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

Abstract

The present invention provides a method for manufacturing a substrate having a black pattern, comprising: a film formation step of forming an unexposed film formed from a negative photosensitive composition on a substrate; an exposure step for obtaining an exposed film by selectively irradiating the unexposed film with light having a maximum spectral value at least in the wavelength range of 350-380 nm and in the wavelength range of 390-420 nm; and a developing step for developing the exposure film to form a pattern. In the manufacturing method, the negative photosensitive composition contains a black colorant having a minimum absorbance value in the wavelength range of 380-420 nm, an oxime ester-based photoinitiator, an acylphosphine oxide-based photoinitiator, and a curable component that is cured by an active species generated by the oxime ester-based photoinitiator or the acylphosphine oxide-based photoinitiator.

Description

Technical Field

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

[0002] Various methods have been studied for manufacturing patterned substrates using negative photosensitive compositions, or for manufacturing various final products using patterned substrates. As a specific example, a method for forming banks in a display device using a negative photosensitive composition has been studied.

[0003] In manufacturing light-emitting elements for display devices such as organic EL displays, micro LED displays, and quantum dot displays, a known method for forming an organic layer with light-emitting functions includes: dropping ink onto recesses with a raised or recessed pattern formed on a substrate using, for example, inkjet printing, and then drying and / or solidifying the ink. In this method, the raised or recessed pattern is referred to as a bank. When ink is dropped onto the recesses of the pattern, the bank acts as a barrier to prevent the ink from mixing with each other. Preferably, the bank has a moderately non-sticky ink property. This is to prevent ink dropped onto one recess from flowing "along" the side of the bank into adjacent recesses.

[0004] From the perspective of light blocking, partitions are mostly black.

[0005] The separator is preferably formed by photolithography using a negative photosensitive composition.

[0006] Patent Document 1 discloses a negative photosensitive resin composition as a composition that can be preferably used for the formation of a separator for optical elements, comprising: an alkali-soluble resin or alkali-soluble monomer having an alkali double bond, a photopolymerization initiator, a thiol compound having three or more mercapto groups in one molecule, and an ink repellent.

[0007] Patent Document 2 discloses a curable resin composition comprising: an alkali-soluble resin, a free radical 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 Patent Document 2, the patterned cured film obtained using such a composition has a conical shape. However, Patent Document 2 does not disclose the use of the curable resin composition for forming a separator in a display device.

[0008] Existing technical documents Patent documents Patent Document 1: International Publication No. 2014 / 084279 Patent Document 2: Japanese Patent Application Publication No. 2015-22175 Summary of the Invention

[0009] (a) Technical problems to be solved If a black pattern of a separator is formed by irradiating a film made of a negatively photosensitive composition containing a black pigment with light, the cross-sectional shape of the pattern tends to be an inverted cone or an undercut shape, that is, the width of the upper part of the pattern tends to be greater than the width of the lower part of the pattern. This is because the black pigment absorbs light and the light does not reach the bottom of the film sufficiently.

[0010] If we consider the way the partition is used in the above-mentioned display device (drip ink into the recess with a raised pattern), the cross-sectional shape of the pattern is preferably rectangular or conical.

[0011] The present invention was made in view of the above circumstances. One of the objects of the present invention is to improve the cross-sectional shape of the pattern in the formation of black patterns using photolithography.

[0012] (II) Technical Solution The inventors of this application have completed the invention provided below, thereby solving the aforementioned technical problem. 1. A method for manufacturing a substrate having a black pattern, comprising: In the film formation process, an unexposed film made of a negative photosensitive composition is formed on a substrate; The exposure process involves selectively irradiating the unexposed film with light having spectral maxima in the wavelength range of at least 350-380 nm and in the wavelength range of 390-420 nm to obtain an exposed film; and In the developing process, the exposed film is developed to form a pattern, wherein... The negative photosensitizing composition comprises: Black colorants that have extremely low absorbance in the wavelength range of 380~420nm. Oxime ester photoinitiators Acylphosphine oxide photoinitiators, and A curable component that is cured by active species generated by the oxime ester photoinitiator or the acylphosphine oxide photoinitiator. 2. According to the substrate manufacturing method of claim 1, the absorbance of the black colorant at a wavelength of 365 nm is greater than the minimum absorbance of the black colorant in the wavelength range of 380~420 nm. 3. The method for manufacturing a substrate according to item 1 or 2, wherein, When the content of the oxime ester photoinitiator in all non-volatile components of the negative photosensitizing composition is set as m1 and the content of the acylphosphine oxide photoinitiator is set as m2, the proportion of the acylphosphine oxide photoinitiator, expressed as {m2 / (m1+m2)}×100(%), is 45~95% by mass. 4. The method for manufacturing a substrate according to any one of claims 1 to 3, wherein the black colorant is a mixture of two or more non-black colorants. 5. The method for manufacturing a substrate according to any one of claims 1 to 4, wherein the black colorant comprises blue pigment, purple pigment and orange pigment. 6. The method for manufacturing a substrate according to any one of claims 1 to 5, wherein the ratio of the black colorant in all non-volatile components of the negative photosensitive composition is 5 to 15 by mass. 7. The method for manufacturing a substrate according to any one of claims 1 to 6, wherein the curable component comprises a compound having an olefinic carbon-carbon double bond. 8. The method for manufacturing a substrate according to any one of claims 1 to 7, wherein the negative photosensitive composition further comprises an alkali-soluble resin. 9. The method for manufacturing a substrate according to any one of claims 1 to 8, wherein the negative photosensitive composition further comprises a fluorinated resin. 10. The method for manufacturing a substrate according to any one of claims 1 to 9, wherein the negative photosensitive composition further comprises a chain transfer agent. 11. A substrate having a black pattern is manufactured by the substrate manufacturing method described in any one of claims 1 to 10. 12. According to the substrate of item 11, the optical density of the black patterned portion is 0.5 to 5. 13. A light-emitting element comprising a light-emitting layer or a wavelength conversion layer disposed in a region defined by a black pattern in a substrate described in item 11 or 12. 14. A negative photosensitizing composition comprising: Black colorants that have extremely low absorbance in the wavelength range of 380~420nm. Oxime ester photoinitiators Acylphosphine oxide photoinitiators, and A curable component that is cured by active species generated by the oxime ester photoinitiator or the acylphosphine oxide photoinitiator. 15. According to the negative photosensitizing composition of item 14, the absorbance of the black colorant in the wavelength range of 355~375nm is greater than the minimum absorbance of the black colorant in the wavelength range of 380~420nm. 16. According to the negative photosensitizing composition of item 14 or 15, wherein, When the content of the oxime ester photoinitiator in all non-volatile components is set as m1 and the content of the acylphosphine oxide photoinitiator is set as m2, the proportion of the acylphosphine oxide photoinitiator, expressed as {m2 / (m1+m2)}×100(%), is 45% by mass or more. 17. The negative photosensitizing composition according to any one of items 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 claims 14 to 17, wherein the black colorant comprises a blue pigment, a purple pigment, and an orange pigment. 19. The negative photosensitizing composition according to any one of items 14 to 18, wherein the ratio of the black colorant in all non-volatile components is 5 to 15 by mass. 20. The negative photosensitizing composition according to any one of claims 14 to 19, wherein the curable component comprises a compound having an olefinic carbon-carbon double bond. twenty one. The negative photosensitizing composition according to any one of claims 14 to 20 further comprises an alkali-soluble resin. twenty two. The negative photosensitizing composition according to any one of claims 14 to 21 further comprises a fluorinated resin. twenty three. The negative photosensitizing composition according to any one of claims 14 to 22 further comprises a chain transfer agent.

[0036] (III) Beneficial Effects According to the present invention, the cross-sectional shape of the pattern can be improved in the process of forming a black pattern using photolithography. Attached Figure Description

[0037] Figure 1 The light absorption spectrum of the black colorant dispersion 1 used in the examples is shown.

[0038] Figure 2 This refers to the spectrum of light emitted by the light source (mercury lamp) used in the embodiment. Detailed Implementation

[0039] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0040] The accompanying drawings are for illustrative purposes only. The invention is not to be construed as limited by the drawings.

[0041] In this specification, the expression "X~Y" in the description of numerical ranges means above X and below Y unless otherwise specified. For example, "1~5% by mass" means "more than 1% by mass and less than 5% by mass".

[0042] In the description of "base" (atomic group) in this specification, the expression "unsubstituted" or "unsubstituted" includes both the absence of a substituent and the presence of a substituent. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0043] The term "(meth)acrylic acid" in this specification indicates that it includes both acrylic acid and methacrylic acid. The same applies to terms such as "(meth)acrylate".

[0044] Unless otherwise specified, the term "organic group" in this specification refers to a group of atoms that has had one or more hydrogen atoms removed from an organic compound. For example, "monovalent organic group" refers to a group of atoms that has had one hydrogen atom removed from any organic compound.

[0045] Hereinafter, the method of manufacturing a substrate with a black pattern will sometimes be omitted and referred to as "the method of manufacturing a substrate".

[0046] Furthermore, in this specification, "all non-volatile components" refers to all components in the negative photosensitizing composition except for the solvent, unless otherwise specified.

[0047] <Manufacturing method of substrate with black pattern> The substrate manufacturing method of this embodiment includes the following steps: • The process of forming an unexposed film made of a negative photosensitive composition on a substrate. • An exposure process in which the unexposed film is selectively irradiated with light having spectral maxima in at least the wavelength range of 350-380 nm and the wavelength range of 390-420 nm to obtain an exposed film. • The developing process that develops the exposed film to form a pattern.

[0048] The above three processes are preferably performed in the order described above.

[0049] The negative photosensitive composition used in the substrate manufacturing method of this embodiment contains the following components: • A black colorant that has extremely low absorbance in the wavelength range of 380~420nm · Oxime ester photoinitiators Acylphosphine oxide photoinitiators • A curable component that is cured by active species generated by the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

[0050] The reason why this substrate manufacturing method can improve the cross-sectional shape of the black pattern can be explained as follows. It should be noted beforehand that the following description contains speculation. Furthermore, the present invention is not limited to the following description.

[0051] The black colorant contained in the aforementioned negative photosensitive composition has a very low absorbance in the wavelength range of 380-420 nm. Therefore, the film formed using the aforementioned negative photosensitive composition is unlikely to absorb light in the wavelength range of 380-420 nm. Consequently, if light with a wavelength range of 390-420 nm is irradiated onto the film formed on the substrate using the aforementioned negative photosensitive composition, most of the light will reach the lower part of the film.

[0052] In the view of the inventors of this application, acylphosphine oxide-based photoinitiators readily absorb light with wavelengths of 390-420 nm, such as h-rays emitted from a mercury lamp (wavelength 405 nm), thus generating active species (it can be said that they have high sensitivity to light with wavelengths of 390-420 nm). By presenting such an initiator in the film, active species are generated in the lower part of the film. These active species cause the curable components to cure, thereby carrying out a curing reaction in the lower part of the film. As a result, the lower part of the film is fully cured compared to conventional methods.

[0053] Furthermore, the aforementioned negative photosensitizing composition further comprises an oxime ester-based photoinitiator. In the view of the inventors of this application, oxime ester-based photoinitiators readily absorb light with wavelengths of 350-380 nm, such as i-rays emitted from a mercury lamp (wavelength 365 nm), to generate active species (or, in other words, they have high sensitivity to light with wavelengths of 350-380 nm). Since light with wavelengths of 350-380 nm does not easily reach the lower part of the film due to the influence of the black colorant, active species are mainly generated from the oxime ester-based photoinitiator in the upper part of the film due to light with wavelengths of 350-380 nm, and these active species cause the curable component to cure. Thus, a curing reaction occurs in the upper part of the film.

[0054] Thus, in this embodiment, the curing reaction in the lower part of the membrane is mainly carried out by active species generated from an acylphosphine oxide-based photoinitiator highly sensitive to light with wavelengths of 390-420 nm, while the curing reaction in the upper part of the membrane is mainly carried out by active species generated from an oxime ester-based photoinitiator highly sensitive to light with wavelengths of 350-380 nm. In particular, the former curing reaction helps to improve the problem of deterioration of the pattern cross-sectional shape due to insufficient light reaching the bottom of the membrane in previous methods.

[0055] The following describes the components or other characteristics of the negative photosensitive composition used in the substrate manufacturing method of this embodiment, as well as the specific conditions of each process.

[0056] [Negative photosensitizing composition] (Black colorant (or its dispersion)) The black colorant has a minimum absorbance in the wavelength range of 380–420 nm. In other words, the black colorant has a "window" for light absorption in the wavelength range of 380–420 nm. By using such a black colorant, the film formed with the negative photosensitive composition becomes more easily transmissible to light (such as h-rays) with wavelengths of 390–420 nm.

[0057] The black colorant preferably has a minimum absorbance in the wavelength range of 390~420nm, and more preferably has a minimum absorbance in the wavelength range of 395~415nm.

[0058] The black colorant only needs to be black enough to achieve the black pattern that the substrate will subsequently have, and to have the blackness required to achieve, for example, the blackness of a partition in a display device. Therefore, the black colorant can also be non-pure black, and can be a colorant that is slightly colored when viewed with the naked eye, for example, it can be a black that looks gray or a bluish black (a black with a bluish tint).

[0059] The black colorant preferably has the ability to block light with a wavelength around 365 nm. This suppresses light with a wavelength around 365 nm from reaching the lower part of the film, thereby allowing for more precise control over the shape of the pattern.

[0060] Specifically, the absorbance of the preferred black colorant at a wavelength of 365 nm is greater than the minimum absorbance of the black colorant in the wavelength range of 380~420 nm.

[0061] More specifically, the minimum absorbance of the black colorant in the wavelength range of 380~420nm is set as A. min Let A be the absorbance of the black colorant at a wavelength of 365nm. 365 At that time, A 365 / A minPreferably, it is 1.05 or higher, more preferably 1.05 to 2, even more preferably 1.1 to 1.75, and particularly preferably 1.1 to 1.5.

[0062] The black colorant preferably comprises one or more selected from black pigments, black dyes and non-black colorants, and more preferably comprises one or more selected from black pigments and non-black pigments.

[0063] Examples of black pigments include carbon black, titanium black, perylene black, aniline black, anthocyanin black, and lactam black.

[0064] As a non-black pigment, two or more organic pigments can be selected from the group consisting of red organic pigments, orange organic pigments, yellow organic pigments, green organic pigments, blue organic pigments, and purple organic pigments.

[0065] Black colorants with minimal absorbance in the wavelength range of 380–420 nm can typically be obtained by mixing two or more non-black colorants.

[0066] As an example, black colorant can be obtained by mixing blue, purple, and orange pigments.

[0067] As another example, a black colorant can be made by combining blue, purple, green, red, and orange pigments. In this case, the red and orange pigments are preferably used in smaller amounts than the blue, purple, and green pigments.

[0068] As another example, one could consider using a small amount of black pigments such as carbon black or titanium black in combination with non-black pigments to create a black colorant with minimal absorbance in the wavelength range of 380-420 nm.

[0069] Examples of blue pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, and 80. Among these, CI Pigment Blue 60 is preferred from the perspective of dispersibility or opacity.

[0070] Examples of purple pigments include CI pigments 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, CI pigment 23 is preferred from the perspective of dispersibility or opacity.

[0071] Examples of orange pigments include CI 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, CI Pigment Orange 43 is preferred from the perspective of dispersibility or opacity.

[0072] As green pigments, examples include CI pigments green 1, 2, 4, 7, 8, 10, 13, 14, 15, 16, 17, 17Blk, 18, 19, 20, 21, 22, 23, 24, 26, 36, 38, 39, 41, 42, 45, 48, 50, 51, 55, 56, etc.

[0073] Examples of red pigments include CI pigments 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.

[0074] In addition, known pigments such as perylene pigments, lactam pigments, azo pigments, phthalocyanine pigments, carbon pigments such as carbon black, and metal oxide pigments such as iron black or titanium dioxide, not listed above, may be used.

[0075] From the perspective of solubility or dispersibility in solvents and compatibility with other components, black colorants preferably contain organic pigments.

[0076] For most commercially available pigments, absorption spectra are shown in the literature, or the manufacturers / sellers possess spectral data. Furthermore, the light absorption spectrum of a mixture of multiple pigments is, in principle, the superposition of the light absorption spectra of each pigment. Therefore, even without actually mixing more than two pigments, simulations or paper studies can determine whether a pigment mixture has a minimum absorbance value in the wavelength range of 380–420 nm, thus enabling the design of appropriate black colorants.

[0077] It is preferable to perform a dispersion treatment on the black colorant. Dispersion can be achieved, for example, by processing the pigment, dispersant, and solvent as needed using a bead mill. There is no particular limitation on the type of dispersant; for example, a dispersant obtained from BYK-Chemie can be used.

[0078] Furthermore, when dispersing pigments to produce a pigment dispersion in a solvent (usually an organic solvent), an alkali-soluble resin can be further used. Since pigments are difficult to remove with alkaline developing solutions and tend to remain as developing residue, including an alkali-soluble resin in the pigment dispersion can be expected to reduce developing residue. Specific alkali-soluble resins listed above can be used.

[0079] Furthermore, when the black colorant is a black colorant dispersion, it is preferable that the black colorant dispersion satisfies the above-mentioned various indicators regarding light absorption.

[0080] The proportion of black colorant in all non-volatile components of the negative photosensitive composition is preferably 5-15% by mass, more preferably 7-13% by mass. By using a certain amount of black colorant, the blackness of the obtained pattern can be improved. Furthermore, by ensuring that the amount of black colorant is not excessive, the proportion of other components will be relatively increased, making it easier to improve the balance of various properties such as photocurability or cured film characteristics.

[0081] When the black colorant is a black colorant dispersion, it is preferable that the ratio of the black colorant dispersion in all non-volatile components of the negative photosensitive composition is within the above-mentioned numerical range.

[0082] (Oxime ester photoinitiators and acylphosphine oxide photoinitiators) Oxime ester photoinitiators and acylphosphine oxide photoinitiators are usually compounds that generate free radicals by irradiation with light, i.e., photoradical initiators.

[0083] As an oxime ester-based photoinitiator, there are no particular limitations as long as it is a substance having an oxime ester structure that generates active species such as free radicals upon irradiation with ultraviolet light (preferably light with a wavelength of 350~380nm).

[0084] As oxime ester photoinitiators, substances having the structure represented by the following general formula (8) can be listed.

[0085] [Chemical Formula 1] In general formula (8), R 14 It consists of a hydrogen atom or a monovalent organic group. R 15 and R 16 Each of the organic groups is independently monovalent, preferably alkyl or aromatic hydrocarbon groups.

[0086] R 14The monovalent organic group can be an alkyl group. The alkyl group can be straight-chain or branched. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10. The alkyl group may have substituents. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, etc. Among these, methyl, ethyl, propyl, or isopropyl are preferred, and methyl or ethyl are more preferred.

[0087] R 15 The alkyl group can be straight-chain, branched, or cyclic. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10. The alkyl group may also have substituents. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. Among these, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, and cyclohexylmethyl are preferred, and hexyl, cyclopentylmethyl, and cyclohexylmethyl are more preferred.

[0088] R 15 The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. The aromatic hydrocarbon group may have substituents. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, and anthraceneyl.

[0089] R 16 The alkyl group can be straight-chain, branched, or cyclic. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10. The alkyl group may have substituents. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. Among these, methyl, ethyl, propyl, and isopropyl are preferred, and methyl and ethyl are more preferred.

[0090] R 15 The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. The aromatic hydrocarbon group may have substituents. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, and anthraceneyl. Among these, phenyl is preferred.

[0091] Other substances that can be listed as oxime ester photoinitiators include those having the structure represented by the following general formula (9).

[0092] [Chemical Formula 2] In general formula (9), R 17 R in general formula (8) 14 Same meaning R 18 With R 19 Each is independently a hydrogen atom or a monovalent organic group, with the monovalent organic group preferably being an alkyl group. R 20 R in general formula (8) 16 Same meaning R 21 R in general formula (8) 15 They have the same meaning.

[0093] R 18 With R 19 The alkyl group can be straight-chain, branched, or cyclic. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10. The alkyl group may have substituents. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Butyl is preferred.

[0094] Other substances that can be listed as oxime ester photoinitiators include those having the structure represented by the following general formula (10).

[0095] [Chemical Formula 3] In general formula (10), R 22 With R 23 Each is an organic group that is independently monovalent. R 24 R in general formula (8) 16 Same meaning R 25 R in general formula (8) 15 They have the same meaning.

[0096] R 22 With R 23 The monovalent organic group can be an alkyl or aromatic hydrocarbon group. The alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 10. The alkyl or aromatic hydrocarbon group may have substituents. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. The aromatic hydrocarbon group may have substituents. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, and anthraceneyl.

[0097] Other substances that can be listed as oxime ester photoinitiators include those having the structure represented by the following general formula (11).

[0098] [Chemical Formula 4] In general formula (11), R 27 R of general formula (10) 23 Same meaning R 26 With R 28 Each independently of R in general formula (8) 16 Same meaning R 29 With R 30 Each independently of R in general formula (8) 15 They have the same meaning.

[0099] Other substances that can be listed as oxime ester photoinitiators include those having the structure represented by the following general formula (12).

[0100] [Chemical Formula 5] In general formula (12), R 31 R of general formula (10) 23 They have the same meaning.

[0101] R 32 R in general formula (8) 16 They have the same meaning.

[0102] R 33 R in general formula (8) 15 They have the same meaning.

[0103] R 34 R of general formula (10) 22 They have the same meaning.

[0104] Other substances that can be listed as oxime ester photoinitiators include those having the structure represented by the following general formula (13).

[0105] [Chemical Formula 6] In general formula (13), R 35 R of general formula (10) 23 They have the same meaning.

[0106] R 36 With R 39 Each independently of R in general formula (8) 16 They have the same meaning.

[0107] R 37 With R 38Each independently of R in general formula (8) 15 They have the same meaning.

[0108] As an acylphosphine oxide-based photoinitiator, there are no particular limitations as long as it is a substance with an acylphosphine oxide structure that generates active species such as free radicals when irradiated by ultraviolet light (preferably light with a wavelength of 390~420nm).

[0109] As acylphosphine oxide photoinitiators, substances having the structure represented by the following general formula (14) can be listed.

[0110] [Chemical Formula 7] In general formula (14), R 40 It is a monovalent organic group. R 41 ~R 50 Each is an independent hydrogen atom or a monovalent organic group.

[0111] As R 40 Examples of monovalent organic groups include alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, alkyl carbonyl groups with 6 to 15 carbon atoms, and aryl carbonyl groups with 7 to 15 carbon atoms. 40 A monovalent organic group can have substituents.

[0112] Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, etc.

[0113] Specific examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

[0114] Specific examples of aryl groups with 6 to 14 carbon atoms include phenyl, naphthyl, and anthracene.

[0115] Specific examples of aryloxy groups with 6 to 14 carbon atoms include phenoxy, toluoxy, and naphthoxy.

[0116] Specific examples of alkyl carbonyl groups with 6 to 15 carbon atoms include acetyl, propionyl, n-butyryl, isobutyryl, n-valeryl, and n-hexanoyl.

[0117] Specific examples of aryl carbonyl groups with 7 to 15 carbon atoms include benzoyl, 2-methylbenzoyl, 4-methylbenzoyl, 3,5-dimethylbenzoyl, 2,4,6-trimethylbenzoyl, naphthoyl, etc.

[0118] As R 41 ~R 50 The monovalent organic groups can be exemplified by alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, and aryl groups with 6 to 14 carbon atoms. 41 ~R 50 A monovalent organic group can have substituents.

[0119] Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, etc.

[0120] Specific examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

[0121] Specific examples of aryl groups with 6 to 14 carbon atoms include phenyl, naphthyl, and anthracene.

[0122] Specific examples of oxime ester photoinitiators include BASF's CGI-325, Irgacure OXE01, Irgacure OXE02, and ADEKA's N-1919.

[0123] Specific examples of acylphosphine oxide photoinitiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

[0124] For purposes such as fine-tuning performance, photoinitiators other than those mentioned above may be used, or they may not be used. Examples of usable photoinitiators include benzophenone-based, acetophenone-based, diketone-based, quinone-based, and acetoin-based photoradical initiators.

[0125] 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. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

[0126] Examples of acetophenone-based photoradical initiators include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

[0127] Examples of diketone-based photoradical initiators include 4,4'-dimethoxybenzoiloyl, methyl benzoylformate, and 9,10-phenanthroquinone. Among these, 4,4'-dimethoxybenzoiloyl and methyl benzoylformate are preferred.

[0128] Examples of quinone initiators include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Camphorquinone and 1,4-naphthoquinone are preferred.

[0129] Examples of benzoin-based initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

[0130] The negative photosensitizing composition may contain only one oxime ester photoinitiator or two or more oxime ester photoinitiators.

[0131] The negative photosensitizing composition may contain only one acylphosphine oxide photoinitiator or two or more acylphosphine oxide photoinitiators.

[0132] By adjusting the ratio of oxime ester-based photoinitiators to acylphosphine oxide-based photoinitiators, the shape of the obtained pattern can sometimes be further optimized.

[0133] Specifically, when the content ratio of oxime ester photoinitiator in all non-volatile components of the negative photosensitizing composition is set as m1 and the content ratio of acylphosphine oxide photoinitiator is set as m2, the proportion of acylphosphine oxide photoinitiator, expressed as {m2 / (m1+m2)}×100(%), is preferably 45~95% by mass, more preferably 45~90% by mass, further preferably 50~85% by mass, and particularly preferably 60~80% by mass.

[0134] By optimizing the ratio of the two photoinitiators, the curing balance between the lower and upper parts of the film can be optimized, and the pattern shape is considered to be further improved.

[0135] Furthermore, the negative photosensitizing composition may further include known photoinitiators other than oxime ester-based photoinitiators and acylphosphine oxide-based photoinitiators. Examples of photoinitiators other than oxime ester-based and acylphosphine oxide-based photoinitiators include, for example, hydroxyalkylphenyl ketone-based photoinitiators and thioxanone-based photoinitiators.

[0136] (Curing components) There are no particular limitations on the curing component as long as it is a substance that is cured (by increasing its molecular weight or undergoing a cross-linking reaction) by an active species generated by an autooxime ester photoinitiator and / or an acylphosphine oxide photoinitiator.

[0137] The curing component is preferably a curing agent that reacts with both the active species generated by the autooxime ester-based photoinitiator and the active species generated by the autophosphine oxide-based photoinitiator.

[0138] Curable components typically include compounds with olefinic carbon-carbon double bonds. These compounds polymerize and cure due to the action of active free radicals. The following section provides a detailed explanation of compounds with olefinic carbon-carbon double bonds that serve as curable components.

[0139] "Alkene carbon-carbon double bonds" refer to carbon-carbon double bonds that can react with the action of free radicals. Conjugated and stabilized double bonds, such as those in the benzene ring, are not considered "alkene carbon-carbon double bonds".

[0140] From the perspective of improving reactivity, compounds with olefinic carbon-carbon double bonds are preferably those with olefinic carbon-carbon double bonds at their ends.

[0141] Compounds containing olefinic carbon-carbon double bonds can be monofunctional or polyfunctional. That is, a compound containing olefinic carbon-carbon double bonds can have only one olefinic carbon-carbon double bond in one molecule, or it can have two or more (specifically 2 to 8, more specifically 2 to 6) olefinic carbon-carbon double bonds in one molecule.

[0142] From the perspective of further improving sensitivity or improving the physical properties when forming a cured film, compounds with alkene carbon-carbon double bonds are preferred as having high functionality.

[0143] As compounds having an olefinic carbon-carbon double bond, (meth)acrylate compounds are preferably listed, that is, compounds having a (meth)acryloyl group as a structure containing an olefinic carbon-carbon double bond. As compounds having an olefinic carbon-carbon double bond, (meth)acrylate compounds are more preferably listed.

[0144] The following are specific examples of compounds containing alkene carbon-carbon double bonds. Of course, compounds containing alkene carbon-carbon double bonds are not limited to these.

[0145] Polyol polyacrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy acrylates such as bisphenol A diglycidyl ether di(meth)acrylate and hexanediol diglycidyl ether di(meth)acrylate; and urethane (meth)acrylates obtained by reacting polyisocyanates with hydroxyl-containing (meth)acrylates such as hydroxyethyl (meth)acrylate.

[0146] Negative photosensitizing compositions may contain only one curing component or two or more curing components.

[0147] The content of the curing component is typically 5 to 60% by mass of all non-volatile components in the negative photosensitive composition, preferably 10 to 55% by mass, and more preferably 15 to 50% by mass.

[0148] (Alkali-soluble resin) Negative photosensitizing compositions preferably contain alkali-soluble resins. By using alkali-soluble resins, especially when forming patterns (septa) using alkaline developing solutions, there is a tendency to make it easier to form patterns of the desired shape.

[0149] Alkali-soluble resins typically possess alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups and phenolic hydroxyl groups.

[0150] Furthermore, in this specification, resins containing fluorine atoms and being alkali-soluble are generally classified as fluorinated resins as described later. That is, alkali-soluble resins generally do not contain fluorine atoms.

[0151] Examples of alkali-soluble resins include alkali-soluble phenolic varnish resins. Alkali-soluble phenolic varnish resins can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

[0152] 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, phlorogallol, thymol, carvacrol, etc. These phenols can be used alone or in combination of two or more.

[0153] Specific examples of aldehydes include formaldehyde, paraformaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.

[0154] Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethyl sulfate, and p-toluenesulfonic acid. These acid catalysts can be used alone or in combination of two or more.

[0155] Examples of alkali-soluble resins include alkali-soluble epoxy resins or acid-modified (meth)acrylate epoxy ester resins derived from epoxy resins. Epoxy resins or acid-modified (meth)acrylate epoxy ester resins may have polymerizable substituents such as hydroxyl or (meth)acryloyl groups on their side chains. Examples of epoxy resins include bisphenol-type epoxy resins, and examples of acid-modified (meth)acrylate epoxy ester resins include substances obtained by reacting (meth)acrylate with bisphenol-type epoxy resins. Specific examples include bisphenol-type epoxy resins or acid-modified (meth)acrylate epoxy ester resins having structural units represented by the following general formula (e).

[0156] [Chemical Formula 8] In general formula (e), Each of the two Rs independently represents a straight-chain alkyl group with 1 to 3 carbon atoms, a branched alkyl group with 3 carbon atoms, a straight-chain perfluoroalkyl group with 1 to 3 carbon atoms, or a hydrogen atom. Z represents a monovalent organic group or a hydrogen atom.

[0157] In the alkali-soluble resin (E), at least a portion of the structural units represented by general formula (e) are Z, which are monovalent organic groups having a carboxyl group.

[0158] When R is a straight-chain alkyl group with 1 to 3 carbon atoms or a branched alkyl group with 3 carbon atoms, specific examples of R include methyl, ethyl, propyl, and isopropyl. Among these, methyl is preferred from the perspective of ease of acquisition.

[0159] Specific examples of straight-chain perfluoroalkyl groups having 1 to 3 carbon atoms include trifluoromethyl, pentafluoroethyl, and heptafluoropropyl. Among these, trifluoromethyl is preferred from the perspective of ease of acquisition.

[0160] Each R can have the same structure or different structures.

[0161] When Z is a monovalent organic group, Z is preferably an alkyl group with 1 to 10 carbon atoms. This alkyl group with 1 to 10 carbon atoms can be linear, branched, or cyclic. At least one hydrogen atom in the monovalent organic group of Z can be replaced by a carboxyl or hydroxyl group. This improves alkali solubility.

[0162] The carboxyl or hydroxyl groups of alkyl groups with 1 to 10 carbon atoms in Z can react with esterifying agents. Examples of esterifying agents include acyl halides, acid anhydrides, acids, and condensing agents.

[0163] When Z is a hydrogen atom, -OZ can react with an esterifying agent. Examples of esterifying agents similar to those described above can be listed.

[0164] Examples of acid anhydrides include acrylic anhydride, methacrylic anhydride, succinic anhydride, phthalic anhydride, and 1,2,3,4-tetrahydrophthalic anhydride. By reacting these acid anhydrides with the resin, olefinic unsaturated bonds or carboxyl groups can be introduced into the resin.

[0165] The amount of carboxyl or hydroxyl groups in the alkali-soluble resin that reacts with acid anhydrides can be adjusted appropriately, taking into account the required solubility of the alkali-soluble resin in alkali.

[0166] (Meth)acrylate epoxy resins having the structural units represented by general formula (e) can be obtained from, for example, Nippon Kayaku Co., Ltd.

[0167] In addition to the above, alkali-soluble epoxy resins or acid-modified (meth)acrylate epoxy ester resins can also be used. Specific examples include alkali-soluble phenolic varnish-type epoxy resins, biphenyl-type epoxy resins, and acid-modified (meth)acrylate epoxy ester resins derived from these epoxy resins.

[0168] In addition, commercially available products as acid-modified (meth)acrylate epoxy esters can be listed. Commercially available acid-modified acrylate epoxy esters can use, for example, product names manufactured by Nippon Kayaku Co., Ltd.: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZFR-1185, ZCR-1569H, etc.

[0169] As an alkali-soluble resin, a substance having a polycyclic aromatic backbone such as a fluorene backbone can be used. By using such an alkali-soluble resin, the heat resistance and durability of the cured pattern can sometimes be improved. As a specific example of the aforementioned acid-modified (meth)acrylate epoxy resin, a substance having a polycyclic aromatic backbone can be used, and a substance having a polycyclic aromatic backbone can also be selected from resins of a different system than the acid-modified (meth)acrylate epoxy resin. Furthermore, resins having a fluorene backbone are sometimes described as "cardo resin".

[0170] Alkali-soluble resins with polycyclic aromatic skeletons such as fluorene skeletons are similar to other alkali-soluble resins, and preferably have alkali-soluble groups such as carboxyl or hydroxyl groups.

[0171] Alkali-soluble resins can possess olefinic carbon-carbon double bonds. During the curing process of the composition, alkali-soluble resins with olefinic carbon-carbon double bonds are believed to form bonds with the aforementioned curing components and bind to the cured product. This is considered to contribute to improving the stability, heat resistance, and other properties of the cured product.

[0172] As a precaution, it should be stated beforehand that alkali-soluble resins containing alkene carbon-carbon double bonds are not classified as curing components as described above.

[0173] From the perspective of the developability or resolution of the photosensitive composition, the weight-average molecular weight of the alkali-soluble resin is preferably 1,000 to 50,000.

[0174] The acid value of an alkali-soluble resin (the number of milligrams of potassium hydroxide required to neutralize 1 g of sample) can serve as an indicator of its alkali solubility. In this embodiment, the acid value of the alkali-soluble resin is preferably 20-80, more preferably 30-70, and even more preferably 40-60. The acid value of the alkali-soluble resin used in the examples disclosed later is within this range.

[0175] When using alkali-soluble resins, you can use only one type of alkali-soluble resin or two or more types of alkali-soluble resins.

[0176] When using an alkali-soluble resin, its amount is typically 10 to 70% by mass, preferably 15 to 60% by mass, and more preferably 20 to 55% by mass, of all non-volatile components in the negative photosensitizing composition.

[0177] (Fluoropolymer) The negative photosensitive composition preferably contains a fluorinated resin. By using a photosensitive composition containing a fluorinated resin to form a pattern (septum) with raised and recessed areas, the resulting pattern (septum) becomes more resistant to ink used to form the organic layer. This helps to prevent ink dripping into a recess from flowing "along" the side of the recess into adjacent recesses. That is, it can suppress accidental mixing of pigments between pixels.

[0178] There are no particular limitations on the fluorinated resins that can be used. The following describes the preferred fluorinated resins.

[0179] Fluorinated resins preferably have the structure represented by the following general formula (1), and more preferably have the structure represented by the following general formula (2).

[0180] [Chemical Formula 9] In general formula (1), Each of the two Rf values ​​independently represents a straight-chain, branched, or cyclic perfluoroalkyl group or fluorine atom with 1 to 6 carbon atoms, or with 3 to 6 carbon atoms. R 2 It refers to an alkyl group consisting of 1 to 6 straight chains, 3 to 6 branched chains, or 3 to 6 cyclic chains with hydrogen atoms.

[0181] [Chemical Formula 10] In general formula (2), Each of the two Rf values ​​independently represents a straight-chain, branched, or cyclic perfluoroalkyl group or fluorine atom with 1 to 6 carbon atoms, or with 3 to 6 carbon atoms. R 1 Indicates a hydrogen atom, a fluorine atom, or a methyl group. R 2 It refers to an alkyl group consisting of 1 to 6 straight chains, 3 to 6 branched chains, or 3 to 6 cyclic chains with hydrogen atoms.

[0182] In general formula (2), R 1 Preferably, it contains hydrogen atoms or methyl groups. Furthermore, as R... 2 Examples of suitable materials include hydrogen atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, isopentyl, 1,1-dimethylpropyl, 1-methylbutyl, 1,1-dimethylbutyl, n-hexyl, cyclopentyl, cyclohexyl, etc., with hydrogen atoms, methyl, ethyl, n-propyl, and isopropyl being preferred, and hydrogen atoms and methyl being more preferred.

[0183] In general formula (1) or general formula (2), Rf is preferably a fluorine atom, trifluoromethyl, difluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 3,3,3-trifluoropropyl, hexafluoroisopropyl, heptafluoroisopropyl, nonafluoron-butyl, nonafluoroisobutyl, or nonafluorotert-butyl, more preferably a fluorine atom, trifluoromethyl, difluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoron-propyl, 2,2,3,3,3-pentafluoropropyl, 3,3,3-trifluoropropyl, or hexafluoroisopropyl, and Rf is preferably a fluorine atom, difluoromethyl, or trifluoromethyl.

[0184] As a preferred specific structure for the above-mentioned structural unit, the structures described in paragraphs 0060 to 0061 of International Publication No. 2021 / 235541 can be cited.

[0185] Considering the solubility in solvents or the tolerance to various treatments in the manufacture of light-emitting elements, the content of the structural unit represented by general formula (2) in the fluorinated resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0186] Fluorinated resins may also contain the structure represented by the following general formula (3).

[0187] [Chemical Formula 11] In general formula (3), R 3 R 4 Each can be used independently to represent a hydrogen atom or a methyl group.

[0188] In general formula (3), W 1 This indicates a divalent linker group. Preferably, it represents -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-.

[0189] Preferably, it is -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-. In particular, by making W... 1 The -OC(=O)-NH- form exhibits superior ink repellency after UV ozone treatment or oxygen plasma treatment during the manufacturing of light-emitting elements, and is therefore preferred.

[0190] In general formula (3), A 1 The term indicates a 2- to 4-valent linking group, preferably a straight-chain, branched-chain, or cyclic alkylene group with 1 to 10 carbon atoms, or with 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be represented by a hydroxyl group or -OC(=O)-CH3 replace.

[0191] When the divalent linker A 1 When it is a straight-chain alkylene group having 1 to 10 carbon atoms, examples include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene.

[0192] When the divalent linker A 1 When it is a branched alkylene group with 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene, and isohexylene.

[0193] When the divalent linker A 1 When it is a cyclic alkylene group with 3 to 10 carbon atoms, examples include 2-substituted cyclopropane, 2-substituted cyclobutane, 2-substituted cyclopentane, 2-substituted cyclohexane, 2-substituted cycloheptane, 2-substituted cyclooctane, 2-substituted cyclodecane, and 2-substituted 4-tert-butylcyclohexane.

[0194] When any number of hydrogen atoms in these alkylene groups are replaced by hydroxyl groups, examples of hydroxylated alkylene groups include, for example, hydroxyethylene, 1-hydroxypropylene, 2-hydroxypropylene, hydroxyisopropylene (-CH(CH2OH)CH2-), 1-hydroxybutylene, 2-hydroxybutylene, hydroxysec-butylene (-CH(CH2OH)CH2CH2-), hydroxyisobutylene (-CH2CH(CH2OH)CH2-), and hydroxytert-butylene (-C(CH2OH)(CH3)CH2-).

[0195] Furthermore, when any number of hydrogen atoms in these alkylene groups are replaced by -OC(=O)-CH3, the substituted alkylene groups can be exemplified by replacing the hydroxyl groups of the hydroxyl-substituted alkylene groups exemplified above with groups of -OC(=O)-CH3.

[0196] Among them, the divalent linker group A 1 Preferably, it is methylene, ethylene, propylene, n-butylene, isobutylene, sec-butylene, cyclohexyl, 2-hydroxypropylene, hydroxyisopropylene (-CH(CH2OH)CH2-), 2-hydroxybutylene, hydroxysec-butylene (-CH(CH2OH)CH2CH2-), more preferably ethylene, propylene, 2-hydroxypropylene, hydroxyisopropylene (-CH(CH2OH)CH2-), and particularly preferably ethylene and 2-hydroxypropylene. As a trivalent linking group A... 1 Examples include -C(CH2-)2CH3, which serves as a tetravalent linker group A. 1 Examples include C(CH2-)4.

[0197] In general formula (3), Y 1 The linking group represents a divalent group, preferably -O- or -NH-, more preferably -O-.

[0198] In general formula (3), u represents an integer from 1 to 3, and u is particularly preferred to be 1.

[0199] In general formula (3), n represents an integer from 1 to 3, and n is particularly preferably 1. The substitution positions of the aromatic rings are each independently represented as adjacent, meta, or para, and para is preferred.

[0200] The existence of multiple W 1 They can be the same as each other or different from each other. Furthermore, there are multiple A's. 1 They can be the same as each other or different from each other. Furthermore, there are multiple Y's. 1 They can be the same as each other or different from each other. Multiple R's exist. 4 They can be the same as each other or different from each other. From the perspective of ease of synthesis, etc., the multiple W's that exist are preferred. 1 If they are the same, then the multiple A's that exist are preferred. 1 The same among them, preferably the multiple Y that exist. 1 If they are the same, then the preferred option is to have multiple R values. 4 They are the same.

[0201] As a specific preferred structure represented by general formula (3), the structures described in paragraphs 0081 to 0084 of International Publication No. 2021 / 235541 can be listed.

[0202] Considering the solubility in solvents or the tolerance to various treatments in the manufacture of light-emitting elements, the content of the structural unit represented by general formula (3) in the fluorinated resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0203] Fluorinated resins may also contain the structure represented by the following general formula (4).

[0204] [Chemical Formula 12] In general formula (4), R 5 R 6 Each can be used independently to represent a hydrogen atom or a methyl group.

[0205] In equation (4), W 2The linking group represents a divalent group, preferably -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH- are preferred. Especially when W 2 When the value is -OC(=O)-NH-, the ink repellency is better after UV ozone treatment or oxygen plasma treatment during the manufacturing of the light-emitting element, and therefore it is preferred.

[0206] In general formula (4), A 2 The linking group represents a divalent group, preferably a straight-chain, branched, or cyclic alkylene group with 1 to 10 carbon atoms, or with 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group can be replaced by a hydroxyl group or -OC(=O)-CH3.

[0207] In general formula (4), A 3 The term indicates a 2- to 4-valent linking group, preferably a straight-chain, branched, or cyclic alkylene group with 1 to 10 carbon atoms, or with 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group may be replaced by a hydroxyl group or -OC(=O)-CH3.

[0208] When the divalent linker A 2 A 3 When it is a straight-chain alkylene group having 1 to 10 carbon atoms, examples include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene.

[0209] When the divalent linker A 2 A 3 When each is an alkylene group with 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene, and isohexylene.

[0210] When the divalent linker A 2 A 3 When each is an alkylene ring with 3 to 10 carbon atoms, examples include 2-substituted cyclopropane, 2-substituted cyclobutane, 2-substituted cyclopentane, 2-substituted cyclohexane, 2-substituted cycloheptane, 2-substituted cyclooctane, 2-substituted cyclodecane, and 2-substituted 4-tert-butylcyclohexane.

[0211] When any number of hydrogen atoms in these alkylene groups are replaced by hydroxyl groups, examples of hydroxylated alkylene groups include 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 1-hydroxypropylene, 2-hydroxypropylene, hydroxyisopropylene (-CH(CH2OH)CH2-), 1-hydroxybutylene, 2-hydroxybutylene, hydroxysec-butylene (-CH(CH2OH)CH2CH2-), hydroxyisobutylene (-CH2CH(CH2OH)CH2-), and hydroxytert-butylene (-C(CH2OH)(CH3)CH2-).

[0212] Furthermore, when any number of hydrogen atoms in these alkylene groups are replaced by -OC(=O)-CH3, substituted alkylene groups can be listed as groups formed by replacing the hydroxyl groups of the aforementioned hydroxyl-substituted alkylene groups with -OC(=O)-CH3.

[0213] Among them, the divalent linker group A 2 A 3 Each of the following is preferred independently: methylene, ethylene, propylene, n-butylene, isobutylene, sec-butylene, cyclohexylene, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 2-hydroxyn-propylene, hydroxyisopropylene (-CH(CH2OH)CH2-), 2-hydroxyn-butylene, hydroxysec-butylene (-CH(CH2OH)CH2CH2-), ethylene, propylene, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 2-hydroxyn-propylene, hydroxyisopropylene (-CH(CH2OH)CH2-), and particularly preferred: ethylene, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-).

[0214] As a trivalent linker group A 3 Examples include -C(CH2-)2CH3, which serves as a tetravalent linker group A. 3 Examples include C(CH2-)4.

[0215] In general formula (4), Y 2 Y 3 Each of the connecting groups independently represents a divalent group, preferably -O- or -NH-, more preferably -O-.

[0216] In general formula (4), n represents an integer from 1 to 3. Preferably, n is 1.

[0217] Multiple Ys 3 They can be the same as each other or different from each other. Furthermore, there are multiple R's.6 They can be the same as each other or different from each other. From the perspective of ease of synthesis, etc., the preferred option is the combination of multiple Y values. 3 If they are the same, then the preferred option is to have multiple R values. 6 They are the same.

[0218] In general formula (4), r represents 0 or 1. When r is 0, "(-C(=O)-)" is used. r Indicates a single key.

[0219] As a specific preferred structure represented by general formula (4), the structures described in paragraphs 1005 to 0109 of International Publication No. 2021 / 235541 can be cited.

[0220] Considering the solubility in the solvent or the adhesion of the pattern (partition) to the substrate, the content of the structural unit represented by the general formula (4) in the fluorinated resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0221] Fluorinated resins may contain structural units represented by general formula (5).

[0222] [Chemical Formula 13] In general formula (5), R 7 It represents a hydrogen atom or a methyl group.

[0223] In general formula (5), R 8 It refers to a linear alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cyclic alkyl group with 3 to 15 carbon atoms, wherein any number of hydrogen atoms in these alkyl groups are replaced by fluorine atoms, and the fluorine content in the structural unit is 30% by mass or more.

[0224] In R 8 When the hydrocarbon group is a straight-chain hydrocarbon group, specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or any number of hydrogen atoms of a straight-chain alkyl group with 10 to 14 carbon atoms that are replaced by fluorine atoms.

[0225] When R 8 When the hydrocarbon group is a straight chain, the structural unit represented by general formula (5) is preferably the structural unit represented by the following general formula (5-1).

[0226] [Chemical Formula 14] In general formula (5-1), R 9 R in general formula (5) 7 They have the same meaning.

[0227] In general formula (5-1), X is a hydrogen atom or a fluorine atom. X is preferably a fluorine atom.

[0228] In general formula (5-1), p is an integer from 1 to 4, and q is an integer from 1 to 14. Preferably, p is an integer from 1 to 2 and q is an integer from 2 to 8.

[0229] As a specific preferred structural unit represented by general formula (5), the structures described in paragraphs 0125 to 0128 of International Publication No. 2021 / 235541 can be listed.

[0230] The content of the structural unit represented by general formula (5) in the fluorinated resin can be appropriately determined by considering factors such as the ease of ink repulsion when forming a pattern (partition) or the ease of solubility in the solvent when preparing a photosensitive composition. Specifically, the content of the structural unit represented by general formula (5) in the fluorinated resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 30% by mass.

[0231] Fluorinated resins may contain the structure represented by the following general formula (6).

[0232] [Chemical Formula 15] In general formula (6), R 10 It represents a hydrogen atom or a methyl group.

[0233] In general formula (6), B independently represents a hydrogen atom, hydroxyl group, carboxyl group, -C(=O)-OR group, etc. 11 (R 11 R 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, wherein any number of hydrogen atoms in the alkyl group are replaced by fluorine atoms. 11 The fluorine content is 30% or more by mass) or -OC (=O)-R 12 (R 12 This refers to alkyl groups that are straight-chain (1-6 carbon atoms), branched (3-6 carbon atoms), or cyclic (3-6 carbon atoms).

[0234] In addition, m represents an integer from 0 to 3.

[0235] As a specific preferred structure represented by general formula (6), the structures described in paragraphs 0137 to 0138 of International Publication No. 2021 / 235541 can be cited.

[0236] Considering the full effect of the structural unit represented by general formula (6) or solvent solubility, the content of the structural unit represented by general formula (6) in the fluorinated resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass.

[0237] In general formula (6), when B 1 When the group is hydroxyl or carboxyl, the structural unit represented by general formula (6) has solubility in alkaline developing solutions. Therefore, when particularly good alkaline developing properties are desired, fluorinated resins containing B are preferred. 1 The structural unit represented by the general formula (6) when it is a hydroxyl or carboxyl group.

[0238] Fluorinated resins may contain the structure represented by the following general formula (7).

[0239] [Chemical Formula 16] In general formula (7), R 13 It represents a hydrogen atom or a methyl group.

[0240] In general formula (7), A 4 The linking group represents a divalent group, preferably a straight-chain, branched, or cyclic alkylene group with 1 to 10 carbon atoms, or with 3 to 10 carbon atoms. Any number of hydrogen atoms in the alkylene group are replaced by hydroxyl groups or -OC(=O)-CH3.

[0241] When the divalent linker A 4 When it is a straight-chain alkylene group having 1 to 10 carbon atoms, examples include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene.

[0242] When the divalent linker A 4 When it is a branched alkylene group with 3 to 10 carbon atoms, examples include isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene, and isohexylene.

[0243] When the divalent linker A 4 When it is a cyclic alkylene group with 3 to 10 carbon atoms, examples include 2-substituted cyclopropane, 2-substituted cyclobutane, 2-substituted cyclopentane, 2-substituted cyclohexane, 2-substituted cycloheptane, 2-substituted cyclooctane, 2-substituted cyclodecane, and 2-substituted 4-tert-butylcyclohexane.

[0244] When any number of hydrogen atoms in these alkylene groups are replaced by hydroxyl groups, examples of hydroxylated alkylene groups include 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 1-hydroxypropylene, 2-hydroxypropylene, hydroxyisopropylene (-CH(CH2OH)CH2-), 1-hydroxybutylene, 2-hydroxybutylene, hydroxysec-butylene (-CH(CH2OH)CH2CH2-), hydroxyisobutylene (-CH2CH(CH2OH)CH2-), and hydroxytert-butylene (-C(CH2OH)(CH3)CH2-).

[0245] Furthermore, when any number of hydrogen atoms in these alkylene groups are replaced by -OC(=O)-CH3, the substituted alkylene groups can be listed as groups that replace the hydroxyl groups of the aforementioned hydroxyl-substituted alkylene groups with -OC(=O)-CH3.

[0246] Among them, the divalent linker group A 4 Preferably, it is methylene, ethylene, propylene, n-butylene, isobutylene, sec-butylene, cyclohexylene, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 2-hydroxyn-propylene, hydroxyisopropylene (-CH(CH2OH)CH2-), 2-hydroxyn-butylene, hydroxysec-butylene (-CH(CH2OH)CH2CH2-), more preferably ethylene, propylene, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-), 2-hydroxyn-propylene, hydroxyisopropylene (-CH(CH2OH)CH2-), particularly preferably ethylene, 1-hydroxyethylene (-CH(OH)CH2-), 2-hydroxyethylene (-CH2CH(OH)-).

[0247] In general formula (7), Y 4 The linking group represents a divalent group, preferably -O- or -NH-, more preferably -O-.

[0248] In general formula (7), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

[0249] In general formula (7), E 1 It indicates a hydroxyl, carboxyl, or epoxy group.

[0250] When E 1 When the radical is epoxy group, examples include ethylene oxide, 1,2-epoxypropane, and 1,3-epoxypropane. Among these, ethylene oxide is preferred.

[0251] In general formula (7), s represents 0 or 1. When s is 0, (-Y4 -A 4 -) indicates a single bond. When r is 0 and s is 0, the main chain forming the structural unit contains E bonds. 1 The structure.

[0252] As a specific and limited structure represented by general formula (7), the structure described in paragraph 0156 of International Publication No. 2021 / 235541 can be listed.

[0253] The weight-average molecular weight of the fluorinated resin, as determined by gel permeation chromatography (GPC) using polystyrene as a standard, is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000.

[0254] By adjusting the molecular weight of the fluorinated resin, the strength of the formed pattern (partition) can sometimes be increased, or the coating properties can be improved by increasing its solubility in the solvent.

[0255] The dispersion (Mw / Mn) of the fluorinated resin is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.

[0256] Fluorinated resins can be random copolymers, alternating copolymers, block copolymers, or graft copolymers. From the perspective of moderately dispersing rather than localizing their respective properties, random copolymers are preferred.

[0257] The desired fluorine content of the fluorinated resin is 20-50% by mass, and more preferably 25-40% by mass. By maintaining the fluorine content within this range, the fluorinated resin is readily soluble in solvents. Furthermore, by maintaining the fluorine content within this range, patterns (septa) with excellent liquid-repellent properties can be easily obtained.

[0258] The determination of the fluorine content of fluorinated resins can be carried out according to, for example, paragraph 0174 of International Publication No. 2021 / 235541.

[0259] When using fluorinated resins, you can use only one type of fluorinated resin or two or more types of fluorinated resins.

[0260] From the perspective of balancing sufficient liquid repellency and good alkaline developability of the obtained pattern (partition), the amount of fluorinated resin used is generally 0.1 to 10% by mass of all non-volatile components in the photosensitive composition, preferably 0.1 to 8% by mass, and more preferably 0.2 to 5% by mass.

[0261] In addition, for information on fluorinated resins, please refer to, for example, International Publication No. 2021 / 235541.

[0262] (Chain transfer agent) Negative photosensitizing compositions preferably contain a chain transfer agent. Chain transfer agents, as known in the field of polymer synthesis, are components that, in free radical polymerization systems, self-growing polymer chains absorb free radicals to generate new free radicals. By using chain transfer agents, the degree of polymerization can sometimes be adjusted, thereby enabling the modification of the properties of the cured film.

[0263] As a chain transfer agent, known chain transfer agents can be used without particular restriction. Preferably, the chain transfer agent comprises a thiol compound. The thiol compound may have only one thiol group per molecule, or it may have two or more (specifically two to eight) thiol groups per molecule.

[0264] As thiol compounds, the compounds represented by the following general formula (b) can be specifically listed.

[0265] [Chemical Formula 17] In general formula (b), R is a hydrogen atom, an alkyl group, or a cycloalkyl group. X is either -CO- or -CH2-. L is an n-valent linker group. n is an integer greater than or equal to 2, preferably 2 to 8, and more preferably 2 to 6.

[0266] The multiple Rs can be the same as each other or different from each other. Similarly, the multiple Xs can be the same as each other or different from each other. From the perspective of ease of synthesis, it is preferable that the multiple Rs are the same as each other, and it is also preferable that the multiple Xs are the same as each other.

[0267] The alkyl group of R can be straight-chain or branched. The number of carbon atoms in the alkyl group is preferably 1 to 16, more preferably 1 to 10. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, etc. Among these, methyl, ethyl, propyl, or isopropyl are preferred, more preferably methyl or ethyl.

[0268] Examples of L as an n-valent linking group include, for example, straight-chain or branched alkylene chains (with, for example, 2 to 6 carbon atoms), trimethylolpropane residues, and chains with 3 -(CH2) groups. p -(p is 2~6) isocyanurate ring and other trivalent linking groups, pentaerythritol residue and other quadrivalent or pentavalent linking groups, dipentaerythritol residue and other hexavalent linking groups.

[0269] Commercially available thiol compounds include, for example, the "Karenz" series manufactured by Showa Denko KK. The thiols in this series are secondary thiols. Additionally, product numbers such as PEMP, TMMP, DPMP, and TEMPIC from SC Organic Chemical Co., Ltd. can be listed. These thiols are primary thiols.

[0270] The content of thiol groups in the thiol compound is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and particularly preferably 10 to 30% by mass, relative to the molecular weight of the thiol compound.

[0271] When using chain transfer agents, you can use only one chain transfer agent or two or more chain transfer agents.

[0272] When using a chain transfer agent, the amount is not particularly limited, but as an option, it is, for example, 0.1 to 10% by mass, specifically 0.5 to 8% by mass, and more specifically 1 to 5% by mass, of all non-volatile components in the negative photosensitizing composition. Furthermore, when using a chain transfer agent, the amount relative to 100 parts by mass of the curing component is, for example, 0.2 to 25 parts by mass, specifically 1 to 20 parts by mass, and more specifically 2 to 15 parts by mass.

[0273] (Other arbitrary ingredients) The negative photosensitizing composition may contain any ingredients other than those mentioned above. Examples of such ingredients include dissolution inhibitors, plasticizers, stabilizers, surfactants, thickeners, leveling agents, defoamers, compatibilizers, adhesion improvers, and antioxidants. Commercially available products may be used as these ingredients. For example, as an adhesion improver, products from the "KAYAMER" series manufactured by NipponKayaku Co., Ltd. may be used.

[0274] (solvent) Negative photosensitizing compositions are typically compositions formed by dissolving or dispersing the above-mentioned components in a solvent. The solvent usually includes organic solvents.

[0275] There are no particular limitations on the solvents that can be used. Specific examples include ketones, alcohols, polyols and their derivatives, ethers, esters, aromatic solvents, and fluorinated solvents. These can be used alone or in combination of two or more.

[0276] Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isopentyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0277] Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isoamyl alcohol, tert-amyl alcohol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, sec-amyl alcohol, tert-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, dodecanol, hexyldecanol, oleyl alcohol, etc.

[0278] Examples of polyols and their derivatives include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), and monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and monophenyl ethers of dipropylene glycol or dipropylene glycol monoacetate.

[0279] Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

[0280] 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.

[0281] Examples of aromatic solvents include xylene and toluene.

[0282] Examples of fluorinated solvents include Freon, alternative Freon, perfluorinated compounds, and hexafluoroisopropanol.

[0283] In addition, to improve coatability, turpentine-based naphtha solvents or paraffin-based solvents, which are high-boiling-point weak solvents, can be used.

[0284] The solvent preferably comprises at least one selected from the group consisting of methyl ethyl ketone, cyclohexanone, methyl isopentyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol 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 hexafluoroisopropanol.

[0285] Furthermore, the solvent preferably includes methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

[0286] When using solvents, you can use only one solvent or two or more solvents.

[0287] When using a solvent, the amount of solvent in the negative photosensitizing composition shall be such that the concentration of all solid components is, for example, 5 to 85% by mass, specifically 10 to 60% by mass.

[0288] The thickness of the formed film can be adjusted by changing the amount of solvent. If it is within the above range, it is particularly easy to obtain a film thickness suitable for obtaining the separator in an organic EL element.

[0289] [Membrane Formation Process] In the film formation process, an unexposed film formed from the above-mentioned negative photosensitive composition is formed on the substrate.

[0290] There are no particular limitations on the type of substrate. The appropriate substrate should be selected based 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 (such as polyimide, polycarbonate, and polyester).

[0291] Certain layers may be formed on at least one side of the substrate, or some layers may not be formed. For example, when it is desired to manufacture a light-emitting element, 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 of organic EL light-emitting materials, LED light-emitting materials such as mini LEDs, micro LEDs, and nano LEDs, and quantum dot light-emitting materials. The first light-emitting layer may be a monochromatic layer or a multicolor layer, but a monochromatic layer is preferred. Furthermore, the first light-emitting layer is preferably a light-emitting layer that emits monochromatic blue light.

[0292] When a first light-emitting layer is disposed on at least one surface of a 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 lower layer of multilayer resist, a barrier layer, etc., may be present. Furthermore, a driving circuit, electrodes, a planarization layer, etc., may also be formed between the substrate and the first light-emitting layer.

[0293] In addition, a wavelength conversion layer can be set to replace the first light-emitting layer.

[0294] As a precaution, it should be noted beforehand that a substrate without a first light-emitting layer or other layers formed on its surface can be used as the substrate.

[0295] There are no particular limitations on the method for coating negative photosensitive compositions. Known methods such as spin coating, rod coating, and screen coating can be used. Inkjet coating can also be used sometimes.

[0296] When using a solvent-containing composition as a negative photosensitizing composition, it is preferable to dry the solvent by heating after coating the composition. The heating temperature can be set, for example, 50-150°C, preferably 50-100°C, more preferably 60-90°C, further preferably 70-90°C, and particularly preferably 80-90°C. Furthermore, the heating time can be set to 60-200 seconds.

[0297] The membrane thickness (dry membrane thickness) is typically 0.5~20μm, preferably 1~15μm.

[0298] [Exposure Process] In the exposure process, the unexposed film formed in the film formation process is selectively irradiated with light having spectral maxima in at least the wavelength range of 350-380 nm (preferably 355-375 nm) and in the wavelength range of 390-420 nm (preferably 395-415 nm). Thus, the unexposed film becomes the exposed film. Specifically, "selective irradiation" means irradiating the unexposed film with light through a photomask, creating areas that are illuminated and areas that are not illuminated. By selectively irradiating the unexposed film and then performing a subsequent development process, a desired pattern can be formed on the substrate.

[0299] Typically, the light emitted from a mercury lamp has spectral maxima in at least the wavelength range of 350–380 nm and the wavelength range of 390–420 nm. The light emitted from a mercury lamp usually includes an i-line at wavelength 365 nm and an h-line at wavelength 405 nm as glow lines. That is, the mercury lamp is one of the preferred light sources. When using a mercury lamp, the unexposed film is simultaneously irradiated with light in the wavelength range of 350–380 nm and light in the wavelength range of 390–420 nm.

[0300] Of course, light sources other than mercury lamps can also be used. For example, a light-emitting diode (LED) emitting monochromatic light in the wavelength range of 350-380 nm can be combined with an LED emitting monochromatic light in the wavelength range of 390-420 nm, and the light emitted by the two LEDs can be used to illuminate the unexposed film. In this case, the light emitted from the two LEDs can illuminate the unexposed film simultaneously or separately, but considering industrial production, the former is preferred.

[0301] Light illuminating an unexposed film can contain only wavelengths in the range of 350–380 nm and 390–420 nm, and may also include wavelengths outside these ranges. In the field of free lithography, the light emitted by mercury lamps typically contains i-lines or h-lines in a continuous spectrum. Therefore, if light emitted directly from a mercury lamp is not spectrally dispersed, it typically contains i-lines and h-lines, and further includes wavelengths outside these ranges.

[0302] [Developing process] In the developing process, a developing solution is typically used to develop the film after the exposure process. As a result, the unexposed areas within the film usually dissolve, creating a pattern (spacers).

[0303] As the developer, an alkaline aqueous solution is preferred. Specifically, aqueous solutions of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), sodium hydroxide, and potassium hydroxide can be used.

[0304] As the developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred, based on its excellent developability and long-standing proven track record in the field of photosensitizing compositions. The concentration of the TMAH aqueous solution is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass.

[0305] In addition, as a developer, a developer with organic solvents as the main component can sometimes be used.

[0306] As a developing method, known methods can be used. Examples include immersion, paddle, and spraying. The developing time (the time the developing solution contacts the film) is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.

[0307] After development, a cleaning process using deionized water or similar materials can be added as needed. The cleaning time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.

[0308] [Heating Process] It is preferable to heat the pattern formed after the developing process. That is, it is preferable to perform the heating process after the developing process.

[0309] In the heating process, the developed pattern is heated. This allows the residual reactive groups in the pattern obtained in the developing process to react as much as possible, thus solidifying the film.

[0310] In the heating process, the developed film is heated, for example, at 50~250°C, preferably 50~230°C, more preferably 60~220°C, and even more preferably 70~200°C. By not excessively increasing the heating temperature at this point, it is easy to suppress the deterioration / deterioration of pigments or other materials in the light-emitting element.

[0311] In addition, the heating time is, for example, 10 minutes to 3 hours, preferably 15 minutes to 1 hour.

[0312] [Any process following the heating process] The cured film obtained in the heating process can be treated with UV ozone or oxygen plasma. This can remove organic matter remaining in the recesses of the pattern (cured film), or reduce the uneven wetting of the added ink during the ink drop process described later.

[0313] To obtain a light-emitting element, it is preferable to perform a second light-emitting layer formation process, in which a second light-emitting layer is formed in the recesses of the pattern (cured film), i.e., in the area divided by the partition, and the second light-emitting layer emits light using light from the first light-emitting layer as excitation light. Preferably, the second light-emitting layer comprises conventionally known materials such as quantum dot light-emitting materials.

[0314] For example, as described in one of the background art materials, the second light-emitting layer can be formed by dripping ink onto the recesses of a pattern (cured film) using an inkjet method, and then allowing the ink to dry and / or cure. That is, sometimes a light-emitting element can be obtained by dripping ink used to form the second light-emitting layer onto the recesses of a pattern (cured film) using an inkjet method.

[0315] Alternatively, to obtain a light-emitting element that emits RGB light, ink containing red, green, or blue pigments (typically a liquid with dispersed pigments) can be dropped into the recesses of the pattern (cured film), i.e., the areas divided by the partitions, and then the ink can be dried and / or cured.

[0316] The above methods can be used to manufacture substrates with black patterns.

[0317] The optical density of the black pattern portion in the substrate with the 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, even with a high optical density, a black pattern with a good cross-sectional shape can still be obtained, and a substrate with such a black pattern can be manufactured.

[0318] The specific method for measuring optical density is described in the examples.

[0319] [Additional explanation regarding the pattern shape] The degree of conicity or inverted conicity when a cross-section of a pattern formed on a substrate in the manner described above (e.g., a cross-section of the line portion of a line and space pattern) is photographed using a scanning electron microscope can be quantified as an indicator for evaluating the pattern shape.

[0320] Specifically, • Define the height from the top surface of the substrate to the top of the pattern as the pattern height; • Set the maximum width of the pattern in the upper part of the pattern, that is, the range from the top of the pattern to half the height of the pattern, as width A; • Define the minimum width of the pattern in the lower part of the pattern, that is, from the contact surface between the substrate and the pattern to half the height of the pattern, as width B; When setting it up as described above, the value of width A - width B can be set as the index of the pattern shape.

[0321] From the perspective of improving the pattern shape, the value of width A - width B is preferably -2~7μm, more preferably -2~2μm, even more preferably 0~1μm, and can also be -2~0μm. The closer this value is to 0, the closer the cross-sectional shape of the pattern is to a rectangle.

[0322] Alternatively, the value of width A / width B can be set as an indicator of the pattern shape.

[0323] From the perspective of improving the shape of the pattern, 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 can also be 1.0 to 1.2. The closer this value is to 1.0, the closer the cross-sectional shape of the pattern is to a rectangle.

[0324] <Negative photosensitizing composition> The above mainly describes the implementation scheme of the present invention from the perspective of the substrate manufacturing method.

[0325] From the perspective of a method different from the substrate manufacturing process, the negative photosensitizing composition described in the section on [negative photosensitizing composition] can be considered novel and industrially useful. That is, the negative photosensitizing composition described in the following paragraphs can function independently of the substrate manufacturing process.

[0326] A negative photosensitizing composition comprising: Black colorants that have extremely low absorbance in the wavelength range of 380~420nm. Oxime ester photoinitiators Acylphosphine oxide photoinitiators, and A curable component that is cured by active species generated by the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

[0327] The specific form of this negative photosensitizing composition, as described in the section on [negative photosensitizing compositions], will not be further described.

[0328] The embodiments of the present invention have been described above, but these are merely examples. The present invention can employ various configurations other than those described above. Furthermore, the present invention is not limited to the above embodiments, and modifications and improvements made within the scope of achieving the objectives of the present invention are all included within the scope of the present invention.

[0329] Example The embodiments of the present invention will be described in detail with reference to examples and comparative examples. For the sake of caution, the invention is not limited to the embodiments described herein.

[0330] First, record the various measurement methods.

[0331] [Determination of the molar ratio of each building unit in the polymer] Depend on 1 H-NMR, 19 F-NMR or 13 The C-NMR values ​​were determined.

[0332] [Determination of the molecular weight of polymers] The weight-average molecular weight (Mw) and molecular weight dispersion (the ratio of number-average molecular weight (Mn) to weight-average molecular weight (Mw); Mw / Mn) of the polymer were determined using a high-performance gel permeation chromatography (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 the standard and tetrahydrofuran (THF) as the developing solvent. A refractive index difference detector was used.

[0333] <Preparation of raw materials (synthesis or preparation)> [Synthesis of Fluorine Resin 1] At room temperature (approximately 20°C), add 2.9 parts by weight of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd., hereinafter referred to as BTFBE), 2.9 parts by weight of 4-acetoxystyrene (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St), 12.5 parts by weight of 2-(perfluorohexyl)ethyl methacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MA-C6F), 6.0 parts by weight of glyceryl monomethacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as Gly-MA), and 125 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to a 300 mL glass flask equipped with a stirrer.

[0334] Add 2.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) to the flask and degas while stirring.

[0335] Then, the inside of the flask was purged with nitrogen, and the temperature was raised to 79°C to allow the reaction to proceed overnight. This yielded a precursor solution containing fluorinated resin 1.

[0336] On a molar basis, the composition ratio of each structural unit of the precursor of fluorinated resin 1 is: structural unit from BTFBE: structural unit from p-AcO-St: structural unit from MA-C6F: structural unit from Gly-MA = 15:18:29:38.

[0337] The structure of the precursor of fluorinated resin 1 is shown below.

[0338] [Chemical Formula 18] After purging the flask with dry air, the precursor solution was cooled to an internal temperature of 60°C. Then, 0.01 parts by weight of butylated hydroxytoluene (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 11.4 parts by weight of ethyl 2-isocyanate (Showa Denko KK, product name: Karenz AOI) were added.

[0339] Then, stir for 4 hours. After stirring, cool the solution to room temperature (20°C). This yields a solution containing fluorinated resin 1.

[0340] According to GPC measurements, the Mw of fluorinated resin 1 is 13,300, and the Mw / Mn ratio is 1.7.

[0341] Synthesis of Fluorine-Containing Resin 2 At room temperature (approximately 20°C), add the following to a 300 mL glass flask equipped with a stirrer: 9.5 g (0.05 mol) of BTFBE, 13.0 g (0.10 mol) of hydroxyethyl methacrylate (HEMA), 43.2 g (0.1 mol) of MA-C6F, 8.6 g (0.10 mol, Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as MAA), 7.8 g (0.75 mol, Tokyo Chemical Industry Co., Ltd. product, hereinafter referred to as St), and 82 g of MEK (methyl ethyl ketone).

[0342] Then, 1.6 g (0.005 mol) of AIBN was added to the flask, and the gas was degassed while stirring.

[0343] Next, the inside of the flask was purged with nitrogen, and the internal temperature was raised to 75°C to allow the reaction to proceed for 6 hours. This yielded a precursor solution containing fluorinated resin 2.

[0344] The structure of the precursor of fluorinated resin 2 is shown below.

[0345] Furthermore, in molar ratio, the composition ratio of each structural unit of the precursor of fluorinated resin 2 is structural unit from BTFBE: structural unit from HEMA: structural unit from MA-C6F: structural unit from MAA: structural unit from St = 15:25:30:10:20.

[0346] [Chemical Formula 19] After the reaction was complete, the inside of the flask was purged with dry air, and the reaction solution was cooled to an internal temperature of 60°C. After cooling, 0.01 parts by weight of butylated hydroxytoluene (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BHT) and 12.1 parts by weight of ethyl 2-isocyanate (Showa Denko KK, product name: KarenzAOI) were added to the flask, and the mixture was stirred for 4 hours. Then, the stirred solution was cooled to room temperature (20°C).

[0347] A solution containing fluorinated resin 2 was obtained in the manner described above.

[0348] According to GPC measurements, Mw = 7,200, Mw / Mn = 1.3.

[0349] [Preparation of Black Colorant Dispersion 1] Pigments 1-3, dispersant, alkali-soluble resin, and solvent as listed in Table 1 are mixed to the mass ratios shown in Table 1 to form a mixture. A bead mill with a 0.5mm diameter is used. The mixture was dispersed at 25°C for 12 hours using zirconia beads. After dispersion, the beads were removed by filtration. This prepared a black colorant dispersion 1.

[0350] [Table 1] The light absorption spectrum of black colorant dispersion 1 was measured.

[0351] Specifically, firstly, the black colorant dispersion 1 was diluted to 1% by mass using propylene glycol monomethyl ether acetate as the dispersion medium to prepare a diluted solution. This diluted solution was then placed in a quartz cell with a 1 cm optical path length, and the cell was placed in a commercially available spectrophotometer to obtain the optical absorption spectrum. The measurement wavelength range was set to 330–800 nm.

[0352] The obtained light absorption spectrum is shown in Figure 1 .

[0353] Figure 1 The absorption spectrum has a minimum value at a wavelength of 390 nm, with a minimum value A. min It is 0.42.

[0354] In addition, the absorbance A at a wavelength of 365 nm 365 A is 0.55. 365 / A min It is 1.31.

[0355] <Preparation of Negative Photosensitizing Compositions> First, the components used in the embodiments and comparative examples are shown.

[0356] [Black colorant (dispersion)] Black colorant dispersion 1: The black colorant dispersion prepared above Black colorant dispersion 2: Carbon black dispersion "NX-545" manufactured by Dainippon Seika Co., Ltd. (for comparative example; carbon black containing minimal absorbance in the wavelength range of 380~420nm. Absorbance at 365nm > 4.0) [Photoinitiator] Oxime ester 1: BASF's "OXE-01" (oxime ester photoradical initiator) Oxime ester 2: TR-PBG-305 (oxime ester photoradical initiator) manufactured by Tronly Acylphosphine oxide 1: "Omnirad TPO" (acylphosphine oxide initiator) manufactured by BASF. Acylphosphine oxide 2: "Omnirad 819" (acylphosphine oxide initiator) manufactured by BASF. Hydroxyalkylphenyl ketones: "Omnirad 184" (a hydroxyalkylphenyl ketone free radical initiator) manufactured by iGM RESINS. Thioxanone: "KAYACURE DETX-S" (thioxanone-based initiator) manufactured by Nippon Kayaku Co., Ltd. [Curing components] Alkene unsaturated compound 1: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. Alkene unsaturated compound 2: “TMMT” (pentaerythritol tetraacrylate) manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD. [Alkali-soluble resin] Alkali-soluble resin 1: "ZAR-2050H" manufactured by Nippon Kayaku Co., Ltd. (Special BIS-A type acrylate epoxy ester, containing the structural unit represented by the above-disclosed general formula (e). Contains no fluorine atoms.) Alkali-soluble resin 2: "ZCR-1569H" (biphenyl-type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd. Alkali-soluble resin 3: "CCR-1171H" (cresol phenolic varnish type acrylic epoxy ester) manufactured by Nippon Kayaku Co., Ltd. Alkali-soluble resin 4: "TR-B20101" manufactured by Tronly (a Cardo resin with the structure represented by the following structural formula. In the structural formula, parentheses indicate repeating units). [Chemical Formula 20] Fluoropolymer resin Fluorinated resin 1: Fluorinated resin 1 synthesized in the manner described above Fluorinated resin 2: Fluorinated resin 2 synthesized in the manner described above Fluorinated resin 3: "MEGAFACE RS-72A" (fluorinated, polyether structure) manufactured by DIC Company. [Chain transfer agent] Chain transfer agent 1: "Karenz-MTPE1" manufactured by Showa Denko KK. Chain transfer agent 2: "DPMP" manufactured by SC Organic Chemical Co., Ltd. [additive] Additive 1: Adhesion improver "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd. The negative photosensitizing composition is prepared by uniformly stirring / mixing the components listed in the table disclosed later with PGMEA as a solvent. The amount of PGMEA is set such that the concentration of the non-volatile component is 50% by mass.

[0357] <Evaluation> [Formation of the partition used for evaluation] Form partitions (patterns) on a substrate by following these steps.

[0358] (1) Clean the 10cm square ITO substrate with ultrapure water, followed by cleaning with acetone. Then, treat the substrate with UV ozone for 5 minutes using a UV ozone treatment device (manufactured by SEN LIGHTS Co., Ltd., model PL17-110).

[0359] (2) The prepared negative photosensitive composition was coated onto the obtained UV ozone-treated substrate using a spin coater at a speed of 300 rpm. Then, the substrate was heated on a heating plate at 80°C for 150 seconds. A resin film with a thickness of about 11 μm was thus obtained.

[0360] (3) Using a photomask alignment machine (SUSS MicroTec SE product), with a mask having a line width: line spacing = 10μm: 10μm, the cumulative exposure E is such that the width of the developed lines is 10±0.5μm. o Irradiation light. The light source of this lithography machine is an ultra-high pressure mercury lamp, and the spectrum of the light emitted from this mercury lamp is as follows: Figure 2 As shown, it contains a glow line spectrum including the i-line (wavelength 365 nm) and the h-line (wavelength 405 nm).

[0361] (4) Spray development using a 0.04% KOH aqueous solution for 40 seconds. After development, rinse with pure water for 10 seconds. Then, remove residual developer and / or rinsing solution by purging with N2.

[0362] (5) Heat the substrate on a heating plate at 200°C for 60 minutes.

[0363] The performance of the separator was evaluated using a cured film with a thickness of approximately 10 μm.

[0364] [Optimal Exposure] The cumulative exposure E in the above [formation of the partition used for evaluation] o The optimal exposure can be set to the exposure of a pattern whose line width and line spacing are basically the same as those of the mask.

[0365] [Pattern Shape] A cross-section of the line gap pattern under optimal exposure was captured using a scanning electron microscope.

[0366] • Define the height from the top surface of the substrate to the top of the pattern as the pattern height; • Set the maximum width of the pattern in the upper part of the pattern, that is, the range from the top of the pattern to half the height of the pattern, as width A; • Define the minimum width of the pattern in the lower part of the pattern, that is, from the contact surface between the substrate and the pattern to half the height of the pattern, as width B; At this point, the value of width A minus width B is set as an indicator of the pattern shape. The closer this value is to 0, the closer the cross-sectional shape of the pattern is to a rectangle.

[0367] [Optical density] The optical density (OD value) of the cured material was measured using a black and white transmission density meter (manufactured by Ihara Electronic Industries Co., Ltd.: T5plus, wavelength 400~700nm). Measurements were taken at five random locations on the cured material. The average of the five measured values ​​was then used as the optical density (OD value).

[0368] Information and evaluation results regarding the incorporation of negative photosensitizing compositions are presented in the table below.

[0369] The table below lists the molar ratios of non-volatile components used in the preparation of compositions in the form of solutions or dispersions.

[0370] [Table 2] [Table 3] [Table 4] As shown in Tables 2-4 above, by irradiating a negative photosensitive composition comprising a black colorant, an oxime ester-based photoinitiator, and an acylphosphine oxide-based photoinitiator with minimum absorbance values ​​in the wavelength range of 380-420 nm with light (including i-line and h-line light) having spectral maxima in the wavelength range of at least 350-380 nm and in the wavelength range of 390-420 nm, a pattern with a good (nearly rectangular) cross-sectional shape can be formed compared to the comparative example. Furthermore, a substrate with such a pattern can be obtained.

[0371] A more detailed examination of the embodiments reveals that a higher ratio of acylphosphine oxide photoinitiators, represented by {m2 / (m1+m2)}×100(%), tends to further improve the cross-sectional shape of the pattern.

[0372] Compared to the examples, a distinct inverted cone-shaped pattern was obtained in Comparative Example 1. This can be presumed to be because the composition of Comparative Example 1 does not contain an acylphosphine oxide-based photoinitiator, resulting in insufficient free radical generation in the lower part of the film.

[0373] Furthermore, no pattern could be formed in Comparative Example 2. This can be presumed to be because the composition of Comparative Example 2 did not contain an oxime ester-based photoinitiator, thus failing to generate a sufficient amount of free radicals on the upper part of the film.

[0374] Furthermore, no pattern could be formed in Comparative Example 3. It can be inferred that this is because the black colorant used is carbon black with a very low absorbance value in the wavelength range of 380~420nm, so the light did not reach the bottom of the film sufficiently.

[0375] As can be understood from the comparison between Comparative Examples 1-7 and the Examples, by using all of (i) black colorants with minimum absorbance values ​​in the wavelength range of 380-420 nm, (ii) oxime ester photoinitiators and (iii) acylphosphine oxide photoinitiators simultaneously, the cross-sectional shape of the pattern can be improved. If one of (i) to (iii) is lacking, the cross-sectional shape of the pattern will deteriorate.

[0376] This application claims priority based on Japanese Patent Application No. 2023-128366 filed in Japan on August 7, 2023, all of the disclosures of which are incorporated herein by reference.

Claims

1. A method for manufacturing a substrate with a black pattern, characterized in that, It includes: In the film formation process, an unexposed film made of a negative photosensitive composition is formed on a substrate; The exposure process involves selectively irradiating the unexposed film with light that has spectral maxima in the wavelength range of at least 350-380 nm and in the wavelength range of 390-420 nm to obtain an exposed film. and The developing process involves developing the exposed film to form a pattern. The negative photosensitizing composition comprises: Black colorants that have extremely low absorbance in the wavelength range of 380~420nm. Oxime ester photoinitiators Acylphosphine oxide photoinitiators, and A curable component that is cured by active species generated by the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

2. The method for manufacturing a substrate according to claim 1, wherein, The absorbance of the black colorant at a wavelength of 365 nm is greater than the minimum absorbance of the black colorant in the wavelength range of 380~420 nm.

3. The method for manufacturing a substrate according to claim 1 or 2, wherein, When the content of the oxime ester photoinitiator in all non-volatile components of the negative photosensitizing composition is set as m1 and the content of the acylphosphine oxide photoinitiator is set as m2, the proportion of the acylphosphine oxide photoinitiator, expressed as {m2 / (m1+m2)}×100(%), is 45~95% by mass.

4. The 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. The method for manufacturing a substrate according to claim 1 or 2, wherein, The black colorant contains blue, purple, and orange pigments.

6. The method for manufacturing a substrate according to claim 1 or 2, wherein, The ratio of the black colorant in all non-volatile components of the negative photosensitive composition is 5 to 15 by mass.

7. The method for manufacturing a substrate according to claim 1 or 2, wherein, The curable component comprises compounds having alkene carbon-carbon double bonds.

8. The method for manufacturing a substrate according to claim 1 or 2, wherein, The negative photosensitizing composition further comprises an alkali-soluble resin.

9. The method for manufacturing a substrate according to claim 1 or 2, wherein, The negative photosensitizing composition further comprises a fluorinated resin.

10. The method for manufacturing a substrate according to claim 1 or 2, wherein, The negative photosensitizing composition further comprises a chain transfer agent.

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

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

13. A light-emitting element comprising a light-emitting layer or a wavelength conversion layer disposed in a region defined by a black pattern in a substrate according to claim 11.

14. A negative photosensitizing composition comprising: Black colorants that have extremely low absorbance in the wavelength range of 380~420nm. Oxime ester photoinitiators Acylphosphine oxide photoinitiators, and A curable component that is cured by active species generated by the oxime ester photoinitiator or the acylphosphine oxide photoinitiator.

15. The negative photosensitizing composition according to claim 14, wherein, The absorbance of the black colorant in the wavelength range of 355~375nm is greater than the minimum absorbance of the black colorant in the wavelength range of 380~420nm.

16. The negative photosensitizing composition according to claim 14 or 15, wherein, When the content of the oxime ester photoinitiator in all non-volatile components is set as m1 and the content of the acylphosphine oxide photoinitiator is set as m2, the proportion of the acylphosphine oxide photoinitiator, expressed as {m2 / (m1+m2)}×100(%), is 45% by mass or more.

17. The negative photosensitizing composition according to claim 14 or 15, wherein, The black colorant is a mixture of two or more non-black colorants.

18. The negative photosensitizing composition according to claim 14 or 15, wherein, The black colorant contains blue, purple, and orange pigments.

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

20. The negative photosensitizing composition according to claim 14 or 15, wherein, The curable component comprises compounds having alkene carbon-carbon double bonds.

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

22. The negative photosensitizing composition according to claim 14 or 15, further comprising a fluorinated resin.

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

Images