A dianhydride compound containing triazine group and its preparation method and application

Abstract

The invention discloses a dianhydride compound containing a triazine group, a preparation method and an application thereof. The dianhydride compound contains a triazine group, which has the function of improving the light transmittance of a polyimide polymer. After the dianhydride compound is introduced into a polyimide resin precursor and further prepared into a polyimide photosensitive resin composition, the polyimide photosensitive resin composition containing the dianhydride compound can obtain a higher sensitivity during the exposure and development process, which can significantly improve the photolithography performance of the photosensitive resin composition.

Description

Technical Field

[0001] The present invention relates to a novel dianhydride compound, and more particularly to a dianhydride compound containing a triazine group and a preparation method thereof, and also to a resin precursor prepared from the dianhydride compound and a photosensitive resin composition containing the resin precursor. The photosensitive resin composition is suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., and has excellent performance. Background Art

[0002] In recent years, semiconductor devices and electronic components are developing towards miniaturization, high performance and low cost. In order to meet future development needs, resin compositions that can be patterned by photolithography need to have high resolution, low stress, high adhesion, high insulation reliability, good heat resistance and other characteristics. Polyimide materials have the advantages of good heat resistance, excellent insulation and excellent mechanical properties. On the other hand, based on the reasons of large-scale substrates and improved productivity, in order to shorten the exposure time, higher sensitivity is required for photosensitive resin compositions.

[0003] As photosensitive resin compositions capable of being highly sensitized, there are known methods: adding phenolic resin to polyimide resin or polybenzoxazole resin (patent CN 112654927 A); adding phenolic hydroxyl-modified styrene resin to polyimide, polybenzoxazole or polybenzoxazine (patent CN 109863206 B). The above solutions can improve the sensitivity of the photosensitive resin composition, but the mechanical properties of the obtained cured film are poor and the adhesion to the substrate is insufficient. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a dianhydride compound containing a triazine group, wherein the dianhydride compound contains a triazine group and an ether bond, and the group has the characteristics of high light transmittance, low refractive index and improved elongation. After the dianhydride compound is introduced into a resin precursor and further prepared into a photosensitive resin composition, the light transmittance of the photosensitive resin composition containing the dianhydride compound structure is improved, and it has higher sensitivity during exposure and development; in addition, the presence of the triazine group and the ether bond results in a cured film having better flexibility, which can significantly improve the sensitivity, mechanical properties and adhesion to the substrate of the photosensitive resin composition.

[0005] The first aspect of the present invention is to provide a dianhydride compound containing a triazine group, wherein the dianhydride compound has a structural formula shown in the following formula (1):

[0006]

[0007] Furthermore, in formula (1), R1 is selected from a hydrogen atom, a halogen atom, an alkoxy group, and a group represented by formula Y. The halogen atom may be fluorine, chlorine, bromine, or iodine; the alkoxy group is an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, and the like.

[0008]

[0009] Preferably, R1 is selected from hydrogen atom, fluorine atom, methoxyl group, .

[0010] The second aspect of the present invention is to provide a method for preparing the above-mentioned dianhydride compound containing a triazine group, the method comprising the following steps:

[0011] (i) 2,4-dichloro-1,3,5-triazine is reacted with a dimethylphenol derivative to obtain an intermediate represented by formula a1. The reaction formula is as follows:

[0012]

[0013] (ii) Carboxylating the methyl group in the intermediate of formula a1 to obtain the intermediate of formula a2. The reaction formula is as follows:

[0014]

[0015] (iii) Dehydrating and cyclizing the carboxyl group in the intermediate represented by formula a2 to obtain a dianhydride compound containing a triazine group represented by formula (1), and the reaction formula is as follows:

[0016] .

[0017] Furthermore, in the above formula a1, formula a2, and formula (1), the definition of R1 is consistent with that described above.

[0018] Furthermore, in step (i), in the dimethylphenol derivative, the definition of R1 is consistent with that described above. The molar ratio of 2,4-dichloro-1,3,5-triazine to the dimethylphenol derivative is 1:1.5-2.5, preferably 1:2.

[0019] Furthermore, in step (i), the reaction is carried out in an organic solvent. There is no specific requirement for the organic solvent, as long as it can completely dissolve the compounds involved in the reaction, such as acetone, tetrahydrofuran, toluene, xylene, etc.

[0020] Furthermore, in step (i), during the reaction, an organic amine is preferably added as a scavenger of HCl, and the organic amine may be DIPEA (N,N-diisopropylethylamine) or the like.

[0021] Further, in step (i), the reaction needs to be carried out at a low temperature, preferably 5°C to -20°C, for example 5°C, 4°C, 3°C, 2°C, 1°C, 0°C, -1°C, -2°C, -3°C, -4°C, -5°C, -6°C, -7°C, -8°C, -9°C, -10°C, -11°C, -12°C, -13°C, -14°C, -15°C, -16°C, -17°C, -18°C, -19°C, -20°C, more preferably 0°C to -10°C.

[0022] Furthermore, in step (i), the reaction time is generally 3 to 5 hours, for example, 3 hours, 4 hours, or 5 hours. After the reaction, the reaction solution is transferred to a separatory funnel, washed three times with brine, and magnesium sulfate is added to the organic layer to remove water and dry it. After filtering, the filtrate is concentrated under reduced pressure to generate a white solid to obtain the intermediate represented by formula a1.

[0023] Further, in step (ii), the reaction is carried out in the presence of water, pyridine and potassium permanganate. During the reaction, the intermediate represented by formula a1, pyridine and water can be mixed first, and then potassium permanganate is added to react. Preferably, the amount of water used is 4 to 5 times the mass of the intermediate a1, the amount of pyridine used is 8 to 10 times the mass of the intermediate a1, and the amount of potassium permanganate used is 2.2 to 2.5 times the mass of the intermediate a1.

[0024] Furthermore, in step (ii), the reaction needs to be carried out under high temperature conditions of heating, the temperature is 105-115° C., for example, 105° C., 110° C., 115° C. During the reaction, the temperature can be raised to the reaction temperature, and then potassium permanganate is added to the mixture containing the intermediate shown in a1, pyridine and water. Potassium permanganate can be added all at once or in batches, for example, twice, three times, four times, etc.

[0025] Furthermore, in step (ii), after adding potassium permanganate, the stirring reaction time is generally 3 to 6 hours, for example 3 hours, 4 hours, 5 hours, or 6 hours.

[0026] Furthermore, in step (iii), the dehydration cyclization is preferably carried out under vacuum conditions, and the water generated by the reaction is preferably continuously separated. The vacuum degree of the reaction is preferably less than or equal to 0.05 MPa, for example, any value of 0.01 MPa, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa or a range therebetween.

[0027] Further, in step (iii), high temperature conditions are required for dehydration treatment, and the temperature is preferably 100-180° C., such as 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C., 170° C., 175° C., 180° C. More preferably, the reaction temperature is 120-160° C., and even more preferably, the reaction temperature is 140-150° C.

[0028] The third aspect of the present invention provides a resin precursor, which is obtained by reacting at least one dianhydride monomer and two or more diamine monomers, wherein the dianhydride monomer contains at least one of the above-mentioned dianhydride compounds containing triazine groups.

[0029] Furthermore, in the above resin precursor, the total amount of the triazine group-containing dianhydride compound of the present invention is 70% or more of the total molar amount of the diamine monomers, for example, 70%, 75%, 80%, 85%, 90%, 95%, 100%. When it is 100%, it means that all the dianhydride monomers are triazine group-containing dianhydride compounds shown in formula (1).

[0030] Furthermore, the resin precursor is at least one of polyamic acid, polyamide ester and polyimide.

[0031] Furthermore, when the resin precursor is different, the reaction raw materials used are different. For example, when the resin precursor is polyamic acid, it can be obtained by reacting at least one dianhydride monomer and at least two diamine monomers. When the resin precursor is polyamic acid ester, it can be obtained by reacting at least one dianhydride monomer, at least two diamine monomers, and an esterification agent as raw materials. The specific reaction method is not limited. For example, the dianhydride monomer and the diamine monomer can be reacted to obtain polyamic acid, and then an esterification agent is added to react to obtain polyamic acid ester; or, the dianhydride monomer can be reacted with an esterification agent first, and then reacted with a diamine monomer to obtain polyamic acid ester. When the resin precursor is polyimide, it is first reacted to obtain polyamic acid or polyamide ester, and then imidized to obtain polyimide.

[0032] Furthermore, the dianhydride monomer may contain other dianhydrides in addition to the dianhydride compound containing a triazine group as shown in formula (1). The other dianhydrides may be selected from reports in the prior art, such as one, two or more of 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,3,3',4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-(hexafluoroisopropylene)diphthalic anhydride, and the like.

[0033] Furthermore, the diamine monomer of the present invention can be selected from at least one of the following diamine compounds: hydroxyl-containing diamines, carboxyl-containing diamines, sulfonic acid-containing diamines, thiol-containing diamines, aromatic diamines, alicyclic diamines, and aliphatic diamines having a siloxane structure.

[0034] Furthermore, the hydroxyl-containing diamine may be selected from at least one of the following compounds: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxy)biphenyl, and the like.

[0035] Furthermore, the carboxyl-containing diamine may be selected from at least one of the following compounds: 3,3'-dicarboxyl-4,4'-diaminodiphenylmethane and the like.

[0036] Furthermore, the sulfonic acid-containing diamine may be selected from at least one of the following compounds: 3-sulfonic acid-4,4'-diaminodiphenyl ether and the like.

[0037] Furthermore, the thiol-containing diamine may be selected from at least one of the following compounds: dithiophenylene diamine and the like.

[0038] Furthermore, the alicyclic diamine may be at least one selected from the following compounds: alicyclic diamines such as cyclohexanediamine and methylenebiscyclohexylamine.

[0039] Furthermore, the aromatic diamine is a substituted or unsubstituted aromatic diamine, and can be selected from at least one of the following compounds:

[0040]

[0041]

[0042] Furthermore, the aliphatic diamine having a siloxane structure may be bis(3-aminopropyl)tetramethyldisiloxane or the like. The aliphatic diamine having a siloxane structure can improve the adhesion between the photosensitive resin composition containing the resin precursor and the silicon substrate, and at the same time does not reduce the heat resistance of the cured film formed by the photosensitive resin composition. Preferably, the aliphatic diamine having a siloxane structure accounts for 1 to 15% of the total molar amount of the diamine monomer, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%.

[0043] Furthermore, in order to better adjust the molecular weight of the resin precursor of the present invention, a certain end-capping agent may be added during polymerization, and the end-capping agent may be a combination of one or more of the following monofunctional aromatic amines and monofunctional aromatic anhydrides, but is not limited thereto:

[0044] Monofunctional aromatic amines: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-o-methyl benzoic acid, 3-amino-m-methyl benzoic acid, 1-amino-2-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-carboxy-2-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-3-hydroxyquinoline, 4-aminophenylacetylene, etc.

[0045] Monofunctional aromatic anhydrides: maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, cyclohexanepentanedicarboxylic anhydride, 4-alkynylphthalic anhydride, etc.

[0046] Furthermore, the introduction ratio of the above-mentioned end-capping agent accounts for 0.1% to 50% of the total molar amount of all diamine monomers or dianhydride monomers input, for example, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, preferably 1% to 30%; this dosage range can maintain the stability of the resin without reducing the molecular weight of the resin and improve its mechanical properties.

[0047] Furthermore, the esterification agent can also be selected from reports in the prior art, such as one or more of methanol, ethanol, n-butanol, hydroxyethyl methacrylate, N,N-dimethylformamide dimethyl methyl acetal, N,N-dimethylformamide dimethyl acetal, 4-nitrobenzyl alcohol, etc.

[0048] Furthermore, the detailed preparation methods of polyamic acid, polyamide ester and polyimide can be selected from reports in the prior art, which is not difficult for those skilled in the art.

[0049] Furthermore, in the synthesis process of the resin precursor, an organic solvent is required. Examples of the organic solvent include: amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclopentane sulfone, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate, etc., but are not limited to these.

[0050] Furthermore, during the synthesis of the resin precursor, the obtained product needs to be put into a large amount of water or a mixture of methanol and water to precipitate it, and then filtered and dried to obtain a pure resin precursor. The drying temperature is preferably 40 to 100° C., more preferably 50 to 80° C. Through this operation, unreacted monomers, dimers, trimers and other oligomer components can be removed, and the film properties after thermal curing can be improved.

[0051] Furthermore, the resin precursor can be represented by the general structural formula shown in the following formula (2) and / or (3):

[0052]

[0053]

[0054] Furthermore, in the above formulae (2) and (3), m and n are integers in the range of 10 to 100,000, such as 10, 50, 100, 500, 1000, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000. X1 and X2 are introduced through dianhydride monomers, which contain at least one dianhydride compound containing a triazine group according to the present invention, and R2 is a hydrogen atom or an alkyl group. When R2 is an alkyl group, it is introduced through an esterification agent. Y1, Y2 and Y3 are introduced through diamine monomers.

[0055] A fourth aspect of the present invention provides a photosensitive resin composition, which includes the above-mentioned resin precursor.

[0056] Furthermore, the photosensitive resin composition includes a photosensitizer, an auxiliary agent and a solvent in addition to the resin precursor.

[0057] Furthermore, when the photosensitizer is a photoacid generator, when the resin precursor and the photoacid generator are used together, the obtained photosensitive resin composition is a positive photosensitive resin composition.

[0058] Furthermore, as a photoacid generator for a positive photosensitive resin composition, a quinonediazide compound can be preferably used. As a quinonediazide compound, there can be cited a compound obtained by ester-bonding a sulfonic acid of a quinonediazide to a polyhydroxy compound, a compound obtained by ester-bonding a sulfonic acid of a quinonediazide to a polyamino compound, and a compound obtained by ester-bonding a sulfonic acid of a quinonediazide to a polyhydroxypolyamino compound. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted by quinonediazide groups, but preferably, on average, more than 40 mol% of the functional groups as a whole are substituted by quinonediazide groups. By using such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to the usual ultraviolet rays, i.e., the i-line (wavelength 365nm), h-line (wavelength 405nm), and g-line (wavelength 436nm) of a mercury lamp can be obtained.

[0059] Furthermore, the quinonediazide compound preferably comprises an ester of a phenol compound and naphthoquinonediazide-4-sulfonyl group. Thus, high sensitivity and higher resolution can be obtained under i-line exposure.

[0060] Preferably, the photosensitizer of the present invention is at least one of 4-hydroxyphenyl-2,3,4-trihydroxyphenyl ketone and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid (Toyo Gosei Kogyo Co., Ltd., 4NT-300), 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid (Toyo Gosei Kogyo Co., Ltd., 4NT-350), etc.

[0061] The content of the quinonediazide compound used in the photosensitive resin composition of the present invention is preferably 3 to 80 parts by mass relative to 100 parts by mass of the resin, for example, 3 parts by mass, 5 parts by mass, 10 parts by mass, 15 parts by mass, 20 parts by mass, 25 parts by mass, 30 parts by mass, 35 parts by mass, 40 parts by mass, 45 parts by mass, 50 parts by mass, 55 parts by mass, 60 parts by mass, 65 parts by mass, 70 parts by mass, 75 parts by mass, 80 parts by mass, and more preferably 10 to 50 parts by mass. By making the content of the quinonediazide compound within this range, the contrast between the exposed part and the unexposed part can be obtained, thereby achieving higher sensitivity, and the residue generated when the content is high is not observed, so it is preferred. In addition, a sensitizer or the like can be added as needed.

[0062] Furthermore, the auxiliary agent in the photosensitive resin composition is to improve the adhesion between the resin film and the substrate. The auxiliary agent is an adhesion promoter, wherein the adhesion promoter is preferably a silane coupling agent, including a combination of one or more of p-phenyltrimethoxysilane, trimethoxyaminopropyl silane, trimethoxyepoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxymercaptopropyl silane, trimethoxyepoxycyclohexylethylsilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.

[0063] The preferred content of the adhesion promoter is 0.01 to 15 parts by mass, such as 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts by mass relative to 100 parts by mass of the resin precursor. By controlling the range, the adhesion between the substrate and the cured film obtained by curing the resin composition can be improved.

[0064] Furthermore, the solvent in the photosensitive resin composition can include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, etc.; tetrahydrofuran, dioxane, propylene glycol, etc. Ether solvents such as monomethyl ether and propylene glycol monoethyl ether; ketone solvents such as acetone, methyl ethyl ketone, and diisobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate; alcohol solvents such as diacetone alcohol and 3-methyl-3-methoxybutanol; aromatic hydrocarbon solvents such as toluene and xylene, etc. The solvent can be one kind or a combination of multiple kinds.

[0065] Regarding the content of the solvent, in order to dissolve the photosensitive resin composition, the solvent is 70 to 1800 parts by mass, for example, 70 parts by mass, 100 parts by mass, 200 parts by mass, 300 parts by mass, 400 parts by mass, 500 parts by mass, 600 parts by mass, 700 parts by mass, 800 parts by mass, 900 parts by mass, 1000 parts by mass, 1100 parts by mass, 1200 parts by mass, 1300 parts by mass, 1400 parts by mass, 1500 parts by mass, 1600 parts by mass, 1700 parts by mass, 1800 parts by mass, to form a coating having a film thickness of 1 μm or more, the solvent is preferably 100 to 1500 parts by mass.

[0066] Further, the method for producing the resin composition of the present invention is described. For example, the resin composition can be obtained by mixing and dissolving the above-mentioned resin precursor, photosensitizer, auxiliary agent and solvent. As the method of dissolving, heating and stirring can be cited. In the case of heating, the heating temperature is preferably set within the range that does not damage the performance of the resin composition, usually room temperature to 80°C. In addition, there is no particular restriction on the dissolution order of each component. In the case of stirring, the rotation speed is preferably set within the range that does not damage the performance of the resin composition, usually 200rpm to 2000rpm. In the case of stirring, heating can also be performed as needed, usually room temperature to 80°C.

[0067] Further, the viscosity of the resin composition is preferably 2 to 5000 mPa·s, such as 2 mPa·s, 50 mPa·s, 100 mPa·s, 500 mPa·s, 1000 mPa·s, 2000 mPa·s, 3000 mPa·s, 4000 mPa·s, and 5000 mPa·s. By adjusting the solid content concentration so that the viscosity is above 2 mPa·s, it is easy to obtain the desired film thickness. On the other hand, when the viscosity is below 5000 mPa·s, it is easy to obtain a coating film with high coating uniformity. A resin composition with such a viscosity can be easily obtained, for example, by making the solid content concentration 5 to 60% by mass.

[0068] In order to ensure the purity of the photosensitive resin composition, the photosensitive resin composition may be filtered using a filtering device such as filter paper, filter membrane, filter, etc. The filtering method is not particularly limited, but preferably, pressure filtration is performed using a filter with a pore size of 0.2 to 5 μm.

[0069] A fifth aspect of the present invention provides a photosensitive resin composition cured film, wherein the cured film is obtained by curing the photosensitive resin composition of the present invention.

[0070] Furthermore, the method for preparing the cured film may include the following steps: coating the photosensitive resin composition on a substrate, drying to form a photosensitive resin layer, and then exposing, developing, and heating the photosensitive resin layer to form a cured film.

[0071] As a method for coating the photosensitive resin composition on the substrate, spin coating, spray coating, roll coating, screen printing, or coating methods using a blade coater, a calender coater, a slit coater, a roll coater, a comma roll coater, a gravure coater, etc. can be cited. The coating film thickness varies depending on the coating method, the solid content of the photosensitive resin composition, the viscosity of the photosensitive resin composition, etc., and the film thickness after drying is preferably in the range of 0.5 to 100 μm.

[0072] The drying method can be an oven, a heating plate, an infrared heater, etc. The drying temperature and the drying time can be controlled within the range that allows the organic solvent to volatilize. It is preferred to appropriately set the photosensitive resin composition film to an uncured or semi-cured state. The specific drying temperature is preferably 40 to 120°C, and the drying time is preferably 1 to 60 minutes. Furthermore, staged heating can also be used, for example, heat treatment at 70°C, 80°C, and 90°C for 1 minute each.

[0073] The obtained photosensitive resin composition film is irradiated with chemical rays through a mask for exposure. Chemical rays used for exposure include ultraviolet rays, visible rays, electron rays, X-rays, etc. In the present invention, it is preferred to use i-rays (365nm), h-rays (405nm) or g-rays (436nm) of a mercury lamp.

[0074] When forming a pattern, the unexposed part is removed with a developer after exposure. As a developer, tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, 1,6-hexanediamine and other alkaline compound aqueous solutions are preferred. Depending on the circumstances, one or more polar solvents selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide and the like; alcohols such as methanol, ethanol, isopropanol; esters such as ethyl lactate and propylene glycol azomethyl ether acetate; compounds such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may also be added to these alkaline aqueous solutions.

[0075] The development can be carried out by spraying the above-mentioned developer on the film-attached surface of the substrate or immersing the film in the developer together with the substrate. Ultrasonic waves can also be applied while immersing the substrate in the developer. In addition, the developer can be sprayed on the film surface while rotating the substrate. The development time, development steps, and temperature of the developer are not limited, as long as the unexposed part can be removed. In order to process fine patterns or remove residues between patterns, it is preferred to further develop after removing the unexposed part.

[0076] After development, the surface may be rinsed with water, or an alcohol such as ethanol or isopropyl alcohol and ethyl lactate, propylene glycol monomethyl ether acetate, or the like may be added to water for rinsing.

[0077] In order to further improve the resolution and expand the development process range, a baking treatment may be performed before development. The baking treatment temperature is preferably 50 to 180° C., more preferably 60 to 120° C. The baking treatment time is preferably 5 s to 60 min.

[0078] From the viewpoint of reducing the solvent, solid content, water content, etc. of the photosensitive resin composition film remaining after pattern formation, it is preferably heated and dried at 60 to 200° C. after development. The heating and drying time is preferably 1 to 60 minutes.

[0079] The thickness of the cured film can be arbitrarily set, but is preferably 0.5 um to 100 um.

[0080] The photosensitive resin composition of the present invention is suitable for surface protection films of semiconductor elements, ultra-thin flexible circuit boards, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.

[0081] A sixth aspect of the present invention provides an electronic component or semiconductor device, wherein the electronic component or semiconductor device is used to bond multiple substrates or to bond a substrate to other components through a cured film of the photosensitive resin composition of the present invention. The cured film of the photosensitive resin composition can be prepared by directly coating the photosensitive resin composition as a raw material on a substrate.

[0082] When preparing a semiconductor device, the steps may include: coating a photosensitive resin composition on a semiconductor wafer having an image sensor element formed thereon to form a photosensitive resin composition film. Exposing and developing the photosensitive resin composition film, removing the resin film on the sensor portion, and retaining the resin film around the sensor to obtain a sensor wafer with a wiring pattern.

[0083] The present invention has the following beneficial effects:

[0084] The present invention provides a dianhydride monomer with a special structure, wherein the dianhydride structure contains a triazine group, which has the function of reducing the refractive index. When the triazine group is introduced into the molecular chain of a resin precursor, a photosensitive resin composition containing the resin precursor has a higher light transmittance during exposure, which can significantly improve the development resolution of the photosensitive resin composition, and can obtain a higher sensitivity, which can significantly improve the photolithographic performance of the photosensitive resin composition. Moreover, the ether bond contained in the dianhydride monomer can improve the flexibility, thereby improving the mechanical properties of the cured film of the photosensitive resin composition and the adhesion to the substrate. DETAILED DESCRIPTION

[0085] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the embodiments of the present invention will be described clearly and completely below. The described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the technical scheme of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention. If the specific conditions are not specified in the embodiments, they shall be carried out according to the conventional conditions or the conditions recommended by the manufacturer.

[0086] Furthermore, the weight average molecular weight Mw and number average molecular weight Mn of the photosensitive resin or the photosensitive resin composition precursor in the embodiment of the present invention can be easily measured in the form of polystyrene-converted values ​​by gel permeation chromatography (GPC).

[0087] Ingredients used in the following examples:

[0088] Solvent:

[0089] THF, tetrahydrofuran; NMP, N-methylpyrrolidone;

[0090] Raw materials for synthesizing dianhydride:

[0091]

[0092] 2,4-Dichloro-1,3,5-triazine 3,4-dimethylphenol

[0093]

[0094] 3-Fluoro-4,5-dimethylphenol 2-Fluoro-3,4-dimethylphenol

[0095]

[0096] 2-Fluoro-4,5-dimethylphenol 2-Methoxy-4,5-dimethylphenol

[0097]

[0098] 2-(2-Amino-1H-benzo[D]imidazol-1-yl)-4,5-dimethylphenol

[0099] Raw materials for synthetic resin precursors:

[0100] Dianhydride: Dianhydride containing triazine group (a-1, a-2, a-3, a-4, a-5), the structure of which is shown in the synthesis example;

[0101] ODPA, 4,4'-oxydiphthalic anhydride;

[0102] BPDA, 3,3',4,4'-biphenyltetracarboxylic dianhydride;

[0103] 6FDA, hexafluorodianhydride.

[0104] Diamine: BAHF, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane;

[0105] SiDA, 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

[0106] Capping agent: 3-aminophenol.

[0107] Esterification reagent: DMFDMA, N,N-dimethylformamide dimethyl acetal.

[0108] Ingredients for preparing the resin composition:

[0109] Photosensitizer: 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid quinone diazide compound, 4NT-350 (produced by Toyo Gosei Kogyo Co., Ltd., Japan).

[0110] Additive: KBM-1403 (p-phenylenedimethoxysilane, Shin-Etsu Chemical, Japan).

[0111] Synthesis of Dianhydride Monomers Containing Triazine Groups

[0112] Synthesis Example 1: Synthesis of Dianhydride Compound a-1

[0113] Add 150 ml of THF and 44.99 g (0.3 mol) of 2,4-dichloro-1,3,5-triazine to a four-necked reaction flask with stirring, stir and dissolve, then dissolve 73.30 g (0.6 mol) of 3,4-dimethylphenol in 160 ml of THF, then dropwise add to the above reaction flask, stir at -10°C to 0°C for 3 hours, take 77.544 g (0.6 mol) of N,N-diisopropylethylamine (DIPEA) as an HCl remover and add to the reaction solution, stir for 2 hours. Transfer the reaction solution to a separatory funnel, wash with 100 g of a 10 wt% sodium chloride aqueous solution, then extract with 100 g of carbon tetrachloride solvent, stand for stratification, separate the liquids to obtain the organic layer, repeat the above operation 3 times, dry the organic layer over 100 g of anhydrous MgSO4, filter, and concentrate the filtrate under reduced pressure to generate a white solid a1.

[0114] 25g of the above-mentioned a1 compound, 200ml of pyridine and 100ml of water were placed in a 1L three-necked flask equipped with a magnetic stirrer and a condenser, and heated to 110°C. At this temperature, KMnO4 powder (a total of 0.35mol, 55g) was added three times. After reflux for 3h, the hot reaction mixture was filtered to remove MnO2, and the filtrate was concentrated to 50g on a rotary evaporator. The concentrated filtrate was acidified with HCl to a pH of 2, and the solid compound was collected by recrystallization in pure water. The obtained solid compound was placed in a vacuum environment (0.03MPa) and gradually heated to 140°C, dehydrated for 24h to obtain the dianhydride compound a-1, whose structural formula is as follows:

[0115]

[0116] The NMR information of dianhydride compound a-1 is as follows:

[0117] 1 H NMR: δ: 7.58 (2H, dd, J = 7.9, 1.5 Hz), 7.67-7.87 (4H, 7.73 (dd, J= 7.9, 0.5 Hz), 7.82 (dd, J = 1.5, 0.5 Hz)), 8.43 (1H, s).

[0118] Synthesis Example 2: Synthesis of Dianhydride Compound a-2

[0119] The dianhydride compound a-2 was prepared in the same manner as in Synthesis Example 1, except that 73.30 g (0.6 mol) of 3,4-dimethylphenol was replaced with 84.09 g (0.6 mol) of 3-fluoro-4,5-dimethylphenol to obtain the dianhydride compound a-2, the structure of which is as follows:

[0120]

[0121] The NMR information of dianhydride compound a-2 is as follows:

[0122] 1 H NMR: δ: 7.68-7.83 (4H, 7.74 (d, J = 1.5 Hz), 7.78 (d, J = 1.5Hz)), 8.43 (1H, s).

[0123] Synthesis Example 3: Synthesis of Dianhydride Compound a-3

[0124] The dianhydride compound a-3 was prepared in the same manner as in Synthesis Example 1, except that 73.30 g (0.6 mol) of 3,4-dimethylphenol was replaced with 84.09 g (0.6 mol) of 2-fluoro-3,4-dimethylphenol to obtain the dianhydride compound a-3, the structure of which is as follows:

[0125]

[0126] The NMR information of dianhydride compound a-3 is as follows:

[0127] 1 H NMR: δ: 7.64 (2H, d, J = 7.9 Hz), 7.95 (2H, d, J = 7.9 Hz), 8.43 (1H, s).

[0128] Synthesis Example 4: Synthesis of Dianhydride Compound a-4

[0129] The dianhydride compound a-4 was prepared in the same manner as in Synthesis Example 1, except that 73.30 g (0.6 mol) of 3,4-dimethylphenol was replaced with 84.09 g (0.6 mol) of 2-fluoro-4,5-dimethylphenol to obtain the dianhydride compound a-4, the structure of which is as follows:

[0130]

[0131] The NMR information of dianhydride compound a-4 is as follows:

[0132] 1 H NMR: δ: 7.95~8.13 (4H, 8.00 (d, J = 0.5 Hz), 8.08 (d, J = 0.5Hz)), 8.43 (1H, s).

[0133] Synthesis Example 5: Synthesis of Dianhydride Compound a-5

[0134] The dianhydride compound a-5 was prepared in the same manner as in Synthesis Example 1, except that 73.30 g (0.6 mol) of 3,4-dimethylphenol was replaced with 91.314 g (0.6 mol) of 2-methoxy-4,5-dimethylphenol to obtain the dianhydride compound a-5, the structure of which is as follows:

[0135]

[0136] The NMR information of dianhydride compound a-5 is as follows:

[0137] 1 H NMR: δ: 3.79 (6H, s), 7.86 (2H, d,J = 0.5 Hz), 7.98 (2H, d,J = 0.5Hz), 8.43 (1H, s).

[0138] Synthesis Example 6: Synthesis of Dianhydride Compound a-6

[0139] 5.066 g (0.02 mol) of 2-(2-amino-1H-benzo[D]imidazol-1-yl)-4,5-dimethylphenol was added to a 500 ml three-necked flask, and 50 g of ethanol and 50 g of water were added. Then, 2.18 g (0.01 mol) of di-tert-butyl dicarbonate and 0.01 g of triethylamine as a catalyst were added. The mixture was stirred at room temperature for 4 h, and then filtered, rinsed with 100 g of ethanol for 3 times, and dried under vacuum at 50° C. to obtain the following amino-protected compound K, whose structure is as follows:

[0140]

[0141] The dianhydride compound a-6 was prepared in the same manner as in Synthesis Example 1, except that 73.30 g (0.6 mol) of 3,4-dimethylphenol was replaced with 222.708 g (0.6 mol) of compound K to obtain the dianhydride compound a-6, the structure of which is as follows:

[0142]

[0143] The NMR information of dianhydride compound a-6 is as follows:

[0144] 1 H NMR: δ 1.35-1.46 (18H, 1.40 (s), 1.41 (s)), 4.44 (1H, dd, J = 8.1,3.4 Hz), 4.79 (1H, dd, J = 8.1, 3.8 Hz), 5.69-5.91 (2H, 5.76 (dd, J = 10.5,3.4 Hz), 5.84 (dd, J = 10.7, 3.8 Hz)), 6.54-6.69 (2H, 6.61 (dd, J = 10.5, 1.9Hz), 6.62 (dd, J = 10.7, 1.9 Hz)), 7.19 (1H, ddd, J = 8.1, 7.6, 1.6 Hz), 7.43(1H, ddd, J = 7.9, 7.6, 1.3 Hz), 7.82 (1H, ddd, J = 8.1, 1.3, 0.4 Hz), 7.89-8.06 (2H, 7.94 (d, J = 0.5 Hz), 8.00 (ddd, J = 7.9, 1.6, 0.4 Hz)), 8.14 (1H,d, J = 0.5 Hz), 8.44 (1H, s), 8.54-8.71 (2H, 8.59 (d, J = 0.5 Hz), 8.65 (d, J = 0.5 Hz)).

[0145] Synthesis of resin precursor and preparation of photosensitive resin composition

[0146] Example 1

[0147] Under nitrogen flow, add 40.50g (0.1 mol) of dianhydride compound a-1 and 100g of N-methylpyrrolidone (NMP) to a 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, and stir and dissolve at room temperature to obtain a dianhydride solution. Take another three-necked flask equipped with a stirrer, add 29.30g (0.08mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2.48g (0.01mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 100g of N-methylpyrrolidone, and stir and dissolve to obtain a diamine solution. Add the diamine solution dropwise to the above dianhydride solution, react at room temperature for 1h after the addition is complete, and then react at 50℃ for 2h. After the reaction is completed, add 2.18g (0.02mol) of 3-aminophenol as a capping agent and react at 50℃ for 2h. Then, a solution of 11.915 g of N,N-dimethylformamide dimethyl acetal diluted with 25 g of NMP was added dropwise, and the mixture was reacted at 50°C for 3 h. After the reaction was completed, the reaction solution was poured into 3 L of deionized water, and a polymer was precipitated to obtain a white precipitate. After filtering, the mixture was washed three times with deionized water, placed in a vacuum oven, and dried at 50°C for 72 h to obtain polyamide ester A-1. The number average molecular weight was determined to be 14684, and the weight average molecular weight was 19705.

[0148] 10.0 g of the polyamide ester A-1 obtained above and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid quinone diazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After fully dissolved, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition Q-1.

[0149] Example 2

[0150] Polyamide ester A-2 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 44.41 g (0.1 mol) of dianhydride monomer a-2. The number average molecular weight and weight average molecular weight of polyamide ester A-2 were measured to be 14654 and 19769, respectively.

[0151] A photosensitive resin composition Q-2 was prepared in the same manner as in Example 1, except that 10.0 g of the polyamide ester A-1 was replaced with 10.0 g of the polyamide ester A-2 obtained above.

[0152] Example 3

[0153] Polyamide ester A-3 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 44.41 g (0.1 mol) of dianhydride monomer a-3. The number average molecular weight and weight average molecular weight of polyamide ester A-3 were measured to be 14083 and 18753, respectively.

[0154] A photosensitive resin composition Q-3 was prepared in the same manner as in Example 1, except that 10.0 g of the polyamide ester A-1 was replaced with 10.0 g of the polyamide ester A-3 obtained above.

[0155] Example 4

[0156] Polyamide ester A-4 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 44.41 g (0.1 mol) of dianhydride monomer a-4. The number average molecular weight and weight average molecular weight of polyamide ester A-4 were measured to be 14487 and 19527, respectively.

[0157] A photosensitive resin composition Q-4 was prepared in the same manner as in Example 1, except that 10.0 g of the polyamide ester A-1 was replaced with 10.0 g of the polyamide ester A-4 obtained above.

[0158] Example 5

[0159] Polyamide ester A-5 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 46.50 g (0.1 mol) of dianhydride monomer a-5. The number average molecular weight and weight average molecular weight of polyamide ester A-5 were measured to be 14537 and 19668, respectively.

[0160] A photosensitive resin composition Q-5 was prepared in the same manner as in Example 1, except that 10.0 g of the polyamide ester A-1 was replaced with 10.0 g of the polyamide ester A-5 obtained above.

[0161] Example 6

[0162] Polyamide ester A-6 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 90.12 g (0.1 mol) of dianhydride monomer a-6. The number average molecular weight and weight average molecular weight of polyamide ester A-6 were measured to be 15379 and 19961, respectively.

[0163] A photosensitive resin composition Q-6 was prepared in the same manner as in Example 1, except that 10.0 g of the polyamide ester A-1 was replaced with 10.0 g of the polyamide ester A-6 obtained above.

[0164] Comparative Example 1

[0165] Polyamide ester A-7 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride. The number average molecular weight of polyamide ester A-7 was 14276, and the weight average molecular weight was 19681.

[0166] 10.0 g of the polyamide ester A-7 obtained above and 20.0 g of N-methylpyrrolidone (NMP) solvent were added to a three-necked flask and stirred. After the resin was completely dissolved, 2.0 g of 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid quinone diazide compound 4NT-350 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 0.04 g of KBM-1403 (p-phenylenediamine trimethoxysilane, Shin-Etsu Chemical, Japan) were added. After fully dissolved, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition R-1.

[0167] Comparative Example 2

[0168] Polyamide ester A-8 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 29.42 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride. The number average molecular weight of polyamide ester A-8 was 13778, and the weight average molecular weight was 18524.

[0169] A photosensitive resin composition R-2 was prepared in the same manner as in Comparative Example 1, except that 10.0 g of the polyamide ester A-7 was replaced with 10.0 g of the polyamide ester A-8 obtained above.

[0170] Comparative Example 3

[0171] Polyamide ester A-9 was prepared in the same manner as in Example 1, except that 40.50 g (0.1 mol) of dianhydride monomer a-1 was replaced with 44.42 g (0.1 mol) of hexafluorodianhydride. The number average molecular weight and weight average molecular weight of polyamide ester A-9 were measured to be 14361 and 19286, respectively.

[0172] A photosensitive resin composition R-3 was prepared in the same manner as in Comparative Example 1, except that 10.0 g of the polyamide ester A-7 was replaced with 10.0 g of the polyamide ester A-9 obtained above.

[0173] The development resolution and cured film mechanical properties of the photosensitive resin compositions prepared in the above examples and comparative examples were tested as follows:

[0174] 1. Resolution test

[0175] The photosensitive resin composition samples of the above examples and comparative examples were coated on a 4-inch silicon wafer, and then soft-baked at 120°C for 3 minutes using a heating table to obtain a resin film with a thickness of 15 μm. The UV lamp (i and g line) was used with an exposure dose of 400 mJ / cm -2 , and then exposed through a mask. After exposure, spray development was performed using a 2.38% tetramethylammonium hydroxide developer for 180 seconds to remove the unexposed portion. The pattern was observed using an optical microscope (MX63-F, Olympus) at a magnification of 100 times, and the minimum size of the through-hole pattern was taken as the resolution.

[0176] 2. Tensile strength test

[0177] The photosensitive resin composition samples of the above embodiments and comparative examples were coated on a 4-inch silicon wafer, and then soft-baked at 120°C for 3 minutes using a heating table to obtain a resin film with a film thickness of 10 to 20 μm. The film was then placed in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. Specifically as follows: first, the temperature was raised to 170°C for 30 minutes of heat treatment, and then the temperature was raised to 350°C after 1 hour and continued to be heat treated for 1 hour, and finally a cured film was obtained. The silicon wafer with the cured film was placed in a hydrofluoric acid solution, and the silicon wafer was corroded and stripped to obtain a cured resin film. The obtained cured film resin film (film thickness of 10 to 20 μm) was cut into sample strips with a length of 40 mm and a width of 5 mm. The sample strips were subjected to a tensile strength test using TA's TMA 450, with a temperature of 150°C, a tensile range of 0-18N, and a rate of 3N / min.

[0178] 3. Adhesion test between cured film and substrate

[0179] The photosensitive resin composition samples of the above-mentioned embodiments and comparative examples were uniformly coated on a copper substrate using a coating machine, and then placed on a heating table at 120°C for 3 minutes for soft baking to obtain a resin film with a film thickness of 10-20 um. The resin film was engraved with a grid of 10 rows × 10 columns using a gridding machine (BYK-Gardner A-5125), and then the film was placed in a vacuum oxygen-free oven (MOLZK-32D1) for heat treatment: heat treatment at 170°C for 30 minutes, then the temperature was raised to 350°C after 1 hour, and treated at 350°C for 1 hour to finally obtain a cured film. The cured film was placed in a PCT test chamber for a 200-hour PCT aging test (121°C, 2 atmospheres of saturated steam; PCT-30 of Dongguan Hongjin Technology). After the PCT test, a peeling test was performed using tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 Cross-cutting test for paint and varnish films. The number of cross-cutting strips was recorded as the peeling condition after the PCT test.

[0180] In the adhesive peeling test, the number of peeled pieces was considered "best" when it was less than 5, "good" when it was less than 10, "slightly good" when it was less than 30, and "poor" when it was 30 or more.

[0181] 4. Test Results

[0182]

[0183] It can be seen from the results of Examples 1 to 6 that the resolution, tensile strength and adhesion to the substrate of the photosensitive resin composition obtained by introducing the dianhydride compound containing a triazine group in the main chain are significantly better than those of the photosensitive resin composition in the comparative example.

[0184] From the results of Comparative Examples 1 to 3, it can be seen that the photosensitive resin composition synthesized from the dianhydride compound without triazine group in the main chain has low resolution, low tensile strength, and poor adhesion to the substrate after PCT-200hr. Among them, the photosensitive resin composition synthesized from the dianhydride compound containing ether bond in Comparative Example 1 has better tensile strength and adhesion to the substrate than Comparative Examples 2 and 3, but its resolution is very poor; the photosensitive resin composition synthesized from the dianhydride containing hexafluoro group in Comparative Example 3 has better resolution, but its tensile strength and adhesion to the substrate are very poor.

Claims

1. A dianhydride compound containing a triazine group, characterized in that: It has the structural formula shown in the following formula (1): ； In formula (1), R1 is selected from a hydrogen atom, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, .

2. The dianhydride compound containing a triazine group according to claim 1, characterized in that: In formula (1), R1 is selected from hydrogen atom, fluorine atom, methoxyl group, .

3. The method for preparing the dianhydride compound containing a triazine group according to claim 1, characterized in that The following steps are involved: (i) 2,4-dichloro-1,3,5-triazine is reacted with a dimethylphenol derivative to obtain an intermediate represented by formula a1. The reaction formula is as follows: (ii) Carboxylating the methyl group in the intermediate of formula a1 to obtain the intermediate of formula a2. The reaction formula is as follows: (iii) Dehydrating and cyclizing the carboxyl group in the intermediate represented by formula a2 to obtain a dianhydride compound containing a triazine group represented by formula (1), and the reaction formula is as follows: ； In formula a1, formula a2 and formula (1), the definition of R1 is the same as that in claim 1.

4. The preparation method according to claim 3, characterized in that: In step (i), at least one of the following conditions is included: (i1), the molar ratio of 2,4-dichloro-1,3,5-triazine to the dimethylphenol derivative is 1:1.5-2.5; (i2), the reaction temperature is -20°C to 5°C; In step (ii), at least one of the following conditions is included: (ii1), the reaction is carried out in the presence of water, pyridine and potassium permanganate; (ii2), the reaction temperature is 105-115°C; In step (iii), at least one of the following conditions is included: (iii1) The reaction is carried out in a vacuum environment; (iii2) The reaction temperature is 100-180°C.

5. The preparation method according to claim 4, characterized in that: In step (i), the reaction temperature is -10°C to 0°C.

6. The preparation method according to claim 4, characterized in that: In step (iii), the reaction temperature is 120-160°C.

7. The preparation method according to claim 4, characterized in that: In step (iii), the reaction temperature is 140-150°C.

8. A resin precursor, characterized in that: The resin precursor is obtained by reacting at least one dianhydride monomer and two or more diamine monomers, wherein the dianhydride monomer comprises at least one dianhydride compound containing a triazine group according to claim 1.

9. The resin precursor according to claim 8, characterized in that: The total amount of the triazine group-containing dianhydride compound according to claim 1 is 70% or more of the total molar amount of the dianhydride monomer.

10. The resin precursor according to claim 8, characterized in that: The resin precursor is at least one of polyamic acid, polyamide ester and polyimide.

11. The resin precursor according to claim 8, characterized in that: It has the structural formula shown in the following formula (2) and / or (3): In formula (2) and (3), X1 and X2 are introduced from dianhydride monomers, the dianhydride monomers contain at least one dianhydride compound containing a triazine group according to claim 1, R2 is a hydrogen atom or an alkyl group, when R2 is an alkyl group, it is introduced through an esterification agent; Y1, Y2 and Y3 are introduced from diamine monomers; m and n are both integers of 10 to 100,000.

12. The resin precursor according to any one of claims 8 to 11, characterized in that: The dianhydride monomer further contains at least one of the following compounds: 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,3,3',4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-(hexafluoroisopropylene)diphthalic anhydride; the diamine monomer is selected from at least one of hydroxyl-containing diamines, carboxyl-containing diamines, sulfonic acid-containing diamines, thiol-containing diamines, aromatic diamines, alicyclic diamines and aliphatic diamines with a siloxane structure.

13. The resin precursor according to claim 12, characterized in that: The aliphatic diamine having a siloxane structure accounts for 1 to 15% of the total molar amount of the diamine monomer.

14. A photosensitive resin composition, characterized in that: The invention comprises the resin precursor according to any one of claims 8 to 13.

15. The photosensitive resin composition according to claim 14, characterized in that: The photosensitive resin composition further comprises a photosensitizer, an auxiliary agent and a solvent.

16. The photosensitive resin composition according to claim 15, characterized in that: The photosensitizer is a photoacid generator; the auxiliary agent is a silane coupling agent.

17. The photosensitive resin composition according to claim 16, characterized in that: The photosensitizer is a quinonediazide compound; the auxiliary agent is at least one of p-phenylenediaminetrimethoxysilane, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxymercaptopropylsilane, trimethoxyepoxycyclohexylethylsilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

18. The photosensitive resin composition according to claim 14, characterized in that: The content of the photosensitizer is 3 to 80 parts by mass based on 100 parts by mass of the resin precursor.

19. The photosensitive resin composition according to claim 18, characterized in that: The content of the photosensitizer is 10 to 50 parts by mass based on 100 parts by mass of the resin precursor.

20. The photosensitive resin composition according to claim 14, characterized in that: The content of the auxiliary agent is 0.01 to 15 parts by mass based on 100 parts by mass of the resin precursor.

21. The photosensitive resin composition according to claim 14, characterized in that: The amount of the solvent is 70 to 1800 parts by mass based on 100 parts by mass of the resin precursor.

22. A photosensitive resin composition cured film, characterized in that: Obtained by curing the photosensitive resin composition according to any one of claims 14 to 21.

23. The cured film of the photosensitive resin composition according to claim 22, wherein: The photosensitive resin composition according to any one of claims 14 to 21 is coated on a substrate, and then dried to form a photosensitive resin layer, and then the photosensitive resin layer is exposed, developed, and heated to form a cured film.

24. Use of the cured film of the photosensitive resin composition according to claim 22 or 23 as a surface protective film of a semiconductor element, an ultra-thin flexible circuit board, an interlayer insulating film of a semiconductor element, or an insulating layer of an organic electroluminescent element.

25. An electronic component or semiconductor device, characterized in that: The electronic component or semiconductor device is formed by bonding a plurality of substrates or bonding a substrate to another member via the cured film of the photosensitive resin composition according to claim 22 or 23.

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