solvents are not particularly limited. Specific examples include ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorine-containing solvents. These may be used alone or in combination of two or more.

[0182] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0183] Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

[0184] Examples of polyhydric alcohols and derivatives thereof include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of dipropylene glycol or dipropylene glycol monoacetate.

[0185] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0186] Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and γ-butyrolactone.

[0187] Examples of aromatic solvents include xylene and toluene.

[0188] Examples of fluorine-based solvents include chlorofluorocarbons, chlorofluorocarbon substitutes, perfluoro compounds, and hexafluoroisopropyl alcohol.

[0189] In addition, for the purpose of improving the coating property, it is possible to use a turpentine-based petroleum naphtha solvent or a paraffin-based solvent, which is a high-boiling weak solvent.

[0190] Among these, the solvents include methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monoacetate Preferably, the solvent contains at least one selected from the group consisting of dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monobutyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, γ-butyrolactone, and hexafluoroisopropyl alcohol. Furthermore, the solvent preferably contains methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, or γ-butyrolactone.

[0191] When a solvent is used, only one solvent may be used, or two or more solvents may be used. When a solvent is used, the amount of solvent in the negative photosensitive composition is preferably used in an amount such that the total solids concentration becomes, for example, 5 to 85 mass %, specifically 10 to 60 mass %. By adjusting the amount of solvent, the thickness of the film to be formed can be adjusted. Within the above range, it is easy to obtain a film with a thickness suitable for forming partition walls in organic EL elements.

[0192] [Film Forming Step] In the film forming step, an unexposed film is formed on a substrate using the above-described negative photosensitive composition.

[0193] 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). A layer may or may not be formed on at least one side of the substrate. For example, when manufacturing a light-emitting device, a first light-emitting layer may be disposed on at least one side of the substrate. Examples of the first light-emitting layer include layers formed from organic electroluminescent (EL) materials, LED light-emitting materials such as mini-LEDs, μ-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 a monochromatic layer is preferred. Furthermore, the first light-emitting layer is preferably a monochromatic blue light-emitting layer. When a first light-emitting layer is disposed on at least one side of the substrate, an organic or inorganic film may be disposed between the substrate and the first light-emitting layer. For example, an anti-reflective film, a multilayer resist underlayer, a barrier layer, or the like may be present. In addition, a driving circuit, an electrode, a planarization layer, etc. may be formed between the substrate and the first light-emitting layer. In addition, a wavelength conversion layer may be provided instead of the first light-emitting layer. Just to be clear, the substrate may not have a layer such as the first light-emitting layer formed on its surface.

[0194] The method for applying the negative photosensitive composition is not particularly limited. Known methods such as spin coating, bar coating, and curtain coating can be used. Inkjet printing may also be applicable. When a solvent-containing negative photosensitive composition is used, it is preferable to dry the solvent by heating after application of the 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 film thickness (dry thickness) of the film is usually 0.5 to 20 μm, preferably 1 to 15 μm.

[0195] [Exposure Step] In the exposure step, the unexposed film formed in the film formation step is selectively irradiated with light having a spectral maximum at least in the wavelength range of 350 to 380 nm (preferably in the wavelength range of 355 to 375 nm) and in the wavelength range of 390 to 420 nm (preferably in the wavelength range of 395 to 415 nm). This converts the unexposed film into an exposed film. "Selective irradiation" specifically refers to irradiating the unexposed film with light through a photomask so that some areas are exposed to light and some areas are not. By selectively irradiating the unexposed film with light and then performing a subsequent development step, a desired pattern can be formed on the substrate.

[0196] Typically, light emitted from a mercury lamp has spectral maxima at least within the wavelength range of 350 to 380 nm and within the wavelength range of 390 to 420 nm. Light emitted from a mercury lamp typically includes the i-line at 365 nm and the h-line at 405 nm as emission lines. In other words, a mercury lamp is one of the preferred light sources. When a mercury lamp is used, light within the wavelength range of 350 to 380 nm and light within the wavelength range of 390 to 420 nm are simultaneously irradiated onto the unexposed film. Of course, light sources other than mercury lamps can also be used. For example, a light-emitting diode emitting monochromatic light within the wavelength range of 350 to 380 nm and a light-emitting diode emitting monochromatic light within the wavelength range of 390 to 420 nm may be combined, and the light emitted from these two light-emitting diodes may be irradiated onto the unexposed film. In this case, the light emitted from the two light-emitting diodes may be irradiated onto the unexposed film simultaneously or separately, although the former is preferred in terms of industrial productivity and other factors. The light irradiated onto the unexposed film may contain only light in the wavelength range of 350 to 380 nm and light in the wavelength range of 390 to 420 nm, or may contain light of wavelengths other than these. Light emitted from mercury lamps commonly used in the field of photolithography contains emission lines such as i-line and h-line in its continuous spectrum. Therefore, if light emitted from a mercury lamp is irradiated as is without being spectrally separated, the light will usually contain i-line and h-line, as well as light of wavelengths other than these.

[0197] [Development Step] In the development step, the film after the exposure step is typically developed using a developer, which usually dissolves the unexposed areas in the film, thereby obtaining a pattern (partition wall).

[0198] An alkaline aqueous solution is preferably used as the developer. Specifically, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, etc. can be used. As the developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is particularly preferred in view of its good developability and long track record of use in the field of photosensitive compositions. The concentration of the TMAH aqueous solution is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass. Incidentally, a developer containing an organic solvent as its main component may be used in some cases.

[0199] As the developing method, a known method can be used, such as a dipping method, a puddle method, a spray method, etc. The developing 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.

[0200] After the development treatment, if necessary, a step of washing the pattern with deionized water etc. The washing time is preferably from 10 seconds to 3 minutes, more preferably from 30 seconds to 2 minutes.

[0201] [Heating Step] The pattern formed through the development step is preferably heated. That is, it is preferable to carry out the heating step after the development step. In the heating step, the developed pattern is heated. This allows the remaining reactive groups in the pattern obtained in the development step to react as much as possible, thereby hardening the film. In the heating step, 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. By not raising the heating temperature too much, it is easy to suppress alteration and deterioration of the dye and other materials in the light-emitting element. The heating time is, for example, 10 minutes to 3 hours, preferably 15 minutes to 1 hour.

[0202] [Optional Steps After Heating Step] The cured film obtained by the heating step may be subjected to UV ozone treatment or oxygen plasma treatment, which can remove organic matter remaining in recesses of the pattern (cured film) and reduce uneven wetting of the dropped ink during the ink dropping process described below.

[0203] To obtain a light-emitting element, it is preferable to perform a second light-emitting layer formation 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 partition walls. The second light-emitting layer preferably contains a conventionally known material, such as a quantum dot light-emitting material. As described in the Background Art section, the second light-emitting layer can be formed, for example, by dropping ink into the recesses of the pattern (cured film) using an inkjet method and then drying and / or solidifying the ink. In other words, a light-emitting element can sometimes be obtained by dropping ink for forming the second light-emitting layer into the recesses of the pattern (cured film) using an inkjet method.

[0204] Alternatively, in order to obtain a light-emitting element that emits RGB light, ink containing a red, green, or blue dye (typically a liquid in which a pigment is dispersed) may be dropped into the recesses of the pattern (cured film), i.e., the areas defined by the partition walls, and then the ink may be dried and / or solidified.

[0205] In this manner, a substrate having a black pattern can be produced. The optical density of the black pattern portion of the substrate having a black pattern is preferably 0.5 to 5.0, more preferably 1.0 to 5.0, and even more preferably 2.0 to 4.5. In this embodiment, a black pattern having a good cross-sectional shape can be obtained despite a relatively high optical density, and a substrate having such a black pattern can be produced. Please refer to the description of the Examples for specific methods for measuring the optical density.

[0206] [Additional Explanation Regarding Pattern Shape] When a cross section of a pattern formed on a substrate as described above (for example, a cross section of a line portion of a line and space pattern) is photographed with a scanning electron microscope, the degree of taper or reverse taper can be quantified and used as an index for evaluating the pattern shape.

[0207] Specifically, when the height from the top surface of the substrate to the top of the pattern is defined as the pattern height, the maximum value of the pattern width at the top of the pattern, i.e., in the range from the top of the pattern to 1 / 2 of the pattern height, is defined as width A, and the minimum value of the pattern width at the bottom of the pattern, i.e., in the range from the contact surface between the substrate and the pattern to 1 / 2 of the pattern height, is defined as width B, the value of width A - width B can be used as an index of the pattern shape. From the viewpoint of improving the pattern shape, the value of width A - width B is preferably -2 to 7 μm, more preferably -2 to 2 μm, even more preferably 0 to 1 μm, and may be -2 to 0 μm. It can be said that the closer this value is to 0, the closer the cross-sectional shape of the pattern is to a rectangle.

[0208] The value of width A / width B can also be used as an index of the pattern shape. From the viewpoint of improving the pattern shape, the ratio of width B to width A (width B / width A) is preferably 0.4 to 1.2, more preferably 0.8 to 1.2, even more preferably 0.9 to 1.0, and may be 1.0 to 1.2. The closer this value is to 1.0, the more rectangular the cross-sectional shape of the pattern is.

[0209] <Negative Photosensitive Composition> The above describes the embodiments of the present invention mainly from the viewpoint of a method for manufacturing a substrate. From the viewpoint separate from the method for manufacturing a substrate, the negative photosensitive composition described in the section [Negative Photosensitive Composition] is itself considered to be novel and may be industrially useful. In other words, the negative photosensitive composition described in the next paragraph may be useful in itself, independently of the method for manufacturing a substrate.

[0210] A negative photosensitive composition comprising: a black colorant having a minimum absorbance within a wavelength range of 380 to 420 nm; an oxime ester photoinitiator; an acylphosphine oxide photoinitiator; and a curable component that is cured by active species generated from the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

[0211] Specific embodiments of this negative photosensitive composition are as explained in the section [Negative Photosensitive Composition], and therefore will not be explained again.

[0212] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0213] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. However, it should be noted that the present invention is not limited to the Examples.

[0214] First, various measurement techniques will be described.

[0215] [Measurement of the molar ratio of each structural unit in the polymer] １ H-NMR, １９ F-NMR or １３ It was determined from C-NMR measurements.

[0216] [Measurement of molecular weight of polymer] The weight average molecular weight Mw and molecular weight dispersity (ratio of number average molecular weight Mn to weight average molecular weight Mw; Mw / Mn) of the polymer were measured using high performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, Model HLC-8320GPC) with one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) connected in series, using polystyrene as a standard substance and tetrahydrofuran (THF) as a developing solvent. A refractive index difference detector was used as the detector.

[0217] <Preparation (Synthesis or Preparation) of Raw Materials> [Synthesis of Fluorine-Containing Resin 1] Into a 300 mL glass flask equipped with a stirrer, 2.9 parts by mass of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd.; hereinafter referred to as BTFBE), 2.9 parts by mass of 4-acetoxystyrene (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as p-AcO-St), 12.5 parts by mass of 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as MA-C6F), 6.0 parts by mass of glycerin monomethacrylate (product of Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as Gly-MA), and 125 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed at room temperature (approximately 20°C). 2.3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was further added to the flask, and the mixture was degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 79°C, followed by reaction overnight. This yielded a precursor solution of fluororesin 1.

[0218] The composition ratio of the structural units of the precursor of fluororesin 1, in terms of molar ratio, was (structural units derived from BTFBE):(structural units derived from p-AcO-St):(structural units derived from MA-C6F):(structural units derived from Gly-MA)=15:18:29:38. The structure of the precursor of fluororesin 1 is shown below.

[0219]

[0220] After the atmosphere in the flask was replaced with dry air, the internal temperature of the precursor solution was lowered to 60°C. Then, 0.01 parts by mass of dibutylhydroxytoluene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 11.4 parts by mass of 2-isocyanatoethyl acrylate (a product of Showa Denko K.K., product name: Karenz AOI) were added. Thereafter, the mixture was stirred for 4 hours. After stirring was completed, the solution was cooled to room temperature (20°C). In this way, a solution of fluororesin 1 was obtained. Based on GPC measurement, fluororesin 1 had Mw=13,300 and Mw / Mn=1.7.

[0221] [Synthesis of Fluorine-Containing Resin 2] Into a 300 mL glass flask equipped with a stirrer, at room temperature (approximately 20°C), 9.5 g (0.05 mol) of BTFBE, 13.0 g (0.10 mol) of hydroxyethyl methacrylate (hereinafter referred to as HEMA), 43.2 g (0.1 mol) of MA-C6F, 8.6 g (0.10 mol) of methacrylic acid (Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as MAA), 7.8 g (0.75 mol) of styrene (Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as St), and 82 g of MEK (methyl ethyl ketone) were placed. Thereafter, 1.6 g (0.005 mol) of AIBN was further placed in the flask and degassed while stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, the internal temperature was raised to 75°C, and the mixture was allowed to react for 6 hours. In this manner, a precursor solution of fluorine-containing resin 2 was obtained.

[0222] 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 molar ratio, was 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=15:25:30:10:20.

[0223]

[0224] After completion of the reaction, the atmosphere in the flask was replaced with dry air, and the reaction solution was then cooled to an internal temperature of 60°C. After cooling, 0.01 parts by mass of dibutylhydroxytoluene (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 12.1 parts by mass of 2-isocyanatoethyl acrylate (a product of Showa Denko K.K., product name: Karenz AOI) were added to the flask and stirred for 4 hours. The stirred solution was then cooled to room temperature (20°C). In this way, a solution of fluororesin 2 was obtained. Based on the results of GPC measurement, Mw was 7,200 and Mw / Mn was 1.3.

[0225] [Preparation of Black Colorant Dispersion 1] Pigments 1 to 3, a dispersant, an alkali-soluble resin, and a solvent shown in Table 1 below were mixed together in the mass ratios shown in Table 1 to prepare a mixture. This mixture was subjected to a dispersion treatment in a bead mill at 25°C for 12 hours using zirconia beads with a diameter of 0.5 mm. After completion of the dispersion treatment, the beads were removed by filtration. In this manner, Black Colorant Dispersion 1 was prepared.

[0226]

[0227] The optical absorption spectrum of Black Colorant Dispersion 1 was measured. Specifically, Black Colorant Dispersion 1 was first diluted to 1% by mass using propylene glycol monomethyl ether acetate as a dispersion medium to prepare a diluted solution. This diluted solution was placed in a quartz cell with an optical path length of 1 cm, and the cell was then set in a commercially available spectrophotometer to obtain an optical absorption spectrum. The measurement wavelength range was 330 to 800 nm.

[0228] The obtained optical absorption spectrum is shown in Figure 1. The absorption spectrum in Figure 1 has a minimum at a wavelength of 390 nm, and a minimum value A ｍｉｎ The absorbance A at a wavelength of 365 nm was 0.42. ３６５ is 0.55, and A ３６５ / A ｍｉｎ was 1.31.

[0229] <Preparation of Negative Photosensitive Composition> First, the components used in the examples and comparative examples will be shown. [Black colorant (dispersion)] Black colorant dispersion 1: black colorant dispersion prepared above Black colorant dispersion 2: carbon black dispersion "NX-545" manufactured by Dainichiseika Color & Chemicals Co., Ltd. (for comparison; contains carbon black that does not have an absorbance minimum in the wavelength range of 380 to 420 nm. Absorbance at 365 nm > 4.0) [Photoinitiator] Oxime ester 1: "OXE-01" manufactured by BASF (oxime ester-based photoradical initiator) Oxime ester 2: "TR-PBG-305" manufactured by Tronly (oxime ester-based photoradical initiator) Acylphosphine oxide 1: "Omnirad TPO" manufactured by BASF (acylphosphine oxide-based initiator) Acylphosphine oxide 2: "Omnirad 819" manufactured by BASF (acylphosphine oxide-based initiator) Hydroxyalkylphenone: iGM "Omnirad 184" (hydroxyalkylphenone radical initiator) manufactured by RESINS Thioxanthone: "KAYACURE DETX-S" (thioxanthone initiator) manufactured by Nippon Kayaku Co., Ltd. [Curable components] 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. [Alkali-soluble resins] Alkali-soluble resin 1: "ZAR-2050H" (special BIS-A type epoxy acrylate, containing a structural unit represented by the above general formula (e). Contains no fluorine atoms) manufactured by Nippon Kayaku Co., Ltd. Alkali-soluble resin 2: "ZCR-1569H" (biphenyl type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd. Alkali-soluble resin 3: "CCR-1171H" (cresol novolac epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd. Alkali-soluble resin 4: "TR-B20101" (a cardo resin having the structure shown in the following structural formula, where the parentheses represent repeating units) manufactured by Tronly.

[0230] [Fluororesin] Fluororesin 1: Fluororesin 1 synthesized as described above Fluororesin 2: Fluororesin 2 synthesized as described above Fluororesin 3: "Megafac RS-72A" manufactured by DIC Corporation (fluorine-based, polyether structure) [Chain transfer agent] Chain transfer agent 1: "Karenz-MTPE1" manufactured by Showa Denko K.K. Chain transfer agent 2: "DPMP" manufactured by SC Organic Chemical Industry Co., Ltd. [Additive] Additive 1: Adhesion improver "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd.

[0231] Each of the components shown in the table below was mixed uniformly with PGMEA as a solvent and stirred to prepare a negative photosensitive composition. The amount of PGMEA was adjusted so that the non-volatile component concentration was 50% by mass.

[0232] <Evaluation> [Formation of Partition Ribs for Evaluation] Partition ribs (patterns) were formed on a substrate by the following procedure. (1) A 10 cm square ITO substrate was washed with ultrapure water and then with acetone. Then, the substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone treatment device (manufactured by Sen Special Light Sources Co., Ltd., model number PL17-110). (2) The prepared negative photosensitive composition was applied to the resulting UV ozone-treated 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 way, a resin film with a film thickness of approximately 11 μm was obtained. (3) Using a mask aligner (manufactured by SUSS MicroTec K.K.), a cumulative exposure dose E was measured through a mask with a line:space = 10 μm:10 μm, resulting in a line width of 10±0.5 μm after development. Ｏ The light source of this mask aligner was an ultra-high pressure mercury lamp, and the spectrum of light emitted from this mercury lamp contained bright line spectra of i-line (wavelength 365 nm) and h-line (wavelength 405 nm), as shown in Figure 2. (4) Spray development was carried out for 40 seconds using a 0.04 mass % KOH aqueous solution. After development, the sample was rinsed with pure water for 10 seconds. The remaining developer and / or rinse solution was then removed by N ２ (5) The substrate was heated on a hot plate at 200° C. for 60 minutes. The resulting cured film having a thickness of about 10 μm was used to evaluate the barrier rib performance.

[0233] [Optimum exposure dose] The integrated exposure dose E in the above [Formation of barrier ribs for evaluation] Ｏ That is, the optimum exposure dose was determined as the exposure dose that could obtain a pattern that was almost faithful to the line width and space width of the mask.

[0234] [Pattern Shape] The cross section of a line and space pattern at the optimum exposure dose was photographed with a scanning electron microscope. The height from the top surface of the substrate to the top of the pattern was defined as the pattern height, the maximum value of the pattern width at the top of the pattern, i.e., in the range from the top of the pattern to 1 / 2 of the pattern height, was defined as width A, and the minimum value of the pattern width at the bottom of the pattern, i.e., in the range from the contact surface between the substrate and the pattern to 1 / 2 of the pattern height, was defined as width B. The value of width A minus width B was used as an index of the pattern shape. The closer this value is to 0, the closer the cross section of the pattern is to a rectangle.

[0235] [Optical Density] The optical density (OD value) of the cured product was measured using a black and white transmission densitometer (Ihara Electronics Co., Ltd.: T5plus, wavelength range 400-700 nm). Measurements were performed at five arbitrary points on the cured product. The average of the five measured values ​​was then used as the optical density (OD value).

[0236] The information on the formulation of the negative photosensitive composition and the evaluation results are summarized in the table below. In the table below, the ratio of the amount of nonvolatile components is shown, even for components used in the preparation of the composition in the form of a solution or dispersion.

[0237]

[0238]

[0239]

[0240] As shown in Tables 2 to 4 above, by irradiating a negative photosensitive composition containing a black colorant having a minimum absorbance in the wavelength range of 380 to 420 nm, an oxime ester photoinitiator, and an acylphosphine oxide photoinitiator with light (light including i-line and h-line) having a spectral maximum at least in the wavelength range of 350 to 380 nm and in the wavelength range of 390 to 420 nm, it was possible to form a pattern with a good (close to rectangular) cross-sectional shape compared to the comparative examples. Furthermore, it was possible to obtain a substrate on which such a pattern was formed. Looking at the examples in more detail, {m ２ / (m １ +m ２ )}×100(%), the cross-sectional shape of the pattern tends to be further improved.

[0241] In contrast to the Examples, a pattern with a significant reverse tapered shape was obtained in Comparative Example 1. This is presumably because the composition of Comparative Example 1 did not contain an acylphosphine oxide-based photoinitiator, resulting in an insufficient amount of radicals being generated at the bottom of the film. Furthermore, pattern formation was not possible in Comparative Example 2. This is presumably because the composition of Comparative Example 2 did not contain an oxime ester-based photoinitiator, resulting in an insufficient amount of radicals being generated at the top of the film. Furthermore, pattern formation was also not possible in Comparative Example 3. This is presumably because the black colorant used was carbon black, which does not have a minimum absorbance in the wavelength range of 380 to 420 nm, and light did not sufficiently reach the bottom of the film.

[0242] Comparing Comparative Examples 1 to 7 with Examples, it can be seen that the cross-sectional shape of the pattern can be improved by simultaneously using all of (i) a black colorant having a minimum absorbance in a wavelength range of 380 to 420 nm, (ii) an oxime ester photoinitiator, and (iii) an acylphosphine oxide photoinitiator, and that the cross-sectional shape of the pattern deteriorates if any one of (i) to (iii) is missing.

[0243] This application claims priority based on Japanese Patent Application No. 2023-128366, filed August 7, 2023, the disclosure of which is incorporated herein in its entirety by reference.

Claims

1. A method for manufacturing a substrate having a black pattern, comprising: a film formation step of forming an unexposed film on a substrate from a negative photosensitive composition; an exposure step of selectively irradiating the unexposed film with light having a spectral maximum at least in the wavelength range of 350 to 380 nm and in the wavelength range of 390 to 420 nm to obtain an exposed film; and a development step of developing the exposed film to form a pattern, wherein the negative photosensitive composition comprises: a black colorant having an absorbance minimum in the wavelength range of 380 to 420 nm; an oxime ester photoinitiator; an acylphosphine oxide photoinitiator; and a curable component that is cured by active species generated from the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

2. A method for manufacturing a substrate as described in claim 1, wherein the absorbance of the black colorant at a wavelength of 365 nm is greater than the minimum absorbance value of the black colorant within a wavelength range of 380 to 420 nm.

3. The method for producing a substrate according to claim 1 or 2, wherein the content of the oxime ester photoinitiator in the total non-volatile components in the negative photosensitive composition is m １ The content of the acylphosphine oxide photoinitiator is m ２ Then, {m ２ / (m １ +m ２ )}×100(%) is 45 to 95 mass % of the acylphosphine oxide-based photoinitiator.

4. A method for manufacturing a substrate according to claim 1 or 2, wherein the black colorant is a mixture of two or more non-black colorants.

5. A method for manufacturing a substrate according to claim 1 or 2, wherein the black colorant includes a blue pigment, a purple pigment and an orange pigment.

6. A method for producing a substrate according to claim 1 or 2, wherein the ratio of the black colorant in the total non-volatile components of the negative photosensitive composition is 5 to 15 mass %.

7. A method for producing a substrate according to claim 1 or 2, wherein the curable component contains a compound having an ethylenic carbon-carbon double bond.

8. A method for producing a substrate according to claim 1 or 2, wherein the negative photosensitive composition further contains an alkali-soluble resin.

9. A method for producing a substrate according to claim 1 or 2, wherein the negative photosensitive composition further contains a fluorine-containing resin.

10. A method for producing a substrate according to claim 1 or 2, wherein the negative photosensitive composition further contains a chain transfer agent.

11. A substrate having a black pattern, manufactured by the method for manufacturing a substrate according to claim 1 or 2.

12. The substrate according to claim 11, wherein the optical density of the black pattern portion is 0.5 to 5.

13. A light-emitting device comprising a light-emitting layer or a wavelength conversion layer disposed in an area defined by the black pattern on the substrate according to claim 11.

14. A negative type photosensitive composition comprising: a black colorant having a minimum absorbance within a wavelength range of 380 to 420 nm; an oxime ester photoinitiator; an acylphosphine oxide photoinitiator; and a curable component that is cured by active species generated from the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

15. A negative-type photosensitive composition according to claim 14, wherein the absorbance of the black colorant within a wavelength range of 355 to 375 nm is greater than the minimum value of the absorbance of the black colorant within a wavelength range of 380 to 420 nm.

16. The negative photosensitive composition according to claim 14 or 15, wherein the content of the oxime ester photoinitiator in the total non-volatile components is m １ The content of the acylphosphine oxide photoinitiator is m ２ Then, {m ２ / (m １ +m ２ )}×100(%) is 45 mass % or more of the acylphosphine oxide-based photoinitiator.

17. A negative-acting photosensitive composition according to claim 14 or 15, wherein the black colorant is a mixture of two or more non-black colorants.

18. The negative photosensitive composition according to claim 14 or 15, wherein the black colorant comprises a blue pigment, a purple pigment and an orange pigment.

19. The negative-type photosensitive composition according to claim 14 or 15, wherein the ratio of the black colorant in all non-volatile components is 5 to 15 mass %.

20. The negative-type photosensitive composition according to claim 14 or 15, wherein the curable component comprises a compound having an ethylenic carbon-carbon double bond.

21. The negative photosensitive composition according to claim 14 or 15, further comprising an alkali-soluble resin.

22. The negative-type photosensitive composition according to claim 14 or 15, further comprising a fluorine-containing resin.

23. The negative photosensitive composition according to claim 14 or 15, further comprising a chain transfer agent.

Images