Photosensitive compound, resin composition, cured film, and electronic device

Abstract

According to the photosensitive compound, the resin composition, the cured film and the electronic device provided by the invention, the benzo-aza polycyclic group is introduced to the ester group of the o-nitrobenzyl formate, so that the photosensitive compound can be photolyzed under the action of optical radiation to generate the organic alkali; and the organic alkali molecules can promote the polyamic acid or polyamic acid ester to carry out imidization reaction. The alkali production efficiency of the photosensitive compound is high, the catalytic effect is good, the patterning effect of the resin composition can be improved, a pattern formed by the resin composition has good pattern resolution and film retention rate, and a cured film prepared from the resin composition can effectively improve the reliability of device packaging.

Description

Technical Field

[0001] The present application relates to the technical field of polymer films, and in particular, to photosensitive compounds, resin compositions, cured films and electronic devices. Background Art

[0002] Polyimide is a type of polymer material with excellent comprehensive properties. It has been widely used in the field of microelectronics and semiconductor packaging due to its excellent thermal stability, mechanical properties and dielectric properties.

[0003] In practical applications, polyamic acid or polyamic acid ester glue needs to be heated and cured to form a film to complete the high-temperature imidization reaction, and the heating temperature is generally above 350°C. With the continuous development of advanced packaging, the wafer size is larger and the thickness is thinner. During the high-temperature imidization reaction, the wafer may warp due to stress, and the higher curing temperature required by the common polyimide precursors polyamic acid (PAA) or polyamic acid ester (PAE) often damages semiconductor devices.

[0004] Traditional photobase generators (PBG) and photoacid generators are important components of chemically amplified photoresists. At present, traditional photobase generators have poor light absorption, low sensitivity, and low base production efficiency during the resin patterning process, resulting in poor resolution and low film retention rate during the patterning process of thick coatings, which in turn causes the coatings to be easily warped and deformed during the high-temperature imidization reaction, reducing the reliability of device packaging. Summary of the invention

[0005] In view of this, the present application proposes a photosensitive compound, a resin composition, a cured film and an electronic device. The photosensitive compound can be photolyzed under light radiation to produce an organic base. The organic base molecules can promote the imidization reaction of polyamic acid or polyamic acid ester. The photosensitive compound in the present application has a high base production efficiency and a good catalytic effect, which can improve the patterning effect of the resin composition. The pattern formed by the resin composition has good pattern resolution and film retention rate. The cured film made therefrom can effectively improve the reliability of device packaging.

[0006] In a first aspect, the present application provides a photosensitive compound, the photosensitive compound comprising a compound having a structure shown in Formula I, and the photosensitive compound can be photolyzed under light radiation to produce an organic base;

[0007]

[0008] In Formula I, M is an organic base structural unit having Formula I-1;

[0009] R1, R2 and R3 are each independently selected from a hydrogen atom, an electron withdrawing group or an electron pushing group; m is selected from a natural number of 2 to 10.

[0010] The photosensitive compound provided in the embodiment of the present application can red-shift the absorption peak to around 365nm by introducing a benzazapyridine polycyclic group into the ester group of the o-nitrobenzyl formate, so that the light absorption is stronger, and the R1 in the o-nitrobenzyl formate group and the R2 in the benzazapyridine polycyclic group can enhance the conjugation degree of the π electrons, so that the transition probability between the ground state and the singlet excited state is increased, thereby increasing the photosensitivity of the photobase generator near 365nm. The photosensitive compound has high sensitivity and high base production efficiency, and can be photolyzed to produce organic bases under the action of light radiation. The organic base contains active groups such as primary amine groups and secondary amine groups. These active groups have good catalytic effects, which can improve the patterning effect of the coating film, so that the pattern has good resolution and film retention rate, and the cured film made thereof can effectively improve the reliability of device packaging.

[0011] In some embodiments, the aziridine polycyclic group in the organic base structural unit represented by Formula I-1 is selected from at least one of aziridine, azetidinyl, aziridine, aziridine, and azepanyl.

[0012] In some embodiments, the number of substituents R2 on the benzene ring in the organic base structural unit represented by Formula I-1 is 1 to 3; when the number of R2 is 2 or 3, the substituents R2 may be the same or different.

[0013] In some embodiments, the photosensitive compound can be photolyzed under light radiation to generate an organic base having a structural formula selected from any one of the following:

[0014]

[0015] Wherein, R2 is selected from a hydrogen atom, an electron withdrawing group or an electron pushing group.

[0016] In some embodiments, the electron-withdrawing group is selected from at least one of a nitro group, a halogen atom, a cyano group, a sulfonic acid group, an acyl group, and a carboxyl group; and / or the electron-pushing group is selected from at least one of an amine group, a hydroxyl group, an alkoxy group, an amide group, an acyloxy group, and an alkyl group.

[0017] It can be understood that the introduction of electron-withdrawing groups or electron-pushing groups can enhance the conjugation degree of π electrons, red-shift the absorption peak to around 365nm, make the light absorption stronger, increase the transition probability between the ground state and the singlet excited state, and thus increase the photosensitivity of the photobase generator near 365nm. Preferably, R2 is selected from a hydrogen atom or an electron-pushing group.

[0018] In some embodiments, the photosensitive compound is selected from at least one of the compounds of the following structural formulas:

[0019]

[0020] In a second aspect, the present application further provides a resin composition, which comprises a resin or a resin precursor and the photosensitive compound according to the first aspect.

[0021] In the resin composition, the photosensitive compound can be used as a photobase generator. The resin composition of the present application can be a negative resin composition. After the negative resin composition is exposed and developed, the unexposed part is washed away and the exposed part is retained. The patterning principle of the negative resin composition of the present application embodiment is: the photobase generator is irradiated by a light source to generate organic base molecules. During the subsequent heat treatment process, the generated organic base molecules continuously catalyze the cross-linking agent to cross-link, or the cross-linking agent and the polymer resin to cross-link, resulting in an obvious solubility difference between the exposed area and the unexposed area of ​​the polymer resin in the developer, that is, the solubility of the exposed area drops sharply due to cross-linking, while the unexposed area still maintains good solubility, and finally the unexposed area is washed away, and the exposed area is retained, thereby displaying a pattern.

[0022] In some embodiments, the resin comprises a polymer composed of repeating units shown in Formula II;

[0023]

[0024] In formula II, R4 is selected from a tetravalent aromatic organic group, R5 and R6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic hydrocarbon group or a monovalent organic group having a carbon-carbon unsaturated double bond; R7 is selected from a divalent aromatic organic group or a divalent aliphatic organic group, and n is selected from a natural number greater than or equal to 3.

[0025] In some embodiments, the R4 is selected from a tetravalent aromatic hydrocarbon group or a tetravalent aromatic heterocyclic group; and the R7 is selected from an aromatic hydrocarbon group or a cyclic aliphatic group.

[0026] In some embodiments, based on 100% of the mass of the resin composition, the mass of the polymer composed of the repeating units represented by Formula II accounts for 1% to 40%.

[0027] In some embodiments, the weight average molecular weight of the polymer composed of the repeating units represented by Formula II is 5,000 to 100,000; preferably, the weight average molecular weight of the polymer is 10,000 to 80,000.

[0028] In some embodiments, based on 100% of the mass of the resin composition, the mass of the photosensitive compound accounts for 0.1% to 10%, and preferably, the mass of the photosensitive compound accounts for 5% to 10%.

[0029] In some embodiments, the organic base generated by the photolysis of the photosensitive compound under light radiation is a compound having a primary amine or a secondary amine;

[0030] In some embodiments, the solid content of the resin composition is 1% to 50%.

[0031] In some embodiments, the resin composition further includes an organic solvent, and the organic solvent may be one or more of ester, ketone, ether or amide organic solvents.

[0032] In some embodiments, in the polymer composed of the repeating units shown in Formula II, R4 is selected from any one of the following structures:

[0033]

[0034] Wherein, A is selected from an oxygen atom, a sulfur atom or a branched carbon atom, and B and C are each independently selected from a divalent organic group or a single bond bonded to a benzene ring and not conjugated.

[0035] In some embodiments, in the polymer composed of the repeating units shown in Formula II, R4 is selected from any one of the following structures:

[0036]

[0037] In some embodiments, in the polymer composed of the repeating units shown in Formula II, R7 is selected from any one of the following structures:

[0038]

[0039] In some embodiments, the exposure amount required to act on the resin composition when patterning is performed using the resin composition is 600 mJ / cm 2 ~3000mJ / cm 2 .

[0040] In a third aspect, the present application provides a cured film, wherein the cured film is prepared according to the resin composition described in the second aspect.

[0041] In a fourth aspect, the present application provides an electronic device, wherein the electronic device comprises a cured film, or the electronic device comprises a cured film formed by curing a resin composition comprising the photosensitive compound.

[0042] In some embodiments, the cured film serves as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarization layer, a shielding layer, or a rewiring layer in the electronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1a is the ultraviolet absorption spectrum of Example 1 of the present application;

[0044] Figure 1b This is the ultraviolet absorption spectrum of Comparative Example 1 of the present application;

[0045] Figure 2 It is a comparison diagram of patterns formed by the coating films formed by the resin compositions of Example 1-1 and Comparative Example 1-1 under the same conditions;

[0046] Figure 3 It is a comparison diagram of patterns formed by the coating films formed by the resin compositions of Example 2-1 and Comparative Example 1-2 under the same conditions;

[0047] Figure 4 The circular hole pattern formed after the resin composition provided in Example 1-1 is developed for 1 minute;

[0048] Figure 5 The circular hole pattern formed after the resin composition provided in Example 1-2 is developed for 4 minutes;

[0049] Figure 6 A line pattern formed by the resin composition provided in Example 3-1;

[0050] Figure 7 A groove pattern formed by the resin composition provided in Example 3-1;

[0051] Figure 8 A polygonal pattern formed by the resin composition provided in Example 4-1;

[0052] Fig. 9 Another polygonal pattern formed by the resin composition provided in Example 4-1,

[0053] Fig.10 This is a pattern formed by the resin composition provided in Example 8-1. DETAILED DESCRIPTION

[0054] The technical solution provided by the present invention is further described below in conjunction with specific embodiments and comparative examples, but the present application is not limited to the following embodiments.

[0055] Traditional photobase generators (PBG) and photoacid generators are important components of chemically amplified photoresists. Photobase generators can generate alkaline groups under light radiation to catalyze the imidization reaction of polyamic acid or polyamic acid esters. The imidization temperature can be reduced to below 250°C, and it can effectively avoid the potential corrosion problem of strong acidic substances on integrated circuit devices. Therefore, it has become one of the effective ways to prepare polyimide.

[0056] At present, traditional photobase generators have poor light absorption, low sensitivity, and low base production efficiency, which results in poor resolution and low film retention rate during patterning of thick coatings, which in turn causes the coatings to easily warp and deform during the high-temperature imidization reaction, reducing the reliability of device packaging.

[0057] The present application provides a photosensitive compound, characterized in that the photosensitive compound includes a compound having a structure shown in Formula I, and the photosensitive compound can be photolyzed to produce an organic base under the action of light radiation;

[0058]

[0059] In Formula I, M is an organic base structural unit having Formula I-1;

[0060] R1, R2 and R3 are each independently selected from a hydrogen atom, an electron withdrawing group or an electron pushing group; m is selected from a natural number of 2 to 10.

[0061] The photosensitive compound provided in the embodiment of the present application can red-shift the absorption peak to around 365nm by introducing a benzazapyridine polycyclic group into the ester group of the o-nitrobenzyl formate, so that the light absorption is stronger, and the R5 in the o-nitrobenzyl formate group and the R7 in the benzazapyridine polycyclic group can enhance the conjugation degree of the π electrons, so that the transition probability between the ground state and the singlet excited state increases, thereby increasing the photosensitivity of the photo-induced base generator near 365nm. The photosensitive compound has high sensitivity and high base production efficiency, and can be photolyzed to produce organic bases under the action of light radiation. The organic base contains active groups such as primary amine groups and secondary amine groups. The active groups participate in the imidization reaction of polyamic acid in a nucleophilic manner, and the polyamic acid is cured and cross-linked to form polyimide; these active groups have good catalytic effects, which can improve the patterning effect of the coating, so that the pattern has good resolution and film retention rate, and the cured film made thereof can effectively improve the reliability of device packaging.

[0062] In other embodiments, an organic base can also be directly added to the resin composition, but this low-temperature organic base catalyst is difficult to directly realize photolithography, and a photosensitizer needs to be added; and the direct addition of an organic base will easily lead to a decrease in the stability of the resin composition glue, thereby causing the resin to be coated and formed into a film. The adhesion of the interface with copper and the like decreases. In the present application, a photosensitive compound is added as a photo-induced base generator, and the resin composition has strong glue stability when stored in a dark state, and can produce an organic base after a small dose of exposure, with a high base production efficiency. Under the catalytic action of the organic base, the curing temperature of the imidization of the polyamic acid can be reduced, and direct photolithography can be achieved, and the formed pattern is clear and the film retention rate is high.

[0063] In some embodiments, the nitrogen-polycyclic group in the organic base structural unit shown in Formula I-1 is selected from at least one of aziridine, azetidinyl, aziridine, aziridine, and azepanyl. It can be understood that the nitrogen-polycyclic group in the organic base structural unit can generate active groups containing primary amine groups, secondary amine groups, etc. These active groups have good catalytic effects, can improve the patterning effect of the coating film, and make the pattern have good resolution and film retention rate. The cured film made therefrom can effectively improve the reliability of device packaging.

[0064] In some embodiments, the number of substituents R2 on the benzene ring in the organic base structural unit of formula I-1 is 1 to 3; when the number of R2 is 2 or 3, the substituents R2 may be the same or different. Considering the difficulty and cost of the synthesis process, the number of R7 substituents on the benzene ring in the organic base structural unit is 1.

[0065] In some embodiments, the electron-withdrawing group is selected from at least one of a nitro group (-NO2), a halogen atom, a cyano group (-CN), a sulfonic acid group (-SO3H), an acyl group (-COR), and a carboxyl group (-COOH).

[0066] In some embodiments, the electron-pushing group is selected from at least one of an amine group (-NH2), a hydroxyl group (-OH), an alkoxy group (-OR), an amide group (-NHCOR), an acyloxy group (-OCOR), and an alkyl group. Specifically, in Formula I, R1 and R2 are each independently selected from at least one of a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a hydroxyl group, and an amine group. Preferably, R1 is selected from an electron-pushing group.

[0067] For example, when the electron-pushing group is selected from an alkyl group, it may be a methane group, an ethane group, a propane group, a butane group, etc., and the hydrogen atoms on the alkyl group may be substituted or unsubstituted.

[0068] It can be understood that the electron withdrawing group and the electron pushing group can effectively adjust the electron cloud density of the benzene ring. The introduction of the electron pushing group can enhance the degree of π electron conjugation, increase the transition probability between the ground state and the singlet excited state, and give the photobase generator the characteristics of adjusting alkali solubility, absorbance and photosensitivity. The number of substituents represented by R2 in Formula I is 1, 2 or 3. Preferably, the number of substituents represented by R2 in Formula I is 1 or 2.

[0069] In some embodiments, the photosensitive compound can be photolyzed under light radiation to generate an organic base having a structural formula selected from any one of the following:

[0070]

[0071] Wherein, R2 is selected from a hydrogen atom, an electron withdrawing group or an electron pushing group, preferably, R2 is selected from a hydrogen atom or an electron pushing group.

[0072] In some embodiments, the photosensitive compound is selected from at least one of the compounds of the following structural formulas:

[0073]

[0074] In a second aspect, the present application further provides a resin composition, which comprises a resin or a resin precursor and the photosensitive compound according to the first aspect.

[0075] In the resin composition, the photosensitive compound can be used as a photobase generator. The resin composition of the present application can be a negative resin composition. After the negative resin composition is exposed and developed, the unexposed part is washed away, and the exposed part is retained. The patterning principle of the negative resin composition of the present application embodiment is: the photobase generator is irradiated by a light source to generate organic base molecules. During the subsequent heat treatment process, the generated organic base molecules continuously catalyze the cross-linking agent to cross-link, or the cross-linking agent and the polymer resin to cross-link, resulting in an obvious solubility difference between the exposed area and the unexposed area of ​​the polymer resin in the developer, that is, the solubility of the exposed area drops sharply due to cross-linking, while the unexposed area still maintains good solubility, and finally the unexposed area is washed away, and the exposed area is retained, thereby displaying a pattern.

[0076] In some embodiments, the resin comprises a polymer composed of repeating units shown in Formula II;

[0077]

[0078] In formula II, R4 is selected from a tetravalent aromatic organic group, R5 and R6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic hydrocarbon group or a monovalent organic group having a carbon-carbon unsaturated double bond; R7 is selected from a divalent aromatic organic group or a divalent aliphatic organic group, and n is selected from a natural number greater than or equal to 3.

[0079] In some embodiments, the R4 is selected from a tetravalent aromatic hydrocarbon group or a tetravalent aromatic heterocyclic group; and the R7 is selected from an aromatic hydrocarbon group or a cyclic aliphatic group.

[0080] In some embodiments, the R4 is selected from a tetravalent aromatic hydrocarbon group or a tetravalent aromatic heterocyclic group. Specifically, the group may be a group of the following structural formula:

[0081]

[0082] Wherein, A is selected from an oxygen atom, a sulfur atom or a branched carbon atom, and B and C are each independently selected from a divalent organic group or a single bond bonded to a benzene ring and not conjugated.

[0083] In some other embodiments, R4 is selected from the group of the following structural formula:

[0084]

[0085] In some embodiments, in the polymer composed of the repeating units represented by Formula II, R2 is selected from an aromatic hydrocarbon group or a cyclic aliphatic group.

[0086] In some embodiments, R7 is selected from any one of the following structures,

[0087]

[0088] In the actual preparation process, the dianhydride monomer and the diamine monomer can be subjected to a condensation polymerization reaction, followed by a precipitation treatment to obtain a polyamic acid solution.

[0089] In some feasible embodiments, the dianhydride monomer can be specifically an aromatic dianhydride monomer or an aliphatic dianhydride monomer. Aromatic tetracarboxylic dianhydride pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride, aromatic dianhydride monomers can be exemplarily pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropene The monomers include 1,2,3,4-dicarboxyphenyl tetracarboxylic acid, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, and 2,3,5,6-pyridinetetracarboxylic acid; the aliphatic dianhydride monomers may be exemplarily butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, etc., and may also be other aromatic tetracarboxylic acids or aliphatic tetracarboxylic acids.

[0090] The above-mentioned aromatic tetracarboxylic dianhydride monomer can be used directly, or can be used in the form of derivatives such as anhydride or active ester. In addition, these dianhydride monomers of more than two kinds can be used in combination. Considering from the stress angle of polyimide film, they can be used alone or in combination of more than two kinds.

[0091] From the viewpoints of low stress, good light transmittance (especially light with a wavelength of 365 nm) and heat resistance, the aromatic dianhydride monomer is preferably pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride; illustratively, it can be selected from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl. They can be used alone or in combination of two or more.

[0092] In some embodiments, the diamine monomer includes an aromatic diamine monomer and / or an aliphatic diamine monomer. Depending on the different active groups on the diamine monomer, the diamine monomer can be a hydroxyl-containing diamine monomer, a thiol-containing diamine monomer, an aromatic diamine monomer, an aliphatic diamine monomer, etc., wherein at least a portion of the hydrogen atoms of the aromatic ring in the aromatic diamine monomer can be substituted with an alkyl group or a halogen atom, which is not limited here.

[0093] Specifically, the diamine monomer is selected from C5-C40 aromatic diamine monomers or C5-C40 cyclic aliphatic diamine monomers.

[0094] In some embodiments, the diamine monomer includes an aromatic diamine monomer selected from bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, etc. As the diamine containing a thiol group, for example, dithiophenylene diamine, etc. can be mentioned. Examples of the aromatic diamine include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis((4-aminophenoxy)benzene))benzene, and 1,3-bis((3-aminophenoxy)benzene). 4-aminophenoxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, etc.

[0095] In some embodiments, the diamine monomer includes a fatty diamine monomer, and the fatty diamine monomer is selected from at least one of 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, methylenebiscyclohexylamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane.

[0096] In some embodiments, the molar ratio of the dianhydride monomer to the diamine monomer is 1:(0.95-1.1), specifically 1:0.95, 1:1.0, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.08, 1:1.09 or 1:1.1, etc., and of course other values ​​within the above range may also be used. By controlling the molar ratio of the dianhydride monomer to the diamine monomer, the polymerization reaction is facilitated to proceed fully.

[0097] In some embodiments, the resin composition can be prepared by uniformly mixing a resin or a resin precursor, a photosensitive compound, and a solvent.

[0098] The polyamic acid or polyamic acid ester in the resin composition provided in the present application can reduce the thermal expansion coefficient and stress of the resin after curing, increase the crosslinking density during the curing process, and limit the movement of the molecular chains, thereby increasing the glass transition temperature and reducing the thermal expansion coefficient, and reducing the residual stress of the polyimide cured film.

[0099] In the embodiment of the present application, the resin or resin precursor in the resin composition can be selected according to the actual application requirements, and the resin composition can be one or more resin components. In some embodiments, the resin includes the polymer resin shown in the above formula II, and can also include one or more of phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, and polyimide resin. In some embodiments, the resin precursor can also include one or more of phenolic resin precursor, epoxy resin precursor, acrylic resin precursor, benzocyclobutene resin precursor, benzoxazole resin precursor, and polyimide resin precursor.

[0100] In some embodiments, based on the mass of the resin composition being 100%, the mass content of the polymer is 1% to 40%, specifically 1%, 5%, 10%, 15%, 20%, 25%, 28%, 30%, 35% or 40%, etc., which are not limited here. Preferably, the mass content of the polymer is 5% to 30%.

[0101] In some embodiments, based on the mass of the resin composition as 100%, the mass proportion of the photosensitive compound is 0.1% to 10%, specifically 0.1%, 0.5%, 0.8%, 1.5%, 2%, 2.5%, 3%, 3.5%, 5%, 6%, 7%, 8% or 10%, etc., which are not limited here. Preferably, the mass proportion of the photosensitive compound is 1 to 5%. The photosensitive compound of the embodiment of the present application has a high absorbance at the i-line as a photobase generator, and the photobase generator has high photosensitivity and strong alkali production ability, so that it can better catalyze the occurrence of cross-linking reactions, improve the solubility difference between the exposed area and the non-exposed area, and improve the resolution of the pattern.

[0102] In order to make the polyimide have excellent electrical properties, mechanical properties, heat resistance, moisture resistance and film retention rate, the weight average molecular weight of the polymer (resin) in the resin composition can be selected from 5000 to 100000. For example, the weight average molecular weight can be 5000, 6000, 7000, 8000, 9000, 10000, 50000, 80000 or 100000, etc., which are not limited here. Preferably, the weight average molecular weight of the polymer in the resin composition is 10000 to 80000; more preferably, it is 20000 to 50000.

[0103] In some embodiments, the solid content of the resin composition is 1% to 50%, and may be 1%, 2%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 50%, etc., which is not limited here.

[0104] The resin composition provided in the present application may also contain a solvent, and the solvent may be an alcohol organic solvent, a ketone organic solvent, an ether organic solvent, an ester organic solvent or an amide organic solvent. There is no particular limitation on the type of solvent, as long as the various components can be uniformly dissolved. In order to improve the comprehensive performance of the prepared cured film, the solvent may be used alone or in combination of two or more.

[0105] In some embodiments, based on 100% weight of the resin composition, the weight of the solvent accounts for 50% to 95%, and preferably, the weight of the solvent accounts for 80% to 90%.

[0106] In some embodiments, the solvent is selected from solvents having a boiling point of 110 to 250° C. at atmospheric pressure. Controlling the boiling point of the solvent to be above 110° C. is conducive to rapid evaporation of the solvent during coating and drying of the resin composition, thereby obtaining a uniformly coated film. The boiling point of the solvent is lower than 250° C., which is conducive to removing the residual solvent in the coating film, reducing the shrinkage of the coating film during curing, and making the cured film smoother.

[0107] In some optional embodiments, the solvent is selected from at least one of N-methyl-2-pyrrolidone (abbreviated as NMP), N,N-dimethylacetamide (abbreviated as DMAc), N,N-dimethylformamide (abbreviated as DMF), dimethyl sulfoxide (abbreviated as DMSO), γ-butyrolactone (abbreviated as GBL), acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol.

[0108] In some embodiments, the resin composition may further include an auxiliary agent, and the auxiliary agent may include a copper discoloration inhibitor, a photosensitizer, an adhesion promoter, a thermal bridging agent, and the like.

[0109] In some embodiments, based on 100% weight of the resin composition, the amount of the additive added is 0.01% to 20% of the resin composition, preferably, the amount of the additive added is 0.05% to 15% of the resin composition, and more preferably, the amount of the additive added is 0.1% to 10% of the resin composition.

[0110] In some embodiments, the resin composition may further include a filler, which may be an inorganic filler such as silica powder, talcum powder, magnesium carbonate, mica powder, etc. The addition of the inorganic filler can improve the hardness and wear resistance of the cured film.

[0111] In a second aspect, the present application provides a method for preparing a resin composition, comprising:

[0112] S01, dissolving polyamic acid or polyamic acid ester and a photobase generator in a solvent under stirring to obtain a resin composition;

[0113] S02, coating the resin composition on a substrate, pre-baking, and stripping to form a coating film;

[0114] S03, under the protection of an inert atmosphere, exposing the coating film and developing the exposed coating film with a developer to obtain a resin pattern;

[0115] S04, heat-treating the resin pattern to cure it, and obtaining a cured film.

[0116] In some embodiments, the substrate may be a glass substrate, a silicon-based material or a metal material (e.g., copper), and the thickness of the coating may be adjusted according to actual needs. After the coating is formed, a portion of the solvent may be volatilized by heat treatment. The present application does not specifically limit the manner in which the resin composition is coated on the substrate, and may be a screen printing method, an inkjet method, a spin coating method, and the like. The coating formed by the coating is exposed to solidify and form.

[0117] In some embodiments, the exposure dose is 600 mJ / cm 2 ~3000mJ / cm 2 , specifically 600mJ / cm 2 、800mJ / cm 2 、1000mJ / cm 2 、1200mJ / cm 2 、1400mJ / cm 2 、1800mJ / cm 2 、2000mJ / cm 2 、2500mJ / cm 2 or 3000mJ / cm 2, of course, it can also be other values ​​within the above range, which is not limited here.

[0118] The pre-baking temperature is 60°C to 250°C, preferably, the pre-baking temperature is 100°C to 220°C. Specifically, the resin composition glue can be smeared on a hot plate at 100°C for pre-baking, so that most of the solvent evaporates, and then the pre-baked film is placed under a mask, exposed, and then the patterned resin pattern is washed with a developer to remove the unexposed part. The resin pattern is then heat-treated by step-by-step heating (for example, 100°C for 1 hour, then heated to 180°C for 1 hour, and then heated to 250°C for 1 hour). The drying time is not limited as long as the solvent is fully removed. Step-by-step heating and curing is conducive to complete curing, and the thickness of the formed cured film is uniform and the quality is stable and reliable.

[0119] It should be noted that exposure refers to irradiation with light, and the light can be visible light, ultraviolet light, electron beam, X-ray, etc. At present, based on process cost and convenience, irradiation with visible light and ultraviolet light is preferred. More preferably, the light is selected from light between 200nm and 800nm, and specifically can be light generated by a 365nm mercury lamp light source.

[0120] The cross-linking and curing of the polyamic acid is promoted by generating an organic base by exposing the photobase generator in the resin composition. In the present application, the resin composition is a negative resin composition, which can be insoluble relative to the developer. Therefore, by coating and pre-baking the photosensitive resin composition, a pre-baked film that can be dissolved in the developer is prepared, and the pre-baked film is irradiated with light through a mask. Since the exposed part is insoluble in the developer, the unexposed part can be removed by the developer to form a negative pattern.

[0121] The greater the difference in solubility of the exposed part and the unexposed part in the developer, the flatter the cross-section of the negative pattern formed, the better the patterning effect, and the better the film retention rate after development.

[0122] In some embodiments, the solution used as the developer includes a mixture of at least one or more of a tetramethylammonium hydroxide (TMAH) aqueous solution, isopropyl alcohol, and cyclopentanone.

[0123] The present application combines polyamic acid or polyamic acid ester with a photosensitive compound of a specific structure to achieve direct patterning of polyamic acid or polyamic acid ester, and can significantly reduce the curing temperature of the polyimide precursor (≤250°C). The photobase generator designed with a specific structure has strong light absorption, high sensitivity, high photobase generation efficiency, and good catalytic effect of the generated organic base molecules, which can achieve patterning of thick film systems of more than 4μm, with good pattern formation, high contrast, and high film retention rate.

[0124] In a fourth aspect, the present application provides an electronic device, wherein the electronic device comprises a cured film, or the electronic device comprises a cured film formed by curing a resin composition comprising the photosensitive compound.

[0125] In some embodiments, the cured film serves as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarization layer, a shielding layer, or a rewiring layer in the electronic device.

[0126] The application of the resin composition of the present application and the resin composition composed thereof include but are not limited to: application in the insulating layer, passivation layer, dielectric layer or stress buffer layer in electronic packaging; or application in the preparation of interlayer dielectric or insulating diaphragm of multi-layer metal wiring interconnection structure; or application in the preparation of protective layer or insulating layer of liquid crystal display device. The cured film formed by the resin composition of the present application has excellent properties such as low dielectric constant and dielectric loss, high breakdown voltage, good patterning resolution, low thermal expansion coefficient, good interface adhesion, high elongation at break, and low curing temperature.

[0127] The following is a further description of the embodiments of the present invention in multiple embodiments. The embodiments of the present invention are not limited to the following specific embodiments. The embodiments can be appropriately modified within the scope of the unchanged main rights.

[0128] First, synthesis of photosensitive compound 1:

[0129] (1) Compound 1a (0.85 g, 4 mmol) was dissolved in 15 mL of dry N,N-dimethylacetamide (DMAc), 3 mL of triethylamine (TEA) was added dropwise to the reaction solution under an ice-water bath, and p-nitrophenyl chloroformate (0.81 g, 4 mmol) was added to the reaction solution, and the reaction was carried out at room temperature for 15 h. After the reaction was completed, the reaction solution was poured into ice water (100 mL) to precipitate, and the light yellow precipitate was collected by filtration, washed with water, and dried under vacuum at 55 ° C for 7 h. The yellow solid compound 1b (453 mg, yield 30%) was obtained by column chromatography separation and purification using dichloromethane: petroleum ether with a volume ratio of 1:2 as the eluent.

[0130] (2) Compound 1b (0.3 g, 0.8 mmol), tetrahydroquinoline (0.15 mL, 1 mmol) and 1-hydroxybenzotriazole (0.15 mL, 1 mmol) were dissolved in 5 mL of dry N,N-dimethylacetamide (DMAc) and stirred at 110°C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, 1% sodium bicarbonate aqueous solution (80 mL) was poured into it, the crude product was collected by filtration, the precipitate was washed with water, and vacuum dried at 55°C for 8 h. The crude product was quickly separated and purified by silica gel chromatography using dichloromethane as the eluent to obtain a light yellow solid compound 1 (250 mg, 63%).

[0131] The compound 1 prepared in this example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0132]

[0133] The NMR data of compound 1 are: 1 1H NMR (400MHz, CDCl3) δ: 7.73 (d, 1H, J=8.4Hz), 7.65 (d, 1H, J=7.1Hz), 7.18-7.11 (m, 2H), 7.06-7.02 (m, 1H), 6.97 (s, 1H), 5.64 (d, 2H, J=10.1Hz), 4.00 (s, 4H), 3.96 (d, 4H, J=8.0Hz), 2.80 (t, 2H, J=7.63Hz), 2.02-1.95 (m, 2H).

[0134] Synthesis of photosensitive compound 2:

[0135] The difference from Example 1 is:

[0136] (2) Compound 1b (0.3 g, 0.8 mmol), imidazoline (0.1 g, 1 mmol) and 1-hydroxybenzotriazole (0.15 mL, 1 mmol) were dissolved in 5 mL of dry N,N-dimethylacetamide (DMAc) and stirred at 85°C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, 1% sodium bicarbonate aqueous solution (80 mL) was poured into it, the crude product was collected by filtration, the precipitate was washed with water, and vacuum dried at 55°C for 8 h. The crude product was quickly separated and purified by silica gel chromatography using dichloromethane: petroleum ether in a volume ratio of 1:2 as the eluent to obtain a yellow solid compound 2 (276 mg, 69%).

[0137] The compound 2 prepared in this example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0138]

[0139] The NMR data of compound 2 are: 1 H NMR (400MHz, CDCl3) δ: 7.71 (s, 1H), 7.01 (s, 1H), 5.55 (s, 2H), 4.40 (t, 2H, J=13.3Hz), 3.96 (s, 6H), 1 .75 (t, 1H, J=12.1Hz), 1.65 (t, 1H, J=9.3Hz), 1.61 (s, 3H), 1.52-1.47 (m, 1H), 1.27 (d, 6H, J=7.0Hz).

[0140] Synthesis of photosensitive compound 3:

[0141] The difference from Example 1 is:

[0142] (2) Compound 1b (0.3 g, 0.8 mmol), 6-methoxy-1,2,3,4-tetrahydroquinoline (0.13 g, 1 mmol) and 1-hydroxybenzotriazole (0.15 mL, 1 mmol) were dissolved in 5 mL of dry N,N-dimethylacetamide (DMAc) and stirred at 110°C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, 1% sodium bicarbonate aqueous solution (80 mL) was poured into it, the crude product was collected by filtration, the precipitate was washed with water, and vacuum dried at 55°C for 8 h. The crude product was quickly separated and purified by silica gel chromatography using dichloromethane as the eluent to obtain a yellow solid compound 3 (170 mg, 53%).

[0143] The compound 3 prepared in this example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0144]

[0145] The NMR data of compound 3 are: 1 H NMR (400MHz, CDCl3) δ: 7.73 (d, 1H, J = 4.5Hz), 7.65 (s, 1H), 7.23 (s, 1H), 6.99-6.83 (t, 2H, J = 7.1Hz), 5.05 (d, 2H, J=9.8Hz), 3.95 (d, 6H), 3.70 (d, 3H, J=3.4Hz), 2.80 (t, 2H, J=6.83Hz), 2.02-1.95 (m, 2H).

[0146] Synthesis of photosensitive compound 4:

[0147] (1) Chloroacetyl chloride (637.33 mg, 5.64 mmol) was slowly added to a solution of 4a (1.00 g, 5.64 mmol) and trimethylamine (3 mL) in CH2Cl2 (20 mL) and dissolved in CH2Cl2 (10 mL) at 0°C. The reaction mixture was stirred at room temperature overnight. After the reaction was complete, water (30 mL) was added to quench the reaction. The mixture was extracted with CH2Cl2 (3×20 mL), and the combined organic phases were washed with brine (2×50 mL), dried over anhydrous sodium sulfate, and filtered. The filtrate was evaporated under vacuum, and the crude product was purified by rapid separation on a silica gel column using petroleum ether:ethyl acetate in a volume ratio of 10:1 as the eluent to obtain compound 4 (1.05 g, 73.35%).

[0148] (2) To a solution of 4b (1.00 g, 3.94 mmol) and 1a (785.09 mg, 3.94 mmol) in acetone, K2CO3 (2.3 g, 7.88 mmol) was added at room temperature. The reaction mixture was stirred at 60°C for 12 h. After the reaction was completed, the insoluble matter in the mixture was filtered. The filtrate was evaporated under reduced pressure and purified by column chromatography (methanol / dichloromethane with a volume ratio of 30:1) to give compound 4 (800 mg, 48.74%).

[0149] The compound 4 prepared in this example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0150]

[0151] The NMR data of compound 4 are: 1 H NMR (400MHz, CDCl3) δ: 12.00 (s, 1H), 8.13 (s, 1H), 7.94 (d, 1H), 7.76 (d, 1H, J = 9.3Hz), 7.73 (d, 1H, J = 13.3Hz), 7.25 ( s, 1H), 5.05 (s, 2H), 4.31 (m, 2H, J=12.1Hz), 3.96 (s, 3H), 3.75 (s, 3H), 2.79 (m, 2H, J=8.1Hz), 1.80 (d, 2H, J=7.0Hz).

[0152] Synthesis of photosensitive compound 5:

[0153] The difference from Example 1 is:

[0154] (2) Compound 1b (0.3 g, 0.8 mmol), 2,3-dihydroindole-5-ol (0.14 g, 1 mmol) and 1-hydroxybenzotriazole (0.15 mL, 1 mmol) were dissolved in 5 mL of dry N,N-dimethylacetamide (DMAc) and stirred at 85°C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, 1% sodium bicarbonate aqueous solution (80 mL) was poured into it, the crude product was collected by filtration, the precipitate was washed with water, and vacuum dried at 55°C for 8 h. The crude product was quickly separated and purified by silica gel chromatography using dichloromethane: petroleum ether in a volume ratio of 1:2 as the eluent to obtain solid compound 5 (270 mg, 65%).

[0155] The compound 5 prepared in this example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0156]

[0157] The NMR data of compound 5 are: 1H NMR (400MHz, CDCl3) δ: 7.73 (s, 1H), 7.38 (s, 1H), 7.23 (s, 1H), 6.85 (s, 2H), 5.05 (s, 2H), 3.96 (t, 5H, J=12.1Hz), 3.75 (s, 3H), 3.20 (t, 2H, J=12.2Hz).

[0158] Synthesis of photosensitive compound 6:

[0159] (1) 4,5-dimethoxy-2-nitrophenol (300 mg, 1.51 mmol), chloroformyl chloride (125 mg, 1.26 mmol), and 5-nitroindole (247 mg, 1.51 mmol) were dissolved in 15 mL of dry acetonitrile. The mixture was refluxed for 4 hours in a nitrogen atmosphere. After cooling to room temperature, the solvent was evaporated and the residue was washed with ethyl acetate by adjusting the pH to 5.0 with 100 mmol of sodium phosphate. The organic phase was dried and evaporated to obtain a brown oil. Flash chromatography (ethyl acetate:hexane 1:1 by volume) gave yellow crystalline compound 6 (400 mg, 79%).

[0160] The compound 6 prepared in this example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0161]

[0162] The NMR data of compound 6 are: 1 H NMR (400MHz, DMSO, ppm): 8.24(d,1H),8.01(d,1H),7.91(d,1H),7.73(t,1H),7.23(s,1H),5.05(d,2H),3.96(m,3H),3.75(m,3H),3.26(m,3H).

[0163] Synthesis of photosensitive compound 7:

[0164] The difference from Example 1 is:

[0165] (2) Compound 1b (0.3 g, 0.8 mmol), 2,6-dimethylpiperidine (0.14 mL, 1 mmol) and 1-hydroxybenzotriazole (0.15 mL, 1 mmol) were dissolved in 5 mL of dry N,N-dimethylacetamide (DMAc) and stirred at 90°C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, 1% sodium bicarbonate aqueous solution (80 mL) was poured into it, the crude product was collected by filtration, the precipitate was washed with water, and vacuum dried at 55°C for 8 h. The crude product was quickly separated and purified by silica gel chromatography using dichloromethane: petroleum ether in a volume ratio of 1:2 as the eluent to obtain a light yellow solid compound 7 (203 mg, 72%).

[0166] The compound 7 prepared in this comparative example is used as a photobase generator, and the reaction mechanism is shown in the following formula:

[0167]

[0168] The NMR data of compound 7 are: 1 1H NMR (400MHz, CDCl3) δ: 7.71 (s, 1H), 7.01 (s, 1H), 5.55 (s, 2H), 4.40 (t, 2H, J=13.3 Hz), 3.96 (s, 6H), 1.75 (t, 1H, J=12.1Hz), 1.65 (t, 1H, J=9.3Hz), 1.61 (s, 3H), 1.52 1.47 (m, 1H), 1.27 (d, 6H, J=7.0Hz).

[0169] Second, the synthesis of polyamic acid:

[0170] Under nitrogen protection, m-tolidine (DMBZ) (8.5 g, 40 mmol) was dissolved in 81.4 mL of N-methylpyrrolidine (NMP) solution, and then 4,4'-oxydiphthalic anhydride (ODPA) (12.4 g, 40 mmol) was added in batches. The mixture was stirred at room temperature to obtain a viscous liquid PAA (solid content of about 20%), which was diluted with 153 mL of N-methylpyrrolidine to obtain a liquid PAA with a solid content of about 8%.

[0171] The liquid PAA prepared in this embodiment is used as polyamic acid, and the reaction mechanism is shown in the following formula:

[0172]

[0173] Synthesis of Polyamide Ester:

[0174] Under nitrogen protection, add diphenyl ether tetraacid dianhydride (18.613g, 60mmol) and methanol (3.845g, 120mmol) to a 500mL three-necked flask in turn, rinse the filter paper, beaker, measuring cylinder and feeding funnel with 60mL N-methylpyrrolidone, and add 3mL pyridine at room temperature. Pass nitrogen protection, raise the solution temperature to 60℃, mechanically stir for 4 hours and then naturally cool to room temperature. Slowly add thionyl chloride SOCl2 (15g, 126mmol) dropwise under ice-water bath conditions. After the addition is complete, the ice bath reaction naturally transitions to room temperature and reacts at room temperature for 4 hours. Dissolve 2,2'-dimethylbenzidine (12.4827g, 58.8mmol) in 50mL N-methylpyrrolidone in a 250mL single-necked flask, add triethylamine (25.5g, 252mmol) and mix well. Under ice-water bath conditions, the clear solution of 2,2'-dimethylbenzidine is dripped into a three-necked flask slowly using a constant pressure funnel. The ice bath reaction naturally transitions to room temperature, and then continues to react at room temperature overnight. After the reaction is completed, the reaction liquid is filtered to obtain a clear filtrate. It is precipitated while stirring in deionized water, and the resin powder after final filtration is dried in a vacuum to obtain a polyimide ester (PAE) resin.

[0175] Third, preparation of resin composition

[0176] The photobase generator prepared in the example and the polymer (polyamic acid or polyimide ester) were dissolved in N-methylpyrrolidone and mixed evenly using a planetary mixer to obtain resin composition examples 1 to 10 and comparative examples 1 to 3, the specific contents of which are shown in Table 1:

[0177] Table 1. Components of the resin composition

[0178]

[0179] Performance Testing

[0180] 1) Catalytic performance test of photobase generator:

[0181] The prepared resin composition was coated on a glass sheet to form a film, and pre-baked on a hot plate at 60°C for 30 minutes to evaporate part of the solvent. 2 After exposure, the temperature is raised in steps, and the temperature is raised according to the program of 100°C (keeping temperature for 15 min), 140°C (keeping temperature for 15 min), 180°C (keeping temperature for 15 min), and 220°C (keeping temperature for 15 min).

[0182] The infrared spectra were tested to compare the imidization rates of the composition films cured at different temperatures.

[0183] The imidization rates of the composition films at the same temperature are compared to evaluate the catalytic performance of the organic base generated by the photobase generator. Understandably, at the same temperature, the higher the imidization rate of the composition film, the more complete its imidization, and the better the catalytic effect of the organic base, where "-" indicates a poor effect, "+" indicates a good effect, and the number of "+" and "-" represents the degree of the corresponding effect, as shown in Table 2.

[0184] Table 2. Test results of catalytic performance of photobase generator

[0185]

[0186] According to the data in Table 2, an appropriate amount of a photobase generator with a special structural design of the present application is added in the above embodiments. The photobase generator is mixed with the polyamic acid and polyimide ester provided in the present application to form a resin composition. The photobase generator can photolyze to produce an organic base, and the organic base can effectively catalyze the imidization reaction of the polyamic acid, and the catalytic effect is good.

[0187] 2) Performance test of photosensitive compounds:

[0188] The prepared photosensitive compound was dissolved in acetonitrile, and the UV-visible absorption spectra of the photosensitive compound at different exposure doses at the same concentration were tested to compare the changes in the absorption peak of the photobase generator. Understandably, at the same exposure dose, the more obvious the change in the absorption peak, the more complete the decomposition of the photosensitive compound after light exposure, and the higher the quantum efficiency of base generation, where "-" indicates a poor effect, "+" indicates a good effect, and the number of "+" and "-" represents the degree of the corresponding effect, as shown in Table 3.

[0189] Table 3. Stability test results of photosensitive compounds

[0190]

[0191] According to the data in Table 3, the photosensitive compounds provided in the embodiments of the present application decompose more completely and produce alkali more efficiently as the exposure increases. Under the same exposure dose, the decomposition rate of the photosensitive compounds in the embodiments is better than that of the photosensitive compounds in the comparative examples. This is because the presence of the benzene ring of the organic base structure in the photosensitive compounds provided in the embodiments enhances the degree of π electron conjugation, and the red shift of the absorption peak makes the light absorption at 365nm stronger, while increasing the transition probability between the ground state and the singlet excited state, thereby improving the photosensitivity of the alkali generator.

[0192] Figure 1a This is the ultraviolet absorption spectrum of Comparative Example 1 of the present application, Figure 1a The ultraviolet absorption spectrum of Example 1 of the present application is as follows: Figure 1a as well as Figure 1bAs shown, the resin compositions prepared in Example 1 and Comparative Example 1 have a wavelength of 365 nm and a power density of 20 mW / cm 2 After being exposed to ultraviolet light for different periods of time, Figure 1a is the absorption curve of Comparative Example 1, and the molar absorption coefficient of the resin composition at 365 nm is 4.82×10 3 L·mol -1 cm -1 1b in FIG1 is the absorption curve of Example 1, and the molar absorption coefficient of the resin composition at 365 nm is 5.8×10 3 L·mol -1 cm -1 It can be seen that the resin composition of Example 1 absorbs light more strongly than that of Comparative Example 1. This is because a photosensitive compound with a specific structure is added to the resin composition of Example 1, which is sensitive to 365nm light and has stronger absorption.

[0193] 3) Film performance evaluation

[0194] The prepared resin composition is patterned. First, a film is formed by spin coating on a silicon wafer using a coating machine, and then heated on a hot plate before baking to volatilize part of the solvent to obtain a dried composition coating. The film is placed under a mask and exposed using a 365nm mercury lamp light source. The exposed film is then post-baked on a hot plate. After manual spin coating development in a developer, it is rinsed with deionized water, and nitrogen is blown off the residual liquid on the silicon wafer. The film retention rate after development is tested, and the graphic resolution, line clarity, etc. are observed under a microscope. "-" indicates a poor effect, "+" indicates a good effect, and the number of "-" and "+" represents the degree of the corresponding effect.

[0195] 3.1 Film resolution: The minimum value of the mask size for forming a clear line pattern of polyimide is used as an evaluation index of film resolution.

[0196] 3.2 Contrast: Observe the contrast of the clear pattern formed by polyimide.

[0197] 3.3 Base film cleanliness: Observe the clarity of the unexposed area after development and rinsing. When the base film is clean and no composition remains, the cleanliness is better.

[0198] 3.4 Pattern formation: The pattern formed in the exposed area has good edge sharpness and uniform line width. The greater the difference in solubility of the exposed and unexposed parts in the developer, the smoother the pattern surface and the free of cracks, and the better the pattern formation.

[0199] 3.5 Taper: Use a scanning electron microscope to observe whether the upper and lower surfaces of the pattern edge are flush and whether the cross section is flat. When the upper and lower surfaces of the exposed part of the pattern are flush and the cross section is perpendicular to the silicon wafer surface, the taper is the smallest and the effect is the best.

[0200] 3.6 Film retention rate after development: The film thickness before and after development was measured using a film thickness meter. The film retention rate after development = (film thickness after development / film thickness before development) × 100%.

[0201] Table 4. Process parameters of patterning treatment of resin compositions prepared in Examples and Comparative Examples

[0202]

[0203] Table 5. Main performance parameters of polyimide cured film

[0204]

[0205] According to the data in Table 5, the embodiments of the present application have better resolution, contrast and film retention rate than the comparative examples, and the overall performance of pattern development is more excellent. This is mainly due to the fact that the photosensitive compound provided in the embodiment has a higher alkali production efficiency, and the organic base produced has a better catalytic effect, so that the solubility difference between the exposed area and the non-exposed area is greater, and the film retention rate is higher.

[0206] Figure 2 This is a comparison diagram of the patterns formed by the coating films formed by the resin compositions of Example 1-1 and Comparative Example 1-1 under the same conditions, as shown in Figure 2 As shown, Figure 2 Part a in the figure is a circular hole pattern formed by the resin composition of Example 1-1, and its resolution is 50 μm. Figure 2 Part b in the figure is a line pattern formed by the resin composition of Example 1-1, and its resolution is 15 μm. Figure 2 Part c is a pattern formed by the resin composition of Comparative Example 1-1, the lines are not clear, and the base film is not clean. By comparison, it can be seen that the pattern formed by Example 1-1 has higher resolution than that of Comparative Example 1-1, and the lines are clear, the base film is clean, and the contrast is high.

[0207] Figure 3 This is a comparison diagram of the patterns formed by the coating films formed by the resin compositions of Example 2-1 and Comparative Example 1-2 under the same conditions. Figure 3 Part a in the figure is a circular hole pattern formed by the resin composition of Example 2-1, and its resolution is 30 μm. Figure 3 Part b in the figure is a line pattern formed by the resin composition of Example 2-1, and its resolution is 15 μm. Figure 3 Part c is the pattern formed by the resin composition of Comparative Example 1-2, the lines are not clear, and the base film is not clean. By comparison, it can be seen that the resin pattern formed by Example 2-1 has higher resolution than that of Comparative Example 1-2, and the lines are clear, the base film is clean, and the contrast is high.

[0208] Figure 4 The circular hole pattern formed after the resin composition provided in Example 1-1 was developed for 1 minute has a resolution of 2 μm. Figure 5 The circular hole pattern formed after the resin composition provided in Example 1-2 was developed for 4 minutes has a resolution of 3 μm. It can be seen that increasing the development time improves the resolution of the cured film to 3 μm, the pattern formation is good, and the base film is flat.

[0209] Figure 6 The line pattern formed by the resin composition provided in Example 3-1 has a resolution of 15 μm. Figure 7 The groove pattern formed by the resin composition provided in Example 3-1 has a resolution of 30 μm, good pattern forming properties, and a smooth and clean base film.

[0210] Figure 8 The polygonal pattern formed by the resin composition provided in Example 4-1 has a resolution of 200 μm. Fig. 9 Another polygonal pattern formed by the resin composition provided in Example 4-1 has a resolution of 100 μm. It can be seen that the formed pattern has a high resolution, high contrast, clear pattern, and a clean base film.

[0211] Fig.10 A pattern formed by the resin composition provided in Example 8-1, wherein: Fig.10 The resolution of the mask pattern in part a is 120 μm. Fig.10 The resolution of the mask pattern in part b is 100 μm. Fig.10 The resolution of the mask pattern in part c is 80 μm, and the obtained pattern has high resolution, clear lines and high contrast.

[0212] 4) Performance evaluation of polyimide cured film

[0213] First, the prepared resin composition was spin-coated on a silicon wafer using a coating machine to form a film, and then pre-baked on a hot plate at 100°C for 3 minutes to form a resin composition layer with a thickness of 15-20 μm on the silicon wafer. The film was placed under a specific mask and heated with 1000 mJ / cm 2 Energy ultraviolet light source for exposure. Use tetramethylammonium hydroxide (TMAH) / isopropanol / water mixed solution for development, rinse with deionized water, and spin dry the solvent to obtain the corresponding pattern. The silicon wafer with the pattern was transferred to an oxygen-free oven, and the temperature was raised to 220°C at 3°C / min in a nitrogen atmosphere, and maintained at 220°C for 2 hours. The patterned film was peeled off from the silicon wafer using a 1% hydrofluoric acid solution, and the mechanical and thermal properties of the corresponding specimens were tested. "-" indicates poor performance, "+" indicates better performance, and the number of "-" and "+" represents the degree of goodness of the corresponding performance.

[0214] Table 6. Mechanical properties of polyimide cured films

[0215] Example Elongation at break Maximum tensile stress Glass transition temperature Example 1 +++ +++ +++ Example 2 ++ ++ +++ Comparative Example 1 + + ++

[0216] The organic base produced in the embodiment of the present application has a better catalytic effect, so that the film has better mechanical and thermal properties after being cured at 220°C.

[0217] Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the claims. Any technical personnel in this field may make several possible changes and modifications without departing from the concept of the present application. Therefore, the scope of protection of the present application shall be based on the scope defined by the claims of the present application.

Claims

1. A photosensitive compound, characterized in that The photosensitive compound includes a compound having a structure shown in Formula I, and the photosensitive compound can be photolyzed to generate an organic base under the action of light radiation; In Formula I, M is an organic base structural unit having Formula I-1; R1, R2 and R3 are each independently selected from a hydrogen atom, an electron withdrawing group or an electron pushing group; m is selected from a natural number of 2 to 10.

2. The photosensitive compound according to claim 1, characterized in that The aziridine polycyclic group in the organic base structural unit represented by formula I-1 is selected from at least one of aziridine, azetidinyl, azopentyl, aziridine and azepanyl.

3. The photosensitive compound according to claim 1, characterized in that It meets at least one of the following characteristics: a. The number of substituents R1 is 1 to 3; b. The substituent R1 is selected from an electron-pushing group; c. The number of substituents R2 on the benzene ring in the organic base structural unit represented by formula I-1 is 1 to 3; when the number of R2 is 2 or 3, the substituents R2 may be the same or different.

4. The photosensitive compound according to claim 3, characterized in that The structural formula of the organic base generated by photolysis of the photosensitive compound under light radiation is selected from any one of the following: Wherein, R2 is selected from a hydrogen atom, an electron withdrawing group or an electron pushing group.

5. The photosensitive compound according to any one of claims 1 to 4, characterized in that The electron-withdrawing group is selected from at least one of a nitro group, a halogen atom, a cyano group, a sulfonic acid group, an acyl group, and a carboxyl group; and / or the electron-pushing group is selected from at least one of an amine group, a hydroxyl group, an alkoxy group, an amide group, an acyloxy group, and an alkyl group.

6. The photosensitive compound according to claim 1, characterized in that The photosensitive compound is selected from at least one of the compounds of the following structural formulas:

7. A resin composition, characterized in that The resin composition comprises a resin or a resin precursor and the photosensitive compound according to any one of claims 1 to 6.

8. The resin composition according to claim 7, characterized in that The resin comprises a polymer composed of repeating units shown in formula II; In formula II, R4 is selected from a tetravalent aromatic organic group, R5 and R6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic hydrocarbon group or a monovalent organic group having a carbon-carbon unsaturated double bond; R7 is selected from a divalent aromatic organic group or a divalent aliphatic organic group, and n is selected from a natural number greater than or equal to 3.

9. The resin composition according to claim 8, characterized in that The R4 is selected from a tetravalent aromatic hydrocarbon group or a tetravalent aromatic heterocyclic group; the R7 is selected from an aromatic hydrocarbon group or a cyclic aliphatic group.

10. The resin composition according to claim 8, characterized in that It meets at least one of the following characteristics: a. Based on the mass of the resin composition being 100%, the mass of the polymer composed of the repeating unit represented by formula II accounts for 1% to 40%; b. The weight average molecular weight of the polymer composed of the repeating unit represented by formula II is 5000 to 100000; c. Based on the mass of the resin composition being 100%, the mass of the photosensitive compound accounts for 0.1% to 10%; d. The organic base produced by photolysis of the photosensitive compound under light radiation is a compound having a primary amine or a secondary amine; e. The solid content of the resin composition is 1% to 50%.

11. The resin composition according to claim 8, characterized in that In the polymer composed of the repeating units shown in formula II, R4 is selected from any one of the following structures: Wherein, A is selected from an oxygen atom, a sulfur atom or a branched carbon atom, and B and C are each independently selected from a divalent organic group or a single bond bonded to a benzene ring and not conjugated.

12. The resin composition according to claim 8, characterized in that In the polymer composed of the repeating units shown in formula II, R4 is selected from any one of the following structures:

13. The resin composition according to claim 8, characterized in that In the polymer composed of the repeating units shown in formula II, R7 is selected from any one of the following structures, 14. The resin composition according to any one of claims 8 to 13, characterized in that When the resin composition is used for patterning, the exposure amount required to act on the resin composition is 600mJ / cm 2 ~3000mJ / cm 2 .

15. A cured film, characterized in that: The cured film is prepared from the resin composition according to any one of claims 7 to 13.

16. An electronic device, characterized in that: The electronic device comprises the cured film according to claim 15, or the electronic device comprises a cured film formed by curing a resin composition comprising the photosensitive compound according to any one of claims 1 to 6.

17. The electronic device according to claim 16, characterized in that: The cured film is used as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarization layer, a shielding layer, or a rewiring layer in the electronic device.

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