Compound containing ureido structure, negative photosensitive resin composition and preparation method and application of negative photosensitive resin composition

Abstract

The invention provides a compound containing a ureido structure, a negative photosensitive resin composition and a preparation method and application of the negative photosensitive resin composition. The compound containing the ureido structure can be used as a photo-crosslinking agent; when being added into the photosensitive resin composition, the compound can improve the resolution ratio and mechanical property of a photosensitive resin composition cured film and the adhesiveness with a base material, and can effectively inhibit the oxidation discoloration of a copper base material.

Description

Technical Field

[0001] The present invention relates to a compound containing a urea structure, a method for preparing the compound containing a urea structure, a negative photosensitive resin composition containing the compound containing a urea structure, and an application of the negative photosensitive resin composition, belonging to the technical field of electronic device packaging materials. Background Art

[0002] Polyimides are a class of polymers containing imide rings in their main chains. Based on their molecular structure, they are classified into aromatic polyimides and aliphatic polyimides. Aromatic polyimides offer low dielectric properties, high mechanical strength, ease of preparation, and, in particular, high thermal stability. They are the primary polymers used in insulation layers, protective layers, and circuit packaging for multi-layer wiring and multi-chip assemblies in next-generation integrated circuits.

[0003] With the integration and miniaturization of semiconductor devices, the wiring and mounting methods of semiconductor devices have changed. For example, the traditional gold or aluminum wiring has been replaced by copper or copper alloy wiring with lower resistance, and the traditional lead-tin eutectic soldering has been replaced by ball grid array and chip-scale mounting for higher density mounting. The cured resin film is in direct contact with the copper or copper alloy and the solder bumps, which requires the photosensitive resin film to have not only excellent resolution but also good adhesion to the copper or copper alloy substrate. The cured resin film is also required to have good chemical resistance, high heat resistance, and excellent mechanical properties, while not causing discoloration of the copper or copper alloy substrate.

[0004] In the prior art, various additives are usually added to the resin to obtain good resin cured film performance. In patent CN109478016A, the adhesion of the resin to the substrate is increased by adding nitrogen-containing aromatic compounds. In patent JP5446203B2, the corrosion of the resin to copper or copper alloy is reduced by adding heterocyclic compounds, and the adhesion is increased. In patent CN102375336B, the adhesion, heat resistance, and chemical resistance are increased by adding purine derivatives, cross-linking agents, and organic titanium compounds, and the discoloration of the copper or copper alloy substrate is suppressed. In order to achieve comprehensive performance, various additives are added in the prior art, which often cause the additive content to be too much, and the performance of the resin material can be reduced. In addition, the presence of various additives often has the problem of whether the compatibility is matched, which easily causes the reduction of another performance while improving the performance on the one hand. Summary of the Invention

[0005] In view of the above situation, the object of the present invention is to provide a compound containing a urea structure, which can be used as a photocrosslinking agent. When added to a photosensitive resin composition, it can improve the resolution, mechanical properties and adhesion to the substrate of the cured film of the photosensitive resin composition, and can effectively inhibit the oxidative discoloration of the copper substrate.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A compound containing a urea structure, the compound having the structural formula shown in the following formula I:

[0008]

[0009] In formula I, R1 is an alkylene group having 2 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms, such as methylene, ethylene, or propylene.

[0010] In formula I, R2 is a divalent organic group having 2 or more carbon atoms.

[0011] Furthermore, the compound containing a urea structure is selected from at least one of the structures represented by the following formulas A-1 to A-8:

[0012]

[0013]

[0014] The present invention also provides a method for preparing the urea-containing compound of Formula I. The compound is obtained by reacting a compound of Formula IV and an aliphatic diamine compound of Formula V as raw materials. The reaction formula is as follows:

[0015]

[0016] In formula IV and formula V, R1 and R2 are as defined above.

[0017] Furthermore, R2 in Formula I is introduced by an aliphatic diamine compound and is a residue of a diamine compound, wherein the aliphatic diamine compound is selected from ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-diaminopentane, 1,6-hexanediamine, 1,8-octanediamine, decanediamine, 1,12-diaminododecane, 1,2-bis(aminomethyl)cyclobutane, 1,8-diamino-3,6-dioxaoctane, polyoxyethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2-methyl-1,3-cyclohexanediamine, 4 ... -(aminomethyl)cyclohexylamine, bicyclo[2.2.1]heptane-2,5-diamine, bicyclo[2.2.1]heptanedimethylamine, bicyclo[2.2.1]heptane-2,5-dimethylamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), 1,1'-dicyclohexyl-4,4'-diamine, 4,4'-isopropyldicyclohexylamine, 1,1'-dicyclohexyl-2,2'-dimethyl-4,4'-diamine, 1,3-adamantanedimethylamine, and 1,1'-diamantane-3,3'-diamine.

[0018] Furthermore, R1 in formula I is introduced from the compound of formula IV, and R1 is methylene, ethylene, or propylene.

[0019] Furthermore, the molar ratio of the aliphatic diamine compound represented by formula V to the compound represented by formula IV is 1:2.0-2.1.

[0020] Furthermore, the reaction is carried out in an organic solvent, which can be selected from at least one of tetrahydrofuran, acetone, toluene, xylene, and the like.

[0021] Furthermore, the mass ratio of the aliphatic diamine compound represented by Formula V to the organic solvent is 1:(2-10), for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10.

[0022] Furthermore, the aliphatic diamine compound represented by formula V, the compound represented by formula IV, and an organic solvent are mixed and reacted. The reaction includes a first reaction stage and a second reaction stage, wherein the temperature of the first reaction stage is 0-10° C., for example, 0° C., 1° C., 2° C., 3° ​​C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., and 10° C., and the time of the first reaction stage is 0.5-5 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, and 5 h; the temperature of the second reaction stage is 20-30° C., for example, 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29° C., and 30° C., and the time of the second reaction stage is 5-15 h, for example, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, and 15 h.

[0023] Furthermore, after the reaction, the solvent is recovered from the reaction solution to obtain a product.

[0024] The present invention also provides a negative photosensitive resin composition, which includes a photosensitive resin and a photocrosslinker, wherein the photocrosslinker includes a photocrosslinker A, and the photocrosslinker A is selected from at least one of the compounds containing a urea structure shown in the above formula I.

[0025] Furthermore, the photocrosslinking agent may contain only photocrosslinking agent A or other photocrosslinking agents. The photocrosslinking agent A accounts for 50-100% of the total mass of the photocrosslinking agent, for example, 50%, 60%, 70%, 80%, 90%, or 100%.

[0026] Furthermore, the photocrosslinking agent may contain a photocrosslinking agent B in addition to the photocrosslinking agent A, and the photocrosslinking agent B may be selected from diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, p-vinylbenzene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, Hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dimethacrylate Pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A At least one of oxidized bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated bisphenol A methacrylate, propoxylated ethoxy bisphenol A diacrylate, propoxyethoxylated bisphenol A dimethacrylate, N-vinyl caprolactam, polyethylene glycol diacrylate, 2-isocyanatoethyl methacrylate, 9,9-bis(4-allyloxyphenyl)fluorene, 9,9-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0027] Furthermore, the photosensitive resin is at least one of polyimide precursors having a double bond structure.

[0028] Furthermore, the polyimide precursor is polyimide acid or polyimide ester, and the polyimide precursor contains the structure shown in the following formula II:

[0029]

[0030] In Formula II, R3 is a tetravalent organic group having 2 to 16 carbon atoms; R4 is a divalent organic group having 2 to 20 carbon atoms; R5 and R6 are each independently selected from a hydrogen atom, a monovalent organic group having the structure represented by Formula III, and a saturated aliphatic group having 1 to 4 carbon atoms;

[0031]

[0032] In formula III, R7, R8, and R9 are independently selected from a hydrogen atom or an organic group having 1 to 3 carbon atoms, and * represents an insertion site;

[0033] In Formula II and Formula III, m is an integer of 2-10, and n is an integer of 2-200.

[0034] Furthermore, the photosensitive resin is synthesized from tetracarboxylic dianhydride and diamine, and in Formula II, R3 is derived from tetracarboxylic dianhydride. Optionally, the tetracarboxylic dianhydride is selected from at least one of pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.

[0035] Furthermore, in Formula II, R4 is derived from a diamine. Optionally, the diamine is selected from p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4 At least one of 1,4-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)benzene, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and 4,4'-diamino-2,2'-dimethylbicyclohexane.

[0036] Furthermore, the formula III is derived from alcohols having unsaturated double bonds. Optionally, the alcohols having unsaturated double bonds are selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamideethanol, 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-cyclohexyloxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methyl At least one of acryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0037] Furthermore, the polyimide precursor can be synthesized according to the method disclosed in the prior art. In a specific embodiment of the present invention, a method for preparing a polyamic acid ester resin is provided, comprising the following steps:

[0038] 1) Tetracarboxylic dianhydride reacts with an alcohol compound in a solvent to generate a diacid diester, wherein the alcohol compound is the above-mentioned alcohol having an unsaturated double bond.

[0039] 2) the diacid diester reacts with an acyl chloride reagent to form a corresponding diacid chloride diester, wherein the acyl chloride reagent is preferably at least one of SOCl2, PCl3, PCl5, oxalyl chloride, and COCl2.

[0040] 3) Dissolve diamine and catalyst pyridine in a solvent to form a homogeneous diamine solution.

[0041] 4) dropping the diamine solution into the diacyl chloride diester solution to carry out polycondensation reaction to form a polyamic acid ester solution.

[0042] 5) The polyamic acid ester solution is mixed with a poor solvent to precipitate a solid resin.

[0043] 6) The solid resin is washed and dried to obtain polyamic acid ester.

[0044] Furthermore, the solvent in steps 1) and 3) is consistent with the organic solvent used in the photosensitive resin composition described below.

[0045] Furthermore, in step 1), tetracarboxylic dianhydride and alcohol compound are reacted under the catalysis of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0046] Furthermore, in step 1), the molar ratio of tetracarboxylic dianhydride to the alcohol compound is 1:2-2.1, and the molar ratio of tetracarboxylic dianhydride to DBU is 1:0.005-0.01, for example, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01.

[0047] Furthermore, in step 1), the reaction temperature is 30-80°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, and the reaction time is 2-6h, for example, 2h, 3h, 4h, 5h, 6h.

[0048] Furthermore, in step 2), the molar ratio of the diacid diester to the acyl chloride reagent is 1:2 to 2.1.

[0049] Furthermore, in step 2), the reaction temperature is 0-10°C, for example, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, and the reaction time is 1-3h, for example, 1h, 2h, 3h.

[0050] Furthermore, in step 3), the molar ratio of diamine to pyridine is preferably 1:2 to 5, for example, 1:2, 1:3, 1:4, or 1:5.

[0051] Furthermore, in step 3), the molar ratio of diamine to the tetracarboxylic dianhydride in step 1) is preferably 0.8 to 1.2:1, for example, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1; the mass percentage concentration of the diamine solution is preferably 10 to 30 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[0052] Furthermore, in step 4), the diamine solution prepared in step 3) is added dropwise to the diacyl chloride diester solution obtained in step 2) at a temperature below 10°C, and the reaction is carried out at 0-10°C for 2-24 hours to form a polyamic acid ester solution. For example, the reaction temperature can be 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, or 10°C, and the reaction time can be 2 hours, 4 hours, 5 hours, 8 hours, 10 hours, 12 hours, 14 hours, 15 hours, 18 hours, 20 hours, or 24 hours.

[0053] Furthermore, in the polycondensation reaction solution of step 4), the concentration of the monomers (including tetracarboxylic dianhydride, diacid diester, and diamine) should, in principle, be sufficient to allow the monomers to fully dissolve and the resulting polymer to not precipitate. If the monomer concentration is too high, the polymer will precipitate; while if the concentration is too low, the molecular weight of the polymer will not increase. Therefore, the monomer concentration of the present invention can be 5 to 35 wt% relative to the total mass of the reaction solution, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, and preferably 10 to 30 wt%.

[0054] Preferably, in steps 1) to 4), the reaction is carried out under the protection of an inert gas such as nitrogen.

[0055] Furthermore, in step 5), the poor solvent can be deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, etc., preferably deionized water, methanol and / or ethanol. The amount of the poor solvent is preferably 3 to 20 times the total amount of the polymer solution by mass, for example, 3 times, 5 times, 8 times, 10 times, 12 times, 14 times, 15 times, 18 times, or 20 times.

[0056] Furthermore, in step 6), the washing is performed using the poor solvent used for precipitation in step 5), and the amount of the poor solvent used for washing is preferably 1 to 6 times the mass of the polymer. The more times the polymer is washed, the less impurities can be obtained. The number of washings is preferably 2 to 6 times. After washing, the polymer is preferably dried under vacuum at 20 to 70° C. to obtain a polyamic acid ester solid resin.

[0057] Furthermore, the polyamic acid ester solid resin obtained in step 6) can be crushed according to application requirements.

[0058] Furthermore, the negative photosensitive resin composition further contains a photoinitiator and an organic solvent.

[0059] Furthermore, the photoinitiator is selected from at least one of benzophenone compounds, benzyl compounds, coumarin compounds, anthraquinone compounds, benzoin compounds, thioxanthone compounds, thiol compounds, glycine compounds, oxime compounds, α-aminoalkylphenone compounds, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name: BAPO, manufactured by Wuhan Yuancheng Technology).

[0060] Furthermore, the benzophenone compound is at least one selected from benzophenone, 4,4-bis(diethylamino)benzophenone, and 3,3,4,4-tetra(tert-butylperoxycarbonyl)benzophenone.

[0061] Furthermore, the coumarin compound is selected from at least one of 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone and the like; 7-diethylamino-3-nonyl coumarin, 4,6-dimethyl-3-ethylamino coumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylbenzimidazolyl) coumarin, and 3-(2-benzothiazolyl)-7-diethylaminocoumarin.

[0062] Furthermore, the anthraquinone compound is selected from anthraquinone compounds such as 2-tert-butylanthraquinone, 2-ethylanthraquinone, and 1,2-benzanthraquinone.

[0063] Furthermore, the benzoin compound is selected from at least one of benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

[0064] Furthermore, the thioxanthone compound is at least one selected from 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-isopropylthioxanthone.

[0065] Furthermore, the mercapto compound is selected from at least one of ethylene glycol di(3-mercaptopropionate), 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole;

[0066] Furthermore, the glycine compound is selected from at least one of N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)glycine, and N-(4-cyanophenyl)glycine.

[0067] Furthermore, the oxime compound is selected from at least one of 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (trade name: OXE-01, manufactured by BASF), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (trade name: OXE-02, manufactured by BASF).

[0068] Furthermore, the α-aminoalkylphenone compound is selected from at least one of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one.

[0069] Furthermore, the organic solvent is selected from at least one 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.

[0070] Furthermore, the weight ratio of the photosensitive resin to the photocrosslinking agent A is 100:(20-150), for example, 100:20, 100:50, 100:80, 100:100, or 100:150.

[0071] Furthermore, the weight ratio of the photosensitive resin to the photoinitiator is 100:(0.1-20), for example, 100:0.1, 100:1, 100:5, 100:10, 100:15, 100:20.

[0072] Furthermore, the weight ratio of the photosensitive resin to the organic solvent is 100:(80-5000), for example, 100:80, 100:100, 100:500, 100:1000, 100:1500, 100:2000, 100:2500, 100:3000, 100:3500, 100:4000, 100:4500, and 100:5000.

[0073] Furthermore, the negative photosensitive resin composition may further contain other components, such as a photosensitizer, a sensitizer, a silane coupling agent, a polymerization inhibitor, etc., which can be adjusted as needed and are not limited herein. The cured resin film formed after curing the negative photosensitive resin composition can be used as an insulating film and packaging film material for precision electronic devices.

[0074] The invention provides a method for preparing a negative photosensitive resin composition, which comprises: mixing a photosensitive resin with a photocrosslinking agent, a photoinitiator, an organic solvent and the like, and stirring until a uniform solution is formed.

[0075] Furthermore, the preparation process of the negative photosensitive resin composition is preferably completed in a Class 1000 clean room equipped with a yellow light source, especially when the formulated amount of photosensitive resin, photocrosslinker, and photoinitiator are added to the organic solvent in sequence at room temperature, the effect is best.

[0076] The present invention also provides the use of the negative photosensitive resin composition in precision electronic devices, for example, as an insulating film or packaging film material.

[0077] The present invention also provides an insulating film or a packaging film obtained by curing the negative photosensitive resin composition.

[0078] The crosslinking agent provided by the present invention contains a urea group, a double bond structure and an aliphatic structure in its structure. When added to a photosensitive resin composition, it can improve the light transmittance and mechanical properties of the resin cured film and the adhesion performance of the cured film to the substrate, and can also inhibit the oxidative discoloration of copper. DETAILED DESCRIPTION

[0079] The present invention will be further described below with reference to specific examples, but the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise specified. The materials described can be purchased from public commercial channels unless otherwise specified.

[0080] Preparation Example 1 Preparation of Photocrosslinker A-1

[0081] Under a nitrogen atmosphere, 6.01 g (0.1 mol) of ethylenediamine and 50 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath, and 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction system temperature below 10°C. The mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-1, the structural formula of which is as follows:

[0082]

[0083] A-1 NMR information is as follows:

[0084] 1 HNMR (DMSO): δ: 3.62 (m, 4H), 4.24 (d, 4H), 5.06 (d, 2H), 5.19 (d, 2H), 5.84 (s, 2H), 6.02 (m, 2H), 6.76 (m, 2H).

[0085] Preparation Example 2 Preparation of Photocrosslinker A-2

[0086] Under a nitrogen atmosphere, 20.04 g (0.1 mol) of 1,12-diaminododecane and 100 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction system temperature below 10°C. The mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-2, the structural formula of which is as follows:

[0087]

[0088] A-2 NMR information is as follows:

[0089] 1 HNMR (DMSO): δ: 1.29 (m, 16H), 1.42 (m, 4H), 3.04 (m, 4H), 4.24 (d, 4H), 5.06 (d, 2H), 5.19 (d, 2H), 5.84 (s, 2H), 6.02 (m, 2H), 6.76 (m, 2H). Preparation Example 3 Preparation of Photocrosslinker A-3

[0090] Under a nitrogen atmosphere, 14.82 g (0.1 mol) of 1,8-diamino-3,6-dioxaoctane and 100 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction system temperature below 10°C. The mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-3, the structural formula of which is as follows:

[0091]

[0092] A-3 NMR information is as follows:

[0093] 1 HNMR (DMSO): δ: 3.24 (m, 4H), 3.52 (m, 4H), 3.67 (m, 4H), 4.24 (d, 4H), 5.06 (d, 2H), 5.19 (d, 2H), 5.84 (s, 2H), 6.02 (m, 2H), 6.76 (m, 2H). Preparation Example 4 Preparation of Photocrosslinker A-4

[0094] Under a nitrogen atmosphere, 11.42 g (0.1 mol) of 1,4-cyclohexanediamine and 100 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction system temperature below 10°C. The mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-4, the structural formula of which is as follows:

[0095]

[0096] A-4 NMR information is as follows:

[0097] 1HNMR (DMSO): δ: 1.49 (m, 4H), 1.74 (m, 4H), 3.54 (m, 2H), 4.24 (d, 4H), 5.06 (d, 2H), 5.19 (d, 2H), 5.84 (s, 2H), 6.46 (m, 2H), 6.76 (m, 2H). Preparation Example 5 Preparation of Photocrosslinker A-5

[0098] Under a nitrogen atmosphere, 12.62 g (0.1 mol) of bicyclo[2.2.1]heptane-2,5-diamine and 100 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction system temperature below 10°C. The mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-5, the structural formula of which is as follows:

[0099]

[0100] A-5 NMR information is as follows:

[0101] 1 HNMR(DMSO): δ: 1.15(m,2H),1.40(m,2H),1.88(m,1H),2.18(m,1H),2.74(m,2H),3.44 (m,2H),4.24(d,4H),5.06(d,2H),5.19(d,2H),5.84(s,2H),6.46(m,2H),6.76(m,2H).

[0102] Preparation Example 6 Preparation of Photocrosslinker A-6

[0103] Under a nitrogen atmosphere, 19.63 g (0.1 mol) of 1,1'-dicyclohexyl-4,4'-diamine and 100 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction system temperature below 10°C. The mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-6, the structural formula of which is as follows:

[0104]

[0105] A-6 NMR information is as follows:

[0106] 1HNMR(DMSO): δ: 1.24-1.74(m,18H),3.54(m,2H),4.24(d,4H),5.06(d,2H),5.19(d,2H),5.84(s,2H),6.46(m,2H),6.76(m,2H).

[0107] Preparation Example 7 Preparation of Photocrosslinker A-7

[0108] Under a nitrogen atmosphere, 19.43 g (0.1 mol) of 1,3-adamantanedimethylamine and 200 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath, and 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise. The reaction system temperature was kept below 10°C and the mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-7, the structural formula of which is as follows:

[0109]

[0110] A-7 NMR information is as follows:

[0111] 1 HNMR(DMSO): δ: 1.07-1.39(m,14H),3.02(s,4H),4.24(d,4H),5.06(d,2H),5.19(d,2H),5.84(s,2H),6.46(m,2H),6.76(m,2H).

[0112] Preparation Example 8 Preparation of Photocrosslinker A-8

[0113] Under a nitrogen atmosphere, 30.05 g (0.1 mol) of 1,1'-diamantane-3,3'-diamine and 200 g of tetrahydrofuran were added to a three-necked flask equipped with a stirring and constant pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved. The mixture was cooled to 0°C in an ice bath, and 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise. The reaction system temperature was kept below 10°C and the mixture was added dropwise within 0.5 h. After the addition was completed, the mixture was naturally heated to room temperature and the reaction was continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a urea-based photocrosslinker A-8, the structural formula of which is as follows:

[0114]

[0115] A-8 NMR information is as follows:

[0116] 1HNMR(DMSO): δ: 1.20-1.67(m,28H),4.24(d,4H),5.06(d,2H),5.19(d,2H),5.84(s,2H),6.46(m,2H),6.76(m,2H).

[0117] Synthesis Example 1 Synthesis of polyimide precursor resin S-1

[0118] Under nitrogen flow, 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride, 0.11 g (0.0007 mol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 26.29 g (0.202 mol) of hydroxyethyl methacrylate, and 100 g of N-methylpyrrolidine (NMP) were added to a 500 mL three-necked flask in sequence, stirred and dissolved, reacted at 55°C for 4 h, and then cooled to 25°C to obtain reaction solution A.

[0119] 24.03 g (0.202 mol) of SOCl2 was added dropwise to the reaction solution A. During the addition process, the temperature of the reaction system was ensured to be controlled below 10°C. After the addition was completed, the reaction system was kept at 0-10°C and the reaction was continued for 2 h to obtain the reaction solution B.

[0120] Under nitrogen flow, 20.02 g (0.1 mol) of 4,4'-diaminodiphenyl ether was weighed and added to a 500 mL three-necked flask, followed by the addition of 100 g of NMP and 27.69 g (0.35 mol) of pyridine. The mixture was stirred and dissolved, and the diamine solution was slowly added dropwise to the reaction solution B. The temperature of the reaction system was controlled below 10°C during the addition process. After the addition was completed, the temperature was maintained at 0-10°C and the reaction was continued for 3 h. The reaction was then terminated. The polymer solution was poured into 3 L of deionized water to precipitate a white polymer precipitate, which was filtered, washed three times with deionized water, and dried under vacuum at 50°C for 48 h to obtain a polyimide precursor resin S-1.

[0121] The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion) using a Shimadzu GPC system. The weight average molecular weight (Mw) of the polyimide precursor resin obtained in Synthesis Example 1 was 20,000 to 30,000.

[0122] Example 1

[0123] In a three-necked flask equipped with a stirrer, 10.0 g of polyimide precursor resin S-1 was dissolved in 20 g of N-methylpyrrolidone (NMP). After sufficient dissolution, 5 g of photocrosslinker A-1 and 0.5 g of photoinitiator 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE-01) were added. After sufficient dissolution, the mixture was filtered using a 1.0 μm filter membrane to obtain a negative photosensitive resin composition.

[0124] Example 2

[0125] Except that the amount of photocrosslinking agent A-1 was changed from 5 g to 2 g, the other ingredients were the same as those in Example 1.

[0126] Example 3

[0127] Except that the amount of photocrosslinking agent A-1 was changed from 5 g to 10 g, other ingredients were the same as those in Example 1.

[0128] Example 4

[0129] Except that the amount of photocrosslinking agent A-1 was changed from 5 g to 15 g, the other ingredients were the same as those in Example 1.

[0130] Example 5

[0131] Except that the photocrosslinking agent A-1 was replaced by A-2, the other steps were the same as those in Example 1.

[0132] Example 6

[0133] Except that the photocrosslinking agent A-1 was replaced by A-3, the other steps were the same as those in Example 1.

[0134] Example 7

[0135] Except that the photocrosslinking agent A-1 was replaced by A-4, the other steps were the same as those in Example 1.

[0136] Example 8

[0137] Except that the photocrosslinking agent A-1 was replaced by A-5, other steps were the same as those in Example 1.

[0138] Example 9

[0139] Except that the photocrosslinking agent A-1 was replaced by A-6, the other steps were the same as those in Example 1.

[0140] Example 10

[0141] Except that the photocrosslinking agent A-1 was replaced by A-7, the other steps were the same as those in Example 1.

[0142] Example 11

[0143] Except that the photocrosslinking agent A-1 was replaced by A-8, the other steps were the same as those in Example 1.

[0144] Example 12

[0145] Except that the photocrosslinking agent A-1 was replaced by 2.5 g A-1 and 2.5 g A-8, the other steps were the same as those in Example 1.

[0146] Example 13

[0147] The same procedures as in Example 1 were followed except that the photocrosslinking agent A-1 was replaced by 2.5 g of ethoxylated bisphenol A dimethacrylate and 2.5 g of A-8.

[0148] Example 14

[0149] Except that the photoinitiator was replaced with 0.5 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), other processes were the same as those in Example 12.

[0150] Example 15

[0151] Except that the photoinitiator was replaced with 0.25 g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (OXE-01) and 0.25 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), the rest was the same as Example 12.

[0152] Comparative Example 1

[0153] Except that the photocrosslinker A-1 is replaced by 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione) (Adamas reagent, formula V), the rest is the same as in Example 1.

[0154]

[0155] Comparative Example 2

[0156] Except that the photoinitiator was replaced with 0.25 g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (OXE-01) and 0.25 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), the other steps were the same as those in Comparative Example 1.

[0157] Comparative Example 3

[0158] The same procedures as in Comparative Example 2 were followed except that 5 g of the photocrosslinking agent, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, was replaced by 5 g of ethoxylated bisphenol A dimethacrylate.

[0159] Comparative Example 4

[0160] Except that the photocrosslinking agent A-1 is not added, other processes are the same as those in Example 1.

[0161] The resolution, film-forming properties, mechanical properties, adhesion, and discoloration on copper substrates of the negative photosensitive resin compositions prepared in Examples 1-15 and Comparative Examples 1-4 were tested. The test results are shown in Table 1. The method is as follows:

[0162] 1. Resolution

[0163] A negative photosensitive resin composition sample was coated on a silicon wafer and soft-baked at 120°C for 3 minutes on a hot plate to obtain a photosensitive composition film. The film thickness was measured using a step profiler (KLA Tencor P-7). The thickness of the photosensitive resin composition film was 15 μm. The film was exposed to UV light (i and g rays) at an exposure dose of 400 mJ / cm 2 , exposed through a mask. After exposure, spray development was performed using cyclopentanone for 120 seconds, the unexposed portion was removed, and the pattern was rinsed with water. The pattern was observed using an optical microscope (MX63-F, Olympus) at 20x magnification, with the minimum size of the through-hole pattern being defined as the resolution. ("None" indicates that the photosensitive composition film was completely dissolved or completely insoluble, resulting in no developed pattern.)

[0164] 2. Film forming test

[0165] A negative-type photosensitive resin composition sample was coated onto a silicon wafer and soft-baked at 120°C for 3 minutes on a hot plate to obtain a 10-20 μm thick photosensitive resin film. This film was then heat-treated in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1). Specifically, the polyimide film was first heat-treated at 150°C for 30 minutes, then heated to 200°C over 20 minutes for 1 hour. The film was then stripped by immersing it in a hydrofluoric acid solution. The surface was then rinsed with deionized water and air-dried to obtain a cured film of the photosensitive resin composition, which was then tested for film-forming properties.

[0166] The standards are as follows:

[0167] "Excellent": The photosensitive resin composition can form a cured film with good toughness and will not break when folded in half;

[0168] “Good”: The photosensitive resin composition can form a cured film with average toughness and breaks when folded in half;

[0169] "Poor": The cured film of the photosensitive resin composition could not be formed and was in a fragmented state.

[0170] 3. Mechanical properties test

[0171] A negative-type photosensitive resin composition sample was coated onto a silicon wafer and soft-baked at 120°C for 3 minutes on a hot plate to obtain a 10-20 μm thick film of the photosensitive composition. This film was then heat-treated in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1). Specifically, the polyimide film was first heat-treated at 150°C for 30 minutes, then heated to 200°C over 20 minutes for 1 hour. The film was then stripped by immersing it in a hydrofluoric acid solution. The surface was then rinsed with deionized water and air-dried to obtain a cured film of the photosensitive resin composition.

[0172] Cut the cured film of the photosensitive resin composition into strips 15 mm long and 3 mm wide. DMA (TA, DMA850) was used to test the tensile strength of the film. The tensile rate was 3 N / min. Five strips were collected per group. The highest and lowest values ​​were removed, and the remaining three values ​​were averaged to obtain the tensile strength.

[0173] 4. Adhesion performance test

[0174] The negative photosensitive resin composition was spin-coated onto a 4-inch silicon wafer and soft-baked at 120°C for 3 minutes on a hot plate to produce a photosensitive composition film. This film was then heat-treated in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1). Specifically, the film was first heat-treated at 150°C for 30 minutes, then heated to 200°C over 20 minutes for 1 hour to produce a cured film. The film thickness was measured using a step profiler (KLA Tencor P-7), and the film thickness was approximately 15 μm.

[0175] A 10-row × 10-column grid was scored on the cured film using a crosshatch cutter (BYK-Gardner A-5125). A peel test was performed using adhesive tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998, Crosshatch Test for Paint and Clear Coatings. The number of squares peeled off was recorded as the peeling condition before PCT.

[0176] Following the same method as above, a grid of 10 rows × 10 columns was scored on the cured film using a grid marker (model, BYK-Gardner A-5125). The gridded cured film was first subjected to a 200-hour PCT test (121°C, 2 atmospheres of saturated steam; Dongguan Hongjin Technology PCT-30). After the PCT test was completed, a peeling test was performed using tape using the same method as above, and the number of peeled grids was recorded as the peeling condition after PCT.

[0177] In the adhesive peeling test, if the number of peeled pieces was less than 10, the adhesiveness was considered good, and if it was 10 or more, the adhesiveness was considered poor.

[0178] The adhesion between the cured film sample prepared above and the substrate was tested according to the aforementioned adhesion peeling test method.

[0179] 5. Copper discoloration test

[0180] The negative photosensitive resin composition was spin-coated onto a 4-inch silicon wafer and soft-baked on a hot plate at 120°C for 3 minutes to obtain a thin film of the photosensitive composition. The film was then spray-developed with cyclopentanone and rinsed with pure water to completely dissolve the coating. The copper substrate after dissolution was evaluated according to the following criteria:

[0181] "Excellent": No discoloration of the copper substrate was observed even under a 200x optical microscope.

[0182] "Good": There is a slight discoloration of the copper substrate when observed under a 200x optical microscope;

[0183] “Medium”: There is a lot of discoloration of the copper substrate when observed with a 200x optical microscope;

[0184] "Poor": Severe discoloration of the copper substrate was observed with the naked eye.

[0185] Table 1

[0186]

[0187]

[0188] Note: " / " indicates that the test cannot be performed.

[0189] As shown in Table 1 for Examples 1-15 and Comparative Examples 1-4, the negative-working photosensitive resin compositions containing urea-based photocrosslinkers exhibit high resolution and excellent film-forming properties. Cured films of these negative-working photosensitive resin compositions exhibit high tensile strength and strong adhesion to substrates, effectively improving copper discoloration.

[0190] It can be seen from Examples 12, 14, and 15 in Table 1 that when the urea-containing photocrosslinking agents A-1 and A-8 are used in combination, the resulting cured films have high tensile strength and excellent mechanical properties.

[0191] It can be seen from Examples 12, 14, 15 and Comparative Examples 1-4 in Table 1 that when the negative photosensitive resin composition of the present application is used in combination with OXE-01 and BAPO, the obtained photosensitive composition film has the best resolution.

Claims

1. A compound containing a urea structure, characterized in that: It has the structural formula shown in the following formula I: In formula I, R1 is an alkylene group or cycloalkylene group having 2 to 20 carbon atoms, and R2 is a divalent organic group having 2 or more carbon atoms.

2. The compound containing urea structure according to claim 1, characterized in that: At least one selected from the structures shown in the following formulas A-1 to A-8:

3. A method for preparing the compound containing a urea structure according to claim 1, characterized in that: It is obtained by reacting a compound represented by formula IV with an aliphatic diamine compound represented by formula V; the reaction formula is as follows: In formula IV and formula V, the definitions of R1 and R2 are consistent with those in claim 1.

4. The preparation method according to claim 3, characterized in that: The method comprises at least one of the following conditions: condition 1, the molar ratio of the aliphatic diamine compound represented by formula V to the compound represented by formula IV is 1:2.0-2.1; The reaction is carried out in an organic solvent, and the organic solvent is preferably at least one of tetrahydrofuran, acetone, toluene and xylene; The mass ratio of the aliphatic diamine compound represented by formula V to the organic solvent is 1:(2-10); After the aliphatic diamine compound represented by formula V and the compound represented by formula IV are mixed, they are first reacted at 0-10° C. for 0.5-5 h, and then reacted at 20-30° C. for 5-15 h.

5. A negative photosensitive resin composition, characterized in that include: Photosensitive resins and photocrosslinkers; The photocrosslinking agent comprises a photocrosslinking agent A, and the photocrosslinking agent A is selected from at least one of the compounds containing a urea structure as shown in claim 1 or 2.

6. The negative photosensitive resin composition according to claim 5, characterized in that: The photosensitive resin is at least one selected from polyimide precursors having a double bond structure.

7. The negative photosensitive resin composition according to claim 5 or 6, characterized in that: The polyimide precursor contains the structure shown in the following formula II: In formula II, R3 is a tetravalent organic group having 2 to 16 carbon atoms; R4 is a divalent organic group having 2 to 20 carbon atoms; R5 and R6 are independently selected from a hydrogen atom, a monovalent organic group having a structure represented by formula III, and a saturated aliphatic group having 1 to 4 carbon atoms; In formula III, R7, R8, and R9 are independently selected from hydrogen atoms or organic groups having 1 to 3 carbon atoms, and * represents the insertion site; m is an integer of 2-10, and n is an integer of 2-200.

8. The negative photosensitive resin composition according to claim 5, characterized in that: The photocrosslinking agent A accounts for 50-100% of the total mass of the photocrosslinking agent; preferably, the weight ratio of the photosensitive resin to the photocrosslinking agent A is 100:(20-150).

9. The negative photosensitive resin composition according to claim 5, characterized in that: It also includes a photoinitiator and an organic solvent; preferably, the weight ratio of the photosensitive resin to the photoinitiator is 100: (0.1-20); Preferably, the weight ratio of the photosensitive resin to the organic solvent is 100: (80～5000)。 10. An insulating film or packaging film, characterized in that: Obtained by curing the negative photosensitive resin composition according to any one of claims 5 to 9.

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