A polyimide precursor and its synthesis method, and a photosensitive resin composition comprising the polyimide precursor.

Abstract

This invention discloses a polyimide precursor, its synthesis method, and a photosensitive resin composition containing the polyimide precursor. The synthesis method involves reacting dianhydride, an alcohol with unsaturated double bonds exhibiting free radical polymerization, and a side-chain modifier in a solvent under the catalysis of an alkaline catalyst; adding a dehydrating condensing agent and stirring; adding a diamine and reacting; finally, adding a capping agent to quench the reaction and filtering; adding the filtrate to a poor solvent within 0-2 hours to precipitate solid polyimide precursor resin, which is then refrigerated. The side-chain modifier is selected from any one or more of alcohol-based, ether-alcohol-based, and amine-based side-chain modifiers; the capping agent is selected from any one or more of alcohol-based, ether-alcohol-based, and amine-based capping agents. This invention improves the solubility of the functional resin and controls its dissolution rate without altering the main structure of the polyimide precursor, thus ensuring the performance of the final polyimide film after heat curing.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyimide, in particular to a polyimide precursor, a synthesis method thereof and a photosensitive resin composition containing the polyimide precursor. BACKGROUND

[0002] Wafer level packaging process has a high requirement on the dissolution rate of the polyimide photoresist used: if the dissolution rate is too fast, it will not only be incompatible with the subsequent fixed automation process, but also bring potential risks of pattern resolution decline due to too fast development; if the dissolution rate is too slow, the development time is too long, causing the risk of development pattern erosion and affecting production efficiency. Therefore, the photoresist development process has strict restrictions on the development time, which puts strict requirements on the dissolution rate of the main component of the photoresist, i.e. the polyimide precursor resin and the resin composition.

[0003] In the prior art, there are mainly three methods to improve the solubility and dissolution rate of the polyimide precursor resin: (1) changing the main structure of the resin main chain, replacing part or all of the rigid aromatic ring monomers in the main structure with flexible aliphatic ring monomers, fluorine-containing monomers (CN 110147031 A), heterocyclic monomers with special groups, thereby improving the solubility and dissolution rate of the resin (CN 105143310B); (2) introducing soluble side chains on the resin main chain, such as side chains with hydroxyl groups, ether bonds, amino groups and the like to improve the solubility and dissolution rate of the resin; (3) without changing the resin structure, replacing the solvent or adding a solubility-promoting additive that does not affect the performance of the resin to improve its solubility and dissolution rate. The first method changes the main structure of the resin, making the performance of the final polyimide film uncontrollable, which may result in that although the solubility and dissolution rate are improved, other performances are changed, leading to the inability to use normally; the second method introduces side groups, which has little effect on the final film performance, but may affect the photosensitive performance, and the residual small molecules after film formation limit the use range of the resin, especially for low-temperature curing polyimide precursor resin; the third method changes the solubility behavior of the resin by passively changing the solubility environment, which has very limited technical operability. And the three mainstream methods only improve the solubility, and there is no literature or patent related to the method of precisely controlling the dissolution rate of the resin.

[0004] Furthermore, there is no method for controlling the dissolution rate of polyimide precursor resin for wafer packaging in the prior art. For example, patent CN 104285184 A replaces part of the photosensitive group HEMA with triethylene glycol monomethyl ether, which improves the solubility to some extent, but the main purpose is to increase the modulus of the cured film. Patent CN 110950781 A improves solubility by inhibiting gelation using N-Boc diamine, but does not precisely control the dissolution rate of the resin. In patent TW I516515B, the polyimide molecule is modified by embedding ester groups and fatty units, which increases the solubility, but does not mention precise control of the dissolution rate. SUMMARY

[0005] To solve the above technical problems, the present application provides a polyimide precursor and a synthesis method thereof, and a photosensitive resin composition comprising the polyimide precursor.

[0006] To achieve the above-mentioned object, the technical scheme adopted by the present application is as follows:

[0007] In one aspect, the present application provides a polyimide precursor, which is any one or several of polyamic acid, polyamic acid ester and polyamic acid salt represented by the following general formula (1);

[0008]

[0009] In formula (1), X is a tetravalent organic group, Y is a divalent organic group, n1 is an integer from 2 to 200, R1 and R2 are independently selected from any one of hydrogen atom, saturated aliphatic group with carbon atom number 1-40, aromatic group, and monovalent organic group represented by the following general formula (2), (3), (4), (5);

[0010]

[0011] In formula (2), R3, R4 and R5 are independently selected from any one of hydrogen atom or organic group with carbon atom number 1-5, and m1 is an integer from 2 to 10;

[0012]

[0013] In formula (3), R6 is a saturated divalent alkyl group with carbon atom number 1-5, R7 is a saturated monovalent alkyl group with carbon atom number 1-10, and m2 is an integer from 0 to 10;

[0014]

[0015] In formula (4), R8 and R9 are independently a saturated divalent alkyl group with carbon atom number 1-10, R 10 , R 11each independently is a saturated monovalent alkyl group having 1 to 10 carbon atoms;

[0016]

[0017] In formula (5), R 12 is any one of a saturated divalent alkyl group having 1 to 20 carbon atoms or an aryl group; R 13 , R 14 each independently is selected from any one of a saturated monovalent alkyl group having 1 to 20 carbon atoms or a monovalent aryl group.

[0018] In another aspect, the present application provides a method for synthesizing the above polyimide precursor, comprising the following steps:

[0019] (1) reacting a dianhydride, an alcohol having an unsaturated double bond of radical polymerizability, and a side chain modifier in a solvent under catalysis of an alkaline catalyst;

[0020] (2) adding a dehydration condensing agent to the reaction system of step (1) and stirring;

[0021] (3) adding a diamine to the reaction system of step (2) and reacting, and finally adding a capping agent to quench the reaction and filtering;

[0022] (4) immediately adding the filtrate to a poor solvent to precipitate a solid polyimide precursor resin and refrigerating;

[0023] wherein the side chain modifier is selected from any one or several of an alcohol side chain modifier, an ether alcohol side chain modifier, and an amine side chain modifier; the capping agent is selected from any one or several of an alcohol capping agent, an ether alcohol capping agent, and an amine capping agent; and the immediate addition of the filtrate to the poor solvent is within 0 to 2 hours, preferably 0.5 hours.

[0024] In the technical solution of the present application, the filtrate needs to be immediately added to the poor solvent, and the precipitated solid needs to be refrigerated, so that the solubility of the polyimide precursor resin can be better controlled.

[0025] As a preferred embodiment, the alcohol side chain modifier has a structure represented by the following general formula (6):

[0026]

[0027] In formula (6), R6 is a saturated divalent alkyl group having 1 to 5 carbon atoms, R7 is a saturated monovalent alkyl group having 1 to 10 carbon atoms, and m2 is an integer of 0 to 10;

[0028] The alcohol side chain modifier having the general formula as described above is preferably any one or more of methanol, ethanol, propanol, butanol, pentanol, isopropanol, n-butanol and n-pentanol, more preferably any one or more of isopropanol, n-butanol and n-pentanol, and most preferably isopropanol.

[0029] As a preferred embodiment, the ether alcohol side chain modifier has a structure represented by the following general formula (7) or the following general formula (8):

[0030]

[0031] In formula (7), R6is a saturated divalent alkyl group having 1 to 5 carbon atoms, R7is a saturated monovalent alkyl group having 1 to 10 carbon atoms, and m3is an integer of 1 to 10; the ether alcohol side chain modifier having formula (7) is preferably any one or more of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether and triethylene glycol monoisopropyl ether, more preferably any one or a mixture of two of diethylene glycol monoisopropyl ether and triethylene glycol monoisopropyl ether, and most preferably triethylene glycol monoisopropyl ether;

[0032] In formula (8), R8and R9independently of each other are any one of a saturated divalent alkyl group having 1 to 10 carbon atoms, and R 10 , R 11 independently of each other are any one of a saturated monovalent alkyl group having 1 to 10 carbon atoms; the ether alcohol side chain modifier having formula (8) is preferably any one or more of 1,3-dimethoxy-2-propanol, 1,3-diethoxy-2-propanol, 1,3-diisopropoxy-2-propanol, 1,3-din-propoxy-2-propanol, 1,5-dimethoxy-3-pentanol, 1,5-diethoxy-3-pentanol, 1,5-diisopropoxy-3-pentanol and 1,5-din-propoxy-3-pentanol, and more preferably 1,3-dimethoxy-2-propanol.

[0033] As a preferred embodiment, the amine side chain modifier has a structure represented by the following general formula (9):

[0034]

[0035] In formula (9), R 12 is any one of a saturated divalent alkyl group having 1 to 20 carbon atoms or an aromatic group; R 13 , R 14each independently selected from any one of a saturated monovalent alkyl group having 1 to 20 carbon atoms or a monovalent aryl group; the amine-based side chain modifier having the formula (9) is preferably any one or more of N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylpropylenediamine, and N,N-dimethylpropylenediamine, more preferably N,N-diethylethylenediamine.

[0036] As a preferred embodiment, the alcohol-based capping agent has a structure represented by the following general formula (6):

[0037]

[0038] In formula (6), R6is a saturated divalent alkyl group having 1 to 5 carbon atoms, R7is a saturated monovalent alkyl group having 1 to 10 carbon atoms, and m2is an integer of 0 to 10;

[0039] The alcohol-based capping agent having the above general formula is preferably any one or more of n-propanol, n-butanol, n-pentanol, isopropanol, isobutanol, and isoamyl alcohol, more preferably any one or more of isopropanol, isobutanol, and isoamyl alcohol, and most preferably isopropanol.

[0040] As a preferred embodiment, the ether alcohol-based capping agent has a structure represented by the following general formula (7) or the following general formula (8):

[0041]

[0042] In formula (7), R6is a saturated divalent alkyl group having 1 to 5 carbon atoms, R7is a saturated monovalent alkyl group having 1 to 10 carbon atoms, and m3is an integer of 1 to 10; the ether alcohol-based capping agent having the formula (7) is preferably any one or more of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, and triethylene glycol mono-isopropyl ether, more preferably any one or more of diethylene glycol mono-isopropyl ether and triethylene glycol mono-isopropyl ether, and most preferably diethylene glycol monomethyl ether.

[0043] In formula (8), R8, R9are each independently any one of a saturated divalent alkyl group having 1 to 10 carbon atoms, and R 10 11 ​each independently of one another is any one of a saturated monovalent alkyl group having from 1 to 10 carbon atoms; the ether alcohol end-capping agent having the formula (8) is preferably any one or several of 1,3-dimethoxy-2-propanol, 1,3-diethoxy-2-propanol, 1,3-diisopropoxy-2-propanol, 1,3-di-n-propoxy-2-propanol, 1,5-dimethoxy-3-pentanol, 1,5-diethoxy-3-pentanol, 1,5-diisopropoxy-3-pentanol, and 1,5-di-n-propoxy-3-pentanol, and more preferably 1,3-dimethoxy-2-propanol.

[0044] As a preferred embodiment, the amine end-capping agent has the structure shown in the general formula (9) below:

[0045]

[0046] In the formula (9), R 12 is any one of a saturated divalent alkyl group having from 1 to 20 carbon atoms or an aryl group; R 13 , R 14 each independently of one another is any one of a saturated monovalent alkyl group having from 1 to 20 carbon atoms or a monovalent aryl group; the amine end-capping agent having the formula (9) is preferably any one or several of N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylpropylenediamine, and N,N-dimethylpropylenediamine, and more preferably N,N-diethylethylenediamine.

[0047] In the technical solution of the present application, the type of the dehydration condensing agent is not particularly limited, and specifically, dicyclohexyl carbodiimide (DCC), diethyl carbodiimide, diisopropyl carbodiimide, diphenyl carbodiimide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide or its hydrochloride, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate, etc. can be listed, which can be used alone or in any mixture.

[0048] In the technical solution of the present application, the kind of the dianhydride is not particularly limited, and specifically, the following can be listed: pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 2,2-bis(3,4-oxyphthalic dianhydride)propane, hydrogenated pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, 2,2-bis(3,4-oxyphthalic dianhydride)-1,1,1,3,3,3-hexafluoropropane, etc., 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride, preferably pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, bisphenol A type diether dianhydride, and more preferably pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, etc., which can be used alone or in any mixture.

[0049] In the technical solution of the present application, the alcohol having an unsaturated double bond with radical polymerizability is not particularly limited, and generally preferably has a structure represented by the following general formula (10):

[0050]

[0051] In formula (10), R3, R4, R5are each independently selected from any one of a hydrogen atom or an organic group having 1-5 carbon atoms, and m1 is an integer of 2-10. Specifically, the following can be listed: 2-propenoyloxy ethanol, 1-propenoyloxy-3-propanol, 2-propenoylamido ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxy ethanol, 1-methacryloyloxy-3-propanol, 2-methacryloylamido ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc., which can be used alone or in any mixture.

[0052] In the technical solution of the present application, the type of the diamine is not particularly limited, and specifically can include p-phenylenediamine, m-phenylenediamine, 4,4'-diamino diphenyl ether, 3,4'-diamino diphenyl ether, 3,3'-diamino diphenyl ether, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-5-aminobenzoxazole, 4,4'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfone, 3,4'-diamino diphenyl sulfone, 3,3'-diamino diphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino benzophenone, 3,4'-diamino benzophenone, 3,3'-diamino benzophenone, 4,4'-diamino diphenyl methane, 3,4'-diamino diphenyl methane, 3,3'-diamino diphenyl methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyl dimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diamino diphenyl sulfone, and 9,9-bis(4-aminophenyl)fluorene, which can be used alone or in any mixture.

[0053] In the technical solution of the present application, the molar ratio of the dianhydride and the side chain modifier is 1:0.01-1:0.9, more preferably 1:0.05-1:0.7, and most preferably 1:0.05-1:0.5.

[0054] In the technical solution of the present application, the molar ratio of the dianhydride and the end-capping agent is 1:0.5-1:3.0, more preferably 1:0.7-1:2.0, and most preferably 1:0.8-1:1.5.

[0055] In the technical solution of the present application, the molar ratio of the dianhydride and the diamine is 1:0.8-1:0.98.

[0056] As a preferred embodiment, in step (1), the reaction is a room temperature reaction for 8-24 h.

[0057] In some specific embodiments, step (2) further comprises a pre-treatment of cooling the reaction system to -20-0°C; the addition of the dehydrating condensing agent is by adding the dehydrating condensing agent or by adding it after dissolving in a solvent; the stirring time is 0.5-2h.

[0058] As a preferred embodiment, in step (3), the addition of the diamine is by dissolving the diamine in a solvent; in the technical solution of the present application, the addition of the diamine monomer in a solution state instead of a suspension state can avoid excessive concentration of the solid-liquid two-phase reaction at the reaction contact surface, and the condensation reaction is too violent;

[0059] In some specific embodiments, the dissolving of the diamine in a solvent is under a nitrogen atmosphere; if the diamine cannot be dissolved at room temperature, heating can be used to promote the dissolution;

[0060] Preferably, in step (3), after the addition of the diamine, the reaction is carried out at a low temperature of -20-0°C for 0.5-5h, and then the temperature is raised to room temperature for continued reaction for 0.5-5h;

[0061] In some specific embodiments, in step (3), after the addition of the diamine, the reaction is carried out under stirring; if the reaction system is too thick to be stirred, a solvent can be added to dilute the reaction system.

[0062] As a preferred embodiment, in step (3), after the addition of the end-capping agent, the quenching of the reaction is by continued stirring for 0.5-5h to quench the reaction.

[0063] In some specific embodiments, in step (4), the refrigeration is at 0-10°C for 2-24h.

[0064] In some specific embodiments, step (4) further comprises a post-treatment; the post-treatment is by dissolving the solid after refrigeration in a good solvent, passing through an ion exchange resin, and then slowly adding to water to precipitate, filtering and drying to obtain the polyimide precursor; in order to improve the degree of purification, the ion exchange resin used is an anion and / or cation exchange resin to remove ionic impurities; the poor solvent is selected from any one or several of methanol, ethanol, isopropanol and water, and is preferably methanol; the good solvent is selected from any one or several of tetrahydrofuran (THF), γ-butyrolactone (GBL), N-methyl pyrrolidone (NMP), and is preferably GBL.

[0065] In the technical solution of the present application, in step (1), the solvent is selected from solvents having a large solubility at room temperature, particularly solvents of the reaction raw materials, specifically, any one or several of tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), butyrolactone, valerolactone, dimethyl sulfoxide, tetramethyl urea, ethyl acetate, dichloromethane, 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, preferably any one or a mixture of both of tetrahydrofuran (THF) and N-methylpyrrolidone (NMP).

[0066] The present application precisely controls the dissolution rate of the polyimide precursor resin by selecting a suitable end-capping agent, introducing different types and proportions of modified side groups, adjusting the synthesis method, and other ways, under the premise of not changing the polyimide resin monomer and maintaining the resin main structure, and the error of the dissolution rate before and after coating the film is controlled within ±200 μg / s.

[0067] In another aspect, the present application provides a photosensitive resin composition comprising the above polyimide precursor, a photosensitizer, and a solvent.

[0068] As a preferred embodiment, the photosensitizer is a photoradical initiator having a structure represented by the following general formula (11):

[0069]

[0070] In formula (11), Z is a sulfur or oxygen atom, R 15 , R 16 , R 17 , R 18 each independently is a hydrogen atom or a monovalent organic group.

[0071] As a preferred embodiment, the photosensitizer having the above structure is selected from at least one of the following general formulas (11A) to (11D):

[0072]

[0073] As a preferred embodiment, the mass fraction of the photosensitizer is 1 to 20 parts by mass, preferably 1 to 8 parts by mass, relative to 100 parts by mass of the polyimide precursor, from the viewpoint of photosensitivity characteristics.

[0074] As a preferable embodiment, the solvent is a polar solvent, and specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-cyclohexylpyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, ethyl lactate, tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, and the like can be exemplified. The above can be used alone or in any mixture.

[0075] As a preferable embodiment, the mass fraction of the solvent is 100 to 500 parts by mass, preferably 100 to 200 parts by mass, with respect to 100 parts by mass of the polyimide precursor.

[0076] The above technical solution has the following advantages or beneficial effects:

[0077] The present application improves the solubility of the functional resin without changing the main structure of the polyimide precursor functional resin, and controls the dissolution rate. Therefore, the synthesis method provided by the present application has universal applicability. The precursor resin with poor solubility, slow dissolution rate, or uncontrolled solubility is increased in solubility and controllable in dissolution rate by using the synthesis process of the modifier and the capping agent and the post-processing process of rapidly precipitating solid polyimide precursor resin and refrigeration, without affecting the performance of the final polyimide film obtained after heating and curing.

[0078] The polyimide precursor resin obtained by the synthesis method provided by the present application is stable and controllable, and the dissolution rate can be adjusted in a certain range after gradient change of corresponding parameters, and the reproducibility is reliable, which brings great stability and controllability to the process of semiconductor packaging.

[0079] The polyimide precursor resin synthesized by the present application can realize adjustable dissolution rate while maintaining excellent photosensitivity of the resin.

[0080] The photoresist prepared from the polyimide precursor resin synthesized by the present application can adapt to various variable photolithography processes. DETAILED DESCRIPTION

[0081] The following examples are only a part of the embodiments of the present application, not all the embodiments. Therefore, the detailed description of the embodiments of the present application provided below is not intended to limit the scope of the claimed application, but only represents selected embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0082] In the present application, all the equipment and raw materials, etc. can be purchased from the market or commonly used in the industry, unless otherwise specified. The methods in the following examples are conventional methods in the art, unless otherwise specified.

[0083] The meanings of the English abbreviations in the following examples are shown in the following table:

[0084] Abbreviations and English Meaning GBL γ-butyrolactone NMP N-methylpyrrolidone HEMA hydroxyethyl methacrylate DCC dicyclohexyl carbodiimide ODPA 4,4'-oxydiphthalic anhydride PMDA pyromellitic dianhydride ODA 4,4'-diaminodiphenyl ether Bz benzidine Mn number average molecular weight Mw weight average molecular weight PDI polydispersity

[0085] Example 1

[0086] (1) 93.21 g (300 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) was weighed into a 1 L split-body glass reactor, and the weighing container was rinsed with 100 mL of γ-butyrolactone (GBL) to ensure that all of the ODPA was transferred to the reactor. Hydroxyethyl methacrylate (HEMA) 70.69 g (540 mmol), 1,3-dimethoxy-2-propanol 7.21 g (60 mmol), and 50 mL of GBL were added at room temperature in one batch. The anchor-shaped stirring paddle was adjusted to a rotation speed of 150 r / min, and the temperature of the system was controlled at 25°C using a circulating constant-temperature cooler. 52.2 g (660 mmol) of pyridine was added dropwise over a period of 1 h, and after the dropwise addition was completed, 90 mL of GBL was added. The rotation speed and reaction temperature were maintained unchanged, and stirring was continued for 16 h.

[0087] (2) The temperature of the reaction system was reduced to -15°C, the stirring paddle was adjusted to a rotation speed of 200 r / min, and a solution of 86.66 g (660 mmol) of dicyclohexyl carbodiimide (DCC) in 120 mL of GBL was added dropwise at a uniform rate over a period of 1 h. Stirring was continued for 1 h after the dropwise addition.

[0088] (3) Under a N2 atmosphere, 56.13 g (279 mmol) of 4,4'-diaminodiphenyl ether (ODA) was dissolved in 240 mL of N-methyl pyrrolidone (NMP) at 50°C, and then added dropwise into the above reaction system at a uniform rate over a period of 1 h under stirring at a rotation speed of 300 r / min (if ODA precipitates, it needs to be heated to prevent precipitation). After stirring at a low temperature (-18°C to -15°C) for 1 h, the temperature was increased uniformly to 25°C over a period of 1 h, the rotation speed of the stirring paddle was adjusted to 400 r / min, and then the reaction was continued at room temperature for 4 h. After 18 mL of isopropyl alcohol was added, stirring was continued for 1 h to quench the reaction.

[0089] (4) The quenched reaction solution was filtered, and the filtrate was immediately poured into 10 L of methanol to precipitate a block-shaped object. The block-shaped solid was refrigerated at 5°C for 4 h, then dissolved in 1.5 L of GBL and stirred for 5 h, and then passed through an ion exchange resin. The ion exchange resin solution was collected and added dropwise into 10 L of deionized water to precipitate, and then filtered to obtain small flaky solids. The solids were washed with 1 L of methanol three times, filtered and dried, and then dried at 50°C under vacuum for 24 h to obtain a polyimide precursor resin.

[0090] The preparation method of the photosensitive resin composition containing the polyimide precursor resin in this and the following examples is as follows: the polyimide precursor resin is prepared into a suspension with a solid content of 40% by using NMP, and then a photoinitiator 11A (structure shown below) corresponding to 5% of the mass of the resin is added to obtain a photosensitive resin composition containing the polyimide precursor, which is ready for use.

[0091]

[0092] The dissolution rate test method of the photosensitive resin composition containing the polyimide precursor resin in this and the following examples is as follows: the above resin composition is manually dispensed onto a 6-inch wafer, and then a wet film with a thickness of 20 μm ± 2 is spin-coated by adjusting the rotation speed of a spin coater, and then soft-baked at 100°C for 5 min, and then weighed by using a METTLER XPR56 / AC balance, and then immersed in a glass tank containing tetrahydrofuran (THF) for 30 s (immersion time Δt), and then quickly blown by using a hair dryer at room temperature after taking out, and then visually observed the surface of the coated film piece against light to determine whether there is solvent residue, and then weighed again, and then the weight difference Δm between the two times is compared, and then the dissolution rate is determined by using v = Δm / Δt. The greater the v, the faster the dissolution rate. The dissolution rate of the polyimide precursor resin in this example is v = 18.9 mg / s, which is measured by using the above method. The dissolution rate test is repeated 3 times for the polyimide precursor resin obtained in each of the 3 times, and the error of the dissolution rate of the polyimide precursor resin composition is ± 107 μg / s. The dissolution rate error in this and all the following examples is measured by using the same method.

[0093] The number average molecular weight M n and the weight average molecular weight M w of the polyimide precursor resin in this and the following examples are determined by using ultra-high performance gel permeation chromatography (APC) under the following conditions: chromatographic column: ACQUITY APC XT45, 1.7 μm, ACQUITY APC XT200, 2.5 μm flow rate: 0.5 mL / min, column temperature: 40°C, detector: Waters 2414 differential refractive index detector, solvent: THF.

[0094] The number average molecular weight M n of the polyimide precursor resin in this example is 14056.

[0095] The weight average molecular weight M w of the polyimide precursor resin in this example is 24629.

[0096] The PDI of the polyimide precursor resin in this example is M w / M n = 1.75.

[0097] Example 2

[0098] The polyimide precursor resin in this example was prepared in the same manner as in Example 1, but with the following modifications:

[0099] In step (1), the amount of HEMA was changed to 66.77 g (510 mmol), and the amount of the side chain modifier, 1,3-dimethoxy-2-propanol, was changed to 10.82 g (90 mmol).

[0100] The dissolution rate v of the polyimide precursor resin in this example was 25.3 mg / s, Mw= 13976, Mz= 24599, PDI = 1.76, and the dissolution rate error was ± 132 μg / s. n w = 24599, PDI = 1.76, and the dissolution rate error was ± 132 μg / s.

[0101] Example 3

[0102] The polyimide precursor resin in this example was prepared in the same manner as in Example 1, but with the following modifications:

[0103] In step (1), the amount of HEMA was changed to 62.84 g (480 mmol), and the amount of the side chain modifier, 1,3-dimethoxy-2-propanol, was changed to 14.42 g (120 mmol).

[0104] The dissolution rate v of the polyimide precursor resin in this example was 33.8 mg / s, Mw= 13787, Mz= 24531, PDI = 1.78, and the dissolution rate error was ± 151 μg / s. n w = 24531, PDI = 1.78, and the dissolution rate error was ± 151 μg / s.

[0105] Example 4

[0106] The polyimide precursor resin in this example was prepared in the same manner as in Example 3, but with the following modifications:

[0107] In step (4), the block precipitated in methanol was refrigerated for 6 h.

[0108] The dissolution rate v of the polyimide precursor resin in this example was 35.2 mg / s, Mw= 13750, Mz= 24613, PDI = 1.79, and the dissolution rate error was ± 166 μg / s. n w = 24613, PDI = 1.79, and the dissolution rate error was ± 166 μg / s.

[0109] Example 5

[0110] The polyimide precursor resin in this example was prepared in the same manner as in Example 3, but with the following modifications:

[0111] In step (4), the block precipitated in methanol was refrigerated for 8 h.

[0112] ​​​The dissolution rate of the polyimide precursor resin in this example is v = 38.3 mg / s, M n = 13620, M w = 24515, PDI = 1.80, with a dissolution rate error of ± 158 pg / s.

[0113] Example 6

[0114] (1) 46.53 g (150 mmol) of 4,4'-oxydiphthalic anhydride (ODPA) and 32.72 g (150 mmol) of pyromellitic dianhydride (PMDA) were weighed into a 1 L split-body glass reactor, and the weighing container was rinsed with 100 mL of gamma-butyrolactone (GBL) to ensure that all the solids were transferred into the reactor. Hydroxyethyl methacrylate (HEMA) 70.69 g (540 mmol), 1,3-dimethoxy-2-propanol 7.21 g (60 mmol), and 50 mL of GBL were added at room temperature in one go. The anchor-shaped stirring paddle was set to a rotation speed of 150 r / min, and the temperature of the system was controlled at 25 °C using a circulating thermostat cooler. 52.2 g (660 mmol) of pyridine was added dropwise over a period of one hour, and after the addition was complete, 90 mL of GBL was added. The rotation speed and reaction temperature were maintained, and stirring was continued for 16 h.

[0115] (2) The temperature of the reaction system was reduced to -15 °C, and the stirring paddle was set to a rotation speed of 200 r / min. A homogeneous mixture of 86.66 g (660 mmol) of dicyclohexyl carbodiimide (DCC) in 120 mL of GBL was added dropwise over a period of one hour, and after the addition was complete, stirring was continued for 1 h.

[0116] (3) Under a N2 atmosphere, 39.72 g (197.4 mmol) of 4,4'-diaminodiphenyl ether (ODA) and 15.59 g (84.6 mmol) of benzidine (Bz) were dissolved in a constant-pressure dropping funnel containing 240 mL of NMP at 50 °C. The solution was added dropwise into the above reaction system over a period of one hour at a stirring paddle rotation speed of 300 r / min (if the diamine precipitates, it needs to be heated to prevent precipitation). After stirring at low temperature (-18 °C to -15 °C) for 1 h, the temperature was increased uniformly to 25 °C over a period of 2 h, the stirring paddle rotation speed was set to 400 r / min, and the reaction was continued at room temperature for 3 h. 18 mL of isopropyl alcohol was added, stirring was continued for 1 h to quench the reaction, and the reaction was terminated.

[0117] (4) The quenched reaction solution was filtered, and the filtrate was immediately poured into 10 L of methanol to precipitate a block-shaped object. The block-shaped object was refrigerated at 5 °C for 8 h, then dissolved in 1.3 L of GBL, stirred for 5 h, and passed through an ion exchange resin. The resin solution was collected and dropped into 10 L of deionized water, and a small flaky solid was obtained by filtration. The filter cake was washed with 1 L of methanol three times, filtered and dried, and the resin was obtained by vacuum drying at 50 °C for 24 h.

[0118] The dissolution rate v of the polyimide precursor resin in this embodiment is 27.1 mg / s, M n = 13878, M w = 25120, PDI = 1.81, the dissolution rate error is ± 113 μg / s.

[0119] Example 7

[0120] The preparation process of the polyimide precursor resin in this embodiment is the same as that in Example 6, but the following changes are made:

[0121] In step (1), the amount of HEMA added is 62.84 g (480 mmol), and the amount of 1,3-dimethoxy-2-propanol is 14.42 g (120 mmol);

[0122] The dissolution rate v of the polyimide precursor resin in this embodiment is 31.8 mg / s, M n = 13941, M w = 24815, PDI = 1.78, the dissolution rate error is ± 171 μg / s.

[0123] As can be seen from the above examples, the dissolution rate of the polyimide precursor resin provided in the present patent is significantly higher than that prepared according to the method disclosed in patent document CN107850844A (the measured dissolution rate is 11.4 mg / s, and the dissolution rate error is 217 μg / s).

[0124] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for synthesizing a polyimide precursor, characterized by, The method comprises the following steps: (1) reacting a dianhydride, an alcohol with radical polymerizable unsaturated double bond, and a side chain modifier in a solvent under the catalysis of an alkaline catalyst; (2) adding a dehydration condensing agent to the reaction system of step (1) and stirring; (3) adding a diamine to the reaction system of step (2) to perform a reaction, and finally adding a capping agent to quench the reaction and filtering; (4) immediately adding the filtrate into a poor solvent to precipitate a solid polyimide precursor resin and refrigerate; the refrigeration is refrigeration at 0-10°C for 2-24 hours; The side chain modifier is an ether alcohol side chain modifier; the capping agent is selected from any one or several of an alcohol capping agent, an ether alcohol capping agent, and an amine capping agent; the step of immediately adding the filtrate into a poor solvent is adding within 0-2 hours; the molar ratio of the dianhydride to the side chain modifier is 1:0.01-1:0.

9. The polyimide precursor is a polyamic acid ester having the general formula (1) shown below: （1）； In formula (1), X is a tetravalent organic group, Y is a divalent organic group, n1 is an integer of 2-200, R1 and R2 are independently selected from any one of the monovalent organic groups shown in the general formulae (2), (3), and (4); （2）； In formula (2), R3, R4, and R5 are independently selected from any one of a hydrogen atom or an organic group with 1-5 carbon atoms, and m1 is an integer of 2-10; （3）； In formula (3), R6 is a saturated divalent alkyl group with 1-5 carbon atoms, R7 is a saturated monovalent alkyl group with 1-10 carbon atoms, and m2 is an integer of 0-10; （4）； In formula (4), R8and R9are each independently a saturated divalent alkyl group having 1 to 10 carbon atoms, and R 10 , R 11 are each independently a saturated monovalent alkyl group having 1 to 10 carbon atoms. The ether alcohol side chain modifier has the structure shown in the general formula (7) or the general formula (8) shown below: （7）； （8）； In formula (7), R6 is a saturated divalent alkyl group with 1-5 carbon atoms, R7 is a saturated monovalent alkyl group with 1-10 carbon atoms, and m3 is an integer of 1-10; In formula (8), R8, R9independently of one another are any of saturated divalent alkyl groups having 1 to 10 carbon atoms, R 10 11 independently of one another are any of saturated monovalent alkyl groups having 1 to 10 carbon atoms;​ The alcohol capping agent has the structure shown in the general formula (6) shown below: （6）； In formula (6), R6 is a saturated divalent alkyl group with 1-5 carbon atoms, R7 is a saturated monovalent alkyl group with 1-10 carbon atoms, and m2 is an integer of 0-10; The ether alcohol capping agent has the structure shown in the general formula (7) or the general formula (8) shown below: （7）； （8）； In formula (7), R6 is a saturated divalent alkyl group with 1-5 carbon atoms, R7 is a saturated monovalent alkyl group with 1-10 carbon atoms, and m3 is an integer of 1-10; In formula (8), R8, R9independently of one another are any of saturated divalent alkyl groups having 1 to 10 carbon atoms, R 10 11 independently of one another are any of saturated monovalent alkyl groups having 1 to 10 carbon atoms;​ The amine capping agent has the structure shown in the general formula (9) shown below: （9）； In formula (9), R 12 is any one of saturated divalent alkyl groups having 1 to 20 carbon atoms or aryl groups; R 13 , R 14 are each independently selected from any one of saturated monovalent alkyl groups having 1 to 20 carbon atoms or monovalent aryl groups.

2. The method of synthesis according to claim 1, wherein, The step of immediately adding the filtrate into a poor solvent is adding within 0.5 hours.

3. The method of synthesis of claim 1, wherein, The molar ratio of the dianhydride to the side chain modifier is 1:0.05-1:0.

7.

4. The method of synthesis of claim 1, wherein, The molar ratio of the dianhydride to the side chain modifier is 1:0.05-1:0.

5.

5. The method of synthesis of claim 1, wherein, The molar ratio of the dianhydride to the capping agent is 1:0.5-1:3.

0.

6. The method of synthesis of claim 1, wherein, The molar ratio of the dianhydride to the capping agent is 1:0.7-1:2.

0.

7. The method of synthesis of claim 1, wherein, The molar ratio of the dianhydride to the capping agent is 1:0.8-1:1.

5.

8. The method of synthesis of claim 1, wherein, The molar ratio of the dianhydride to the diamine is 1:0.8-1:0.

98.

9. The method of synthesis of claim 1, wherein, In step (1), the reaction is a reaction at room temperature for 8-24 hours.

10. The method of synthesis of claim 1, wherein, In step (3), the diamine is added after being dissolved in a solvent.

11. The method of synthesis of claim 1, wherein, In step (3), the reaction after adding the diamine is a low-temperature reaction at -20-0°C for 0.5-5 hours, and then the temperature is raised to room temperature for continuous reaction for 0.5-5 hours.

12. The method of synthesis of claim 1, wherein, In step (3), the quenching reaction after adding the capping agent is continuous stirring for 0.5-5 hours.

13. A photosensitive resin composition, characterized in that, The polyimide precursor, the photosensitizer and the solvent obtained by the synthesis method according to any one of claims 1-12.

14. The photosensitive resin composition according to claim 13, characterized by The photosensitizer is a photoradical initiator, and has the structure shown in the following general formula (11): （11）； In formula (11), Z is a sulfur or oxygen atom, R 15 , R 16 , R 17 , R 18 each independently is a hydrogen atom or a monovalent organic group.

15. The photosensitive resin composition according to claim 14, characterized by The photosensitizer is selected from at least one of the following general formulae (11A)-(11D): (11A); (11B); (11C); (11D).

16. The photosensitive resin composition according to claim 13, characterized by The mass fraction of the photosensitizer is 1-20 parts by mass relative to 100 parts by mass of the polyimide precursor.

17. The photosensitive resin composition according to claim 16, characterized by The mass fraction of the photosensitizer is 1-8 parts by mass relative to 100 parts by mass of the polyimide precursor.

18. The photosensitive resin composition according to claim 13, characterized by The solvent is a polar solvent.

19. The photosensitive resin composition according to claim 13, characterized by The mass fraction of the solvent is 100-500 parts by mass relative to 100 parts by mass of the polyimide precursor.

20. The photosensitive resin composition according to claim 19, characterized by The mass fraction of the solvent is 100-200 parts by mass relative to 100 parts by mass of the polyimide precursor.

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