A negative photosensitive solid gum film for alkaline aqueous development and a preparation method thereof

Abstract

The present invention discloses a negative photosensitive solid film for alkaline aqueous development and a preparation method thereof. It is made of a photosensitive resin composition, and the photosensitive resin composition includes polyamic acid ester, photo-crosslinking agent, photoinitiator, inorganic filler, etc. The present invention uses an alkali-soluble resin of polyamic acid ester, introduces a double bond into the resin side chain, and the resin can participate in crosslinking after exposure, greatly enhancing the performance of the solid film and increasing the stiffness of the solid film in the photo-crosslinking stage. After curing, part of it detaches from the main chain and plays a plasticizing role in the film, well increasing the elongation at break and tensile strength of the solid film, making the solid film have good toughness. The solid film contains a fluorine structure and has good light transmittance, enabling a thick film to have a high resolution.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition applicable to surface protective films / interlayer insulating films of semiconductor elements / insulating layers of organic electroluminescent elements / wiring protective insulating films of circuit boards, etc. More specifically, it relates to a negative photosensitive resin composition that is easily soluble in an alkaline aqueous solution before exposure and insoluble in an alkaline aqueous solution once exposed. It is particularly applicable to electronic components that require a hollow structure, such as elastic filters and MEMS (Micro Electro Mechanical System). Conventionally, a hollow structure is generally formed of inorganic materials such as piezoelectric substrates, glass, and silicon. Background Art

[0002] The formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is carried out through the following complicated and various processes: forming a film of a resist on the surface of a substrate, exposing a specified area, removing unnecessary areas through etching, washing the surface of the substrate, and other operations. Therefore, in order to reduce the processes, in the semiconductor industry recently, it has been common to directly use the resist in the required part as an insulating material after forming a pattern through exposure and development.

[0003] As materials at this time, for example, heat-resistant photosensitive materials such as photosensitive polyimide / photosensitive polybenzoxazole have been developed and industrialized. In particular, a negative photosensitive polyimide developed for alkaline aqueous development is used in the manufacture of many devices because of its excellent heat resistance and easy removal of impurities.

[0004] With the advent of the era of artificial intelligence, various form requirements have been put forward for the packaging form of electronic components. Among them, some are electronic components that require a hollow structure, such as filters. Currently, such a photosensitive solid adhesive film with a hollow structure is generally based on a low-temperature curable soluble polyimide as a base resin, adding a certain amount of inorganic fillers, pressing it into a sheet, directly covering it as a lid on a substrate wall to form a hollow structure, and then performing photolithography and other processes.

[0005] JP2020-166125 provides a negative photosensitive solid adhesive film with a polyimide, polyamic acid, or polyamide as the resin main body. However, cracks are easily generated when the solid adhesive film is peeled off, and no clear results are given for the performance of the solid adhesive film.

[0006] JP2015-118194 provides a solid adhesive film with an alkali-soluble polyimide as the resin main body. By adding a large amount of inorganic fillers, with the highest filler addition amount reaching 70%, the solid adhesive film achieves a certain rigidity, obtaining a lower coefficient of thermal expansion and higher heat resistance. However, the filling of too much inorganic matter reduces the elongation at break of the solid adhesive film and greatly increases its brittleness.

[0007] JP2019 - 138995 provides a method for improving the cracking problem of solid adhesive films by adding a heat - bridging agent with a special structure. However, the addition of the heat - bridging agent with a special structure has little effect during the photo - crosslinking stage, and it will seriously reduce the elongation at break of the solid adhesive film during the thermal cross - linking stage, hindering the expression of film strength, making the solid adhesive film brittle and affecting its application. Summary of the Invention

[0008] The present invention provides a negative - type photosensitive solid adhesive film for alkaline aqueous development, which has high strength, high elongation at break, high toughness, low brittleness, and is not prone to cracking. The solid adhesive film has good light transmittance, enabling a thick film to have a high resolution.

[0009] The negative - type photosensitive solid adhesive film for alkaline aqueous development provided by the present invention is made from a photosensitive resin composition, and the composition of the photosensitive resin composition is as follows: (1) 15 - 40 parts by mass of polyamic acid ester; (2) 3 - 20 parts by mass of a photo - crosslinking agent; (3) 0.01 - 5 parts by mass of a photo - initiator; (4) 15 - 70 parts by mass of an inorganic filler; (5) 10 - 40 parts by mass of a solvent; (6) 1 - 40 parts by mass of an adhesive; (7) 0.01 - 0.3 parts by mass of a polymerization inhibitor; (8) 0.01 - 10 parts by mass of a silane coupling agent.

[0010] The molecular weight of the polyamic acid ester can be 10,000 - 60,000, preferably 20,000 - 40,000;

[0011] The polyamic acid ester is prepared from a dianhydride, a diamine, an alcohol compound containing an unsaturated double bond, and a molecular weight regulator. Among them, the molar ratio of the dianhydride, the diamine, the alcohol compound containing an unsaturated double bond, and the molecular weight regulator is in turn: 0.8 - 1.2:0.8 - 1.2:0.96 - 2.4:0.01 - 0.4.

[0012] The dianhydride is composed of a fluorinated aromatic dianhydride and a non - fluorinated dianhydride, and the fluorinated aromatic dianhydride accounts for 10% - 90% of the total dianhydride.

[0013] The fluorinated aromatic dianhydride is selected from one or a mixture of several of the following: 6FDA, 6FXDA, 3FCDA, 6FBPADA, 6FPMDA, 3FDAPA, 6FDAPA, 10FEDA.

[0014]

[0015] The non-fluorinated aromatic dianhydride is selected from: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2’,3,3’-biphenyltetracarboxylic dianhydride, 4,4'-oxybisphthalic anhydride, 3,4'-oxybisphthalic anhydride, 4,4'-phenylenedioxybisphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride; or a mixture of two or more of these compounds.

[0016] The structural formula of the diamine is as follows:

[0017]

[0018] In the formula, X represents a single bond or any one group selected from the group consisting of -CH2-, -O-, -CO-, -S-, -SO2-, -NHCO-, -C(CF3)2-, and -C(CH3)2-.

[0019] R2, R3, R4, R5, R6, R7, R8, and R9 are each independently selected from a group such as -H, -OH, -SO3, and -COOH.

[0020] The alcohol compound containing an unsaturated double bond is selected from: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-acryloyloxy-3-propanol, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 1-methacryloyloxy-3-propanol, 2-isobutenamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate; or a mixture of two or more of these compounds.

[0021] The molecular weight regulator can be selected from one compound or a mixture of two or more compounds among phthalic anhydride, hydrogenated phthalic anhydride, 4-phenylethynylphthalic anhydride, hydrogenated 4-methylphthalic anhydride, 3-chlorophthalic anhydride, 3-bromophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, perchlorophthalic anhydride, perbromophthalic anhydride, 3,4-dichlorophthalic anhydride, 3,4-dibromophthalic anhydride, aniline, 4-phenylethynylaniline, and 3-phenylethynylaniline.

[0022] The polyamic acid ester is prepared by a method comprising the following steps:

[0023] (1) Reacting a fluorinated aromatic dianhydride with an unsaturated double bond-containing alcohol compound to form a fluorinated aromatic diester diacid;

[0024] (2) Reacting a non-fluorinated aromatic dianhydride with an unsaturated double bond-containing alcohol compound to form a non-fluorinated aromatic diester diacid;

[0025] (3) Mixing the fluorinated aromatic diester diacid formed in step (1) with the non-fluorinated aromatic diester diacid formed in step (2), and then reacting with an acyl chlorination reagent to form a corresponding mixed diester diacyl chloride;

[0026] (4) Adding the diamine to an organic solvent and stirring to dissolve it to form a homogeneous diamine solution;

[0027] (5) Mixing the mixed diester diacyl chloride in step (3), the diamine solution in step (4), and the molecular weight regulator, and carrying out a polycondensation reaction to form a polyamic acid ester resin solution;

[0028] (6) Mixing the polyamic acid ester resin solution with a poor solvent to precipitate a solid resin; after washing and drying the solid resin, polyamic acid ester is obtained.

[0029] In step (1), the molar ratio of the fluorinated aromatic dianhydride to the unsaturated double bond-containing alcohol compound is: 1:1.2 - 2;

[0030] In step (2), the molar ratio of the non-fluorinated aromatic dianhydride to the unsaturated double bond-containing alcohol compound is: 1:1.2 - 2;

[0031] In step (3), the fluorinated aromatic diester diacid accounts for 10 - 90% of the total aromatic diester diacids.

[0032] The molar ratio of the total moles of the fluorinated aromatic diester diacid and the non-fluorinated aromatic diester diacid to the moles of the acyl chlorination reagent is: 1:1.8 - 2.2

[0033] In step (5), the molar ratios of the mixed diester diacyl chloride to the diamine and the molecular weight regulator are successively: 1:0.8 - 1.2:0.01 - 0.4

[0034] In step (6), the poor solvent may specifically be: deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, etc., and deionized water, methanol or ethanol is preferably used.

[0035] In the photosensitive resin composition, the photo-crosslinking agent may be selected from: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, ethylene glycol diethyl ether methacrylate, ethylene glycol diethyl ether acrylate, polyethylene glycol methacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, tricyclodecane dimethanol diacrylate, or a mixture of two or more of these compounds.

[0036] The photoinitiator may be selected from: benzophenone, benzophenone derivatives, acetophenone derivatives, thioxanthone, thioxanthone derivatives, benzil, benzil derivatives, benzoin, benzoin derivatives, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, and 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, or a mixture of two or more of these compounds.

[0037] The inorganic filler may be selected from: silica, mica powder, alumina, talc powder, or a mixture of one or more of these.

[0038] Among them, the silica is preferably angular silica (commercially available), and the size of the silica is 1-6 μm, preferably 1-3 μm.

[0039] The mica powder is preferably mica powder manufactured by a dry method (commercially available), and the size of the mica powder is 1-6 μm, preferably 1-3 μm.

[0040] The size of the alumina is 1-6 μm, preferably 1-3 μm.

[0041] The inorganic filler accounts for 40-60% by mass of the total solids (the total solids refer to polyamic acid ester, photo-crosslinking agent, binder, and inorganic filler).

[0042] The solvent is one or a mixture of two or more of N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, and butyl acetate.

[0043] The binder is a binder having an epoxy group.

[0044] The binder having an epoxy group may be selected from one or a mixture of several of poly(propylene glycol) diglycidyl ester, polyethylene glycol diglycidyl ester, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, aliphatic epoxy resin, bisphenol A diglycidyl ether, South Asia 704, NPES901, etc.

[0045] The inhibitor may be selected from one or two or a mixture of two or more of hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 2-nitroso-5-(N-ethyl-sulfopropylamino)phenol;

[0046] The silane coupling agent may be selected from KH550, KH560, KH570, KH580, KH590 or other commercially available similar products, preferably KH570.

[0047] The above photosensitive resin composition is prepared by a method including the following steps:

[0048] Mix the photocrosslinking agent, photoinitiator, solvent, binder, inhibitor, and silane coupling agent, and stir until a uniform solution is formed. Add an inorganic filler to the obtained solution, and stir until a uniform inorganic dispersion is formed. Finally, add polyamic acid ester and stir until a uniform photosensitive resin composition is formed, thus obtaining it.

[0049] The application of the above polyamic acid ester and the photosensitive resin composition containing the polyamic acid ester in the preparation of a negative photosensitive solid film for alkaline aqueous development also belongs to the protection scope of the present invention.

[0050] The present invention also provides a method for preparing a negative photosensitive solid film for alkaline aqueous development.

[0051] The method for preparing a negative photosensitive solid film for alkaline aqueous development provided by the present invention includes the following steps:

[0052] (1) Coating: Coating the photosensitive resin composition on the surface of a support film;

[0053] (2) Pre-baking: Baking the photosensitive resin composition coated on the surface of the support film to form a photosensitive solid film with the support film;

[0054] (3) Protective film lamination: The protective film is laminated with the photosensitive solid adhesive film with a support film to obtain a photosensitive solid adhesive film with a protective film and a support film.

[0055] In the above method step (1), the material of the support film includes but is not limited to PET or PP materials;

[0056] The coating method can be selected but is not limited to knife coating, spin coating, spraying, screen printing and other methods, but any method can coat a constant thickness;

[0057] In step (2), the photosensitive solid adhesive film is formed by baking on a hot plate, oven or drying tunnel at 60 - 120 °C for 1 - 60 min.

[0058] The solvent content of the photosensitive solid adhesive film after baking is between 3 - 20%, and more preferably 3 - 15%.

[0059] In step (3), the protective film can be selected as PET or PP, but is not limited to PET or PP materials.

[0060] The support film can be treated or not, but it is necessary to allow the solid adhesive film to be peeled off from the support film during use. The thickness of the support film can be selected from 10 - 200 μm, preferably 30 - 100 μm.

[0061] The protective film can be treated or not, but it is necessary to allow the protective film to be peeled off from the solid adhesive film during use. The thickness of the protective film can be selected from 5 - 200 μm, preferably 5 - 50 μm.

[0062] The protective film lamination is carried out at a temperature of 25 - 120 °C, preferably 50 - 100 °C.

[0063] The pressure for the protective film lamination is 0 - 0.3 MPa, preferably 0.1 Mpa - 0.3 Mpa.

[0064] The application of the above negative photosensitive solid adhesive film for alkaline aqueous development in the production of electronic components with a hollow structure also belongs to the protection scope of the present invention.

[0065] The present invention uses an alkali-soluble resin of polyamic acid ester, introduces a double bond into the resin side chain, and after exposure, the resin can participate in crosslinking, greatly enhancing the performance of the solid adhesive film and increasing the stiffness of the solid adhesive film in the photo-crosslinking stage. After curing, part of it detaches from the main chain and plays a plasticizing role in the adhesive film, well increasing the elongation at break and tensile strength of the solid adhesive film, making the solid adhesive film have good toughness. The solid adhesive film contains a fluorine structure and has good light transmittance, which can enable the thick film to have a high resolution.

[0066] The properties of the polyimide film formed after exposure, development, and thermal curing of the photosensitive polyamic acid ester resin described in the present invention are shown in Table 1.

[0067] Table 1 Main properties of the fully cured polyimide film

[0068] Specific embodiments

[0069] The present invention will be further described in detail below in conjunction with specific embodiments. The examples given are only for clarifying the present invention, rather than limiting the scope of the present invention. The following examples can be used as a guide for those of ordinary skill in the art to make further improvements, and do not limit the present invention in any way.

[0070] The experimental methods in the following examples are all conventional methods unless otherwise specified, and are carried out according to the techniques or conditions described in the literature in this field or according to the product instructions. The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

[0071] Example 1

[0072] In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 22.21 g of fluorinated aromatic dianhydride 6FDA, 13.01 g of 2-hydroxyethyl methacrylate (HEMA), 3.95 g of pyridine, and 80 g of N-methylpyrrolidone (NMP) were successively added, and stirred at room temperature for 6 h to generate the corresponding 6FDA-diacid dimethacrylate. In another 100 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 15.51 g of non-fluorinated aromatic dianhydride 4,4'-oxybisphthalic anhydride, 13.01 g of HEMA, 3.95 g of pyridine, and 80 g of NMP were successively added, and stirred at room temperature for 6 h to generate the corresponding 4,4'-oxybisphthalic anhydride-diacid dimethacrylate. The 4,4'-oxybisphthalic anhydride-diacid dimethacrylate solution was added to the 6FDA-diacid dimethacrylate solution, and then reacted with 28.55 g of SOCl2 at 0-10 °C for 2 h and at room temperature for 4 h to generate the corresponding mixed diacyl chloride dimethacrylate.

[0073] In a 1L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 40.29 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 90 g of NMP were added, and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 °C using an ice bath, and the prepared mixed diacyl chloride dimethacrylate was added dropwise to the diamine solution over a period of 0.5 h; then, the reaction was carried out at room temperature for 10 h; 2.96 g of phthalic anhydride was added, and stirring was continued for 1 h; the reaction solution was poured into 5 L of deionized water, the solid was precipitated, filtered, and vacuum dried to obtain a polyamic acid ester resin with a resin molecular weight of 32000.

[0074] In a thousand-class clean room equipped with yellow lights, 1.0 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime (photoinitiator), 0.15 g of hydroquinone (polymerization inhibitor), 15 g of glycidyl methacrylate (photocrosslinking agent), 1.0 g of KH570 (silane coupling agent), and 3 g of bisphenol A diglycidyl ether were successively added to 80 g of NMP, and stirred at room temperature for 1 h to form a homogeneous solution. 40 g of silica and 8 g of mica powder (inorganic filler) were added to the homogeneous solution, and stirred for 3 h to form a homogeneous dispersion. 30 g of polyamic acid ester was added to the homogeneous dispersion, and stirred until a homogeneous negative photosensitive polyamic acid ester resin composition solution was obtained.

[0075] The prepared solution was formed into a wet film on a supporting film PET by means of blade coating. Then, it was baked in a blast drying oven at 80 °C for 20 min to obtain a negative photosensitive solid film, and the film thickness was measured to be 40 μm. A protective film was attached to the surface of the solid film by means of laminating, and the laminating pressure was 0.1 MPa. A negative photosensitive solid film with a supporting film and a protective film and alkaline aqueous development was obtained.

[0076] Exposure was carried out using an ultraviolet lamp (i-line and g-line) for 20 s, developed using 2.38% tetramethylammonium hydroxide, rinsed with deionized water, and baked in a blast drying oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film photolithographic pattern with a pattern resolution of 40 μm. The elongation at break of the obtained solid film was 3.0%, the tensile strength was 108, and the tensile modulus was 5.4. The span was 1300*1300. The coefficient of thermal expansion was 40, the glass transition temperature was 262 °C, and the 5% thermal weight loss temperature was 393 °C.

[0077] Example 2

[0078] The fluorinated aromatic dianhydride in Example 1 was replaced with 22.91 g of fluorinated aromatic dianhydride 6FXDA to produce 6FXDA-diacid dimethacrylate.

[0079] Exposed with ultraviolet lamps (i-line and g-line) for 20 s, developed with 2.38% tetramethylammonium hydroxide, rinsed with deionized water, and baked in a forced-air oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film lithography pattern with a pattern resolution of 40 μm. The obtained solid film had an elongation at break of 2.5%, a tensile strength of 100, and a tensile modulus of 5.8. The span was 1300*1300. The coefficient of thermal expansion was 30, the glass transition temperature was 270 °C, and the 5% thermal weight loss temperature was 401 °C.

[0080] Example 3

[0081] Replace the non-fluorinated aromatic dianhydride in Example 1 with 10.90 g of non-fluorinated aromatic dianhydride pyromellitic dianhydride. Replace bisphenol A diglycidyl ether epoxy resin with 1.5 g of poly(propylene glycol) diglycidyl ester and 1.0 g of 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester.

[0082] The prepared solution was cast on a support film PET to form a wet film by doctor blade coating. Then, it was baked in an 80 °C forced-air oven for 30 min to obtain a negative photosensitive solid film, and the film thickness was measured to be 40 μm. A protective film was attached to the surface of the solid film by laminating, and the lamination pressure was 0.1 MPa to obtain a negative photosensitive solid film with a support film and a protective film for alkaline aqueous development.

[0083] Exposed with ultraviolet lamps (i-line and g-line) for 20 s, developed with 2.38% tetramethylammonium hydroxide, rinsed with deionized water, and baked in a forced-air oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film lithography pattern with a pattern resolution of 40 μm. The obtained solid film had an elongation at break of 2.0%, a tensile strength of 89, and a tensile modulus of 5.2. The span was 1300*1300. The coefficient of thermal expansion was 32, the glass transition temperature was 250 °C, and the 5% thermal weight loss temperature was 380 °C.

[0084] Comparative Example 1

[0085] In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 21.81 g of pyromellitic dianhydride (PMDA), 26.02 g of 2-hydroxyethyl methacrylate (HEMA), 7.80 g of pyridine, and 160 g of N-methylpyrrolidone (NMP) were added, and stirred at room temperature for 6 h to form the corresponding dimethyl methacrylate of pyromellitic acid. The above product was reacted with 28.55 g of SOCl2 at 0-10 °C for 2 h and at room temperature for 4 h to form the corresponding dichloride dimethyl methacrylate.

[0086] In a 1 L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 40.29 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 90 g of NMP were added, and stirred to dissolve to form a homogeneous transparent diamine solution. The mixed diamine solution was cooled to below 10 °C using an ice bath, and the prepared diacyl chloride dimethacrylate was added dropwise to the diamine solution over a period of 0.5 h. Then, the reaction was carried out at room temperature for 10 h. Next, 2.96 g of phthalic anhydride was added, and stirring was continued for 1 h. The reaction solution was poured into 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a polyamic acid ester resin.

[0087] In a thousand-class clean room equipped with yellow lights, 1.0 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 0.15 g of hydroquinone, 15 g of glycidyl methacrylate, 1.0 g of KH570, and 3 g of aliphatic epoxy resin were successively added to 80 g of NMP, and stirred at room temperature for 1 h to form a homogeneous solution. 40 g of silica and 8 g of mica powder were added to the homogeneous solution, and stirred for 3 h to form a homogeneous dispersion. 30 g of polyamic acid ester resin was added to the homogeneous dispersion, and stirred until a homogeneous negative photosensitive polyamic acid ester resin composition solution was obtained.

[0088] The prepared solution was made into a wet film on a support film PET by spin coating. Then, it was baked in a forced-air oven at 80 °C for 20 min to obtain a negative photosensitive solid film, and the film thickness was measured to be 40 μm. A protective film was attached to the surface of the solid film by laminating to obtain a negative photosensitive solid film with a support film and a protective film for alkaline aqueous development.

[0089] Exposure was carried out using an ultraviolet lamp (i-line and g-line) for 20 s, developed using 2.38% tetramethylammonium hydroxide, rinsed with deionized water, and baked in a forced-air oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film photolithographic pattern with a pattern resolution of 70 μm. The elongation at break of the obtained solid film was 1.6%, the tensile strength was 78, and the tensile modulus was 5.4. The span was 1300*1300. The coefficient of thermal expansion was 33, the glass transition temperature was 275 °C, and the 5% thermal weight loss temperature was 400 °C.

[0090] Comparative Example 2

[0091] In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 31.02 g of 4,4'-oxybisphthalic anhydride, 26.02 g of 2-hydroxyethyl methacrylate (HEMA), 7.80 g of pyridine and 160 g of N-methylpyrrolidone (NMP) were added, and stirred at room temperature for 6 h to form the corresponding acrylate. The above product was reacted with 28.55 g of SOCl2 at 0-10 °C for 2 h and at room temperature for 4 h to form the corresponding dichloride dimethacrylate.

[0092] In a 1 L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 40.29 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 90 g of NMP were added, and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 °C using an ice bath, and the above-prepared dichloride dimethacrylate was added dropwise to the diamine solution, and the dropping time was 0.5 h; then, reacted at room temperature for 10 h; then 2.96 g of phthalic anhydride was added, and stirred for 1 h; the reaction solution was poured into 5 L of deionized water, the solid was precipitated, filtered and vacuum dried to obtain a polyamic acid ester resin.

[0093] In a thousand-class clean room equipped with a yellow light, 1.0 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 0.15 g of hydroquinone, 15 g of glycidyl methacrylate, 1.0 g of KH570, and 3 g of bisphenol A diglycidyl ether were successively added to 80 g of NMP, and stirred at room temperature for 1 h to form a homogeneous solution. 40 g of silica and 8 g of mica powder were added to the homogeneous solution, and stirred for 3 h to form a homogeneous dispersion. 30 g of polyamic acid ester resin was added to the homogeneous dispersion, and stirred until a homogeneous negative photosensitive polyamic acid ester resin composition solution was obtained.

[0094] The prepared solution was made into a wet film on a supporting film PET by means of blade coating. Then, it was baked in a blast drying oven at 80 °C for 20 min to obtain a negative photosensitive solid film, and the film thickness was measured to be 40 μm. A protective film was attached to the surface of the solid film by means of laminating to obtain a negative photosensitive solid film with a supporting film and a protective film for alkaline aqueous development.

[0095] Exposed with an ultraviolet lamp (i-line and g-line) for 20 s, developed with 2.38% tetramethylammonium hydroxide, rinsed with deionized water, and baked in a blast drying oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film lithography pattern, and the pattern resolution was 60 μm. The elongation at break of the obtained solid film was 3.5%, the tensile strength was 110, and the tensile modulus was 5.0. The span was 1300*1300. The coefficient of thermal expansion was 45, the glass transition temperature was 252 °C, and the 5% thermal weight loss temperature was 383 °C.

[0096] Comparative Example 3

[0097] Self-made fluorine-containing polyimide resin: Dissolve 40.29 g of 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in 250 g of NMP, and stir at room temperature until dissolved. After the diamine is completely dissolved, add 44.42 g of 6FDA, react for 20 h, then add 2.96 g of phthalic anhydride, and continue to react for 5 h. Add 100 ml of toluene to the reaction system, heat up to 180 °C and reflux to obtain a polyimide resin solution. Pour the polyimide resin solution into 5 L of deionized water, precipitate solids, filter, and vacuum dry to obtain polyimide resin. The molecular weight of the resin is 40,000.

[0098] In a thousand-class clean room equipped with yellow lights, add 1.0 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 0.15 g of hydroquinone, 15 g of glycidyl methacrylate, 1.0 g of KH570, and 3 g of bisphenol A diglycidyl ether epoxy resin to 80 g of NMP in sequence, and stir at room temperature for 1 h to form a homogeneous solution. Add 40 g of silica and 8 g of mica powder to the homogeneous solution, and stir for 3 h to form a homogeneous dispersion. Add 30 g of polyimide resin to the homogeneous dispersion, and stir until a homogeneous negative photosensitive polyimide resin composition solution is formed.

[0099] The prepared solution is made into a wet film on a supporting film PET by means of blade coating. Then, bake it in a blast drying oven at 80 °C for 20 min to obtain a negative photosensitive solid film, and measure the film thickness to be 40 μm. Attach a protective film to the surface of the solid film by means of laminating to obtain a negative photosensitive solid film with a supporting film and a protective film for alkaline aqueous development.

[0100] Expose with an ultraviolet lamp (i-line and g-line) for 20 s, develop with 4.8% tetramethylammonium hydroxide, rinse with deionized water, and bake in a blast drying oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film lithography pattern, and the pattern resolution is 40 μm. The elongation at break of the obtained solid film is 4.0%, the tensile strength is 100, and the tensile modulus is 5.4. The span is 800*800. The coefficient of thermal expansion is 46, the glass transition temperature is 252 °C, and the 5% thermal weight loss temperature is 385 °C.

[0101] Comparative Example 4

[0102] Self-made fluorine-containing polyimide resin: Dissolve 40.29 g of 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in 250 g of NMP, and stir at room temperature until dissolved. After the diamine is completely dissolved, add 44.42 g of 6FDA, react for 20 h, then add 2.96 g of phthalic anhydride, and continue to react for 5 h. Add 100 ml of toluene to the reaction system, heat up to 180 °C and reflux to obtain a polyimide resin solution. Pour the polyimide resin solution into 5 L of deionized water, precipitate solids, filter, and vacuum dry to obtain polyimide resin. The molecular weight of the resin is 40,000.

[0103] In a thousand-class clean room equipped with yellow light lamps, add 1.0 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 0.15 g of hydroquinone, 15 g of glycidyl methacrylate, 1.0 g of KH570, and 3 g of bisphenol A diglycidyl ether epoxy resin to 80 g of NMP in sequence, and stir at room temperature for 1 h to form a homogeneous solution. Add 92 g of silica and 20 g of mica powder to the homogeneous solution, and stir for 3 h to form a homogeneous dispersion. Add 30 g of polyimide resin to the homogeneous dispersion, and stir until a homogeneous negative photosensitive polyamic acid ester resin composition solution is obtained.

[0104] The prepared solution is made into a wet film on a support film PET by means of knife coating. Then, bake it in a blast drying oven at 80 °C for 20 min to obtain a negative photosensitive solid film, and measure the film thickness to be 40 μm. Attach a protective film to the surface of the solid film by means of laminating to obtain a negative photosensitive solid film with a support film and a protective film for alkaline aqueous development.

[0105] Expose it with an ultraviolet lamp (i-line and g-line) for 20 s, develop it with 4.8% tetramethylammonium hydroxide, rinse with deionized water, and then bake it in a blast drying oven (150 °C / 1 h, 200 °C / 1 h, 250 °C / 1 h) to obtain a solid film lithography pattern, and the pattern resolution is 60 μm. The elongation at break of the obtained solid film is 1.0%, the tensile strength is 65, and the tensile modulus is 6.8. The span is 1300*1300. After the silicon powder content increases, the stiffness can indeed be improved, but its elongation at break and tensile strength will both decrease.

[0106] It can be seen from the examples and comparative examples that the negative photosensitive solid film for alkaline aqueous development obtained by the present invention using fluorine-containing aromatic dianhydride, non-fluorine-containing aromatic dianhydride, and diamine with a specific structure as starting materials is superior to the negative photosensitive solid film for alkaline aqueous development obtained using other starting materials in terms of pattern resolution, elongation at break, and span of the formed hollow cavity, and has significant beneficial effects.

[0107] The above has described the present invention in detail. For those skilled in the art, without departing from the spirit and scope of the present invention and without the need for unnecessary experiments, the present invention can be implemented within a relatively wide range under equivalent parameters, concentrations, and conditions. Although specific embodiments of the present invention are given, it should be understood that the present invention can be further improved. In short, according to the principle of the present invention, this application intends to cover any modifications, uses, or improvements to the present invention, including those that depart from the scope disclosed in this application but are made using conventional techniques known in the art. The application of some basic features can be made within the scope of the following appended claims.

Claims

1. A negative photosensitive solid gum film for alkaline aqueous development, which is made of a photosensitive resin composition. The composition of the photosensitive resin composition is as follows: (1) 15 - 40 parts by mass of polyamic acid ester; (2) 3 - 20 parts by mass of a photo-crosslinking agent; (3) 0.01 - 5 parts by mass of a photoinitiator; (4) 15 - 70 parts by mass of an inorganic filler; (5) 10 - 40 parts by mass of a solvent; (6) 1 - 40 parts by mass of an adhesive; (7) 0.01 - 0.3 parts by mass of a polymerization inhibitor; (8) 0.01 - 10 parts by mass of a silane coupling agent; The molecular weight of the polyamic acid ester is 10,000 - 60,000; The polyamic acid ester is prepared from a dianhydride, a diamine, an alcohol compound containing an unsaturated double bond, and a molecular weight regulator, wherein, The molar ratio of dianhydride, diamine, an alcohol compound containing an unsaturated double bond, and a molecular weight regulator is in turn: 0.8 - 1.2 : 0.8 - 1.2 : 0.96 - 2.4 : 0.01 - 0.4; The dianhydride is composed of a fluorine-containing aromatic dianhydride and a non-fluorine-containing aromatic dianhydride, and the fluorine-containing aromatic dianhydride accounts for 10% - 90% of the total dianhydride; The fluorine-containing aromatic dianhydride is selected from one or a mixture of several of the following: 6FDA, 6FXDA, 3FCDA, 6FBPADA, 6FPMDA, 3FDAPA, 6FDAPA, 10FEDA; The non-fluorine-containing aromatic dianhydride is selected from one compound or a mixture of two or more compounds of the following: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2’,3,3’-biphenyltetracarboxylic dianhydride, 4,4'-oxybisphthalic anhydride, 3,4'-oxybisphthalic anhydride, 4,4'-phenylenedioxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride; The structural formula of the diamine is shown as follows: In the formula, X represents a single bond or any one group selected from the group consisting of -CH2-, -O-, -CO-, -S-, -SO2-, -NHCO-, -C(CF3)2-, -C(CH3)2-; R2, R3, R4, R5, R6, R7, R8, R9 are each independently selected from one of the groups -H, -OH, -SO3, -COOH; The alcohol compound containing an unsaturated double bond is selected from: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 1-methacryloyloxy-3-propanol, 2-isobutenamidoethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate; a compound selected from one of the above compounds or a mixture of two or more of the above compounds; The molecular weight regulator is selected from: phthalic anhydride, hydrogenated phthalic anhydride, 4-phenylethynyl phthalic anhydride, hydrogenated 4-methylphthalic anhydride, 3-chlorophthalic anhydride, 3-bromophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, perchlorophthalic anhydride, perbromophthalic anhydride, 3,4-dichlorophthalic anhydride, 3,4-dibromophthalic anhydride, aniline, 4-phenylethynylaniline, and 3-phenylethynylaniline; a compound selected from one of the above compounds or a mixture of two or more of the above compounds.

2. The negative photosensitive solid adhesive film according to claim 1, wherein: The polyamic acid ester is prepared by a method comprising the following steps: (1) Reacting a fluorine-containing aromatic dianhydride with an alcohol compound containing an unsaturated double bond to form a fluorine-containing aromatic diester diacid; (2) Reacting a non-fluorine-containing aromatic dianhydride with an alcohol compound containing an unsaturated double bond to form a non-fluorine-containing aromatic diester diacid; (3) Mixing the fluorine-containing aromatic diester diacid formed in step (1) with the non-fluorine-containing aromatic diester diacid formed in step (2), and then reacting with an acyl chlorination reagent to form a corresponding mixed diester diacyl chloride; (4) Adding the diamine to an organic solvent and stirring to dissolve it to form a homogeneous diamine solution; (5) Mixing the mixed diester diacyl chloride in step (3), the diamine solution in step (4), and the molecular weight regulator, and carrying out a polycondensation reaction to form a polyamic acid ester resin solution; (6) Mixing the polyamic acid ester resin solution with a poor solvent to precipitate a solid resin; after washing and drying the solid resin, a polyamic acid ester is obtained.

3. The negative photosensitive solid adhesive film according to claim 1, characterized in that: In the photosensitive resin composition, the photo-crosslinking agent is selected from: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, glycidyl acrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol methacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, tricyclodecane dimethanol diacrylate; a compound selected therefrom, or a mixture of two or more compounds; The photoinitiator is selected from: benzophenone, benzophenone derivatives, acetophenone derivatives, thioxanthone, thioxanthone derivatives, benzil, benzil derivatives, benzoin, benzoin derivatives, 1-phenyl-1,2-propanedione 2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-butanedione 2-(o-methoxycarbonyl)oxime, and 1,3-diphenylpropanetrione 2-(o-ethoxycarbonyl)oxime; a compound selected therefrom, or a mixture of two or more compounds; The inorganic filler is selected from: silica, mica powder, alumina, talc powder; a mixture of one or more of them; The inorganic filler accounts for 40-60% of the total solid matter; The solvent is selected from: N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, butyl acetate; a mixture of one or two or more of them; The binder is a binder having an epoxy group; The inhibitor is selected from: hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 2-nitroso-5-(N-ethyl-sulfopropylamino)phenol; a mixture of one or two or more of them; The silane coupling agent is selected from: KH550, KH560, KH570, KH580, KH590; a mixture of one or two or more of them.

4. The negative photosensitive solid adhesive film according to claim 3, wherein: The binder having an epoxy group is selected from: poly(propylene glycol) diglycidyl ether, polyethylene glycol diglycidyl ether, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ether, bisphenol A diglycidyl ether, NPES901; a mixture of one or more of them.

5. The negative photosensitive solid adhesive film according to any one of claims 1-4, characterized in that: The photosensitive resin composition is prepared by a method comprising the following steps: Mix a photo-crosslinking agent, a photoinitiator, a solvent, a binder, a polymerization inhibitor, and a silane coupling agent, and stir until a uniform solution is formed. Add an inorganic filler to the obtained solution, and stir until a uniform inorganic dispersion is formed. Finally, add a polyamic acid ester and stir until a uniform photosensitive resin composition is obtained.

6. A method for preparing the negative photosensitive solid film with alkaline aqueous development according to any one of claims 1-5, comprising the following steps: (1) Coating: Coating the surface of a support film with the photosensitive resin composition; (2) Pre-baking: Baking the photosensitive resin composition coated on the surface of the support film to form a photosensitive solid film with a support film; (3) Protective film lamination: Laminating a protective film with the photosensitive solid film with a support film to obtain a photosensitive solid film with a protective film and a support film.

7. The method according to claim 6, wherein: In step (2), the photosensitive solid film is formed by baking on a hot plate, in an oven or in a drying tunnel at 60-120 °C for 1-60 min; The solvent content of the photosensitive solid film after baking is between 3-20%; The protective film lamination is carried out at a temperature of 25-120 °C; The pressure for the protective film lamination is 0-0.3 MPa.

8. Application of the negative photosensitive solid film with alkaline aqueous development according to any one of claims 1-5 in the production of electronic components requiring a hollow structure.

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