CN114326306A - Photosensitive resin composition, photosensitive resin composition film, and patterned cured product - Google Patents
Photosensitive resin composition, photosensitive resin composition film, and patterned cured product Download PDFInfo
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- CN114326306A CN114326306A CN202210008077.8A CN202210008077A CN114326306A CN 114326306 A CN114326306 A CN 114326306A CN 202210008077 A CN202210008077 A CN 202210008077A CN 114326306 A CN114326306 A CN 114326306A
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Abstract
The invention provides a photosensitive resin composition, which comprises polyimide or a polyimide precursor resin A, an additive B, a compound C with more than 2 epoxy groups in a molecule and diazonaphthoquinone sulfonate E, wherein the additive B is a compound shown in a structural formula (1) and simultaneously contains hydroxyl and carboxyl or simultaneously contains hydroxyl and ester; the photosensitive resin composition has small film thickness loss in the developing process, fine images can be obtained with low exposure, and a cured film obtained after the photosensitive resin composition is cured by heat treatment has stronger heat resistance and chemical resistance.
Description
Technical Field
The invention belongs to the technical field of photoelectric display and semiconductor manufacturing, and particularly relates to a photosensitive resin composition, a photosensitive resin composition film and a patterned cured product.
Background
In recent years, with the miniaturization of display light-emitting elements and semiconductor elements, even for surface protective films, interlayer insulating films, pixel defining layers, and the like, resolution and high sensitivity on the order of μm or less have been required, and also, due to the requirements of processes and processing techniques, high requirements have been made on heat resistance, electrical insulation properties, and chemical resistance of photosensitive materials. Therefore, highly photosensitive resin compositions obtained from polyimides, polybenzoxazoles, phenol resins, and the like, which have excellent heat resistance and electrical insulation properties themselves, have been attracting attention and used in this field, particularly positive photosensitive resin compositions in which the exposed portion is soluble in an aqueous alkali solution after exposure to ultraviolet light.
The current common method is to add a photosensitive dissolution resistant compound, namely diazonaphthoquinone compound, into heat-resistant resin or a precursor thereof with good solubility in alkali liquor, inhibit the dissolution of an unexposed area in the alkali liquor through the hydrogen bonding action, the electrostatic action, the alkali catalytic coupling action and the like of the diazonaphthoquinone group, decompose the diazonaphthoquinone group after exposure, convert the diazonaphthoquinone group into carboxyl, eliminate the dissolution inhibition action and increase the solubility of the exposed area. Examples of such a resin composition include a resin composition obtained by adding a diazonaphthoquinone compound to a polyamic acid, a resin composition obtained by adding a diazonaphthoquinone compound to a hydroxyl group-containing polyimide, and the like (patent documents EP0023662a1, CN1275094C, CN105820338A, TW201809072A, EP1037112a1, j.photopolym.sci.tech.,2007,20,175). In addition, in order to increase the dissolution contrast of the light-shielding region and the exposed region and to reduce the exposure amount, a phenolic compound (CN1246389C) is often added to the resin system. However, the introduction of the diazonaphthoquinone compound, the hydroxyl group, and the phenol compound easily causes a problem that the heat resistance and the chemical resistance of the cured film after the heat treatment are deteriorated, and a problem that the balance between the film thinning and the exposure amount during the development is difficult.
Disclosure of Invention
Aiming at the problems of poor heat resistance and chemical resistance of a cured film after heat treatment and difficulty in balancing between film thinning and exposure in the developing process, the invention provides a photosensitive resin composition in a first aspect, which comprises polyimide or a polyimide precursor resin A, an additive B, a compound C with more than 2 epoxy groups in a molecule and diazonaphthoquinone sulfonate E; wherein the additive B is a compound which contains hydroxyl and carboxyl or contains hydroxyl and ester group in the molecule and is shown in the structural formula (1);
in the structural formula (1), m is an integer of 1-4, R4Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R5Represents a hydrogen atom, a hydroxyl group, a carboxyl group, an ester group, an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 5, and k, o, l, q each represents an integer of 0 to 5;
further, the polyimide or polyimide precursor resin a contains one or a combination of more of the structures shown by the structural formula (2);
in the structural formula (2), Q represents an organic group with 2-6 valences, wherein the carbon number of Q is 2-30, and the organic group contains at least one of 0-4 hydroxyl groups and carboxyl groups; d represents an organic group having 2 to 50 carbon atoms and a valence of 2 to 6 containing 0 to 4 of at least one of a hydroxyl group, a carboxyl group and an ester group, and R7Represents an organic group having 1 to 8 hydrogen atoms or carbon atoms;
further, D in the structure shown in the structural formula (2) represents at least one of the structural fragments shown in the structural formula (3);
r in the structural formula (3)1，R2Represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group and fluorine,Chlorine, bromine substituents; p represents an integer of 0 to 2; r3Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; r6Represents hydrogen atom, alkyl or alkoxy with 1-3 carbon atoms and fluorine, chlorine and bromine substituent groups, and X represents one of amido bond or ether bond;
further, Q in the structure shown in the structural formula (2) represents one or more combinations of dianhydride residues corresponding to the following tetracarboxylic acid dianhydrides: pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -tetracarboxylic diphenyl ether dianhydride, 3,3',4,4' -tetracarboxylic benzophenone dianhydride, 3,3',4,4' -tetracarboxylic diphenylsulfonyl dianhydride, 4,4' -hexafluoroisopropylphthalic anhydride, 4,4' -isopropylphthalic anhydride, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, cyclobutanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride;
preferably, the additive B is one or more of the compounds shown in the structural formula (4);
further, the compound C having 2 or more epoxy groups in a molecule is a compound having 2 or more epoxy groups in a molecule, wherein the compound having 2 or more epoxy groups comprises one or more of the following compounds in combination: bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, biphenyl type epoxy compounds;
further, the mass ratio of the additive B to the polyimide or polyimide precursor resin A is 0.01-0.5, and the mass ratio of the compound C having 2 or more epoxy groups in the molecule to the polyimide or polyimide precursor resin A is 0.01-0.6.
The second aspect of the present invention provides a photosensitive resin composition film, which is prepared by coating and drying the photosensitive resin composition.
The third aspect of the present invention provides a patterned cured product, comprising a film prepared by using the above photosensitive resin composition through the processes of exposure, development and curing;
furthermore, the patterned cured product is used for manufacturing an insulating layer and a pixel definition layer of an organic electroluminescent element, and a surface protection film and an insulating layer of a semiconductor element.
Advantageous effects
The present inventors have found that a resin composition film obtained by adding a polyimide or a polyimide precursor resin containing both a hydroxyl group and a carboxyl group or both a hydroxyl group and an ester group to a polyimide or a polyimide precursor resin containing both a hydroxyl group and an ester group, an epoxy compound having a functionality of 2 or more, and diazonaphthoquinone sulfonate is hardly soluble in an alkaline developer before exposure, but is extremely soluble after exposure, and therefore, the loss of film thickness during development is small, the required exposure amount is low, and a fine image can be obtained. Moreover, in the subsequent heat treatment curing process, as ester group structures which are highly crosslinked with each other can be formed between the additive and the polymer, the heat resistance and the chemical resistance of the film after heat treatment are enhanced.
Detailed Description
< photosensitive resin composition >
The photosensitive resin composition of the present invention comprises a polyimide or a polyimide precursor resin, an additive, a compound having 2 or more epoxy groups in the molecule, and diazonaphthoquinone sulfonate, and the components constituting the photosensitive resin composition will be specifically described below.
Polyimide or polyimide precursor resin A
The polyimide or polyimide precursor resin in the present invention is an alkali-soluble resin, and the alkali-soluble resin in the present invention means: coating resin dissolved in solvent or mixed solvent on silicon wafer or glass sheet, and baking at 120 deg.C for 2min to form pre-baking film with thickness of 10 μm + -0.5 μm; the pre-baked film is developed in 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 10s, then washed with water for 30s, and the surface water stain is dried, and the alkali solubility of the pre-baked film can be obtained according to the reduction of the film.
The polyimide or the polyimide precursor resin a of the present invention has high heat resistance and a small amount of outgassing after heat treatment, and is therefore particularly suitable for the production of a pixel defining layer, an insulating layer, a planarizing film, a protective film, and an interlayer insulating film used in an organic light-emitting device, a display device, and a semiconductor element.
In the polyimide or the polyimide precursor resin a of the present invention, there is no particular limitation as long as the polyimide has a polyimide ring, and the polyimide precursor has a polyimide structure having an imide ring formed by ring closure by dehydration, and there is no particular limitation; the polyimide or polyimide precursor resin a in the present invention contains one or a combination of more of the structures shown by the structural formula (2).
In the structural formula (2), Q represents an organic group with 2-6 valences, wherein Q represents 2-30 carbon atoms and contains 0-4 hydroxyl groups and at least one of carboxyl groups; d represents an organic group having 2 to 50 carbon atoms and a valence of 2 to 6 containing 0 to 4 of at least one of a hydroxyl group, a carboxyl group and an ester group, and R7Represents a hydrogen atom or an organic group having 1 to 8 carbon atoms.
The polyimide or polyimide precursor resin A is obtained by reacting a diamine compound with tetracarboxylic dianhydride under certain conditions.
The molecular structure of the diamine compound simultaneously contains hydroxyl and carboxyl or simultaneously contains hydroxyl and ester group; further, D in the above structural formula (2) represents a diamine residue containing one or more combinations of diamine residues represented by the structural formula (3):
wherein R in the structural formula (3)1，R2Represents an alkyl or an alkane having 1 to 3 carbon atomsOxy, hydroxy, carboxy and fluoro, chloro, bromo substituents; p represents an integer of 0 to 2; r3Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; r6Represents a hydrogen atom, an alkyl or alkoxy group having 1 to 3 carbon atoms, and a fluorine, chlorine, bromine substituent, and X represents one of an amide bond or an ether bond.
Preferably, D in the above structural formula (2) represents one or a combination comprising a diamine residue represented by the following structural formula (5):
wherein R in the structural formula (5)1，R2Represents alkyl or alkoxy with 1-3 carbon atoms, hydroxyl, carboxyl, fluorine, chlorine and bromine substituents; p represents an integer of 0 to 2; r3Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; r6Represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and a fluorine, chlorine, or bromine substituent.
Particularly preferably, D in the above formula (2) represents one or a combination of two or more kinds containing a diamine residue represented by the following formula (3-1).
The diamine compounds of the present invention also include those conventional in the art, which means they are commercially available directly or obtained directly by other routes, i.e., D in the above formula (2) further includes one or more combinations of diamine residues corresponding to the following diamine compounds: p-phenylenediamine, m-phenylenediamine, 3-carboxym-phenylenediamine, 3-hydroxym-phenylenediamine benzidine, 4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfide, 4 '-diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, 1, 4-bis (4-aminophenoxy) benzene, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2,3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3,3',4,4 '-tetramethyl-4, 4' -diaminobiphenyl, cycloalkyl groups, and halogen atom-substituted aromatic compounds.
Preferably, the conventional diamine compound in the present invention comprises 4,4 '-diaminodiphenyl ether, i.e., D in the above structural formula (2) represents a diamine residue corresponding to the inclusion of 4,4' -diaminodiphenyl ether.
Although the reactant for synthesizing the polyimide or the polyimide precursor resin a in the present invention contains the above-mentioned conventional diamine compound, it is not essential that the reactant for synthesizing the polyimide or the polyimide precursor resin a in the present invention mainly contains a diamine compound corresponding to a diamine residue represented by the structural formula (3) in an amount of 10 mol% or more, preferably 60 mol% or more.
The tetracarboxylic dianhydride in the invention is selected from the conventional tetracarboxylic dianhydrides in the field, namely, Q in the structural formula (2) represents one or more combinations of dianhydride residues corresponding to the tetracarboxylic dianhydride comprising the following structure: pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -tetracarboxylic diphenyl ether dianhydride, 3,3',4,4' -tetracarboxylic benzophenone dianhydride, 3,3',4,4' -tetracarboxylic diphenyl sulfonyl dianhydride, 4,4' -hexafluoroisopropylphthalic anhydride, 4,4' -isopropylphthalic anhydride, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, cyclobutanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride.
Preferably, Q in the structural formula (2) in the present invention represents one or a combination of more dianhydride residues corresponding to tetracarboxylic dianhydrides comprising the following structure: pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4,4' -hexafluoroisopropylphthalic anhydride, 3',4,4' -tetracarboxylic benzophenone dianhydride, and 3,3',4,4' -tetracarboxylic diphenyl ether dianhydride.
Particularly preferably, Q in the structural formula (2) in the present invention represents one or a combination of two dianhydride residues corresponding to tetracarboxylic dianhydride comprising the following structure: cyclobutanetetracarboxylic dianhydride, 4' -hexafluoroisopropylphthalic anhydride.
In the present invention, in order to ensure that the polyimide or polyimide precursor resin a has a proper solubility in an alkaline developer and that the resin has good heat resistance and elongation after heat treatment, the number of repetitions of the structural unit is preferably in the range of 10 to 1000, more preferably 20 to 500, and particularly preferably 50 to 200; wherein, the ratio of the repeating units containing both hydroxyl and carboxyl or both hydroxyl and ester groups to all the repeating units is preferably between 5% and 100%, and more preferably between 30% and 80%; the dissolution rate of the resin in an alkaline developing solution is controlled by adjusting the proportion of hydrophilic carboxyl and hydroxyl in a resin structure relative to hydrophobic groups, namely aromatic groups and alkyl groups of the resin, and the dissolution rate of an unexposed film in the alkaline developing solution can be 10-3000 nm/min and the dissolution rate of the exposed film in the alkaline developing solution is 200-50000 nm/min by matching with a photosensitizer.
The weight average molecular weight Mw and the number average molecular weight Mn of the polyimide or the polyimide precursor resin a in the present invention are measured as values in terms of polystyrene by Gel Permeation Chromatography (GPC), a light scattering method, a small-angle X-ray scattering method, and the like.
In addition, for better adjustment of the molecular weight of the polyimide or polyimide precursor resin a of the present invention, a certain end-capping agent may be added at the time of polymerization, and specific examples thereof may be, and are not limited to, one or more combinations of the following exemplified compounds:
monofunctional aromatic amine: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 3-aminonaphthalene, and the like, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 3-amino-4, 6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline.
Monofunctional aromatic anhydrides: maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, and cyclohexane dicarboxylic anhydride.
Monofunctional aromatic acid: benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, carboxynaphthalene, 2-hydroxy-naphthoic acid, 3-hydroxy-naphthoic acid, 4-hydroxy-naphthoic acid, 5-hydroxy-naphthoic acid, 6-hydroxy-naphthoic acid, 7-hydroxy-naphthoic acid, 8-hydroxy-naphthoic acid, 9-hydroxy-naphthoic acid.
The end-capping agent described above, which is added in a proportion of 0.005 to 0.5, further 0.01 to 0.4, based on the total molar amount of all the diamine compound and the tetracarboxylic dianhydride added; when the content is within the above range, a resin composition having an appropriate solution viscosity and excellent film properties can be obtained.
Additive B
In order to improve the sensitivity of the photosensitive resin composition, to increase the solubility of the resin composition in an aqueous alkali solution in an exposed portion, and to reduce the exposure amount, a phenolic compound is often added to the resin system in the conventional method. However, the addition of the phenolic compound obviously brings about the reduction of the thermal performance of the cured film, which is reflected by the reduction of the thermal weight loss temperature and the increase of the gas escape amount, thereby leading to the increase of the possibility of the shrinkage of the light-emitting area of the OLED pixel along with the time and the reduction of the light-emitting life.
According to research, the invention discovers that through optimization of molecules, a compound which simultaneously has hydroxyl and carboxyl or simultaneously has hydroxyl and ester group in the molecule is selected, so that the sensitivity of the photosensitive resin composition is ensured, and simultaneously, after heat treatment, thermally unstable acid groups are eliminated, a cross-linked ester bond is formed, and the thermal stability of a cured film is further improved.
The additive B is a compound which contains hydroxyl and carboxyl or contains hydroxyl and ester group in the molecule and is shown in the structural formula (1);
in the structural formula (1), m is an integer of 1-4, R4Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R5Represents a hydrogen atom, a hydroxyl group, a carboxyl group, an ester group, an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 5, k, o, l, q each represents an integer of 0 to 5, wherein at most one of n, l, o is 0.
In the present invention, from the viewpoint of both increasing the solubility of the resin composition in an aqueous alkali solution at an exposed portion and reducing the exposure amount, it is preferable that the additive B comprises one or a combination of more of the compounds represented by the following structural formula (6), wherein r in the structural formula (6) represents an integer of 1 to 3.
In the present invention, from the viewpoint of both increasing the solubility of the resin composition in an aqueous alkali solution at an exposed portion and reducing the exposure amount, it is further preferable that the additive B contains one or a combination of more of the compounds represented by the following structural formula (5).
In the present invention, from the viewpoint of both increasing the solubility of the resin composition in an aqueous alkali solution at an exposed portion and reducing the exposure amount, it is particularly preferable that the additive B contains one or a combination of more of the compounds represented by the following structural formula (7).
In the present invention, the amount of the additive B to be added is 0.01 to 0.5% by mass of the polyimide or polyimide precursor resin A, and particularly preferably 0.05 to 0.3% by mass of the additive B to be added. The compound B may be contained in two or more kinds, and when two or more kinds are contained, the total amount thereof is within the above range.
Compound C having 2 or more epoxy groups in the molecule
The photosensitive resin composition of the present invention contains a compound C having 2 or more epoxy groups in the molecule for the purpose of controlling the thermal reflow property and the crosslinking property of the polyimide or the polyimide precursor resin a and obtaining a desired positive tapered pattern through a curing step, and examples thereof include glycidyl ether type, glycidyl amine type and olefin oxide type compounds.
In the present invention, examples of the compound C having 2 or more epoxy groups in the molecule include bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, biphenyl type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds, spiro type epoxy compounds, bisphenol alkane type epoxy compounds, phenol Novolac type epoxy compounds, o-cresol Novolac type epoxy compounds, trimethylolmethane type epoxy compounds, tetraphenolethane type oxirane type epoxy compounds, alicyclic type epoxy compounds, alcohol type epoxy compounds, and the like.
In the present invention, the compound C having 2 or more epoxy groups in the molecule preferably includes one or a combination of more of the following compounds.
In the present invention, the compound C having 2 or more epoxy groups in the molecule is particularly preferable to include one or a combination of both of the following compounds.
In the present invention, the amount of the compound C having 2 or more epoxy groups in the molecule is preferably 0.01 to 0.6 based on the mass of the polyimide or polyimide precursor resin A, and more preferably 0.05 to 0.4 based on the mass of the polyimide or polyimide precursor resin A. The compound C may be contained in two or more kinds, and when the compound C is contained in two or more kinds, the total amount thereof is within the above range.
Diazonaphthoquinone sulfonate E
The photosensitive resin composition of the present invention contains diazonaphthoquinone sulfonate ester E, and by adding diazonaphthoquinone sulfonate ester, a positive pattern can be formed in which the exposed portion is removed by an alkaline developer.
Diazonaphthoquinone sulfonate, specifically refers to photosensitizer formed by ester bond connection of polyhydroxy phenol compound and diazonaphthoquinone group at 4-position or 5-position; when ultraviolet light irradiates on the compound, the diazonaphthoquinone group is degraded and rearranged to generate an enone structure, and reacts with water to generate indene acid, so that the conversion of the dissolution rate is realized, as shown in the following reaction formula. The functional groups of these polyhydroxy compounds may not be substituted with all of the diazoquinone, but from the viewpoint of contrast between exposed portions and unexposed portions, 60% (mol) or more of the total of the functional groups are preferably substituted with the diazoquinone. By using the diazonaphthoquinone compound described above, a positive photosensitive resin composition which is photosensitive under the i-line (365nm), the h-line (405nm), and the g-line (436nm) of a conventional ultraviolet mercury lamp can be obtained.
The polyhydric phenol compounds used for preparing the photosensitizer include, but are not limited to, bisphenol a, bisphenol AF, bisphenol AP, naphthol, trihydroxybenzophenone, fluorenyl-containing phenol, trityl phenol, tristyryl phenol, phenolic resin oligomers, and the like. They may be used alone or in combination. The amount of addition thereof is 0.01 to 0.70, and more preferably 0.05 to 0.50, based on the mass of the polyimide or the polyimide precursor resin a.
Auxiliary agent
In order to improve the adhesion and film-forming property of the resin film-forming material and the substrate, the auxiliary agent in the photosensitive resin composition provided by the embodiment of the invention comprises an adhesion promoter and a surfactant; wherein the adhesion promoter is preferably silane coupling agent to improve the adhesion between the film and the substrate during development and inhibit the pattern from falling off during development, and preferably comprises one or more of methacryloxy dimethoxy methyl silane, 3-aminopropyl trimethoxy silane, vinyl triacyloxy silane, N-phenyl amino ethyl trimethoxy silane and the like; the amount of the adhesion promoter added is preferably 0.001 to 0.200 relative to the mass of the polymer resin; within this range, the adhesion between the film and the substrate can be maintained without affecting the heat resistance of the film.
The selected surfactant is fluorine-containing surfactant, silicon-containing surfactant, acrylate surfactant, ester and ketone reagent, and ethyl lactate, ethyl acetate, methyl ethyl ketone and cyclohexanone are preferably selected in the embodiment of the invention; the amount of the surfactant added is 0.0003 to 0.05 relative to the total mass of the polymer.
Solvent(s)
The solvent used in the photosensitive resin composition according to the embodiment of the present invention is a solvent with a boiling point lower than 230 ℃, and includes but is not limited to one or more combinations of N, N-dimethylacetamide, N-dimethylformamide, γ -butyrolactone, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol, N-butanol, cyclohexanone, ethyl lactate, and butyl lactate; the amount of the solvent to be added is 3 to 50 times, and more preferably 3 to 20 times the mass of the polyimide or polyimide precursor resin a.
< photosensitive resin composition film and patterned cured product >
The invention also relates to a photosensitive resin composition film, wherein the photosensitive resin composition film is prepared by coating and drying the photosensitive resin composition provided by the invention; the invention also relates to a patterned cured product, which is prepared by the photosensitive resin composition through exposure, development and curing procedures.
The method for heat curing the photosensitive resin composition of the present invention is not particularly limited, and a method commonly used in the art may be used. Spin coating, spray coating, roll coating, slit coating, screen printing, preferably spin coating and slit coating, are used on smooth and orderly substrates such as glass, silicon wafers and the like; the thickness of the dried film is usually 0.1 to 15 μm depending on the coating method and the composition used, such as the component, viscosity, and solid content. Drying the coated film at 40-150 ℃ for several minutes to several hours by using an oven, a hot plate and an infrared furnace; then the dried substrate is placed under an exposure machine for ultraviolet exposure, but the ultraviolet exposure is not limited to the ultraviolet exposure, electron beams or X-rays can also be used for exposure, and the exposed substrate is dissolved in an alkaline developing solution to form patterning; the selected developer includes but is not limited to at least one of aqueous solutions of tetramethylammonium hydroxide, triethylamine, diethanolamine, dimethylaminoethanol, ethylenediamine, cyclohexylamine, hexamethylenediamine, diethylaminoethanol, methylamine and dimethylamine, wherein the aqueous solution of tetramethylammonium hydroxide with 2.38 wt% is preferred, and the developing time is controlled within 5s to 600s, preferably 5s to 300s according to the difference of film thickness.
Washing the developed film with water for fixing treatment, heating the film in a curing furnace to 100-500 deg.c, and heat treatment for 10min to several hr to convert the composition into heat resistant film to obtain the patterned cured matter.
Examples
The present invention will be described with reference to the following examples, but the present invention is not limited to the following examples.
The relevant abbreviations in the examples are as follows:
6 FDA: 4,4' -hexafluoroisopropylphthalic anhydride;
CBDA: cyclobutanetetracarboxylic dianhydride;
6 FAP: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane;
ODA: 4,4' -diaminodiphenyl ether;
B2:
B4:
B5:
B6:
B7:
B8:
C1:
C2:
the above compounds are all obtained in a commercially available manner.
Synthesis example 1
Synthesis of coumarin analogue structure derivative amine hydrolysate (diamine compound M1)
Suspending hydrochloride of 7-aminocoumarin (3.9g,20mmol) in 30mL of n-hexane, irradiating for 48h by a high-pressure mercury lamp with the wavelength of 250-450nm, and filtering to obtain a [2+2] cyclization product of the 7-aminocoumarin hydrochloride. The product is adjusted to neutral pH by saturated aqueous solution of sodium bicarbonate to obtain the [2+2] cyclization product of 7-aminocoumarin.
Under the protection of nitrogen flow, dissolving a [2+2] cyclization product (10.0g,31mmol) of 7-aminocoumarin in 100mL of ethanol, dropwise adding 10mL of 0.01mol/mL NaOH aqueous solution, heating to 60 ℃, reacting for 6h, adjusting pH to 5-6 with dilute hydrochloric acid, extracting with ethyl acetate, and concentrating to obtain a diamine compound M1.
Synthesis example 2
Synthesis of hydrolyzate of amine derivative of coumarin analogous Structure (diamine Compound M2)
Under the protection of nitrogen flow, dissolving a [2+2] cyclization product (10.0g,31mmol) of 7-aminocoumarin in 100mL of methanol, adding sodium methoxide (5.4g,100mmol), heating to 60 ℃, reacting for 8h, adjusting the pH to 5-6 with dilute hydrochloric acid, extracting with ethyl acetate, and concentrating to obtain a diamine compound M2.
Synthesis example 3
Synthesis of 4,4 '-bis (4-aminophenyloxy) -2-hydroxy-2' -carboxybiphenyl (diamine compound M3)
Under the protection of a dry nitrogen stream, 2, 7-dihydroxy-3, 4-benzocoumarin (20g,87.6mmol) is dissolved in 300mL of N-methylpyrrolidone (NMP), 4-fluoro-nitrobenzene (24.7g, 175.3mmol), potassium carbonate (48.5g, 350.6mmol) are added, the mixture is reacted at 50 ℃ for 10h, poured into water, extracted with ethyl acetate, and the organic phase is concentrated to obtain the nitro compound.
Dissolving the obtained 2, 7-bis (4-nitrophenyloxy) -3, 4-benzocoumarin in 500mL of ethanol, adding 80g of reduced zinc scrap, dropwise adding 20mL of 10 wt% hydrochloric acid, heating to 50 ℃, stirring for reacting for 24h, filtering out unreacted zinc scrap, concentrating the filtrate, and recrystallizing to obtain a diamine compound M3.
Synthesis example 4
Synthesis of diamine Compound M4
Under the protection of a dry nitrogen flow, the compound W (9.3g,20mmol) is dissolved in 100mL of methanol, 1mL of hydroxylamine and sodium methoxide (10.8g,200mL) are added, reflux reaction is carried out for 48h, water is poured into the mixture, extraction is carried out by ethyl acetate, an organic phase is concentrated, and recrystallization is carried out to obtain a diamine compound M4.
Synthesis example 5
Synthesis of diazonaphthoquinone Compound (E1)
Under the protection of dry nitrogen flow, raw materials of phenol (57.6g,100mmol) and 5-diazonaphthoquinone sulfonyl chloride (93.9g,350mmol) are dissolved in 500mL of dioxane, under the condition that the system temperature is not higher than 30 ℃, a reagent mixed by 50mL of dioxane/30 mL of triethylamine is dripped in, reaction is carried out for 3h, triethylamine salt is filtered out, filtrate is dripped in water, and the diazonaphthoquinone compound E1 is obtained by filtering, precipitating and drying.
Synthesis example 6
Synthesis of diazonaphthoquinone Compound (E2)
Bisphenol AF (33.6g,100mmo1) and 2, 1, 5-diazonaphthoquinone sulfonyl chloride (51.1g,190mmol) were dissolved in 400mL of dioxane under a dry nitrogen stream, and 15g triethylamine in 100mL of THF was added dropwise at a system temperature of not more than 30 ℃. After the dropwise addition was completed, the reaction was stirred for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration and dried to obtain 55g of a diazonaphthoquinone compound E2.
Synthesis example 7
Synthesis of [2+2] cyclized dimer of 4-hydroxycinnamic acid (Compound B1)
Suspending 4-hydroxy methyl cinnamate (5.34g,30mmol) in 30mL n-hexane, irradiating for 48h by a high-pressure mercury lamp with the wavelength of 250-450nm, and filtering to obtain a [2+2] cyclic dimer product of the 4-hydroxy methyl cinnamate. Then adding the dimer into 100mL of 0.1mmol/L NaOH solution, stirring at room temperature for 10h, neutralizing with dilute hydrochloric acid, extracting with ethyl acetate, and concentrating to obtain a [2+2] cyclic dimer of 4-hydroxycinnamic acid, namely a compound B1.
Synthesis example 8
Synthesis of [2+2] cyclized dimer of caffeic acid (Compound B3)
Suspending methyl caffeate (4.85g,25mmol) in 30mL n-hexane, irradiating for 48h by a 250-nm high-pressure mercury lamp, and filtering to obtain a [2+2] cyclic dimer product of the methyl 4-hydroxycinnamate. Then adding the dimer into 100mL of 0.1mmol/L NaOH solution, stirring at room temperature for 10h, neutralizing with dilute hydrochloric acid, extracting with ethyl acetate, and concentrating to obtain a [2+2] cyclized dimer of caffeic acid, namely a compound B3.
Synthesis example 9 resin precursor A1
Diamine compound M1(7.702g,20mmol), diamine compound M2(27.030g,70mmol), M-aminobenzoic acid (2.741g,20mmol), ODA (0g,0mmol) were dissolved in 200g of N-methylpyrrolidone (NMP) under a dry nitrogen stream, stirred at room temperature for 0.2h, then 6FDA (44.42g,100 mmol 1) and CBDA (0g,0mmol) were added, stirred at room temperature for 8h, and then heated to 90 ℃ for reaction for 6 h. The solution was then poured into 2L of ethanol and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum drying oven at 60 ℃ for 24h to give resin precursor A1.
Synthesis examples 10-17 resin precursor A2-9
The synthesis method of the resin precursor A2-9 was the same as that of the resin precursor A1, except for the differences in the diamine compound and the tetracarboxylic dianhydride and the differences in the imidization method, as shown in Table 1.
TABLE 1
Example 1
A photosensitive resin composition slurry was prepared by dissolving a resin precursor A1(2.0g), a diazonaphthoquinone compound E1(0.5g), E2(0.3g), a compound B1(0.1g) as an additive B, a compound C1(0.5g) and a compound C2(0.1g) as a compound C having 2 or more epoxy groups in the molecule, 3-aminopropyltrimethoxysilane (0.02g) as a silane coupling agent, and a surfactant GO TEGLIDE 300(0.01g) in 4.5g of gamma-butyrolactone and 1.5g of ethyl lactate, stirring the mixture at room temperature for 3 hours, and then filtering the mixture with an organic filter having a pore size of 0.45. mu.m.
Coating the photosensitive resin composition slurry on a silicon chip or a glass substrate, baking for 2min at 120 ℃, exposing, developing for 60s by using 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, then washing for 30s by using water to obtain a film with patterning, and performing heat treatment for 1h at 260 ℃ to obtain the film finally used for performance evaluation.
Examples 2 to 14, comparative examples 1 to 7
The synthesis methods of examples 2-14 and comparative examples 1-7 are the same as example 1, except that the raw materials are selected and mixed in different proportions, and the specific formula is shown in Table 2. The photosensitive resin compositions prepared in examples 1 to 14 and comparative examples 1 to 7 were evaluated for their image-forming ability, adhesion, residual film ratio, water absorption, heat resistance, chemical resistance, etc., and the results are shown in Table 2.
The evaluation method comprises the following steps:
imaging capability
Detecting the state of an etched line of the developed film by using SEM (JEOL JSM-6510), wherein the line with the width less than 5 mu m can still be clearly etched, has no bending and no defect, and has the line width ratio consistent with the design of a mask plate as the best; the lines with the width of 5-10 mu m can be clearly etched, have no bending and defect, and the line width ratio is consistent with the design of a mask plate; only the lines with the width of more than 10 mu m can be clearly etched, no bending and no defect exist, and the line width ratio is inferior to the design of a mask plate.
Adhesion property
The developed film was observed by an optical microscope (OLS5000) for the occurrence of line peeling, preferably, the case of line peeling with a line width of 2 μm or less, preferably, the case of line peeling with a line width of 10 μm or less, and preferably, the case of line peeling with a line width of 5 μm or more.
Residual film rate
The thickness of the film immediately before development and after coating was d1The thickness of the corresponding film after development and heat treatment is d2. The residual film rate is calculated in the following way: d2/d1100%. The film residue rate of the composition film after heat treatment is preferably more than 70%, the film residue rate of the composition film after heat treatment is good at 50-70%, and the film residue rate of the composition film after heat treatment is inferior at less than 50%.
Water absorption
The heat-treated film (having a mass of more than 0.5g) was left in a closed atmosphere having a relative humidity of 60% for 72 hours, and the change in weight of the film sample before and after the leaving was measured. WA＝(W-W0)/W0X 100% where WADenotes the water absorption, W denotes the weight after water absorption, W0The weight before water absorption is shown. With WA<0.5% of the total weight is preferably 0.5%<WA<1.5% is good, WA>1.5% is inferior.
Heat resistance
A small amount of sample was subjected to thermogravimetric analysis (TGA, NETZSCH STA2500 Regulus) to determine the residual weight ratio (R) at 400 degrees of the sample400). With R400>80 percent of the total weight is excellent, and 75 percent of the total weight is excellent<R400<80% is good, R400<75% was inferior.
Chemical resistance
The heat-treated film (area greater than 5 x 5cm, thickness of 2 μm) was placed in a jar for 72 hours, and the change in film thickness before and after soaking the film sample in N-methylpyrrolidone at 40 ℃ for 120 seconds was measured. Δ THK ═ (THK)1-THK0)/THK0X 100%, where Δ THK represents the rate of change of film thickness, THK1The film thickness after immersion is shown, and THK is the film thickness before immersion. With WA<1 percent is excellent, 1 percent<WA<2% is good, WA>2% is inferior.
TABLE 2
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A photosensitive resin composition comprising a polyimide or a polyimide precursor resin A, an additive B, a compound C having 2 or more epoxy groups in the molecule, and a diazonaphthoquinone sulfonate E; wherein the additive B is a compound which contains hydroxyl and carboxyl or contains hydroxyl and ester group in the molecule and is shown in the structural formula (1);
in the structural formula (1), m is an integer of 1-4, R4Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R5Represents a hydrogen atom, a hydroxyl group, a carboxyl group, an ester group, an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 5, and k, o, l, q each represents an integer of 0 to 5.
2. The photosensitive resin composition according to claim 1, wherein the polyimide or polyimide precursor resin a comprises one or a combination of more of the structures represented by structural formula (2);
in the structural formula (2), Q represents an organic group with 2-6 valences, wherein the carbon number of Q is 2-30, and the organic group contains at least one of 0-4 hydroxyl groups and carboxyl groups; d represents an organic group having 2 to 50 carbon atoms and a valence of 2 to 6 containing 0 to 4 of at least one of a hydroxyl group, a carboxyl group and an ester group, and R7Represents a hydrogen atom or an organic group having 1 to 8 carbon atoms.
3. The photosensitive resin composition according to claim 2, wherein D in the structure represented by the structural formula (2) represents at least one of the following structural fragments represented by the structural formula (3);
r in the structural formula (3)1，R2Represents an alkyl or alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, fluorine, chlorine or bromineA substituent group; p represents an integer of 0 to 2; r3Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; r6Represents a hydrogen atom, an alkyl or alkoxy group having 1 to 3 carbon atoms, and a fluorine, chlorine, bromine substituent, and X represents one of an amide bond or an ether bond.
4. The photosensitive resin composition according to claim 2, wherein Q in the structure represented by the structural formula (2) represents a combination comprising one or more dianhydride residues corresponding to the following tetracarboxylic dianhydrides: pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -tetracarboxylic diphenyl ether dianhydride, 3,3',4,4' -tetracarboxylic benzophenone dianhydride, 3,3',4,4' -tetracarboxylic diphenyl sulfonyl dianhydride, 4,4' -hexafluoroisopropylphthalic anhydride, 4,4' -isopropylphthalic anhydride, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, cyclobutanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride.
5. The photosensitive resin composition of claim 1, wherein the additive B comprises one or more combinations of compounds represented by structural formula (4).
6. A photosensitive resin composition according to claim 1, wherein the compound C having 2 or more epoxy groups in a molecule comprises one or more combinations of the following compounds: bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, biphenyl type epoxy compounds.
7. A photosensitive resin composition according to claim 1, wherein the mass ratio of the additive B to the polyimide or polyimide precursor resin A is 0.01 to 0.5, and the mass ratio of the compound C having 2 or more epoxy groups in the molecule to the polyimide or polyimide precursor resin A is 0.01 to 0.6.
8. A photosensitive resin composition film, which is prepared by coating and drying the photosensitive resin composition according to any one of claims 1 to 7.
9. A patterned cured product comprising the photosensitive resin composition film according to claim 8, which is prepared by exposure, development and curing.
10. The patterned cured product according to claim 9, wherein the patterned cured product is used for producing an insulating layer and a pixel defining layer of an organic electroluminescent element, and a surface protective film and an insulating layer of a semiconductor element.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114874412A (en) * | 2022-06-14 | 2022-08-09 | 中国科学院宁波材料技术与工程研究所 | Deep ultraviolet light-promoted degradation epoxy material, composite coating, and preparation method and application thereof |
| WO2023182522A1 (en) * | 2022-03-24 | 2023-09-28 | 積水化学工業株式会社 | Epoxy resin, cured body of same and method for producing epoxy resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023182522A1 (en) * | 2022-03-24 | 2023-09-28 | 積水化学工業株式会社 | Epoxy resin, cured body of same and method for producing epoxy resin |
| CN114874412A (en) * | 2022-06-14 | 2022-08-09 | 中国科学院宁波材料技术与工程研究所 | Deep ultraviolet light-promoted degradation epoxy material, composite coating, and preparation method and application thereof |
| CN114874412B (en) * | 2022-06-14 | 2023-01-03 | 中国科学院宁波材料技术与工程研究所 | Deep ultraviolet light-promoted degradation epoxy material, composite coating, and preparation method and application thereof |
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