Negative photosensitive resin composition, cured film, and resist film

Abstract

The invention provides a negative photosensitive resin composition which can obtain a cured film with high visible light shielding property even if a colorant such as carbon black is reduced. The invention also provides a cured film and a resist film. A negative photosensitive resin composition containing the following components (A)-(C): (A) a novolac phenolic resin in which the molar ratio [(a1): (a2): (a3): (a4)] of a structural unit (a1) derived from cresol, a structural unit (a2) derived from dihydroxynaphthalene, a structural unit (a3) derived from benzaldehyde, and a structural unit (a4) derived from salicylaldehyde is 1: (0.25-4.0): (0.25-4.0): (0.25-4.0); (B) a photosensitizer; and (C) an organic solvent.

Description

Technical Field

[0001] This invention relates to negative photosensitive resin compositions, cured films, and resist films. Background Technology

[0002] Organic EL (OLED) displays are attracting attention as the next generation of flat panel displays. OLED displays are self-emissive display devices that utilize electric fields based on organic compounds to emit light, enabling wide viewing angles and high-speed image display. Furthermore, they allow for thinner and lighter designs. In recent years, the increasing precision of OLED displays has necessitated further miniaturization of the light-emitting elements.

[0003] Organic EL displays (OLEDs) emit light using the energy from the recombination of electrons injected from the cathode and holes injected from the anode. Therefore, if substances exist that create energy levels that hinder the recombination of electrons and holes, the luminous efficiency of the light-emitting element decreases, and the lifespan of the OLED display is reduced. On the other hand, to separate the pixels of the light-emitting element, an insulating layer such as a pixel separation layer is typically formed between metal electrodes on the opposite side of the transparent electrode on the light extraction side. Since this pixel separation layer is formed adjacent to the light-emitting element, degassing and ion leakage from the pixel separation layer can contribute to a reduced lifespan of the OLED display. Therefore, the pixel separation layer is required to have heat resistance and durability.

[0004] From the viewpoint of high heat resistance, a photosensitive resin composition using polyimide resin and polybenzoxazole resin is used in the material of the pixel segmentation layer (for example, Patent Document 1). Since the pixel segmentation layer requires to be black, about 20% of a colorant such as carbon black is added to the solid component of the above-mentioned photosensitive resin composition.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2022 / 070946 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] In the fabrication of fine patterns, the colorant incorporated into the photosensitive resin composition sometimes becomes a residue during development. Furthermore, since carbon black is conductive, it is preferable to use a small amount to improve the insulation of the cured film. With the increasing precision of organic EL displays, in order to fabricate even finer pixel layers without producing residue, photosensitive resin compositions with high visible light shielding capabilities are required, even with reduced colorant amounts.

[0010] The purpose of this invention is to provide a photosensitive resin composition that can produce a cured film with high visible light shielding capability even with a reduced amount of colorant.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the cured film obtained by using a negative photosensitive resin composition of phenolic varnish type phenolic resin (phenolic varnish) with specific structural units has high visible light shielding properties even with a reduction in the amount of colorant used, thus completing the present invention.

[0013] That is, the present invention relates to a negative photosensitive resin composition comprising the following components (A) to (C): (A) a phenolic varnish-type phenolic resin in which the molar ratio of cresol-derived structural unit (a1), dihydroxynaphthalene-derived structural unit (a2), benzaldehyde-derived structural unit (a3), and salicylaldehyde-derived structural unit (a4) [(a1):(a2):(a3):(a4)] is 1:0.25~4.0:0.25~4.0:0.25~4.0; (B) a photosensitizer; and (C) an organic solvent.

[0014] The present invention also relates to a cured film obtained from the above-described negative photosensitive resin composition.

[0015] The present invention also relates to a resist film obtained from the above-described negative photosensitive resin composition.

[0016] Invention Effects

[0017] According to the present invention, a photosensitive resin composition can be provided, which can produce a cured film with high visible light shielding capability even with a reduction in the amount of colorant added. Detailed Implementation

[0018] The following describes the methods used to implement the invention.

[0019] Furthermore, in this specification, "x~y" refers to a numerical range "above x and below y". The upper and lower limits recorded regarding the numerical range can be combined arbitrarily.

[0020] Furthermore, combining two or more of the various embodiments of the present invention described below is also a way of the present invention.

[0021] One embodiment of the negative photosensitive resin composition of the present invention contains the following components (A) to (C).

[0022] (A) A phenolic varnish-type phenolic resin with a molar ratio of (a1):(a2):(a3):(a4) of cresol-derived structural unit (a1), dihydroxynaphthalene-derived structural unit (a2), benzaldehyde-derived structural unit (a3), and salicylaldehyde-derived structural unit (a4) [(a1):(a2):(a3):(a4)] of 1:0.25~4.0:0.25~4.0;

[0023] (B) Photosensitizer;

[0024] (C) Organic solvents.

[0025] In this embodiment, by using the phenolic varnish-type phenolic resin described above (A), a cured film with high visible light shielding properties can be obtained even with a reduced amount of colorant added. The constituent components of the negative photosensitive resin composition will be described below.

[0026] • Ingredient(A)

[0027] The phenolic resin of the varnish type, which is component (A), has a molar ratio of structural units (a1) derived from cresol, (a2) derived from dihydroxynaphthalene, (a3) ​​derived from benzaldehyde, and (a4) derived from salicylaldehyde [(a1):(a2):(a3):(a4)] of 1:0.25~4.0:0.25~4.0:0.25~4.0.

[0028] In this embodiment, the phenolic varnish-type phenolic resin of component (A) contains a structural unit (a2) derived from dihydroxynaphthalene, thereby improving the visible light shielding properties of the cured film. Therefore, the amount of colorant used can be reduced. The visible light shielding performance of the cured film can be adjusted by varying the molar ratio of the aforementioned structural unit (a2).

[0029] In addition to high sensitivity, from the viewpoint of obtaining a cured film with excellent resin compatibility and visible light shielding, the molar ratio [(a1):(a2):(a3):(a4)] is preferably 1:0.3~3.5:0.5~3.0:0.5~2.5.

[0030] In one embodiment, the molar ratio of the total of the cresol-derived structural units (a1) and the dihydroxynaphthalene-derived structural units (a2) in component (A) [(a1)+(a2)] to the total of the benzaldehyde-derived structural units (a3) ​​and the salicylaldehyde-derived structural units (a4) [(a3)+(a4)] [(a1)+(a2):(a3)+(a4)] is 1:0.8 to 1.2, preferably 1:0.9 to 1.1. This makes it easy to adjust the weight-average molecular weight of component (A) to a suitable range. Furthermore, when the negative photosensitive resin composition of this embodiment is used to prepare a photosensitive film, alkali solubility (sensitivity) can be improved.

[0031] In one embodiment, the molar ratio of structural unit (a2) in component (A) to the total of structural units (a1) derived from cresol and (a2) derived from dihydroxynaphthalene [(a1)+(a2)] [(a2) / ((a1)+(a2))] is 0.01 to 0.8. Both structural units (a1) and (a2) are derived from compounds containing hydroxyl groups. By increasing the molar ratio of the aforementioned structural unit (a2), the visible light shielding property of the cured film can be improved. On the other hand, the alkali solubility can be adjusted by adjusting the molar ratio of the aforementioned structural unit (a1). From the viewpoint of balancing alkali solubility and visible light shielding property, the molar ratio [(a2) / ((a1)+(a2))] is preferably 0.1 to 0.7, more preferably 0.3 to 0.6.

[0032] In one embodiment, the molar ratio of structural unit (a3) ​​in component (A) to the total of structural units (a3) ​​derived from benzaldehyde and structural units (a4) derived from salicylaldehyde [(a3) / ((a3)+(a4))] is 0.2 to 0.8. Both structural units (a3) ​​and (a4) are derived from compounds having an aldehyde group. The alkali solubility can be appropriately adjusted by the molar ratio [(a3) / ((a3)+(a4))]. The molar ratio [(a3) / ((a3)+(a4))] is preferably 0.3 to 0.7.

[0033] Component (A) may contain structural units other than the structural units (a1) to (a4) mentioned above. Examples of structural units other than structural units (a1) to (a4) include structural units derived from phenols other than cresol and dihydroxynaphthalene, and aldehydes other than benzaldehyde and salicylaldehyde.

[0034] Examples of the aforementioned phenols include phenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol.

[0035] Examples of aldehydes mentioned above include formalin, paraformaldehyde, acetaldehyde, chloroacetaldehyde, 4-hydroxybenzaldehyde, and 3-hydroxybenzaldehyde.

[0036] In addition to high sensitivity, from the viewpoint of obtaining a resist film and a cured film with excellent resin compatibility and visible light shielding, the total content of the above-mentioned structural units (a1), (a2), (a3) ​​and (a4) in component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 90% by mass or more.

[0037] The total content of the above structural units (a1), (a2), (a3) ​​and (a4) can substantially be 100% by mass. It should be noted that 100% by mass essentially refers to the situation where structural units other than those mentioned above (a1), (a2), (a3) ​​and (a4) are inevitably included.

[0038] The weight-average molecular weight of the phenolic resin in component (A) is preferably 1,000 or more, more preferably 1,500 or more. Furthermore, it is preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 10,000 or less. A weight-average molecular weight of 1,000 or more provides high heat resistance and is therefore preferred. On the other hand, a weight-average molecular weight of 10,000 or less provides high sensitivity and is therefore preferred. It should be noted that in this specification, the weight-average molecular weight was measured under the conditions described in the examples.

[0039] Component (A) is obtained by polycondensation of cresol, dihydroxynaphthalene, benzaldehyde and salicylaldehyde in an organic solvent using an acid catalyst in a molar ratio (cresol: dihydroxynaphthalene: benzaldehyde: salicylaldehyde) of 1:0.25~4.0:0.25~4.0:0.25~4.0.

[0040] Cresol can be any one of o-cresol, m-cresol, and p-cresol. m-cresol is preferred.

[0041] For dihydroxynaphthalene, the position of the hydroxyl group is not particularly limited. Furthermore, dihydroxynaphthalene may also have substituents, as long as the effects of the present invention are achieved. Examples of dihydroxynaphthalene include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. Preferably, it is 1,5-dihydroxynaphthalene having the following structure.

[0042] [Chemistry 1]

[0043]

[0044] In addition to high sensitivity, from the viewpoint of obtaining a resist film and a cured film with excellent resin compatibility and visible light shielding, the molar ratio of cresol, dihydroxynaphthalene, benzaldehyde and salicylaldehyde (cresol: dihydroxynaphthalene: benzaldehyde: salicylaldehyde) is preferably in the range of 1:0.3~3.5:0.5~3.0:0.5~2.5.

[0045] In one embodiment, the molar ratio of the total of cresol and dihydroxynaphthalene to the total of benzaldehyde and salicylaldehyde ((cresol + dihydroxynaphthalene):(benzaldehyde + salicylaldehyde)) is 1:0.8 to 1.2.

[0046] In addition, the molar ratio of dihydroxynaphthalene to cresol and dihydroxynaphthalene (dihydroxynaphthalene / (cresol + dihydroxynaphthalene)) is 0.01 to 0.8.

[0047] In addition, the molar ratio of salicylaldehyde to the total of salicylaldehyde and benzaldehyde [salicylaldehyde / (salicylaldehyde + benzaldehyde)] is 0.2~0.8.

[0048] When cresol, dihydroxynaphthalene, benzaldehyde and salicylaldehyde are condensed in an organic solvent to obtain a phenolic varnish-type phenolic resin as component (A), as described above, phenols and aldehydes other than cresol, dihydroxynaphthalene, benzaldehyde and salicylaldehyde may be included in the organic solvent.

[0049] In addition to high sensitivity, from the viewpoint of obtaining a resist film and a cured film with excellent resin compatibility and visible light shielding, the total mass of cresol, dihydroxynaphthalene, benzaldehyde and salicylaldehyde is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably substantially 100% by mass, relative to the total mass of all the starting materials that can become the structural unit (A) in the organic solvent.

[0050] Examples of organic solvents used in the manufacture of component (A) include methanol, ethanol, 1-propanol, 2-propanol, butanol, hexanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc., preferably one or more selected from ethanol, 1-propanol and 2-propanol, more preferably ethanol.

[0051] From the viewpoint of reaction uniformity, the amount of the aforementioned organic solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the raw material used to derive the structural unit of constituent (A). Furthermore, it is preferably 500 parts by mass or less, more preferably 300 parts by mass or less.

[0052] Examples of acid catalysts used in the manufacture of component (A) include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid, and organic acids such as oxalic acid, acetic acid, and p-toluenesulfonic acid. Among these, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred, in order to further promote the reaction.

[0053] There is no particular limitation on the amount of acid catalyst added, but it is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the raw material used to derive the structural unit of component (A). Furthermore, it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less.

[0054] The reaction temperature during the polycondensation of the raw materials of component (A) should be high enough to promote the reaction and efficiently increase the molecular weight; therefore, 30°C or higher is preferred, and 40°C or higher is more preferred. Furthermore, 100°C or lower is preferred, and 80°C or lower is more preferred.

[0055] The reaction time is preferably 4 hours or more, more preferably 12 hours or more. Furthermore, it is preferably 32 hours or less, more preferably 24 hours or less.

[0056] • Ingredient (B)

[0057] The negative photosensitive resin composition of the present invention preferably contains one or more photosensitizers selected from photoacid generators, photopolymerization initiators and free radical polymerizing compounds as component (B).

[0058] [Photo-acid generator]

[0059] Photoacid generators are compounds that generate acids by inducing bond breaking through exposure. The presence of photoacid generators can promote the curing of the exposed portion and improve sensitivity. Furthermore, there are no particular limitations on photoacid generators that can increase the crosslinking density of the thermosetting negative photosensitive resin composition or improve the chemical resistance of the cured film; known photoacid generators can be used. Examples include organohalogen compounds, sulfonates, onium salts, diazonium salts, and disulfone compounds.

[0060] Specific examples of photoacid-producing agents include the following.

[0061] Tris(trichloromethyl)-S-triazine, tris(tribromomethyl)-S-triazine, tris(dibromomethyl)-S-triazine, 2,4-bis(tribromomethyl)-6-p-methoxyphenyl-S-triazine, (2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-S-triazine) and other alkyl-containing s-triazine derivatives,

[0062] Halogenated paraffinic hydrocarbons such as 1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide, and iodoform.

[0063] Halogenated substituted cycloalkanes such as hexabromocyclohexane, hexachlorocyclohexane, and hexabromocyclododecane.

[0064] Benzene derivatives containing halogenated alkyl groups, such as bis(trichloromethyl)benzene and bis(tribromomethyl)benzene.

[0065] Sulfonates containing alkyl halogens, such as tribromomethylphenyl sulfone and trichloromethylphenyl sulfone.

[0066] Halogenated sulfolane compounds such as 2,3-dibromocyclobutanesulfone,

[0067] Isocyanurate compounds containing halogenated alkyl groups, such as tris(2,3-dibromopropyl)isocyanurate.

[0068] Sulfonates such as triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium hexafluorophosphonate.

[0069] Iodonium salts include diphenyliodonium trifluoromethane sulfonate, diphenyliodonium p-toluene sulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, and diphenyliodonium hexafluorophosphonate.

[0070] Sulfonate compounds including methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2,3-tris(p-toluenesulfonyloxy)benzene, benzoin p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, phenyl methanesulfonate, benzoin methanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, phenyl trifluoromethanesulfonate, benzoin trifluoromethanesulfonate, etc.

[0071] Disulfone compounds such as diphenyl disulfone,

[0072] bis(phenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl- (4-Fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-chlorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl Acyl-(3-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoromethoxyphenyl)diazomethane Cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4-trimethyl ...4-Triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, bis(2-methoxyphenylsulfonyl)diazomethane, bis(3-methoxyphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl- (2,4,6-Triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, and other sulfonyl diazide compounds.

[0073] o-Nitrobenzyl-p-toluenesulfonate and other o-nitrobenzyl ester compounds,

[0074] N,N'-Di(phenylsulfonyl)hydrazide and other sulfonyl hydrazide compounds

[0075] Sulfonate salts are salts of sulfonates such as triarylsulfonium and triarylalkylsulfonium, which are sulfonates of fluoroalkyl sulfonates, aromatic sulfonates, and alkyl sulfonates.

[0076] Iodonium salts are salts of iodonium cations such as diaryliodonium and sulfonates such as fluoroalkane sulfonates, aromatic sulfonates, and alkane sulfonates.

[0077] Bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, bis(perfluoroalkylsulfonyl)diazomethane, bis(arylsulfonyl)diazomethane, bis(arylalkylsulfonyl)diazomethane, and other bissulfonyl diazonium compounds.

[0078] N-sulfonyloxyimide compounds are composed of dicarboxylic acid imide compounds combined with sulfonates such as fluoroalkane sulfonates, aromatic sulfonates, and alkane sulfonates.

[0079] Benzoin sulfonate compounds such as benzoin toluene sulfonate, benzoin methane sulfonate, and benzoin butane sulfonate.

[0080] Polyhydroxy aromatic compounds are polyhydroxy aromatic compounds in which all hydroxyl groups are replaced by sulfonates such as fluoroalkane sulfonates, aromatic sulfonates, and alkane sulfonates.

[0081] Nitrobenzyl sulfonate compounds such as fluoroalkane sulfonates (poly)nitrobenzyl esters, aromatic sulfonates (poly)nitrobenzyl esters, and alkane sulfonates (poly)nitrobenzyl esters.

[0082] Fluoroalkyl benzyl sulfonates, such as fluoroalkyl sulfonates (polyfluoroalkyl), aromatic sulfonates (polyfluoroalkyl), and alkyl sulfonates (polyfluoroalkyl), are fluoroalkyl benzyl sulfonates.

[0083] Bis(arylsulfonyl)alkanes;

[0084] bis-O-(arylsulfonyl)-α-dialkylglyoxime, bis-O-(arylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(arylsulfonyl)-α-diarylglyoxime, bis-O-(alkylsulfonyl)-α-dialkylglyoxime, bis-O-(alkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(alkylsulfonyl)-α-diarylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dialkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-diarylglyoxime, bis Oxime compounds including -O-(arylsulfonyl)-α-dialkyldioxime, bis-O-(arylsulfonyl)-α-dicycloalkyldioxime, bis-O-(arylsulfonyl)-α-diaryldioxime, bis-O-(alkylsulfonyl)-α-dialkyldioxime, bis-O-(alkylsulfonyl)-α-dicycloalkyldioxime, bis-O-(alkylsulfonyl)-α-diaryldioxime, bis-O-(fluoroalkylsulfonyl)-α-dialkyldioxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkyldioxime, and bis-O-(fluoroalkylsulfonyl)-α-diaryldioxime.

[0085] Modified oxime compounds include arylsulfonyloxyiminoaryl acetonitrile, alkylsulfonyloxyiminoaryl acetonitrile, fluoroalkylsulfonyloxyiminoaryl acetonitrile, ((arylsulfonyl)oxyimino-thiophene-pyridyl)aryl acetonitrile, ((alkylsulfonyl)oxyimino-thiophene-pyridyl)aryl acetonitrile, ((fluoroalkylsulfonyl)oxyimino-thiophene-pyridyl)aryl acetonitrile, bis(arylsulfonyloxyimino)aryldiacetonitrile, bis(alkylsulfonyloxyimino)aryldiacetonitrile, bis(fluoroalkylsulfonyloxyimino)aryldiacetonitrile, arylfluoroalkylketone-O-(alkylsulfonyl)oxime, arylfluoroalkylketone-O-(arylsulfonyl)oxime, and arylfluoroalkylketone-O-(fluoroalkylsulfonyl)oxime.

[0086] Photoacid generators can be used alone or in combination with two or more.

[0087] From the perspective of obtaining good sensitivity and the desired pattern, the amount of photoacid generator relative to 100 parts by weight of component (A) is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more. Furthermore, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less.

[0088] [Photopolymerization initiator]

[0089] Photopolymerization initiators are compounds that generate free radicals through bond breaking and / or reaction upon exposure. By incorporating photopolymerization initiators, the exposed portion of the film in a negative photosensitive resin composition becomes insoluble relative to the alkaline developer, thereby enabling the formation of negative patterns. Furthermore, it promotes the curing of the exposed portion and improves sensitivity.

[0090] There are no particular limitations on the photopolymerization initiator, and any known photopolymerization initiator can be used. Examples of photopolymerization initiators include benzyl ketal photopolymerization initiators, α-hydroxy ketone photopolymerization initiators, α-amino ketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, acridine photopolymerization initiators, titanium ceramsite photopolymerization initiators, benzophenone photopolymerization initiators, acetophenone photopolymerization initiators, aromatic ketone ester photopolymerization initiators, or benzoate ester photopolymerization initiators.

[0091] Photopolymerization initiators can be used alone or in combination with two or more.

[0092] From the perspective of obtaining good sensitivity and the desired pattern, the amount of photopolymerization initiator relative to 100 parts by weight of component (A) is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more. Furthermore, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less.

[0093] [Free radical polymerizable compounds]

[0094] Free radical polymerizable compounds are compounds with multiple olefinic unsaturated groups in their molecules. By containing free radical polymerizable compounds, the curing of the exposed portion can be promoted, and the sensitivity during exposure can be improved. Furthermore, the crosslinking density after thermosetting can be increased, thereby improving the hardness of the cured film.

[0095] There are no particular limitations on the free radical polymerizable compound; any known free radical polymerizable compound may be used, but compounds with (meth)acryloyl groups that are readily free radical polymerizable are preferred.

[0096] From the viewpoint of improving the sensitivity during exposure and increasing the hardness of the cured film, compounds having two or more (meth)acryloyl groups in the molecule are preferred.

[0097] Examples of free radical polymerizable compounds include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, and di(trimethylolpropane)tetra(methyl)acrylate. Acrylates, 1,3-Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol Tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3 [(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloyloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloyloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene or 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene or their acid-modified, ethylene oxide-modified or propylene oxide-modified forms.

[0098] Relative to 100 parts by mass of component (A), the amount of the free radical polymerizable compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 5 parts by mass or more. When the content is within the above range, the sensitivity during exposure can be improved. On the other hand, the content of the free radical polymerizable compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less.

[0099] The photosensitizer as component (B) can be used alone, or two or more can be used in combination. For example, it can also be combined with a photopolymerization initiator and a free radical polymerizable compound.

[0100] • Ingredient (C)

[0101] Examples of organic solvents used as component (C) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. One of these solvents may be used alone, or two or more may be used in combination.

[0102] Regarding the amount of component (C) in the negative photosensitive resin composition of this embodiment, from the perspective of adjusting the flowability of the composition and obtaining a uniform coating film by a coating method such as spin coating, the concentration of the solid component in the composition is preferably 5% by mass or more. Furthermore, it is preferably 65% ​​by mass or less.

[0103] • other

[0104] In one embodiment, in addition to the components (A) to (C) described above, various additives may be incorporated into the negative photosensitive resin composition, within a range that does not impair the effects of the present invention. Examples of additives include fillers, surfactants such as leveling agents, adhesion enhancers, and solubilizers.

[0105] In one embodiment, the negative photosensitive resin composition comprises one or more resins (D) selected from polyimides containing olefinic unsaturated groups, polyimide precursors containing olefinic unsaturated groups, polybenzoxazoles containing olefinic unsaturated groups, and polybenzoxazole precursors containing olefinic unsaturated groups. The phenolic varnish-type phenolic resin of the above-mentioned component (A) has good compatibility with resin (D), thus suppressing the occurrence of poor film formation. Furthermore, this results in a negative photosensitive resin composition that yields resist films and cured films with high alkali solubility and excellent elastic modulus in the non-exposed areas.

[0106] The resin (D) can be a resin that has been used in photosensitive resin compositions in the past.

[0107] <Polyimide and Polyimide Precursors>

[0108] Examples of polyimide precursors include substances obtained by reacting a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, the corresponding diisocyanate compound, or a trimethylsilyl diamine, having tetracarboxylic acid and / or its derivative residues and diamine and / or its derivative residues. Examples of polyimide precursors include polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide.

[0109] Examples of polyimides include substances obtained by dehydrating and cyclizing the aforementioned polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide through heating or reaction with an acid or base, which have tetracarboxylic acid and / or derivative residues and diamine and / or derivative residues.

[0110] From the viewpoint of heat resistance, the tetracarboxylic dianhydride used in the synthesis of polyimide is preferably pyromellitic dianhydride. From the viewpoint of heat resistance, the diamine used in the synthesis of polyimide is preferably 4,4-diaminodiphenyl ether.

[0111] The polyimide and polyimide precursor containing unsaturated groups used in this invention have the aforementioned polyimide or polyimide precursor and an olefinically unsaturated group as a free radical polymerizable group. By having the olefinically unsaturated group, the sensitivity during exposure can be improved. Preferably, the polyimide and polyimide precursor containing unsaturated groups are obtained by reacting a portion of the phenolic hydroxyl and / or carboxyl groups of the polyimide and polyimide precursor with the compound containing the olefinically unsaturated group described later. Through the above reaction, olefinically unsaturated groups can be introduced into the resin.

[0112] <Polybenzoxazole and polybenzoxazole precursors>

[0113] Examples of polybenzoxazole precursors include substances obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or an active diester of a dicarboxylic acid with a diaminophenol compound as a diamine, having dicarboxylic acid and / or its derivative residues and a diaminophenol compound and / or its derivative residues. Examples of polyhydroxyamides are also examples of polybenzoxazole precursors.

[0114] Examples of polybenzoxazoles include polybenzoxazoles obtained by dehydrating and cyclizing a dicarboxylic acid with a diaminophenol compound as a diamine through a reaction with polyphosphoric acid, and polybenzoxazoles obtained by dehydrating and cyclizing the aforementioned polyhydroxyamide through heating or a reaction using anhydrous phosphoric acid, a base, or a carbodiimide compound, having dicarboxylic acid and / or its derivative residues and diaminophenol compound and / or its derivative residues.

[0115] From the viewpoint of heat resistance, the diaminophenol used in the synthesis of polybenzoxazole is preferably 3,3-hydroxybenzidine. From the viewpoint of heat resistance, the dicarboxylic acid used in the synthesis of polybenzoxazole is preferably 4,4-biphenyl dicarboxylic acid.

[0116] The polybenzoxazole containing olefinic unsaturated groups and the polybenzoxazole precursor containing olefinic unsaturated groups used in this invention have olefinic unsaturated groups as free radical polymerizable groups. By having olefinic unsaturated groups, the sensitivity during exposure can be improved. Preferably, the polybenzoxazole containing olefinic unsaturated groups and the polybenzoxazole precursor are obtained by reacting a portion of the phenolic hydroxyl groups and / or carboxyl groups of the polybenzoxazole and the polybenzoxazole precursor with the compounds containing olefinic unsaturated groups described later. Through the above reaction, olefinic unsaturated groups can be introduced into the resin.

[0117] <Compounds containing olefinic unsaturated groups>

[0118] Examples of compounds having olefinically unsaturated groups include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thionone compounds, acetate compounds, carboxylic acid chlorides, carboxylic acid anhydrides, carboxylic acid reactive ester compounds, carboxylic acid compounds, haloalkyl compounds, azidoalkyl compounds, trifluoromethanesulfonate alkyl compounds, methanesulfonate alkyl compounds, toluenesulfonate alkyl compounds, or cyanide alkyl compounds.

[0119] <Synthetic methods of polyimide, polybenzoxazole, polyimide precursor or polybenzoxazole precursor>

[0120] Polyimides, polyimide precursors, polybenzoxazoles, or polybenzoxazole precursors can be synthesized by known methods. As a specific method, for example, a diamine or bisaminophenol compound is first dissolved in a reaction solvent, and then a substantially equimolar amount of a carboxylic anhydride is slowly added to the solution. Using a mechanical stirrer, the mixture is stirred preferably at 0–200°C, more preferably at 40–150°C, for 0.5–50 hours, more preferably for 2–24 hours. When using a capping agent, after adding the carboxylic anhydride, the mixture is stirred at a specified temperature for a specified time, and then the capping agent is slowly added while stirring.

[0121] The reaction solvent used in the polymerization reaction only needs to be able to dissolve the diamine or bisaminophenol compounds and carboxylic anhydrides used as raw materials, and a polar solvent is preferred. Examples of reaction solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone; cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, or α-methyl-γ-butyrolactone; carbonates such as ethylene carbonate or propylene carbonate; diols such as triethylene glycol; phenols such as m-cresol or p-cresol; acetophenone; 1,3-dimethyl-2-imidazolinone; sulfolane; dimethyl sulfoxide, and other solvents. When the total amount of diamine or bisaminophenol compounds and carboxylic anhydrides is set at 100 parts by mass, the amount of reaction solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 950 parts by mass.

[0122] The product is preferably prepared by precipitating one or more of the following solvents after the polymerization reaction: methanol, water, or other solvents that are unsuitable for polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor; followed by washing and drying. This reprecipitation process removes low molecular weight components, thus significantly improving the mechanical properties (elastic modulus) of the cured film.

[0123] <Synthetic methods for polyimides containing olefinic unsaturated groups, polyimide precursors containing olefinic unsaturated groups, polybenzoxazoles containing olefinic unsaturated groups, or polybenzoxazole precursors containing olefinic unsaturated groups>

[0124] Polyimides containing olefin unsaturated groups, polyimide precursors containing olefin unsaturated groups, polybenzoxazoles containing olefin unsaturated groups, or polybenzoxazole precursors containing olefin unsaturated groups can be synthesized by known methods.

[0125] For the reaction conditions of further introducing olefinically unsaturated groups into polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor, preferably, after thoroughly purging the reaction vessel with nitrogen under air or by bubbling or degassing under reduced pressure, the polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor and the compound having olefinically unsaturated groups are added to the reaction solvent, and the reaction is carried out at 20-110°C for 30-500 minutes. Alternatively, polymerization inhibitors such as phenolic compounds, acid catalysts, or base catalysts may be used as needed.

[0126] For specific descriptions of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyimides containing olefinic unsaturated groups, polyimide precursors containing olefinic unsaturated groups, polybenzoxazoles containing olefinic unsaturated groups, and polybenzoxazole precursors containing olefinic unsaturated groups, reference may be made to the contents of International Publication No. 2017 / 159876,

[0074] to

[0210] .

[0127] The weight-average molecular weight of resin (D) is preferably 5,000 or more, more preferably 10,000 or more. Furthermore, it is preferably 50,000 or less, more preferably 40,000 or less. A weight-average molecular weight of 5,000 or more provides high heat resistance, and is therefore preferred. On the other hand, a weight-average molecular weight of 50,000 or less is preferred from the viewpoint of solvent solubility.

[0128] From the perspective of obtaining a cured film with good sensitivity and excellent visible light shielding, the amount of resin (D) relative to 100 parts by weight of component (A) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more. Furthermore, it is preferably 2,000 parts by weight or less, more preferably 1,000 parts by weight or less.

[0129] The cured film obtained from the negative photosensitive resin composition of this embodiment has visible light shielding properties, therefore no additional colorant is required. However, when higher visible light shielding properties are required, the negative photosensitive resin composition of this embodiment may also contain a colorant.

[0130] Examples of colorants include benzofuranone black pigments, perylene black pigments, azo black pigments, anthraquinone black pigments, aniline black pigments, azomethyl alkali black pigments, carbon black, graphite and other organic pigments, silver-tin alloys, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, nitrogen oxides and other inorganic pigments of metals (alloys) such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver.

[0131] In one embodiment, the amount of colorant incorporated is 0 to 30 parts by weight relative to 100 parts by weight of the solid content of the negative photosensitive resin composition. Since the negative photosensitive resin composition of this embodiment has visible light shielding properties, the amount of colorant incorporated can be suppressed compared to conventional methods. The negative photosensitive resin composition may or may not contain a colorant. When a colorant is included, the amount may exceed 0 parts by weight or be 0.1 parts by weight or more relative to 100 parts by weight of the solid content of the negative photosensitive resin composition.

[0132] The negative photosensitive resin composition of this embodiment can be prepared by stirring and mixing the above-mentioned components (A) to (C) and, as needed, additives and resin (D) using conventional methods to form a homogeneous liquid.

[0133] When solid substances such as fillers and pigments are incorporated into this composition, it is preferable to use a dispersing device such as a solvent, homogenizer, or three-roll mill for dispersion and mixing. Alternatively, to remove coarse particles and impurities, the composition can be filtered using a screen filter or membrane filter.

[0134] The negative photosensitive resin composition of this embodiment is suitable for forming pixel separation layers in display devices such as negative photoresists, organic underlayer films, thick film resists (bump forming resists), interlayer insulating films, liquid crystal alignment films, heat resistance imparting agents, polyimides, polybenzoxazole resists, or organic EL displays.

[0135] [Curing film / Resist film]

[0136] The cured film of one embodiment of the present invention is obtained by curing the negative photosensitive resin composition of the present invention described above.

[0137] Specifically, the negative photosensitive resin composition of the present invention is coated onto the object to be photolithographically lithographically applied and pre-baked to obtain a film (photosensitive film) of the photosensitive resin composition with the solvent removed.

[0138] Examples of coating methods include spin coating, roller coating, flow coating, dip coating, spray coating, and doctor blade coating. Pre-baking, for example, simply involves heating at a temperature above 60°C and below 150°C for a time of 30 seconds to 600 seconds.

[0139] By exposing the photosensitive film to the alkaline developer, the solubility of the exposure section in the exposure solution is significantly reduced. Examples of light sources used for exposure include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, and electron beams. Among these light sources, ultraviolet light is preferred, and the g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of a high-pressure mercury lamp are particularly preferred.

[0140] After exposure, in order to promote the cross-linking reaction with components (A) and (B) through the catalytic reaction of the acid generated by the exposure, heat treatment is performed at around 100°C.

[0141] The photosensitive film obtained from the negative photosensitive resin composition of the present invention has high alkali solubility, and therefore a large difference in alkali solubility compared to the exposed portion, thus enabling patterning at high resolution. Therefore, it is suitable for use as a resist film.

[0142] Examples of alkaline developing solutions used after exposure include inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkaline aqueous solutions of dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and cyclic amines such as pyrrole and piperidine.

[0143] Alcohols and surfactants can be added to alkaline developing solutions as needed. The preferred alkalinity of alkaline developing solutions is typically in the range of 2-5% by mass, and a 2.38% by mass tetramethylammonium hydroxide aqueous solution is commonly used.

[0144] After development with an alkaline developer, a cured film formed by cross-linking the exposed portions can be obtained, for example, by heating at a low temperature of 150°C or higher and 200°C or lower. The cured film of this embodiment has excellent visible light shielding properties.

[0145] The cured film of this embodiment can be used, for example, as a pixel segmentation layer in a display device such as an organic EL display.

[0146] Example

[0147] The present invention will be described in more detail below with specific examples. It should be noted that the weight-average molecular weight (Mw) of the synthesized resin was measured under the GPC conditions described below.

[0148] [GPC Measurement Conditions]

[0149] Measurement apparatus: HLC-8220GPC manufactured by Tosoh Corporation

[0150] Column: "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm

[0151] + "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm

[0152] + "Shodex KF803" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm

[0153] + "Shodex KF804" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm

[0154] Column temperature: 40℃

[0155] Detector: RI (Differential Refractometer)

[0156] Data processing: Tosoh Corporation, "GPC-8020 Model II Version 4.30"

[0157] Developing solvent: Tetrahydrofuran

[0158] Flow rate: 1.0 mL / min

[0159] Sample: Obtained by filtering a tetrahydrofuran solution, calculated as 0.5% by mass based on resin solids, through a microfilter.

[0160] Injection volume: 0.1 mL

[0161] Standard sample: the following monodisperse polystyrene

[0162] (Standard sample: monodisperse polystyrene)

[0163] "A-500" manufactured by Tosoh Corporation

[0164] "A-2500" manufactured by Tosoh Corporation

[0165] "A-5000" manufactured by Tosoh Corporation

[0166] "F-1" manufactured by Tosoh Corporation

[0167] "F-2" manufactured by Tosoh Corporation

[0168] "F-4" manufactured by Tosoh Corporation

[0169] "F-10" manufactured by Tosoh Corporation

[0170] "F-20" manufactured by Tosoh Corporation

[0171] [Ingredients (A)]

[0172] Synthesis Example 1 (Synthesis of Phenolic Resin (A-1) of Phenolic Varnish Type)

[0173] In a 2000 mL four-necked flask equipped with a cooling tube, 82 g (0.76 mol) of m-cresol, 122 g (0.76 mol) of 1,5-dihydroxynaphthalene, 103 g (0.97 mol) of benzaldehyde, 74 g (0.61 mol) of salicylaldehyde, and 8 g of p-toluenesulfonic acid were added and dissolved in 300 g of ethanol as the reaction solvent. The mixture was then heated to 80 °C using a jacketed heater and stirred under reflux for 16 hours to allow the reaction to proceed. After the reaction was complete, ethyl acetate and water were added, and the mixture was subjected to five separate washings. The solvent was removed from the residual resin solution by vacuum distillation, and the solution was then dried under vacuum to obtain 279 g of black phenolic varnish-type phenolic resin powder (A-1).

[0174] The Mw of the phenolic varnish-type phenolic resin (A-1) obtained by the GPC method is 4,010.

[0175] Synthesis Example 2 (Synthesis of Phenolic Resin (A-2) of Phenolic Varnish Type)

[0176] The starting materials were set as follows: 82g (0.76mol) of m-cresol, 122g (0.76mol) of 1,5-dihydroxynaphthalene, 80g (0.75mol) of benzaldehyde, and 92g (0.75mol) of salicylaldehyde. Otherwise, 283g of phenolic resin powder (A-2) of phenolic varnish type was obtained in the same manner as in Synthesis Example 1.

[0177] The Mw of the phenolic varnish-type phenolic resin (A-2) obtained by the GPC method is 2,910.

[0178] Synthesis Example 3 (Synthesis of Phenolic Resin (A-3) of Phenolic Varnish Type)

[0179] The starting materials were set as follows: 82 g (0.76 mol) of m-cresol, 122 g (0.76 mol) of 1,5-dihydroxynaphthalene, 117 g (1.10 mol) of benzaldehyde, and 58 g (0.47 mol) of salicylaldehyde. Otherwise, 279 g of phenolic varnish-type phenolic resin powder (A-3) was obtained in the same manner as in Synthesis Example 1. The Mw of the phenolic varnish-type phenolic resin (A-3) was 3,020.

[0180] Synthesis Example 4 (Synthesis of Phenolic Resin (A-4) of Phenolic Varnish Type)

[0181] The starting materials were set as follows: 82g (0.76mol) of m-cresol, 122g (0.76mol) of 1,5-dihydroxynaphthalene, 67g (0.63mol) of benzaldehyde, and 115g (0.94mol) of salicylaldehyde. Otherwise, 286g of phenolic varnish-type phenolic resin (A-4) powder was obtained in the same manner as in Synthesis Example 1.

[0182] The Mw of the phenolic varnish-type phenolic resin (A-4) obtained by the GPC method is 3,520.

[0183] Synthesis Example 5 (Synthesis of Phenolic Resin (A-5) of Phenolic Varnish Type)

[0184] The starting materials were set as follows: 123 g (1.14 mol) of m-cresol, 61 g (0.38 mol) of 1,5-dihydroxynaphthalene, 67 g (0.63 mol) of benzaldehyde, and 115 g (0.94 mol) of salicylaldehyde. Otherwise, 282 g of phenolic resin powder (A-5) of phenolic varnish type was obtained in the same manner as in Synthesis Example 1.

[0185] The Mw of the phenolic varnish-type phenolic resin (A-5) obtained by the GPC method is 3,240.

[0186] Synthesis Example 6 (Synthesis of Phenolic Resin (A-6) of Phenolic Varnish Type)

[0187] The starting materials were set as follows: 41 g (0.38 mol) of m-cresol, 182.4 g (1.14 mol) of 1,5-dihydroxynaphthalene, 67 g (0.63 mol) of benzaldehyde, and 115 g (0.94 mol) of salicylaldehyde. Otherwise, 281 g of phenolic resin (A-6) powder of phenolic varnish type was obtained in the same manner as in Synthesis Example 1.

[0188] The Mw of the phenolic varnish-type phenolic resin (A-6) obtained by the GPC method is 3,850.

[0189] Synthesis Example 7 (Synthesis of Phenolic Resin (A-7) of Phenolic Varnish Type)

[0190] By replacing m-cresol with o-cresol, 283g of phenolic varnish-type phenolic resin (A-7) powder was obtained in the same manner as in Synthesis Example 1.

[0191] The Mw of the phenolic varnish-type phenolic resin (A-7) obtained by the GPC method is 4,140.

[0192] Synthesis Example 8 (Synthesis of Phenolic Resin (A-8) of Phenolic Varnish Type)

[0193] By replacing 1,5-dihydroxynaphthalene with 1,6-dihydroxynaphthalene, 282 g of phenolic varnish-type phenolic resin (A-8) powder was obtained in the same manner as in Synthesis Example 1.

[0194] The Mw of the phenolic varnish-type phenolic resin (A-8) obtained by the GPC method is 4,250.

[0195] Synthesis Example 9 (Synthesis of Phenolic Resin (A-9) of Phenolic Varnish Type)

[0196] By replacing 1,5-dihydroxynaphthalene with 1,4-dihydroxynaphthalene, 282 g of phenolic varnish-type phenolic resin (A-9) powder was obtained in the same manner as in Synthesis Example 1.

[0197] The Mw of the phenolic varnish-type phenolic resin (A-9) obtained by the GPC method is 4,690.

[0198] Synthesis Example 10 (Synthesis of Phenolic Resin (A-10) of Phenolic Varnish Type)

[0199] By replacing 1,5-dihydroxynaphthalene with 1,8-dihydroxynaphthalene, 282 g of phenolic varnish-type phenolic resin (A-10) powder was obtained in the same manner as in Synthesis Example 1.

[0200] The Mw of the phenolic varnish-type phenolic resin (A-10) obtained by the GPC method is 4,510.

[0201] Synthesis Example 11 (Synthesis of Phenolic Resin (A-11) of Phenolic Varnish Type)

[0202] By replacing 1,5-dihydroxynaphthalene with 2,7-dihydroxynaphthalene, 282 g of phenolic varnish-type phenolic resin (A-11) powder was obtained in the same manner as in Synthesis Example 1.

[0203] The Mw of the phenolic varnish-type phenolic resin (A-11) obtained by the GPC method is 4,370.

[0204] Synthesis Example 12 (Synthesis of Phenolic Resin (A-12) of Phenolic Varnish Type)

[0205] By replacing ethanol as the reaction solvent with methanol, 281g of phenolic resin powder (A-12) of phenolic varnish type was obtained in the same manner as in Synthesis Example 1.

[0206] The Mw of the phenolic varnish-type phenolic resin (A-12) obtained by the GPC method is 8,240.

[0207] Comparative Synthesis Example 1 (Synthesis of Phenolic Resin (A-13) of Phenolic Varnish Type)

[0208] The starting materials were set to 164 g (1.52 mol) of m-cresol, 103 g (0.97 mol) of benzaldehyde, and 74 g (0.61 mol) of salicylaldehyde. Otherwise, 281 g of phenolic resin powder (A-13) of phenolic varnish type was obtained in the same manner as in Synthesis Example 1.

[0209] The Mw of the phenolic varnish-type phenolic resin (A-13) obtained by the GPC method is 3,100.

[0210] Comparative Synthesis Example 2 (Synthesis of Phenolic Resin (A-14) of Phenolic Varnish Type)

[0211] The starting materials were set to 243 g (1.52 mol) of 1,5-dihydroxynaphthalene, 67 g (0.63 mol) of benzaldehyde, and 115 g (0.94 mol) of salicylaldehyde. Otherwise, 282 g of phenolic resin powder (A-14) of phenolic varnish type was obtained in the same manner as in Synthesis Example 1.

[0212] The Mw of the phenolic varnish-type phenolic resin (A-14) obtained by the GPC method is 3,240.

[0213] [Resin(D)]

[0214] Synthesis Example 13 (Synthesis of polyimide precursor (D-1) containing olefinic unsaturated groups)

[0215] Under a dry nitrogen stream, in a 2000 mL four-necked flask equipped with a cooling tube, 125 g (0.023 mol) of pyromellitic anhydride and 115 g (0.023 mol) of 4,4-diaminodiphenyl ether were dissolved in 1602 g of N-methyl-2-pyrrolidone. The mixture was stirred at 100 °C for 4 hours to allow the reaction to proceed. After the reaction was complete, the solution was added to 2000 g of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 °C for 72 hours to obtain a polymer solid powder.

[0216] 32.8 g of the obtained solid powder was dissolved in 76.5 g of 3-methoxy-n-butyl acetate. After cooling the mixture to 0°C, it was added dropwise to a solution containing 3.2 g of 2-methacryloyloxyethyl isocyanate dissolved in 3.2 g of 3-methoxy-n-butyl acetate. After the addition was complete, the mixture was stirred at 80°C for 1 hour to obtain a polymer solution containing olefinic unsaturated groups. After the reaction was complete, the resulting solution was added to 1000 g of water, and the precipitate of the polymer solid containing olefinic unsaturated groups was collected by filtration. The polymer solid containing olefinic unsaturated groups was dried in a vacuum dryer at 80°C for 72 hours to obtain a polymer powder of polyimide precursor (D-1) containing olefinic unsaturated groups.

[0217] [Negative Photosensitive Resin Composition]

[0218] Example 1

[0219] 4.2 g of phenolic varnish-type phenolic resin (A-1) powder obtained in Synthesis Example 1 as component (A), 1.8 g of polymer powder of polyimide precursor (D-1) containing olefinic unsaturated groups obtained in Synthesis Example 13 as resin (D), 4.0 g of free radical polymerizable compound (dipentaerythritol hexaacrylate: manufactured by Nippon Kayaku Co., Ltd.) as component (B) and 0.9 g of photopolymerization initiator (NCI-831: manufactured by ADEKA Co., Ltd.) as component (C) were dissolved in 98 g of γ-butyrolactone, thereby obtaining a negative photosensitive resin composition.

[0220] Examples 2-12, Comparative Example 1, Comparative Example 2

[0221] In Examples 2 to 12, Comparative Examples 1 and 2, the phenolic varnish-type phenolic resin powders (A-2) to (A-14) shown in Tables 1 and 2 were used as component (A). Otherwise, the negative photosensitive resin composition was obtained in the same manner as in Example 1.

[0222] Comparative Example 3

[0223] 4.2 g of phenolic resin powder (A-13) of varnish type, 1.8 g of polymer powder (D-1) containing polyimide precursor with olefinic unsaturated groups, 4.0 g of free radical polymerizable compound solution (manufactured by Nippon Kayaku Co., Ltd.: dipentaerythritol hexaacrylate), 0.9 g of photopolymerization initiator solution (manufactured by ADEKA Co., Ltd.: NCI-831), 3.4 g of benzofuran black pigment (manufactured by BASF: Bk-S0100CF), and 1.3 g of dispersant (manufactured by BYK Chemicals Japan Co., Ltd.: BYK-167 DISPERBYK) were dissolved in 140 g of γ-butyrolactone to obtain a negative photosensitive resin composition.

[0224] [evaluate]

[0225] The negative photosensitive resin compositions prepared in the examples and comparative examples were used to evaluate resin compatibility, alkali solubility before exposure, visible light shielding, and hardness of the cured film.

[0226] (1) Evaluation of resin compatibility (film-forming properties)

[0227] A negative photosensitive resin composition was coated onto a 5-inch diameter silicon wafer using a spin coater to a thickness of approximately 5 μm. The wafer was then pre-baked at 120°C for 180 seconds to obtain a wafer with a photosensitive film. The photosensitive film formed on the wafer surface was observed using an optical microscope to evaluate the presence or absence of repulsion and inhomogeneity.

[0228] Regarding photosensitive films, those without rejection or unevenness are defined as having good resin compatibility (〇), while those exhibiting rejection or unevenness are defined as having insufficient resin compatibility (×). The evaluation results are shown in Tables 1 and 2.

[0229] (2) Alkali solubility before exposure

[0230] A negative photosensitive resin composition was coated onto a 5-inch diameter silicon wafer using a spin coater to a thickness of approximately 5 μm. The wafer was then pre-baked at 120°C for 180 seconds to obtain a wafer with a photosensitive film. The resulting wafer was immersed in a dish containing 250 mL of developer (2.38 wt% tetramethylammonium hydroxide aqueous solution (TMAH)) for 10 seconds. The wafer was then removed from the dish and rinsed with pure water for 10 seconds. The presence of residue from the photosensitive film on the wafer was observed to evaluate its alkali solubility. No residue was designated as excellent (◎), almost no residue as good (〇), and residue as insufficient (×). The evaluation results are shown in Tables 1 and 2.

[0231] (3) Visible light shielding properties of the resin composition

[0232] The negative photosensitive resin composition was diluted with γ-butyrolactone at a solids concentration of 1%, and its visible light shielding performance was evaluated using UV-vis (Shimadzu SolidSpec-3700 DUV). A transmittance of less than 10% at 600 nm was defined as good (〇), and a transmittance of more than 10% was defined as insufficient (×). The evaluation results are shown in Tables 1 and 2.

[0233] (4) Hardness of the cured film

[0234] A negative photosensitive resin composition was coated onto a 5-inch diameter silicon wafer using a spin coater to a thickness of approximately 10 μm. The wafer was then pre-baked at 120°C for 180 seconds to obtain a wafer with a photosensitive film. The resulting wafer was then irradiated with 200 mJ of ghi lines (g line: wavelength 436 nm, h line: wavelength 405 nm, i line: wavelength 365 nm) using a Ushio multi-lamp, followed by pre-development baking (PEB) for 120 seconds on a hot plate at 130°C. The coated wafer was then heated at 200°C for 1 hour under inert conditions. The wafer was removed when the temperature of the heating device dropped below 50°C, and the film thickness was measured. The film hardness was measured using nanoindentation (ENT-2100: manufactured by Elionix Co., Ltd.). A modulus of indentation of 8 GPa or higher was designated as excellent (◎), 6 GPa or higher as good (○), and less than 6 GPa as insufficient (×). The evaluation results are shown in Tables 1 and 2.

[0235] [Table 1]

[0236]

[0237] [Table 2]

[0238]

[0239] In Tables 1 and 2, "Cr" represents naphthalene, "DiNaph" represents dihydroxynaphthalene, "BzA" represents benzaldehyde, and "SA" represents salicylaldehyde. Regarding the position of the OH group in dihydroxynaphthalene, for example, "1,5" represents 1,5-dihydroxynaphthalene.

[0240] For example, “m-Cr / DiNaph / BzA / SA” in Example 1 is “1 / 1 / 1.28 / 0.8”, which means that component (A) of Example 1, namely the phenolic resin of varnish type, is composed of units derived from m-cresol, units derived from 1,5-dihydroxynaphthalene, units derived from benzaldehyde, and units derived from salicylaldehyde. Regarding the molar ratio, the ratio of units derived from m-cresol to units derived from 1,5-dihydroxynaphthalene to units derived from benzaldehyde to units derived from salicylaldehyde is 1:1:1.28:0.8.

[0241] From Tables 1 and 2, it can be concluded that the photosensitive film obtained from the negative photosensitive resin composition of the present invention exhibits excellent compatibility, thus avoiding rejection and unevenness. Furthermore, alkali solubility is confirmed. Additionally, excellent visible light shielding properties are confirmed even without the addition of black pigment.

Claims

1. A negative photosensitive resin composition comprising the following components (A) to (C): (A) A phenolic resin of varnish type with a molar ratio (a1):(a2):(a3):(a4) of cresol-derived structural unit (a1):(a2):(a3):(a4) of 1:0.25~4.0:0.25~4.0:0.25~4.

0. (B) Photosensitive agent, (C) Organic solvents.

2. The negative photosensitive resin composition according to claim 1, wherein, The component (A) is a phenolic varnish-type phenolic resin obtained by polycondensation of cresol, dihydroxynaphthalene, benzaldehyde and salicylaldehyde in an organic solvent in a molar ratio of cresol:dihydroxynaphthalene:benzaldehyde:salicylaldehyde = 1:0.25~4.0:0.25~4.0:0.25~4.0 using an acid catalyst.

3. The negative photosensitive resin composition according to claim 1 or 2, wherein, The total content of the structural unit (a1) derived from cresol, the structural unit (a2) derived from dihydroxynaphthalene, the structural unit (a3) ​​derived from benzaldehyde, and the structural unit (a4) derived from salicylaldehyde in component (A) is 30% by mass or more.

4. The negative photosensitive resin composition according to claim 1 or 2, wherein, The weight-average molecular weight of component (A) is above 1,000 and below 10,000.

5. The negative photosensitive resin composition according to claim 1 or 2, further comprising one or more resins selected from polyimides containing olefinic unsaturated groups, polyimide precursors containing olefinic unsaturated groups, polybenzoxazoles containing olefinic unsaturated groups, and polybenzoxazole precursors containing olefinic unsaturated groups.

6. The negative photosensitive resin composition according to claim 1 or 2, wherein, The composition comprises 0 to 30 parts by weight of colorant relative to 100 parts by weight of the solid component of the negative photosensitive resin composition.

7. A cured film obtained from the negative photosensitive resin composition of claim 1 or 2.

8. A photoresist film obtained from the negative photosensitive resin composition of claim 1 or 2.

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