Photosensitive polyesteramide, preparation method thereof, composition, polyimide film and application

Abstract

The invention discloses photosensitive polyesteramide, a preparation method thereof, a composition, a polyimide film and application, the photosensitive polyesteramide is obtained by reaction of diester diacyl chloride and a diamine monomer, and the molar ratio of the diester diacyl chloride to the diamine monomer is 1: (0.9-1.1); the diamine monomer comprises # imgabs0, and R is selected from any one of alkyl with 1-5 carbon atoms, one or more aromatic rings and one or more fused rings. The fluorine-free low-dielectric polyimide is obtained by utilizing the secondary relaxation behavior of a polymer chain, can be applied to the fields of printed circuit boards, conductor packaging, signal transmission and the like, and has a good application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of photoresists, and in particular to a photosensitive polyamide ester, a preparation method, a composition, a polyimide film and applications thereof. Background Art

[0002] The progress of mobile communication and microelectronics technology is completely changing our lifestyle. As electronic products develop towards lighter, thinner, shorter and smaller trends, the integration density of flexible circuit boards is getting higher and higher. On the other hand, with the rapid development of the emerging fifth-generation mobile communication technology (5G technology), signal transmission continues to develop in the direction of high frequency and high speed. Both of the above technologies require low dielectric constant (Dk<2.6) and low dielectric loss (Df<5.0×10 -3 ) characteristics, ensuring the speed, integrity and accuracy of signal transmission and improving the service life of electronic components. In principle, there are two strategies to reduce the Dk and Df values ​​of polymer materials. One is to reduce the polymer density. Reducing the polymer density by deliberately introducing porosity has always been the main method for the semiconductor industry to reduce the dielectric constant to below 3.0 (as low as 1.16). However, due to the uncontrolled size and distribution of the pores, the pores are highly hygroscopic and easily collapse at high temperatures, resulting in deterioration of the dielectric properties. Another strategy is to introduce strongly electronegative atoms, such as fluorine, into the polymer structure to reduce the polarizability. The dielectric constant value of fluorinated polymers can reach 2.30, but the poor adhesion between fluorinated polymers and substrates remains a major challenge. At the same time, unlike the photoresist used in semiconductor manufacturing, the photosensitive polyimide (PSPI) film is not removed after preparation, but remains in the final product as a permanent component of the device. Therefore, the fluorine element in the film will also exist in the product for a long time. However, excessive or long-term exposure to fluoride brings many potential health and environmental hazards, including but not limited to damage to human bones and teeth, adverse effects on growth and development, and long-term pollution to the ecological environment.

[0003] Therefore, the development of low dielectric constant and low loss fluorine-free intrinsic polymer circuit materials is currently needed by the industry. Summary of the invention

[0004] The object of the present invention is to solve the above problems and provide a fluorine-free intrinsic polymer circuit material with low dielectric constant and low loss.

[0005] To achieve the above purpose, the technical method adopted by the present invention is as follows:

[0006] A photosensitive polyamide ester, the photosensitive polyamide ester is obtained by reacting a diester dichloride and a diamine monomer, the molar ratio of the diester dichloride to the diamine monomer is 1:(0.9-1.1); the diamine monomer comprises a structure shown in Formula 1:

[0007]

[0008] Wherein, R is selected from any one of an alkyl group having 1 to 5 carbon atoms, a single or multiple aromatic rings, and a single or multiple condensed rings. Further, the diamine monomer comprises at least one of the structures shown in Formula A1 to Formula A5:

[0009]

[0010] Another object of the present invention is to provide a method for preparing a photosensitive polyamide ester, comprising the steps of:

[0011] (1) under a nitrogen atmosphere, dissolving the dianhydride monomer in an organic solvent with stirring, adding an esterification agent, and reacting to obtain a diacid diester solution;

[0012] (2) adding an acyl chloride reagent to the diacid diester solution obtained in step (1) to react to obtain a diester diacyl chloride solution;

[0013] (3) under a nitrogen atmosphere, dissolving a diamine monomer in an organic solvent to obtain a diamine monomer solution, adding the diester dichloride solution obtained in step (2) to the diamine monomer solution, stirring, and reacting to obtain a polyamide ester solution;

[0014] (4) pouring the polyamide ester solution obtained in step (3) into a poor solvent a to precipitate a solid, washing it with a poor solvent b, and drying it to obtain the photosensitive polyamide ester.

[0015] Further, the dianhydride monomer is a fluorine-free dianhydride monomer; preferably, the dianhydride monomer includes at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, isomeric diphenyl sulfide dianhydride, triphenyl diether dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-bisphenol A dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, and 2,3,5,6-pyromellitic dianhydride;

[0016] Further, the organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylcaproamide, γ-butyrolactone, dimethyl sulfoxide, 1,3-dimethylpropyleneurea, and ethylene glycol butyl ether;

[0017] Further, the esterification agent includes at least one of hydroxyethyl methacrylate, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 1-acryloxy-3-propanol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-butoxypropyl acrylate, and 2-hydroxy-3-tert-butoxypropyl acrylate;

[0018] Further, the chlorination agent includes at least one of thionyl chloride, acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, and trichloroacetyl chloride; preferably, the chlorination agent includes thionyl chloride;

[0019] Furthermore, the poor solvent a and the poor solvent b include at least one of ultrapure water, methanol, ethanol, and hexane.

[0020] Further, the molar ratio of the esterification agent to the dianhydride monomer is (1.8-2.2):1, preferably 2:1;

[0021] Further, the molar ratio of the acyl chloride reagent to the diacid diester is (1.5-2.5):1;

[0022] Further, the molar ratio of the diester dichloride to the diamine is 1:(0.9-1.1);

[0023] Furthermore, the mass ratio of the poor solvent a to the polyamide ester solution is (2-20):1;

[0024] Furthermore, the mass ratio of the poor solvent b to the polyamide ester solution is (2-8):1.

[0025] Furthermore, the reaction temperature of step (1) is 10°C to 60°C, and the reaction time is 2h to 24h;

[0026] Furthermore, the reaction temperature of step (3) is -20°C to 60°C, and the reaction time is 2h to 72h;

[0027] Furthermore, the washing times are 2 to 8 times;

[0028] Furthermore, the drying method is vacuum freeze drying, and the drying time is 24h to 96h.

[0029] Another object of the present invention is to provide a photosensitive polyamide ester composition, comprising the above-mentioned photosensitive polyamide ester or the photosensitive polyamide ester prepared by the above-mentioned preparation method of the photosensitive polyamide ester, and also comprising a photoinitiator, a sensitizer, a photopolymerization monomer, an inhibitor and a solvent; in terms of weight parts, preferably 100 parts of the photosensitive polyamide ester, 1 to 10 parts of the photoinitiator, 0.1 to 30 parts of the sensitizer, 0.1 to 30 parts of the photopolymerization monomer, 0.1 to 30 parts of the inhibitor, and 100 to 900 parts of the solvent.

[0030] Further, the photoinitiator includes at least one of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, benzophenone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone;

[0031] Further, the sensitizer includes at least one of Michler's ketone, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 4,4'-bis(diethylamino)chalcone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, and 1,3-bis(4'-dimethylaminobenzylidene)acetone;

[0032] Further, the photopolymerizable monomer includes at least one of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate;

[0033] Further, the polymerization inhibitor includes at least one of 2,6-di-tert-butyl-p-methylphenol, 4-methoxyphenol, p-tert-butylcatechol, 1-nitroso-2-naphthol, and N-nitrosodiphenylamine;

[0034] Furthermore, the solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol butyl ether, and γ-butyrolactone.

[0035] Another object of the present invention is to provide a polyimide film, wherein the polyimide film contains a polyimide resin, wherein the polyimide resin is obtained by imidization treatment of the above-mentioned photosensitive polyamide ester or the photosensitive polyamide ester prepared according to the preparation method of the above-mentioned photosensitive polyamide ester;

[0036] Alternatively, the polyimide film is obtained by subjecting the photosensitive polyamide ester composition to exposure, development and thermal curing.

[0037] Another object of the present invention is to provide a use of the photosensitive polyamide ester composition in electronic circuits.

[0038] The beneficial effects produced by the technical solution of the present invention include:

[0039] The present invention provides a photosensitive polyamide ester, a preparation method, a composition, a polyimide film and an application thereof, and obtains a fluorine-free low-dielectric polyimide by utilizing the secondary relaxation behavior of a polymer chain (also called β relaxation, which refers to the twisting of a group in a polymer main chain or the rotation of a pendant group). When the ambient temperature is lower than the glass transition temperature (Tg), the polyimide segment motion is frozen, but its side groups are still rotatable, which can greatly affect the inherent free volume and thus affect the dielectric properties of the polyimide. The present invention obtains a polyimide with a low dielectric constant and a low dielectric loss without introducing the fluorine element, which can eliminate the potential hazards that the fluorine element may bring in the device, and promote the development of related industries in a more environmentally friendly and healthier direction. DETAILED DESCRIPTION

[0040] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be further described in detail below in conjunction with specific embodiments.

[0041] Unless otherwise defined, technical or scientific terms used in the disclosure of the present invention should have the common meanings that can be understood by those skilled in the art in the field to which the present invention belongs.

[0042] As analyzed in the background technology, in the prior art, intentionally introducing porosity to reduce polymer density and introducing strongly electronegative atoms into the polymer cannot obtain long-term reliable circuit materials with low dielectric constant and low dielectric loss without affecting the adhesion between the substrate, environmental friendliness, health and greenness. To solve this problem, the present invention provides a photosensitive polyamide ester, a preparation method, a composition, a polyimide film and an application thereof.

[0043] In a typical embodiment of the present application, a photosensitive polyamide ester is obtained by reacting a diester dichloride with a diamine monomer, wherein the molar ratio of the diester dichloride to the diamine monomer is 1:(0.9-1.1); the diamine monomer comprises a structure shown in Formula 1:

[0044]

[0045] Wherein, R is selected from any one of an alkyl group having 1 to 5 carbon atoms, a single or multiple aromatic rings, and a single or multiple condensed rings.

[0046] Generally speaking, the most effective way to reduce the dielectric constant and dielectric loss value of fluorine-free non-porous polymer materials is to increase their inherent free volume. This is because the additional free volume in the polymer introduces more ultra-low dielectric constant air components, weakening the interaction between polymer chains. Different from the method of introducing bulky side groups into the polymer structure to expand the free volume between polymer chains, the present invention selects the diamine monomer of the structure shown in Formula 1 as the raw material for preparing photosensitive polyamide ester, and introduces the rotatable aromatic side chain into the molecular structure through polymerization. When the ambient temperature is lower than the glass transition temperature (Tg), the polyimide segment motion is frozen; however, the side group is still rotatable (called secondary relaxation or β relaxation, which refers to the torsion of the group in the polymer main chain or the rotation of the pendant group), which can greatly affect the inherent free volume, and then affect the dielectric properties of the polymer material, thereby obtaining a low dielectric constant. The polymer prepared by the present invention has a simple structure and low manufacturing cost, and is expected to achieve commercial production and industrial application. It is a simple and effective method to increase the free volume of the polymer through a chemical structure design strategy to obtain a fluorine-free constitutive low-k polymer.

[0047] Furthermore, the diamine monomer includes at least one of the structures shown in Formula A1 to Formula A5:

[0048]

[0049] Another object of the present invention is to provide a method for preparing a photosensitive polyamide ester, comprising the steps of:

[0050] (1) under a nitrogen atmosphere, dissolving the dianhydride monomer in an organic solvent with stirring, adding an esterification agent, and reacting to obtain a diacid diester solution;

[0051] (2) adding an acyl chloride reagent to the diacid diester solution obtained in step (1) to react to obtain a diester diacyl chloride solution;

[0052] (3) under a nitrogen atmosphere, dissolving a diamine monomer in an organic solvent to obtain a diamine monomer solution, adding the diester dichloride solution obtained in step (2) to the diamine monomer solution, stirring, and reacting to obtain a polyamide ester solution;

[0053] (4) pouring the polyamide ester solution obtained in step (3) into a poor solvent a to precipitate a solid, washing it with a poor solvent b, and drying it to obtain the photosensitive polyamide ester.

[0054] Furthermore, the dianhydride monomer has no additional requirements, and common dianhydrides can be used. Specifically, the dianhydride monomer is a fluorine-free dianhydride monomer; preferably, the dianhydride monomer includes at least one of pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, isomeric diphenyl sulfide dianhydride, triphenyl diether dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-bisphenol A dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, and 2,3,5,6-pyromellitic acid dianhydride.

[0055] Furthermore, the organic solvent has no additional requirements, and a common organic solvent that can dissolve the above-mentioned diamine monomer and dianhydride monomer can be used. Specifically, the organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylcaproamide, γ-butyrolactone, dimethyl sulfoxide, 1,3-dimethylpropyleneurea, and ethylene glycol butyl ether.

[0056] Furthermore, the esterification agent includes at least one of hydroxyethyl methacrylate, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 1-acryloxy-3-propanol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-butoxypropyl acrylate, and 2-hydroxy-3-tert-butoxypropyl acrylate.

[0057] Further, the acyl chloride reagent includes at least one of thionyl chloride, acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, and trichloroacetyl chloride; preferably, the acyl chloride reagent includes thionyl chloride.

[0058] Furthermore, the poor solvent a and the poor solvent b have no additional requirements, and the polyamide ester can be hardly soluble or insoluble therein. Specifically, the poor solvent a and the poor solvent b include at least one of ultrapure water, methanol, ethanol, and hexane.

[0059] Furthermore, the molar ratio of the esterification agent to the dianhydride monomer is (1.8-2.2):1; preferably 2:1; if the molar ratio of the esterification agent to the dianhydride monomer is too low, all dianhydride monomers cannot be converted into diacid diesters, and if it is too high, monocarboxylic acid triesters or tetraesters are easily produced, hindering subsequent reactions.

[0060] Furthermore, the molar ratio of the acyl chloride reagent to the diacid diester is (1.5-2.5):1; if the molar ratio of the acyl chloride reagent to the diacid diester is too low, not all the diacid diester can be converted into diester dichloride, and if the molar ratio is too high, excess acyl chloride reagent remains in the reaction system and affects subsequent polymerization.

[0061] Furthermore, the molar ratio of the diester dichloride to the diamine is 1:(0.9-1.1); if the molar ratio of the diester dichloride to the diamine is too low or too high, the molecular weight of the product will deviate from the required requirement.

[0062] Furthermore, the mass ratio of the poor solvent a to the polyamide ester solution is (2-20):1; if the mass ratio of the poor solvent a to the polyamide ester solution is too low, the polyamide ester cannot be precipitated in the solvent and is difficult to clean, and if it is too high, the cost is increased;

[0063] Furthermore, the mass ratio of the poor solvent b to the polyamide ester solution is (2-8):1; if the amount of the poor solvent b is too small, the washing effect is not good, and the obtained polyamide ester has too many impurities, which affects its use effect.

[0064] Furthermore, the reaction temperature of step (1) is 10°C to 60°C, and the reaction time is 2h to 24h;

[0065] Furthermore, the reaction temperature of step (3) is -20°C to 60°C, and the reaction time is 2h to 72h. If the reaction temperature is too low, it is not conducive to the reaction, while if the reaction temperature is too high, the molecular weight will increase too fast and it will be difficult to control the degree of polymerization. If the reaction time is too long, it will cause the polymer to decompose, while if the reaction time is too short, the required molecular weight will not be achieved. In short, the required molecular weight cannot be obtained when the temperature and time are unreasonable.

[0066] Furthermore, the washing times are 2 to 8 times, and the more washing times are, the less impurities the obtained photosensitive polyamide ester has.

[0067] Furthermore, the drying method is vacuum freeze drying, and the drying time is 24 hours to 96 hours. The temperature of the cold trap can be adjusted as needed, and is not particularly limited here. Specifically, it can be carried out at a normal setting temperature of the freeze drying equipment, such as -80°C.

[0068] Another object of the present invention is to provide a photosensitive polyamide ester composition, comprising the above-mentioned photosensitive polyamide ester or the photosensitive polyamide ester prepared by the above-mentioned preparation method of the photosensitive polyamide ester, and also comprising a photoinitiator, a sensitizer, a photopolymerization monomer, an inhibitor and a solvent; in terms of weight parts, preferably 100 parts of the photosensitive polyamide ester, 1 to 10 parts of the photoinitiator, 0.1 to 30 parts of the sensitizer, 0.1 to 30 parts of the photopolymerization monomer, 0.1 to 30 parts of the inhibitor, and 100 to 900 parts of the solvent.

[0069] Further, the photoinitiator includes at least one of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, benzophenone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone;

[0070] Further, the sensitizer includes at least one of Michler's ketone, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 4,4'-bis(diethylamino)chalcone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, and 1,3-bis(4'-dimethylaminobenzylidene)acetone;

[0071] Further, the photopolymerizable monomer includes at least one of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate;

[0072] Further, the polymerization inhibitor includes at least one of 2,6-di-tert-butyl-p-methylphenol, 4-methoxyphenol, p-tert-butylcatechol, 1-nitroso-2-naphthol, and N-nitrosodiphenylamine;

[0073] Furthermore, the solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol butyl ether, and γ-butyrolactone.

[0074] Another object of the present invention is to provide a polyimide film, wherein the polyimide film contains a polyimide resin, wherein the polyimide resin is obtained by imidization treatment of the above-mentioned photosensitive polyamide ester or the photosensitive polyamide ester prepared according to the preparation method of the above-mentioned photosensitive polyamide ester;

[0075] Alternatively, the polyimide film is obtained by subjecting the photosensitive polyamide ester composition to exposure, development and thermal curing.

[0076] Furthermore, the thickness of the polyimide film is 20 to 40 micrometers.

[0077] Furthermore, the exposure light source is an ultraviolet lamp (i-line and g-line), and the exposure energy is 200mJ / cm 2 ~1000mJ / cm 2 .

[0078] Furthermore, the developer is at least one of cyclopentanone, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide.

[0079] Furthermore, the thermal curing is performed according to a program of heating, 60°C / 900s—120°C / 1200s—230°C / 3600s—300°C / 3600s.

[0080] Another object of the present invention is to provide a use of the photosensitive polyamide ester composition in electronic circuits.

[0081] The beneficial effects of the present application will be further illustrated below in combination with embodiments and comparative examples.

[0082] Synthesis Example 1: Synthesis of diamine monomer A2

[0083]

[0084] In a nitrogen atmosphere, 28.5 g of 4-fluoronitrobenzene, 18.4 g of 4-phenoxyaniline, 38.0 g of cesium fluoride, and 250 mL of dimethyl sulfoxide (DMSO) were added to a 500 mL three-necked flask, and the reaction temperature was controlled to be 120° C. and refluxed for 12 hours; after the reaction system was cooled, it was poured into 1 L of a mixed solvent (methanol: water = 1:1) to precipitate, and the precipitate was washed with ultrapure water, and the sample was recrystallized with N,N-dimethylformamide and methanol, and washed and dried to obtain 40.2 g of product A2-1;

[0085] Under a nitrogen atmosphere, 40.2 g of A1-1, 500 mL of ethanol and 0.5 g of 10% palladium on carbon were added to a 1L three-necked flask, 40 mL of hydrazine hydrate was slowly added dropwise, and the mixture was refluxed at 80°C for 10 hours; the palladium on carbon was then filtered out and the precipitate was collected by cooling, and the precipitate was vacuum dried at 70°C to obtain 30.8 g of diamine monomer A2.

[0086] Synthesis Example 2: Synthesis of diamine monomer A3

[0087]

[0088] In a nitrogen atmosphere, 28.5 g of 4-fluoronitrobenzene, 17.2 g of 3-bromoaniline, 38.0 g of cesium fluoride, and 250 mL of dimethyl sulfoxide (DMSO) were added to a 500 mL three-necked flask, and the reaction temperature was controlled to be 150° C. and refluxed for 24 hours; after the reaction system was cooled, it was poured into 2 L of a mixed solvent (methanol: water = 1:1) to precipitate, and the precipitate was washed with ultrapure water, and the sample was recrystallized with N,N-dimethylformamide and methanol, and washed and dried to obtain 29.7 g of product A3-1;

[0089] In a 1L three-necked flask under a nitrogen atmosphere, 29.7 g of A3-1, 15.6 g of 4-biphenylboronic acid, 1.2 g of tetrakis(triphenylphosphine)palladium, 150 mL of a 2M potassium carbonate aqueous solution, and 500 mL of tetrahydrofuran were added, and the mixture was refluxed at 65°C for 24 hours; the water layer was then removed, and the yellow precipitate was collected by rotary evaporation and purified on silica gel with dichloromethane / hexane as the eluent; the eluate was then dried to obtain 26.7 g of the product A3-2;

[0090] Under a nitrogen atmosphere, 26.7 g of product A3-2, 500 mL of ethanol and 0.5 g of 10% palladium on carbon were added to a 1L three-necked flask, and 30 mL of hydrazine hydrate was slowly added dropwise. The mixture was refluxed at 80°C for 24 hours. The palladium on carbon was then removed by filtration and the precipitate was collected by rotary evaporation. The product was purified by silica gel chromatography using dichloromethane / hexane as the eluent, and the eluate was dried to obtain 18.7 g of diamine monomer A3.

[0091] Synthesis Example 3: Synthesis of diamine monomer A4

[0092] The 3-bromoaniline in Synthesis Example 2 was replaced by 4-bromoaniline, and the rest of the process was similar to Synthesis Example 2.

[0093] Synthesis Example 4: Synthesis of diamine monomer A5

[0094] The 4-biphenylboronic acid in Synthesis Example 2 was replaced by phenylboronic acid, and the rest of the process was similar to Synthesis Example 2.

[0095] Example 1

[0096] (1) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of dianhydride monomer 4,4'-oxydiphthalic anhydride, 0.2 mol of esterification reagent hydroxyethyl methacrylate (HEMA) and 300 g of N-methylpyrrolidone (NMP) were added in sequence, and stirred at room temperature for 8 hours to generate the corresponding diacid diester;

[0097] (2) Cool the esterification solution to below 10°C in an ice bath, slowly dropwise add 0.16 mol SOCl2, and after the dropwise addition is completed over 30 min, react at 10-20°C for 4 h to generate the corresponding diester dichloride;

[0098] (3) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of diamine monomer A2 and 300 g of NMP were added in sequence and stirred to fully dissolve; the diamine solution was cooled to below 10° C. in an ice bath, and the diester dichloride solution prepared above was added dropwise into the diamine solution for 1 hour, followed by reaction at room temperature for 24 hours;

[0099] (4) Finally, the reaction solution was poured into 3 L of deionized water to precipitate solids, which were washed, filtered, and freeze-dried to obtain photosensitive polyamide ester;

[0100] (5) In a Class 1000 clean room equipped with a yellow light, 40 g of the above-mentioned photosensitive polyamide ester, 2.0 g of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 0.03 g of 2,6-di-tert-butyl-p-methylphenol, and 4.0 g of hydroxyethyl methacrylate were added to 100 g of NMP in sequence, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide ester composition solution;

[0101] (6) In a Class 1000 clean room, the negative photosensitive polyamide ester composition solution was spin-coated on a substrate and baked at 100°C for 150 seconds to obtain a film with a thickness of 30 μm. The exposure energy of the film was 300 mJ / cm2 using an ultraviolet lamp (i-line and g-line). 2 ; After being developed with cyclopentanone and fixed with ethyl acetate, the film was cured in an oxygen-free oven according to the procedure (60°C / 900s, 120°C / 1200s, 230°C / 3600s, 300°C / 3600s) to obtain a polyimide film.

[0102] After testing, the dielectric constant, dielectric loss and resolution of this embodiment are shown in Table 1.

[0103] Example 2

[0104] (1) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of dianhydride monomer 4,4'-oxydiphthalic anhydride, 0.2 mol of esterification reagent hydroxyethyl methacrylate (HEMA) and 300 g of N-methylpyrrolidone (NMP) were added in sequence, and stirred at room temperature for 6 hours to generate the corresponding diacid diester;

[0105] (2) Cool the esterification solution to below 10°C in an ice bath, slowly add 0.16 mol SOC12 dropwise, and after 30 min of addition, react at 10-20°C for 3 h to generate the corresponding diester dichloride;

[0106] (3) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of diamine monomer A3 and 300 g of NMP were added in sequence and stirred to fully dissolve; the diamine solution was cooled to below 10° C. in an ice bath, and the diester dichloride solution prepared above was added dropwise into the diamine solution for 1 hour, followed by reaction at room temperature for 18 hours;

[0107] (4) Finally, the reaction solution was poured into 4 L of deionized water to precipitate solids, which were washed, filtered, and freeze-dried to obtain photosensitive polyamide ester;

[0108] (5) In a Class 1000 clean room equipped with a yellow light, 40 g of the above-mentioned photosensitive polyamide ester, 2.0 g of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 0.03 g of 2,6-di-tert-butyl-p-methylphenol, and 4.0 g of hydroxyethyl methacrylate were added to 100 g of NMP in sequence, and stirred at room temperature for 8 h to form a homogeneous negative photosensitive polyamide ester composition solution;

[0109] (6) In a Class 1000 clean room, the negative photosensitive polyamide ester composition solution was spin-coated on a substrate and baked at 100°C for 120s to obtain a film with a thickness of 30 μm. The film was exposed to ultraviolet light (i-line and g-line) with an energy of 200 mJ / cm 2 ; After being developed with cyclopentanone and fixed with ethyl acetate, the film was cured in an oxygen-free oven according to the procedure (60°C / 900s, 120°C / 1200s, 230°C / 3600s, 300°C / 3600s) to obtain a polyimide film.

[0110] After testing, the dielectric constant, dielectric loss and resolution of this embodiment are shown in Table 1.

[0111] Example 3

[0112] (1) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of dianhydride monomer 4,4'-oxydiphthalic anhydride, 0.2 mol of esterification reagent hydroxyethyl methacrylate (HEMA) and 300 g of N-methylpyrrolidone (NMP) were added in sequence, and stirred at room temperature for 8 hours to generate the corresponding diacid diester;

[0113] (2) Cool the esterification solution to below 10°C in an ice bath, slowly add 0.20 mol SOC12 dropwise, and after 30 min of addition, react at 10-20°C for 6 h to generate the corresponding diester dichloride;

[0114] (3) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of diamine monomer A4 and 300 g of NMP were added in sequence and stirred to fully dissolve; the diamine solution was cooled to below 10° C. in an ice bath, and the diester dichloride solution prepared above was added dropwise into the diamine solution for 1 hour, followed by reaction at room temperature for 24 hours;

[0115] (4) Finally, the reaction solution was poured into 4 L of deionized water to precipitate solids, which were washed, filtered, and freeze-dried to obtain photosensitive polyamide ester;

[0116] (5) In a Class 1000 clean room equipped with a yellow light, 40 g of the above-mentioned photosensitive polyamide ester, 2.0 g of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 0.03 g of 2,6-di-tert-butyl-p-methylphenol, and 4.0 g of hydroxyethyl methacrylate were added to 100 g of NMP in sequence, and stirred at room temperature for 12 h to form a homogeneous negative photosensitive polyamide ester composition solution;

[0117] (6) In a Class 1000 clean room, the negative photosensitive polyamide ester composition solution was spin-coated on a substrate and baked at 100°C for 120s to obtain a film with a thickness of 30 μm. The exposure energy of the film was 300 mJ / cm2 using an ultraviolet lamp (i-line and g-line). 2 ; After being developed with cyclopentanone and fixed with ethyl acetate, the film was cured in an oxygen-free oven according to the procedure (60°C / 900s, 120°C / 1200s, 230°C / 3600s, 300°C / 3600s) to obtain a polyimide film.

[0118] After testing, the dielectric constant, dielectric loss and resolution of this embodiment are shown in Table 1.

[0119] Example 4

[0120] (1) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of dianhydride monomer 4,4'-oxydiphthalic anhydride, 0.2 mol of esterification reagent hydroxyethyl methacrylate (HEMA) and 300 g of N-methylpyrrolidone (NMP) were added in sequence, and stirred at room temperature for 8 hours to generate the corresponding diacid diester;

[0121] (2) Cool the esterification solution to below 10°C in an ice bath, slowly add 0.20 mol SOC12 dropwise, and after 30 min of addition, react at 10-20°C for 6 h to generate the corresponding diester dichloride;

[0122] (3) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of diamine monomer A5 and 300 g of NMP were added in sequence and stirred to fully dissolve; the diamine solution was cooled to below 10° C. in an ice bath, and the diester dichloride solution prepared above was added dropwise into the diamine solution for 1 hour, followed by reaction at room temperature for 36 hours;

[0123] (4) Finally, the reaction solution was poured into 4 L of deionized water to precipitate solids, which were then washed, filtered, and freeze-dried to obtain photosensitive polyamide ester.

[0124] (5) In a Class 1000 clean room equipped with a yellow light, 40 g of the above-mentioned photosensitive polyamide ester, 2.0 g of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 0.03 g of 2,6-di-tert-butyl-p-methylphenol, and 4.0 g of hydroxyethyl methacrylate were added to 100 g of NMP in sequence, and stirred at room temperature for 12 h to form a homogeneous negative photosensitive polyamide ester composition solution;

[0125] (6) In a Class 1000 clean room, the negative photosensitive polyamide ester composition solution was spin-coated on a substrate and baked at 100°C for 150 seconds to obtain a film with a thickness of 30 μm. The exposure energy of the film was 400 mJ / cm2 using an ultraviolet lamp (i-line and g-line). 2 ; After being developed with cyclopentanone and fixed with ethyl acetate, the film was cured in an oxygen-free oven according to the procedure (60°C / 900s, 120°C / 1200s, 230°C / 3600s, 300°C / 3600s) to obtain a polyimide film.

[0126] After testing, the dielectric constant, dielectric loss and resolution of this embodiment are shown in Table 1.

[0127] Example 5

[0128] (1) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of dianhydride monomer 4,4'-oxydiphthalic anhydride, 0.2 mol of esterification reagent hydroxyethyl methacrylate (HEMA) and 300 g of N-methylpyrrolidone (NMP) were added in sequence, and stirred at room temperature for 8 hours to generate the corresponding diacid diester;

[0129] (2) Cool the esterification solution to below 10°C in an ice bath, slowly add 0.20 mol SOC12 dropwise, and after 30 min of addition, react at 10-20°C for 6 h to generate the corresponding diester dichloride;

[0130] (3) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of diamine monomer A1 (diamine monomer A1 can be directly purchased from a commercial product, such as Chongqing Futeng Pharmaceutical Co., Ltd., CAS: 4219-51-6, Catalogue No: CB0587195) and 300 g of NMP are added in sequence and stirred to fully dissolve; the diamine solution is cooled to below 10° C. in an ice bath, and the diester dichloride solution prepared above is added dropwise into the diamine solution for 1 hour, followed by reaction at room temperature for 48 hours;

[0131] (4) Finally, the reaction solution was poured into 4 L of deionized water to precipitate solids, which were washed, filtered, and freeze-dried to obtain photosensitive polyamide ester;

[0132] (5) In a Class 1000 clean room equipped with a yellow light, 40 g of the above-mentioned photosensitive polyamide ester, 2.0 g of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 0.03 g of 2,6-di-tert-butyl-p-methylphenol, and 4.0 g of hydroxyethyl methacrylate were added to 100 g of NMP in sequence, and stirred at room temperature for 8 h to form a homogeneous negative photosensitive polyamide ester composition solution;

[0133] (6) In a Class 1000 clean room, the negative photosensitive polyamide ester composition solution was spin-coated on a substrate and baked at 100°C for 180 seconds to obtain a film with a thickness of 30 μm. The exposure energy of the film was 450 mJ / cm2 using an ultraviolet lamp (i-line and g-line). 2 ; After being developed with cyclopentanone and fixed with ethyl acetate, the film was cured in an oxygen-free oven according to the procedure (60°C / 900s, 120°C / 1200s, 230°C / 3600s, 300°C / 3600s) to obtain a polyimide film.

[0134] After testing, the dielectric constant, dielectric loss and resolution of this embodiment are shown in Table 1.

[0135] Comparative Example 1

[0136] (1) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of dianhydride monomer 4,4'-oxydiphthalic anhydride, 0.2 mol of esterification reagent hydroxyethyl methacrylate (HEMA) and 300 g of N-methylpyrrolidone (NMP) were added in sequence, and stirred at room temperature for 6 hours to generate the corresponding diacid diester;

[0137] (2) Cool the above esterification solution to below 10°C in an ice bath, and slowly add 0.16 mol SOC1 2 After the addition is completed for 30 minutes, the reaction is carried out at 10-20°C for 4 hours to generate the corresponding diester dichloride;

[0138] (3) In a 1L three-necked round-bottom flask equipped with an electric stirrer, 0.1 mol of diamine monomer 4-N-(4-aminophenyl)-4-N-phenyl-1,4-phenylenediamine and 300 g of NMP were added in sequence and stirred to fully dissolve; the diamine solution was cooled to below 10° C. in an ice bath, and the diester dichloride solution prepared above was added dropwise into the diamine solution for 1 hour, followed by reaction at room temperature for 12 hours;

[0139] (4) Finally, the reaction solution was poured into 4 L of deionized water to precipitate solids, which were then washed, filtered, and freeze-dried to obtain photosensitive polyamide ester.

[0140] (5) In a Class 1000 clean room equipped with a yellow light, 40 g of the above-mentioned photosensitive polyamide ester, 2.0 g of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 0.03 g of 2,6-di-tert-butyl-p-methylphenol, and 4.0 g of hydroxyethyl methacrylate were added to 100 g of NMP in sequence and stirred at room temperature for 8 h to form a homogeneous negative photosensitive polyamide ester composition solution.

[0141] (6) In a Class 1000 clean room, the negative photosensitive polyamide ester composition solution was spin-coated on a substrate and baked at 100°C for 120s to obtain a film with a thickness of 30 μm. The film was exposed to ultraviolet light (i-line and g-line) with an energy of 200 mJ / cm 2 ; After being developed with cyclopentanone and fixed with ethyl acetate, the film was cured in an oxygen-free oven according to the procedure (60°C / 900s, 120°C / 1200s, 230°C / 3600s, 300°C / 3600s) to obtain a polyimide film.

[0142] Hereinafter, the sample preparation method (including film lamination, exposure, and development) and the sample evaluation method and evaluation results of the examples and comparative examples will be described.

[0143]

Dielectric performance evaluation

[0144] The Agilent 4294A impedance analyzer was used to test and obtain the dielectric constant and dielectric loss data. The prepared photosensitive polyimide film was dried at 120°C and vacuum conditions for 24 hours to prevent moisture and impurities from affecting it: ensure the flatness and integrity of the sample: the electric field frequency is 40-110Hz: spray gold on both sides of the sample to make electrodes: control the gold spraying area to be a circle with a diameter of 8mm. Then calculate the dielectric constant:

[0145]

[0146] Where: C represents capacitance; ε0 represents the vacuum dielectric constant; d represents the film thickness; A represents the effective electrode area.

[0147]

Resolution evaluation

[0148] The photosensitive polyamic acid solution prepared in the embodiment and the comparative example is spin-coated on a substrate, pre-baked at 100°C for 90 seconds, and then cured at 230°C for 2 hours; the cured photosensitive polyimide film is exposed to ultraviolet light on a mask, and then developed and dried to obtain a pattern. The pattern is observed under a microscope, and the minimum value of the line width that can completely remove the exposed part and remain without distortion or defect is recorded as the resolution value. The smaller the value, the better the resolution.

[0149]

Evaluation results

[0150] The evaluation results of the embodiments and comparative examples are shown in Table 1.

[0151] Table 1: Dielectric constant, dielectric loss and resolution evaluation results of examples and comparative examples

[0152]

[0153]

[0154] As shown in Table 1, the resolution of the embodiment of the present invention can reach or even exceed the resolution level of the comparative example, and the dielectric constant and dielectric loss performance are both better than the comparative example.

[0155] In summary, the use of the photosensitive polyamide ester of the present invention can obtain a low dielectric constant and a low dielectric loss without introducing the fluorine element, which can eliminate the potential harm that the fluorine element may bring in the device and promote the development of related industries in a more environmentally friendly and healthier direction.

[0156] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A photosensitive polyamide polyester, characterized in that: The photosensitive polyamide ester is obtained by reacting a diester dichloride with a diamine monomer, wherein the molar ratio of the diester dichloride to the diamine monomer is 1:(0.9-1.1); the diamine monomer comprises a structure shown in Formula 1: Wherein, R is selected from any one of an alkyl group having 1 to 5 carbon atoms, a single or multiple aromatic rings, and a single or multiple condensed rings.

2. The photosensitive polyamide polyester according to claim 1, characterized in that: The diamine monomer includes at least one of the structures shown in Formula A1 to Formula A5:

3. The method for preparing the photosensitive polyamide ester according to any one of claims 1 to 2, characterized in that: Includes steps: (1) under a nitrogen atmosphere, dissolving the dianhydride monomer in an organic solvent with stirring, adding an esterification agent, and reacting to obtain a diacid diester solution; (2) adding an acyl chloride reagent to the diacid diester solution obtained in step (1) to react to obtain a diester diacyl chloride solution; (3) under a nitrogen atmosphere, dissolving a diamine monomer in an organic solvent to obtain a diamine monomer solution, adding the diester dichloride solution obtained in step (2) to the diamine monomer solution, stirring, and reacting to obtain a polyamide ester solution; (4) pouring the polyamide ester solution obtained in step (3) into a poor solvent a to precipitate a solid, washing it with a poor solvent b, and drying it to obtain the photosensitive polyamide ester.

4. The method for preparing the photosensitive polyamide ester according to claim 3, characterized in that: The dianhydride monomer is a fluorine-free dianhydride monomer; preferably, the dianhydride monomer includes at least one of pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, isomeric diphenyl sulfide dianhydride, triphenyl diether dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-bisphenol A dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, and 2,3,5,6-pyromellitic acid dianhydride; And / or, the organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylcaproamide, γ-butyrolactone, dimethyl sulfoxide, 1,3-dimethylpropyleneurea, and ethylene glycol butyl ether; And / or, the esterification agent includes at least one of hydroxyethyl methacrylate, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 1-acryloxy-3-propanol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-butoxypropyl acrylate, and 2-hydroxy-3-tert-butoxypropyl acrylate; And / or, the chlorination agent includes at least one of thionyl chloride, acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, and trichloroacetyl chloride; preferably, the chlorination agent includes thionyl chloride; And / or, the poor solvent a and the poor solvent b include at least one of ultrapure water, methanol, ethanol, and hexane.

5. The method for preparing the photosensitive polyamide ester according to claim 3, characterized in that: The molar ratio of the esterification agent to the dianhydride monomer is (1.8-2.2):1, preferably 2:1; and / or, the molar ratio of the acyl chloride reagent to the diacid diester is (1.5-2.5):1; and / or, the molar ratio of the diester dichloride to the diamine is 1:(0.9-1.1); And / or, the mass ratio of the poor solvent a to the polyamide ester solution is (2-20):1; And / or, the mass ratio of the poor solvent b to the polyamide ester solution is (2-8):

1.

6. The method for preparing the photosensitive polyamide ester according to claim 3, characterized in that: The reaction temperature of step (1) is 10°C to 60°C, and the reaction time is 2h to 24h; And / or, the reaction temperature of step (3) is -20°C to 60°C, and the reaction time is 2h to 72h; And / or, the washing number is 2 to 8 times; And / or, the drying method is vacuum freeze drying, and the drying time is 24h to 96h.

7. A photosensitive polyamide polyester composition, characterized in that: The photosensitive polyamide ester comprises the photosensitive polyamide ester described in any one of claims 1 to 2 or the photosensitive polyamide ester prepared by the preparation method of the photosensitive polyamide ester described in any one of claims 3 to 6, and also comprises a photoinitiator, a sensitizer, a photopolymerization monomer, an inhibitor and a solvent; in terms of weight parts, preferably 100 parts of the photosensitive polyamide ester, 1 to 10 parts of the photoinitiator, 0.1 to 30 parts of the sensitizer, 0.1 to 30 parts of the photopolymerization monomer, 0.1 to 30 parts of the inhibitor, and 100 to 500 parts of the solvent.

8. The photosensitive polyamide ester composition according to claim 7, characterized in that: The photoinitiator includes at least one of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, benzophenone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone; And / or, the sensitizer includes at least one of Michler's ketone, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 4,4'-bis(diethylamino)chalcone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, and 1,3-bis(4'-dimethylaminobenzylidene)acetone; And / or, the photopolymerizable monomer includes at least one of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate; And / or, the polymerization inhibitor includes at least one of 2,6-di-tert-butyl-p-methylphenol, 4-methoxyphenol, p-tert-butylcatechol, 1-nitroso-2-naphthol, and N-nitrosodiphenylamine; And / or, the solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol butyl ether, and γ-butyrolactone.

9. A polyimide film, characterized in that: The polyimide film contains a polyimide resin, and the polyimide resin is obtained by imidization treatment of the photosensitive polyamide ester according to any one of claims 1 to 2 or the photosensitive polyamide ester prepared by the preparation method of the photosensitive polyamide ester according to any one of claims 3 to 6; Alternatively, the polyimide film is obtained by exposing, developing and thermally curing the photosensitive polyamide ester composition according to any one of claims 7 to 8.

10. Use of the photosensitive polyamide ester composition according to any one of claims 7 to 8 in electronic circuits.

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