Polyimide resin, photosensitive resin composition containing polyimide resin, and photosensitive cured film

Abstract

A polyimide resin, a photosensitive resin composition containing the polyimide resin, and a photosensitive cured film. By introducing an alicyclic structure, an aromatic structure, and a fluorine-containing substituent structure into a polyimide resin structure, good optical characteristics and a relatively low dielectric constant can be achieved, and low-temperature curing characteristics and good heat resistance are guaranteed.

Description

Polyimide resin, photosensitive resin composition containing the same, and photosensitive cured film

[0001] Cross-references

[0002] This application claims priority to Chinese patent application No. 202311240447.1 filed on September 25, 2023, entitled “A polyimide resin, a photosensitive resin composition comprising the polyimide resin, and a photosensitive cured film,” the entire disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to the field of polymer materials, in particular to a polyimide resin, a photosensitive resin composition containing the polyimide resin, and a photosensitive cured film. Background Art

[0004] Due to its unique aromatic ring conjugation and imide ring structure, polyimide exhibits good heat resistance, high insulation, chemical resistance and good mechanical properties, and is widely used in surface passivation layers, stress buffer layers and interlayer insulation layers of semiconductor devices; it also has important application value in signal line distribution, α-particle shielding layers, micro-solder ball processes, stress buffer layers of plastic-encapsulated circuits, flexible packaging substrates, etc. in semiconductor advanced packaging (BGA, CSP, SiP, WLP, etc.); at the same time, in display devices such as organic EL display devices or liquid crystal display devices, photosensitive polyimide resins are widely used in the flat layer and pixel definition layer of the display device to improve interlayer insulation and reduce display color difference.

[0005] With the development of miniaturization, precision and multifunctionality of microelectronic products, higher requirements are placed on the material properties such as dielectric properties, optical properties, thermal properties and low-temperature curing characteristics; however, due to the presence of conjugated structure and imide structure, polyimide has a high water absorption rate and poor dielectric properties. At the same time, it has disadvantages such as poor adhesion to the substrate, poor transparency and high curing temperature, which greatly limits the development of photosensitive polyimide materials in the semiconductor and display fields.

[0006] Summary of the Invention

[0007] In view of the deficiencies in the prior art, the present invention provides a polyimide resin, a photosensitive resin composition comprising the polyimide resin, and a photosensitive cured film.

[0008] In a first aspect, the present invention provides a polyimide resin comprising a structure represented by general formula (1) and a structure represented by general formula (2):

[0009] Wherein, in the general formula (1), Ar1 represents a dianhydride residue, Ar2 represents a diamine residue; R1 represents H or an organic group having 1 to 10 carbon atoms, m is an integer from 10 to 10000, and r is an integer from 0 to 2; wherein the organic group having 1 to 10 carbon atoms is selected from one or more of an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, and an organic group having a carbon-carbon unsaturated double bond;

[0010] In the general formula (2), Ar4 represents a diamine residue; n is an integer from 10 to 10,000; Ar3 represents a dianhydride residue, and the dianhydride forming the dianhydride residue is selected from one or more structures represented by the general formulas (3), (4), (5) and (6).

[0011] Specifically, the structure of general formula (3) is as follows:

[0012] Wherein, R2 and R5 are the same or different and each independently represents -(CH2)- or -(CH2CH2)-; R3 and R4 are the same or different and each independently represents H or F.

[0013] The general formula (4) has the following structure:

[0014] Among them, X I , X2, X3 are the same or different, and each independently represents C t R8, NH, O or S;

[0015] R6, R7, and R8 are the same or different and each independently represents hydrogen, deuterium, halogen, an alkyl group or alkoxy group having 1 to 12 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 12 carbon atoms, an aryl group or aryloxy group having 6 to 12 carbon atoms, an alkylsilanyl group having 1 to 12 carbon atoms, or an arylsilanyl group having 6 to 12 carbon atoms; wherein H in the alkyl group, alkoxy group, alkenyl group, alkenyloxy group, alkynyl group, cycloalkyl group, or cycloalkenyl group may be substituted by F, and one or more non-adjacent -CH2- groups may be substituted by -O-, -NH-, or -S-, provided that the O atoms and the S atoms are not directly connected to each other;

[0016] s=an integer from 0 to 12, t=an integer from 0 to 12.

[0017] Preferably, R6, R7, and R8 are the same or different and each independently represents hydrogen, deuterium, F, an alkyl or alkoxy group having 1 to 6 carbon atoms, an alkenyl or alkenyloxy group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl or cycloalkenyl group having 3 to 12 carbon atoms, or an aryl or aryloxy group having 6 to 12 carbon atoms; wherein H in the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, cycloalkyl, or cycloalkenyl group may be replaced by F, and one or more non-adjacent -CH2- groups may be independently replaced by -O-, provided that the O atoms are not directly connected to each other;

[0018] s=0-6 integer, t=0 or 1 or 2.

[0019] It should be noted that C t The t Cs in R8 are all connected to the ring structure containing X1, X2, and X3, and R8 is a substituent on C and is not connected to the ring.

[0020] When t=0, C t R8 represents a single bond, X1, X2, and X3 cannot all represent single bonds, and at most two of them represent single bonds. When two of X1, X2, and X3 represent single bonds, the ring containing X1, X2, and X3 is a three-membered ring. When only one of X1, X2, and X3 represents a single bond, the ring containing X1, X2, and X3 is a four-membered ring.

[0021] When t=1, C t R8 represents CR8, one C is connected to a ring structure containing X1, X2, and X3, and R8 may represent two hydrogens, or one or both of the hydrogens are replaced by deuterium, halogen, an alkyl or alkoxy group having 1-12 carbon atoms, an alkenyl or alkenyloxy group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, a cycloalkyl or cycloalkenyl group having 3-12 carbon atoms, an aryl or aryloxy group having 6-12 carbon atoms, an alkylsilanyl group having 1-12 carbon atoms, or an arylsilanyl group having 6-12 carbon atoms; wherein H in the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, cycloalkyl, or cycloalkenyl group may be replaced by F, and one or more non-adjacent -CH2- may be independently replaced by -O-, -NH-, or -S-, but the O atoms and the S atoms are not directly connected to each other.

[0022] When t=2, both C atoms are connected to a ring structure comprising X1, X2, and X3, and each C may be connected to two hydrogen atoms, or one or both hydrogen atoms may be replaced by deuterium, a halogen, an alkyl or alkoxy group having 1-12 carbon atoms, an alkenyl or alkenyloxy group having 2-12 carbon atoms, an alkynyl group having 2-12 carbon atoms, a cycloalkyl or cycloalkenyl group having 3-12 carbon atoms, an aryl or aryloxy group having 6-12 carbon atoms, an alkylsilanyl group having 1-12 carbon atoms, or an arylsilanyl group having 6-12 carbon atoms; wherein H in the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, cycloalkyl, or cycloalkenyl group may be replaced by F, and one or more non-adjacent -CH2- groups may be independently replaced by -O-, -NH-, or -S-, provided that the O atoms and the S atoms are not directly connected to each other.

[0023] The structures of general formula (5) and general formula (6) are as follows:

[0024] It should be noted that there is a single-touch connection between X5 and X6, and X9 and X 10 There is a single bond connection between them, which may not be clearly shown in the general structure due to display reasons.

[0025] Among them, X4, X5, X6, X7, X8, X9, X 10 、X 11 The same or different, each independently represents C t R 11 or N, p=0 to 12 integers, q=0 to 12 integers, t=0 to 12 integers; preferably, t=1, C t R 11 CR 11 , C is connected to the ring, R 11 as a substituent.

[0026] R9, R 10 、R 11The same or different, each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted alkyl or alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl or cycloalkenyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl or aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted any one of an alkylthiooxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms which has a heteroatom O, N or S, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 6 to 24 carbon atoms.

[0027] The present invention can achieve good optical properties and a low dielectric constant by introducing the structures represented by general formula (3), (4), (5) and / or (6) into the polyimide resin structure, while ensuring low-temperature curing properties and good heat resistance.

[0028] The dianhydride residue of the present invention refers to a residue obtained by removing two anhydride groups from a dianhydride. The dianhydride includes but is not limited to the dianhydrides represented by general formulas (3), (4), (5) and (6) and the following dianhydrides, such as pyromellitic dianhydride (PMDA), 3,3,3',4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-(hexafluoroisopropylene) diphthalic anhydride (6FDA), One or more of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), p-phenylene-triphthalate dianhydride (TAHQ), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (BSDA), cyclobutanetetracarboxylic dianhydride (CBDA), cyclohexanetetracarboxylic dianhydride (HPMDA), N,N'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxamide) (6FAP-ATA) and N-[5-[3-[(1,3-dioxy-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxy-2-benzofuran-5-carboxamide (6FAP-ASA).

[0029] The diamine residue of the present invention refers to a residue obtained by removing two amino groups from a diamine. The diamine includes but is not limited to the following diamines, such as hydroxyl-containing diamines and hydroxyl-free diamines, hydroxyl-containing diamines such as 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]ether, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 2,2-bis[3-(4-aminobenzamido)- 4-hydroxyphenyl] hexafluoropropane, N-(2-hydroxy-5-amino)phenyl-3-aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propan-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-sulfonyl-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl]benzamide and N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[ (4-aminophenyl)carbamoyl]phenyl]-hexafluoropropane-2-yl]benzamide; does not contain hydroxy diamines such as 1,4-p-phenylenediamine (PDA), m-phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4,4'-diaminodiphenyl ether (ODA), 4,4'-diamino-p-terphenyl (DATP), 4,4'-methylenediaminodiphenylmethane (MDA), and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), p-aminophenyl para-aminobenzoate (APAB), 1,4-bis(4'-aminophenoxy)benzene (1,4,4-APB), 1,3,4-APB:1 ,3-bis(4'-aminophenoxy)benzene (1,3,4-APB), 1,3-bis(3'-aminophenoxy)benzene (1,3,3-APB), 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP), 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (SIDA) or one or more thereof.

[0030] The diamine residues represented by Ar2 and Ar4 in the present invention are the same or different and are selected from the residues formed by the above-mentioned diamines.

[0031] The preparation method of the polyimide resin of the present invention comprises the following steps:

[0032] (1) preparing the desired alicyclic dianhydride (dianhydride having the structure shown in general formula (3), (4), (5) and (6)) according to the designed structure and process, and performing purification and other post-treatments for use;

[0033] (2) Under the protection of inert gas, non-alicyclic monomers are successively dissolved in an organic solvent, and a polyimide precursor solution 1 with a solid content of 10-50% is obtained through polymerization reaction, or a diester solution is obtained through esterification of dianhydride and alcohol, and then further reacted with diamine after chlorination or DCC treatment to obtain a polyimide precursor solution 1 with a solid content of 10-50%; alicyclic dianhydride, other dianhydride (optionally added) and diamine are successively dissolved in an organic solvent, and a polyimide solution 2 with a solid content of 10-50% is obtained through high-temperature polymerization reaction; the two are mixed and stirred at room temperature to obtain a polyimide resin solution (a small amount of copolymerization occurs under room temperature mixing);

[0034] (3) Using a precipitant to precipitate the resin, and obtaining the target polyimide resin after filtering, washing and drying.

[0035] According to the polyimide resin provided by the present invention, the structural unit represented by general formula (1) accounts for more than 50% of the total weight of the polyimide resin; and the structural unit represented by general formula (2) accounts for less than 50% of the total weight of the polyimide resin.

[0036] The present invention has found that the higher the specific gravity of the structural unit represented by general formula (2), the better. When the specific gravity exceeds 50%, it is not conducive to adjusting the photosensitivity and photolithography process window of the photosensitive resin composition, and is likely to affect the control of resolution; it is also likely to affect the adhesion between the photosensitive cured film and the substrate.

[0037] According to the polyimide resin provided by the present invention, the structure represented by the general formula (3) is selected from the group consisting of the following structures:

[0038] According to the polyimide resin provided by the present invention, the structural unit represented by the general formula (4) is selected from the group consisting of the following structures:

[0039] According to the polyimide resin provided by the present invention, the structure shown in the general formula (5) is

[0040] According to the polyimide resin provided by the present invention, the structure shown in the general formula (6) is

[0041] In a second aspect, the present invention provides a photosensitive resin composition comprising (a) a polyimide resin, (b) a photosensitive compound, (c) a crosslinking agent, (d) an adhesion modifier, and (e) a solvent, wherein the (a) polyimide resin comprises any of the above-mentioned polyimide resins.

[0042] According to the photosensitive resin composition provided by the present invention, the (b) photosensitive compound is one of a naphthoquinone azide-type photosensitizer or an oxime ester compound.

[0043] The naphthoquinone azide photosensitizer is an esterified product of a phenolic hydroxyl group-containing compound and naphthoquinone azide sulfonyl chloride. The phenolic hydroxyl group-containing compound includes, but is not limited to, one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).

[0044] The oxime ester compound includes but is not limited to one or more of the following structures:

[0045] Among them, R 12 represents one of H, OH-, COOH-, -O(CH2)OH, -COO(CH2)OH and -COO(CH2)2OH; R 13 and R 14 Each represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and a phenyl group; preferably, OXE-01 (trade name, BASF), the structure of which is shown below:

[0046] R 16 represents an alkyl group having 1 to 6 carbon atoms; R 15 Represents NO2 or toluene carbonyl; R 17 and R 18 represents an alkyl group, a phenyl group or a tolyl group having 1 to 12 carbon atoms;

[0047] R 19 Represents an organic group having an acetal bond; R 20 represents an alkyl group having 1 to 6 carbon atoms; R 21 and R 22 It represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group.

[0048] According to the photosensitive resin composition provided by the present invention, the crosslinking agent (c) has no special requirements and can be a thermally crosslinkable compound that can undergo a crosslinking reaction with the polyimide resin. Specifically, the crosslinking agent (c) includes, but is not limited to, one or more of epoxy compounds, alkoxymethylol compounds, alkoxymethylol triazine ring compounds, and chain extenders.

[0049] The epoxy compound includes but is not limited to one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and propylene glycol diglycidyl ether.

[0050] The alkoxymethylol compound includes but is not limited to polyalkoxymethylolated phenolic hydroxyl compounds, wherein the phenolic hydroxyl compound includes but is not limited to one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).

[0051] The alkoxy hydroxymethyl triazine ring compound is selected from one or more compounds represented by general formula (7);

[0052] Among them, R 23 and R 24 Each independently represents H, CH2OCH3 or CH2OCH2CH3, and not all are H.

[0053] The chain extender is an acrylate compound, including but not limited to the following compounds, such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, styrene, and one or more of hydroxyethyl methacrylate.

[0054] According to the photosensitive resin composition provided by the present invention, the (e) solvent is one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents and other solvents.

[0055] By way of example but not limitation, the ketone solvent is one of acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone.

[0056] The ester solvent is one or more of ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and gamma-butyrolactone.

[0057] The ether solvent is one or more of propylene glycol methyl ether, propylene glycol monoethyl ether, and ethylene glycol monomethyl ether.

[0058] The aromatic hydrocarbon solvent may be one or more of toluene and xylene.

[0059] The other solvents are one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0060] According to the photosensitive resin composition provided by the present invention, the (d) adhesion modifier includes but is not limited to one or more of the following: γ-glycidyloxypropyltrimethoxysilane (KH560), γ-aminopropyltriethoxysilane (KH550), γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-aminophenyltrimethoxysilane, 3-(m-aminophenoxy)trimethoxysilane, 3-mercaptomethyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

[0061] In a third aspect, the present invention provides a photosensitive cured film formed by curing any one of the above-mentioned photosensitive resin compositions.

[0062] Those skilled in the art will appreciate that curing the photosensitive resin composition to form a cured film typically involves some pre-treatment, such as coating, hot plate drying, exposure, and development before curing. Each step employs conventional techniques in the art. For example, coating may be performed using a rotational viscometer, drying may be performed using a hot plate, and curing may be performed thermally under nitrogen.

[0063] According to the photosensitive cured film provided by the present invention, the adhesion of the photosensitive cured film is tested using the Hundred Grid method, and the transfer area is ≤10%; the average transmittance (380-780nm) is greater than 70%; the dielectric constant Dk is ≤3.5, the glass transition temperature Tg is less than 350°C, and the thermal weight loss temperature T5% is greater than 350°C.

[0064] The above performance test results indicate that the photosensitive cured film obtained by the present invention has good adhesion, excellent light transmittance, low dielectric properties and good heat resistance.

[0065] The photosensitive cured film provided by the present invention is suitable for use as a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescent element, and an insulating layer of a thin film transistor.

[0066] The present invention provides a polyimide resin, a photosensitive resin composition and a photosensitive cured film. By introducing structural units represented by general formulas (3), (4), (5) and (6) into the polyimide resin structure, an alicyclic structure, an aromatic structure and a fluorine-containing substituent structure are introduced into the main structure thereof, thereby achieving good optical properties and a low dielectric constant, while ensuring low-temperature curing properties and good heat resistance. DETAILED DESCRIPTION

[0067] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0068] Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art. Unless otherwise specified, the materials and reagents used in the examples of the present invention can be obtained through regular commercial channels.

[0069] The abbreviations of the compounds in the following examples are:

[0070] PDA: p-phenylenediamine

[0071] ODA:4,4'-diaminodiphenyl ether

[0072] ODPA:4,4'-oxydiphthalic anhydride

[0073] 6FAP: 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0074] DMFDEA: N,N'-dimethylformamide diethyl acetal

[0075] MAP: meta-aminophenol

[0076] TrisP-HAP: 1,1,1-tris(4-hydroxyphenyl)ethane

[0077] HEMA: 2-Hydroxyethyl Methacrylate

[0078] DAST: diethylaminosulfur trifluoride.

[0079] Synthesis Example 1 Synthesis of dianhydrides (1-1) and (1-2)

[0080] The synthesis route is as follows:

[0081] (1) Synthesis of compound 1-b

[0082] To a 250ml fluorinated three-necked flask, 1-a (836.244mg, 3.48mmol) dissolved in dichloromethane (150mL) was added. Under nitrogen, the temperature was cooled to -30°C, and DAST (2.42g, 13.92mmol) was added dropwise while maintaining the temperature between -30°C and -35°C. The mixture was allowed to warm to room temperature and stirred overnight. TLC monitored the reaction for completion. The reaction solution was poured into a mixture of 50ml of dichloromethane and 50ml of saturated ammonium bicarbonate solution and stirred for 15min. The layers were separated, and the aqueous layer was extracted with dichloromethane (2 x 100mL). The combined organic layers were washed once with 50ml of saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent removed under reduced pressure to afford 1-b (847.58mg, 85.76%) as a yellow oil.

[0083] 1 H-NMR (400MHz, CDCl36.06-6.12(m,4H),2.83-2.90(m,4H),2.00-2.02(m,4H),1.91–1.99(m,4H),1.19-1.26(m,2H).

[0084] Cl-MS (m / z); 285 (M+1)

[0085] (2) Synthesis of compound 1-c

[0086] To a reaction vessel with a capacity of 1 L, 364 g of methanol, 62 g of chloroform, 136 g (1011 mmol) of copper (II) chloride and 6 g (33.7 mmol) of palladium chloride were added and stirred. After the atmospheric gas in the system was replaced with carbon monoxide, a solution of 1-b19.12 g (67.3 mmol) dissolved in 178 g of chloroform was added dropwise over 3 hours and allowed to react for 4 hours at 20-25 ° C. Next, the atmosphere in the system was replaced with argon from carbon monoxide, and then the solvent was distilled off from the reaction mixture and 621 g of chloroform was added. The same operation was repeated twice. Then, insoluble matter was removed from the obtained tea-green suspension by filtration. The obtained solution was washed 3 times with 324 g of saturated sodium bicarbonate aqueous solution and then washed 3 times with 324 g of pure water. After that, 2.7 g of anhydrous magnesium sulfate and 2.7 g of activated carbon were added to the organic layer and stirred. Then, after filtering the solution, it was concentrated under reduced pressure to obtain 51 g of white solid. The product was then purified by silica gel chromatography (developing solvent; hexane:ethyl acetate = 10:1 (volume ratio)) to obtain 26.62 g of 1,4,5,8-dimethylanthracene-9,10-tetrafluoro-2,3,6,7-tetracarboxymethyl ester (1-c) as a white solid (purity 99.1% by HPLC analysis, yield 76%).

[0087] 1 H-NMR(400MHz, CDCl3)3.67(S,12H),3.11-3.15(dd,4H),2.21-2.27(m,4H),1.81–1.94(m,4H),1.76-1.80(m,2H).1.52-1.57(m,2H).

[0088] Cl-MS (m / z); 521 (M+1)

[0089] (3) Synthesis of Compound 1-1

[0090] Into a reaction vessel with a capacity of 100 mL, 1-c 6.19 g (11.9 mmol), formic acid 26.3 g, and p-toluenesulfonic acid monohydrate 47 mg (0.24 mmol) were added, and the mixture was reacted at a temperature of 98°C for 30 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 30 g of toluene was added to the concentrate. This operation was repeated 6 times to distill off the formic acid almost completely. The resulting suspension was filtered, and the resulting solid was washed with 30 g of toluene and then vacuum-dried at 80°C to obtain 4.0 g of a milky white solid. Thereafter, recrystallization was performed using acetic anhydride, and further recrystallization was performed using N, N'-dimethylacetamide to obtain 4.02 g (based on) of 1,4,5,8-dimethylanthracene-9,10-tetrafluoro-2,3,6,7-dianhydride (1-1) as a white solid. 1 Purity by H-NMR analysis: 98.3%, yield: 79%).

[0091] 1 H-NMR(400MHz, CDCl3)3.14-3.18(dd,4H),2.19-2.25(m,4H),1.88–2.0(m,4H),1.75-1.80(m,2H).0.90-0.95(m,2H).

[0092] Cl-MS (m / z); 429 (M+1)

[0093] The dianhydride (1-2) was prepared by the following synthetic route and a similar synthetic method; in the first step, sodium borohydride was added to THF / methanol at 5-10°C for 7 hours, followed by addition of saturated ammonium chloride solution, heating to 25°C, and filtration; in the second step, DAST was added dropwise in the same manner as in 1-1; the subsequent steps were consistent with the synthetic method of 1-1.

[0094] The synthetic route is as follows:

[0095] Synthesis Example 2 Synthesis of Dianhydrides (1-3), (1-4), (1-5) and (1-6)

[0096] The synthesis route is as follows:

[0097] (1) Synthesis of compounds 1-e and 1-f

[0098] To the reaction flask, add 24.0 g of a 50% aqueous dimethylamine solution. Under ice-cold conditions, add dropwise 33.2 g of a 30% aqueous hydrochloric acid solution. Stir and react for 1 hour to produce the hydrochloride of dimethylamine. Slowly add 9.9 g of paraformaldehyde and 15.0 g of compound 1-d to the reaction flask. Under nitrogen, heat to 85-90°C for 3 hours. Conventional post-treatment is performed. HPLC analysis reveals a 99.3% conversion of compound 1-d in the reaction solution (1-f), which can be directly used in the next step.

[0099] (2) Synthesis of compound 1-g

[0100] The reaction mixture was cooled to 50°C, and 80 ml of methyl cellosolve, 3.8 g of a 50% aqueous solution of dimethylamine, and 25.4 g of cyclopentadiene were slowly added under nitrogen. The mixture was heated to 115-120°C and reacted at this temperature for 1.5 hours. The mixture was then cooled to room temperature (25°C). Conventional post-processing was performed, followed by chromatography purification with n-hexane elution and short-path distillation to obtain 22.8 g of a colorless oily liquid (1-g), GC: 98%, and a yield of 71%.

[0101] (3) Synthesis of compound 1-h

[0102] To the reaction flask were added 50 ml of methanol, 10 ml of chloroform, 0.5 g of copper (II) chloride, and 0.8 g of palladium chloride, and the mixture was stirred. The carbon monoxide was replaced three times. A mixture of 20 g of compound 1-g and 50 ml of chloroform was added dropwise at a temperature of 20-25°C. The mixture was added dropwise over approximately 3 hours. The reaction was continued at this temperature for 4 hours. The atmosphere was replaced with nitrogen three times, and the solvent was evaporated. Conventional post-treatment was carried out and purification was performed by silica gel chromatography (hexane:ethyl acetate = 10:1) to obtain 26.3 g of 1-h as a white solid, LC: 99.4%, yield 73%.

[0103] (4) Synthesis of Compounds 1-3

[0104] To a reaction flask, 25.0 g of 1-h, 20.5 g of formic acid, and 25.0 mg of p-toluenesulfonic acid monohydrate were added and reacted at 98°C for 20 hours. After completion of the reaction, the formic acid was distilled off, the mixture was filtered, and the filter cake was rinsed with toluene. The resulting crude product was recrystallized from acetic anhydride and then from N'N'-dimethylacetamide to yield 16.9 g of a white solid (1-3). LC analysis revealed a 99.5% yield, with a yield of 82%. GC-MS (m / z): 438.47 (M+). Elemental analysis: C: 68.45, H: 5.97, O: 25.54.

[0105] By replacing the starting materials for the synthesis of (1-3), dianhydrides (1-4), (1-5) and (1-6) were synthesized respectively through the following synthetic routes and referring to the synthetic steps of (1-3).

[0106] Synthesis Example 3 Synthesis of photosensitizer (PAC-1)

[0107] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 260 g of dioxane (water was removed with molecular sieves 24 hours in advance) was added, and then 10.60 g (0.025 mol) of TrisP-PA (trade name, made by Honshu Chemical) and 20.1 g (0.075 mol) of naphthoquinone azidosulfonyl chloride were added respectively. A mixed solution of triethylamine (6.3 g) and dioxane (20 g) was slowly added dropwise, and the temperature was controlled within 30°C. After the addition was completed, the mixture was kept at 30°C for 2 hours. The mixture was filtered, washed with deionized water 3 times, rinsed with dilute hydrochloric acid and deionized water 3 times respectively, and dried in a vacuum at 60°C for 24 hours.

[0108] Synthesis Example 4 Synthesis of photosensitizer (PAC-2)

[0109] The photosensitizer PAC-2 was prepared by a similar synthesis method to that in Synthesis Example 3, except that TrisP-PA (trade name, manufactured by Honshu Chemical) was replaced by Trisp-HAP (trade name, manufactured by Honshu Chemical).

[0110] Synthesis Example 5 Synthesis of Crosslinking Agent (C-1)

[0111] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 200 g of water was added, followed by 20 g (0.5 mol) of NaOH and 25.8 g (0.1 mol) of 1,1,1-tris(4-hydroxyphenyl)ethane. After sufficient dissolution, 18 eq of formaldehyde solution was slowly added dropwise, with the temperature controlled below 20°C. After the addition was complete, the temperature was kept at 20°C for 24 hours. Sulfuric acid and water were added to neutralize the product to obtain a white product, which was washed three times with deionized water and dried under vacuum at 50°C for 72 hours.

[0112] The dried white product was further reacted with methanol at room temperature for 24 h, and the methanol was removed by distillation under reduced pressure to obtain cross-linking agent C-1.

[0113] Synthesis Example 6 Synthesis of Crosslinking Agent (C-2)

[0114] Crosslinking agent C-2 was prepared by a similar synthesis method to that in Synthesis Example 5, except that Trisp-HAP (trade name, manufactured by Honshu Chemical) was replaced with melamine.

[0115] Synthesis Example 7 Synthesis of Polyimide Resin A-1

[0116] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 104.31 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours in advance) was added, followed by 4.00 g (0.02 mol) of ODA and 14.65 g (0.04 mol) of compound 6FAP, and the mixture was stirred at 25°C until completely dissolved. 21.71 g (0.07 mmol) of compound ODPA was then added, and the mixture was stirred at room temperature for 12 hours. 2.18 g (0.02 mol) of MAP was added, and the mixture was kept warm for 12 hours. 23.31 g of DMFDEA was added, the temperature was raised to 60°C, kept warm for 4 hours, and then cooled to room temperature to obtain resin solution A-1-1.

[0117] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 70 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours in advance) was added, followed by 6.00 g (0.03 mol) of ODA. The mixture was stirred at 25°C until completely dissolved. Then, 12.84 g (0.03 mmol) of compound 1-1 was added and the mixture was stirred at room temperature for 12 hours. 30 g of toluene was added, the temperature was raised to 160°C, refluxed to remove water, the temperature was maintained for 4 hours, and the mixture was cooled to room temperature to obtain resin solution A-1-2.

[0118] Resin solutions A-1-1 and A-1-2 were mixed and stirred at room temperature for 12 hours to obtain polyimide resin A-1 solution, which was added into 3 L of deionized water, precipitated, filtered, and washed three times; and vacuum dried at 80°C for 72 hours to obtain polyimide resin A-1.

[0119] Synthesis Example 8 Synthesis of Polyimide Resin A-2

[0120] The reaction vessel was vented with nitrogen in advance. After 30 minutes, 158.13 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours in advance) was added, followed by 4.00 g (0.02 mol) of ODA and 5.41 g (0.05 mol) of compound PDA, respectively, and stirred at 25°C until completely dissolved. Then, 21.71 g (0.07 mmol) of compound ODPA was added, and the reaction was stirred at room temperature for 12 hours. 5.00 g of trifluoroacetic anhydride was added dropwise, and the temperature was raised to 60°C. After keeping the temperature for 3 hours, 18.22 g of HEMA was added, and the temperature was kept for 4 hours and then cooled to room temperature to obtain resin solution A-2-1.

[0121] Resin solution A-2-2 was prepared using the same formula and process as resin solution A-1-2;

[0122] Resin solutions A-2-1 and A-2-2 were mixed and stirred at room temperature for 12 hours to obtain polyimide resin A-2 solution, which was then added into 3 L of deionized water, precipitated, filtered, and washed three times; and vacuum dried at 80°C for 72 hours to obtain polyimide resin A-2.

[0123] Synthesis Examples 9 to 13 Synthesis of Polyimide Resins A-3 to A-7

[0124] Resin solutions A-3-1 to A-7-1 were all prepared using the same formula and process as A-2-1; solutions A-3-2 to A-7-2 were prepared by replacing 1-1 with 1-2 / 1-3 / 1-4 / 1-5 / 1-6, respectively, and polymerized according to the A-1-2 method; resin solutions A-3 to A-7 were each prepared by mixing A-3-1 to A-7-1 and A-3-2 to A-7-2 and stirring at room temperature for 12 hours to obtain polyimide resin solutions A-3 to A-7, and then the polyimide resins A-3 to A-7 were obtained by referring to the same post-treatment method as in Synthesis Example 8.

[0125] Synthesis Examples 14 to 16 Synthesis of Polyimide Resins A-8 to A-10

[0126] The diamine and dianhydride were replaced with the ratios shown in Table 1 below, and the corresponding polyimide resin A-8 was prepared in the same manner as in Synthesis Example 7. The corresponding polyimide resins A-9 to A-10 were prepared in the same manner as in Synthesis Example 8.

[0127] Table 1

[0128] Example 1

[0129] 10 g of the polyimide resin A-1 prepared in Synthesis Example 7, 1 g of PAC-1 prepared in Synthesis Example 3, 2 g of PAC-2 prepared in Synthesis Example 4, 0.1 g of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 0.8 g of the cross-linking agent C-1 prepared in Synthesis Example 5, and 0.2 g of the cross-linking agent C-2 prepared in Synthesis Example 6 were dissolved in 30 g of γ-butyrolactone and thoroughly mixed to obtain a photosensitive resin composition.

[0130] Example 2

[0131] 10 g of the polyimide resin A-2 obtained in Synthesis Example 8, 0.5 g of the photosensitive compound OXE-01, 0.1 g of the silane coupling agent γ-glycidyloxypropyltrimethoxysilane and 1 g of the crosslinking agent tetraethylene glycol dimethacrylate were dissolved in 30 g of γ-butyrolactone and mixed thoroughly to obtain a photosensitive resin composition.

[0132] Examples 3 to 7

[0133] In Examples 3 to 7, polyimide resins A-3 to A-7 were used to replace polyimide resin A-2, and photosensitive resin compositions were prepared in the same manner as in Example 2.

[0134] Comparative Example 1

[0135] Comparative Example 1: Polyimide resin A-8 was used instead of polyimide resin A-1, and a photosensitive resin composition was prepared in the same manner as in Example 1.

[0136] Comparative Example 2

[0137] Comparative Example 2: Polyimide resin A-9 was used to replace polyimide resin A-2, and a photosensitive resin composition was prepared in the same manner as in Example 2.

[0138] Comparative Example 3

[0139] Comparative Example 3 A photosensitive resin composition was prepared in the same manner as in Comparative Example 2, except that the silane coupling agent γ-glycidyloxypropyltrimethoxysilane was not added.

[0140] Comparative Example 4

[0141] Comparative Example 4: Polyimide resin A-10 was used instead of polyimide resin A-2, and a photosensitive resin composition was prepared in the same manner as in Example 2.

[0142] The photosensitive resin compositions obtained in the examples and comparative examples were used to prepare photocured films according to the following preparation methods, and the properties of the obtained photocured films were measured according to the following methods. The results are summarized in Table 2.

[0143] Preparation of photosensitive curing film: Use a rotational viscometer (Mikasa: MS-B150+DA-60S) for wet film coating, pre-dry on a hot plate, and then transfer to a nitrogen oven for further curing after exposure and development. Cure at 150-400℃ for 30-120min, then cool to room temperature and take out.

[0144] (1) Adhesion evaluation

[0145] Adhesion was evaluated using a 100-grid test. A grid was made on the surface of the cured film at 1mm intervals in 10 rows and 10 columns. The transferred area was then transferred using tape. The adhesion between the cured film and the substrate was evaluated based on the size of the transferred area. An A rating was assigned for ≤10%; a B rating was assigned for >10% and ≤20%; a C rating was assigned for >20% and ≤30%; and a D rating was assigned for >30%.

[0146] (2) Transmittance (T%)

[0147] The results were obtained using an Agilent UV-visible spectrophotometer Cary 4000 in transmission mode.

[0148] (3) Glass transition temperature (Tg)

[0149] The results were measured using a thermomechanical analyzer (TA Instrument, Model Q400). Atmosphere: nitrogen; Temperature: heating rate: 10°C / min.

[0150] (4) Thermal weight loss temperature (T5%)

[0151] The thermal decomposition temperature was measured using a thermogravimetric analyzer (model TGA-55) at a heating rate of 10°C / min, with a sample size of 3-5 mg and a temperature range of RT to 500°C.

[0152] (5) Dielectric constant (Dk)

[0153] The test was performed using a Keysight N5224B vector network analyzer (cavity resonator method) with a test frequency of 10 GHz and sample sizes of 6*6 cm.

[0154] Table 2

[0155] As can be seen from the data in Table 2, the polyimide resin provided by the present invention, by introducing the structural units represented by general formula (3), (4), (5), and / or (6) into the polyimide resin structure, can achieve good optical properties and a low dielectric constant, while also ensuring low-temperature curing properties and good heat resistance. The proper introduction of a binder can further improve adhesion to the substrate.

[0156] After being coated with a rotational viscometer, dried on a hot plate, exposed, developed, and thermally cured under nitrogen, the photosensitive resin composition produces a photosensitive cured film exhibiting good adhesion, excellent light transmittance, low dielectric properties, and good heat resistance. The adhesion test results are A; the average light transmittance (380-780nm) is greater than 70%; the dielectric constant Dk is ≤3.5, the glass transition temperature Tg is less than 350°C, and the thermal weight loss temperature T5% is greater than 350°C. The composition is suitable for use as surface protective films and interlayer insulating films for semiconductor components, insulating layers for organic electroluminescent components, and insulating layers for thin-film transistors (TFTs).

[0157] However, the proportion of the structure represented by general formula (2) needs to be controlled. When the proportion is too low, the improvement effect on the dielectric properties and optical properties is minimal. When the proportion is too high, the adhesion is poor, and it is not conducive to adjusting the photosensitivity and photolithography process window of the photosensitive resin composition, which can easily affect the control of the resolution. Experiments have found that the structure represented by general formula (2) accounts for less than 50% of the total proportion of the polyimide resin.

[0158] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention. Industrial Applicability

[0159] The present invention relates to the field of polymer materials and provides a polyimide resin, a photosensitive resin composition comprising the polyimide resin, and a photosensitive cured film. The present invention introduces an alicyclic structure, an aromatic structure, and a fluorine-containing substituent structure into the main structure of the polyimide resin, thereby achieving good optical properties and a low dielectric constant, while ensuring low-temperature curing properties and good heat resistance.

Claims

1. A polyimide resin, characterized in that: Including the structure represented by general formula (1) and the structure represented by general formula (2), In the general formula (1), Ar1 represents a dianhydride residue, Ar2 represents a diamine residue; R1 represents H or an organic group having 1 to 10 carbon atoms; m is an integer of 10 to 10000, and r is an integer of 0 to 2; In the general formula (2), Ar4 represents a diamine residue; n is an integer of 10 to 10000; Ar3 represents a dianhydride residue, and the dianhydride forming the dianhydride residue is selected from one or more structures represented by the general formulas (3), (4), (5) and (6), Wherein, R2 and R5 are the same or different and each independently represents -(CH2)- or -(CH2CH2)-; R3 and R4 are the same or different and each independently represents H or F; Wherein, X1, X2, and X3 are the same or different and each independently represents C t R8, NH, O or S; R6, R7, and R8 are the same or different, and each independently represents hydrogen, deuterium, halogen, an alkyl or alkoxy group having 1 to 12 carbon atoms, an alkenyl or alkenyloxy group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl or cycloalkenyl group having 3 to 12 carbon atoms, an aryl or aryloxy group having 6 to 12 carbon atoms, an alkylsilanyl group having 1 to 12 carbon atoms, or an arylsilanyl group having 6 to 12 carbon atoms; wherein H in the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, cycloalkyl, and cycloalkenyl group may be replaced by F, and one or more non-adjacent -CH2- may be independently replaced by -O-, -NH-, or -S-, but the O atom and the S atom are not directly connected to each other; s=0-12 integer, t=0-12 integer; Among them, X4, X5, X6, X7, X8, X9, X 10 , X 11 The same or different, each independently represents C t R 11 or N, p=0-12 integer, q=0-12 integer, t=0-12 integer; R9, R 10 , R 11 are the same or different and each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted alkyl or alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl or cycloalkenyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl or aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted any one of an alkylthiooxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and having a heteroatom O, N or S, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 6 to 24 carbon atoms.

2. The polyimide resin according to claim 1, characterized in that The structure represented by the general formula (1) accounts for more than 50% of the total weight of the polyimide resin.

3. The polyimide resin according to claim 1, characterized in that The structure represented by the general formula (3) is selected from the group consisting of the following structures:

4. The polyimide resin according to claim 1, characterized in that The structure represented by the general formula (4) is selected from the group consisting of the following structures:

5. The polyimide resin according to claim 1, characterized in that The structure shown in the general formula (5) is And / or, the structure shown in the general formula (6) is 6. A photosensitive resin composition, characterized in that: The invention comprises (a) a polyimide resin, (b) a photosensitive compound, (c) a cross-linking agent, (d) a bonding modifier and (e) a solvent, wherein the (a) polyimide resin comprises the polyimide resin according to any one of claims 1 to 5.

7. The photosensitive resin composition according to claim 6, characterized in that: The (d) adhesion modifier is selected from one or more of the following: γ-glycidyloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-aminophenyltrimethoxysilane, 3-(m-aminophenoxy)trimethoxysilane, 3-mercaptomethyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

8. The photosensitive resin composition according to claim 6, characterized in that: The (e) solvent is one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents and other solvents; the other solvents are one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

9. A photosensitive cured film, characterized in that: It is formed by curing the photosensitive resin composition according to any one of claims 6 to 8.

10. The photosensitive cured film according to claim 9, characterized in that: The photosensitive cured film is suitable for use as a surface protection film and an interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescent element, and an insulating layer of a thin film transistor.

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