A compound containing a urea group, a negative photosensitive resin composition, and a preparation method and application thereof

Abstract

The application provides a compound containing a urea group, a negative photosensitive resin composition, and a preparation method and application thereof. The compound containing the urea group can be used as a photocrosslinking agent, added into the photosensitive resin composition, and can improve resolution, mechanical properties, and adhesion to a substrate of a cured film of the photosensitive resin composition, and can effectively inhibit oxidation discoloration of a copper substrate.

Description

Technical Field

[0001] This invention relates to a compound containing a urea group, a method for preparing the compound containing the urea group, a negative photosensitive resin composition containing the compound containing the urea group, and the application of the negative photosensitive resin composition, belonging to the field of electronic device packaging materials technology. Background Technology

[0002] Polyimides are a class of polymers containing an imide ring in their main chain. Based on their molecular structure, they are classified into aromatic polyimides and aliphatic polyimides. Aromatic polyimides, in particular, possess low dielectric properties, high mechanical strength, ease of fabrication, and especially high thermal stability, making them the primary polymers for insulating layers, protective layers, and circuit packaging in next-generation integrated circuits with multilayer wiring and multi-chip modules.

[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 For example, the traditional gold or aluminum wiring has been replaced by copper or copper alloy wiring with lower resistance, and the traditional lead-tin eutectic bonding has been replaced by higher-density ball grid arrays and chip-scale mounting.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 not only have excellent resolution, but also good adhesion to the copper or copper alloy substrate. It also requires the cured resin film 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 existing technologies, multiple additives are typically added to resins to achieve good resin-cured film performance. Patent CN109478016A uses nitrogen-containing aromatic compounds to increase the resin's adhesion to the substrate. Patent JP5446203B2 uses heterocyclic compounds to reduce the resin's corrosion of copper or copper alloys and increase adhesion. Patent CN102375336B uses purine derivatives, crosslinking agents, and organotitanium compounds to increase adhesion, heat resistance, chemical resistance, and inhibit discoloration of copper or copper alloy substrates. To achieve comprehensive performance, existing technologies often add multiple additives, frequently resulting in excessive additive content, which can actually reduce the performance of the resin material. Furthermore, the presence of multiple additives often raises concerns about compatibility, potentially improving one property while reducing another. Summary of the Invention

[0005] In view of the above, the object of the present invention is to provide a compound containing a urea group 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 oxidation and discoloration of the copper substrate.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A compound containing a urea group has the structural formula shown in Formula I:

[0008]

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

[0010] In Formula I, R2 is a divalent organic group with two or more carbon atoms.

[0011] Furthermore, the compound containing the urea group is selected from at least one of the structures shown in formulas A-1 to A-8:

[0012]

[0013]

[0014] This invention also provides a method for preparing a compound containing a urea group as shown in Formula I, wherein the compound is obtained by reacting a compound shown in Formula IV and an aliphatic diamine compound shown in Formula V as starting materials. The reaction formula is as follows:

[0015]

[0016] In Equations IV and V, the definitions of R1 and R2 are consistent with those described above.

[0017] Furthermore, R2 in Formula I is introduced by an aliphatic diamine compound, which is a residue of the diamine compound selected from ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-diaminopentane, 1,6-hexanediamine, 1,8-octanediamine, decanediamine, 1,12-diaminododecane, 1,2-bis(aminomethyl)cyclobutane, 1,8-diamino-3,6-dioxaoctane, polyoxyethylene diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2-methyl-1,3-cyclohexanediamine, 4 At least one of the following: (aminomethyl)cyclohexylamine, bicyclo[2.2.1]heptane-2,5-diamine, bicyclo[2.2.1]heptane-dimethylamine, bicyclo[2.2.1]heptane-2,5-dimethylamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), 1,1'-bicyclohexyl-4,4'-diamine, 4,4'-isopropyldicyclohexylamine, 1,1'-bicyclohexyl-2,2'-dimethyl-4,4'-diamine, 1,3-adamantane-dimethylamine, and 1,1'-biadamantane-3,3'-diamine.

[0018] Furthermore, R1 in Formula I is introduced from the compound of Formula IV, where 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 may be selected from at least one of tetrahydrofuran, acetone, toluene, xylene, etc.

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

[0022] Further, 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. 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, or 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, or 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, or 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, or 15 h.

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

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

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

[0026] Furthermore, in addition to photocrosslinker A, the photocrosslinker may also contain photocrosslinker B, which 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, etc. 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, tricyclodecanediethanol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, di... 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 methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, ethoxylated bisphenol A diacrylate, ethyl At least one of the following: bisphenol A dimethacrylate oxidized, bisphenol A dimethacrylate oxidized, bisphenol A methacrylate oxidized, propoxylated ethoxylated bisphenol A dimethacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, N-vinylcaprolactam, polyethylene glycol diacrylate, ethyl 2-isocyanate 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 a polyimide precursor having a double bond structure.

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

[0029]

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

[0031]

[0032] In Formula III, R7, R8, and R9 are each independently selected from organic groups with 1 to 3 hydrogen atoms or carbon atoms, and * indicates the insertion site;

[0033] In Equations II and III, m is an integer from 2 to 10, and n is an integer from 2 to 200.

[0034] Furthermore, the photosensitive resin is synthesized from tetracarboxylic dianhydride and diamine, wherein R3 in Formula II is derived from tetracarboxylic dianhydride. Optionally, the tetracarboxylic dianhydride is selected from at least one of pyromellitic dianhydride, 4,4'-oxobisphthalic anhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-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 '-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, Formula III is derived from alcohols having unsaturated double bonds. Optionally, the alcohols with unsaturated double bonds are selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-acryloyloxyethanol, 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-cyclohexyloxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methyl... Acryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamide ethanol, 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 methods 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 acid dianhydride reacts with an alcohol compound in a solvent to form a diacid diester, wherein the alcohol compound is an alcohol with an unsaturated double bond as described above.

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

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

[0041] 4) The diamine solution is added dropwise to the diacyl chloride diester solution to carry out a polycondensation reaction to form a polyamic acid ester solution.

[0042] 5) When polyamide ester solution is mixed with a poor solvent, solid resin precipitates out.

[0043] 6) After washing and drying, the solid resin yields polyamic acid ester.

[0044] Furthermore, the solvents described in steps 1) and 3) are the same as the organic solvents used in the following photosensitive resin compositions.

[0045] Furthermore, in step 1), the tetracarboxylic acid dianhydride and the alcohol compound react 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 alcohol is 1:2 to 2.1, and the molar ratio of tetracarboxylic dianhydride to DBU is 1:0.005 to 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 to 80°C, for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, and the reaction time is 2 to 6 hours, for example 2 hours, 3 hours, 4 hours, 5 hours, 6 hours.

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

[0049] Furthermore, in step 2), the reaction temperature is 0 to 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 to 3 hours, for example 1 hour, 2 hours, 3 hours.

[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 the diamine to the tetracarboxylic acid dianhydride described 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, or 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%, or 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 monomers (including tetracarboxylic dianhydride, diacid diester, and diamine) should, in principle, be sufficient to ensure that the monomers are fully dissolved and that the resulting polymer does not precipitate. If the monomer concentration is too high, the polymer will precipitate; if the concentration is too low, the molecular weight of the polymer will not increase. Therefore, the monomer concentration of the present invention relative to the total mass of the reaction solution can be 5–35 wt%, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, preferably 10–30 wt%.

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

[0055] Furthermore, in step 5), the unsuitable solvent can be deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, etc., with deionized water, methanol, and / or ethanol being preferred. The amount of unsuitable solvent relative to the total amount of polymer solution is preferably 3 to 20 times 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 same undesirable solvent used in step 5) for precipitation. The amount of the undesirable solvent used for washing is preferably 1 to 6 times the polymer by mass. The more times the polymer is washed, the fewer impurities are obtained. Preferably, 2 to 6 times are used. 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 pulverized according to application requirements.

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

[0059] Furthermore, the photoinitiator is selected from at least one of benzophenone compounds, benzyl derivatives, coumarin compounds, anthraquinone compounds, benzoin compounds, thioxanone compounds, mercapto compounds, glycine compounds, oxime compounds, α-aminoalkylphenyl ketone 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 selected from at least one of 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 the following: 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidinone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidinone, etc.; 7-diethylamino-3-nonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylbenzimidazolyl)coumarin, and 3-(2-benzothiazolyl)-7-diethylaminocoumarin.

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

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

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

[0065] Furthermore, the thiol 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-benzoyl oxime) (trade name: OXE-01, manufactured by BASF), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone 1-(O-acetyl oxime) (trade name: OXE-02, manufactured by BASF).

[0068] Furthermore, the α-aminoalkylphenyl ketone 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 photocrosslinker 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, 100:5000.

[0073] Furthermore, the negative photosensitive resin composition may also contain other components, such as photosensitizers, sensitizers, silane coupling agents, polymerization inhibitors, etc., which can be adjusted as needed and are not limited herein. The resin-cured film formed after the negative photosensitive resin composition is cured can be used as an insulating film and encapsulation film material for precision electronic devices.

[0074] This invention provides a method for preparing a negative photosensitive resin composition, comprising: mixing a photosensitive resin with a photocrosslinking agent, a photoinitiator, an organic solvent, etc., and stirring until a homogeneous solution is formed, thereby obtaining the composition.

[0075] Furthermore, the preparation process of the negative photosensitive resin composition is preferably carried out in a Class 1000 cleanroom equipped with a yellow light source. In particular, the best results are achieved when the prescribed amounts of photosensitive resin, photocrosslinking agent, and photoinitiator are added to the organic solvent in sequence at room temperature.

[0076] The present invention also provides the application of the above-mentioned negative photosensitive resin composition in precision electronic devices, such as as insulating film or encapsulation film material.

[0077] The present invention also provides an insulating film or encapsulating film, which is obtained by curing the above-mentioned negative photosensitive resin composition.

[0078] The crosslinking agent structure provided by this invention contains urea groups, as well as double bond structures and aliphatic structures. When added to a photosensitive resin composition, it can improve the light transmittance, mechanical properties, and adhesion performance between the cured resin film and the substrate, and can also inhibit the oxidation and discoloration of copper. Detailed Implementation

[0079] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. Unless otherwise specified, the methods described are conventional methods. Unless otherwise specified, the materials described are commercially available.

[0080] Preparation Example 1: Preparation of photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, then cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction temperature below 10°C, and the addition was completed over 0.5 h. After the addition was complete, the mixture was naturally warmed to room temperature, and the reaction continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent, yielding urea-based photocrosslinking agent A-1, with the following structural formula:

[0082]

[0083] The 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 photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, then cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, keeping the reaction system temperature below 10°C, and the addition was completed within 0.5 h. After the addition was completed, the mixture was naturally warmed to room temperature and the reaction continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent, yielding urea-based photocrosslinking agent A-2, with the following structural formula:

[0087]

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

[0089] 1 ¹H NMR (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 photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, then cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction temperature below 10°C, over 0.5 h. After the addition was complete, the mixture was allowed to naturally warm to room temperature, and the reaction continued for 8 h. After the reaction was complete, the reaction solution was distilled under reduced pressure to remove the solvent, yielding urea-based photocrosslinking agent A-3, with the following structural formula:

[0091]

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

[0093] 1 ¹H NMR (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 photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, then cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction temperature below 10°C, over 0.5 h. After the addition was complete, the mixture was allowed to naturally warm to room temperature, and the reaction continued for 8 h. After the reaction was complete, the reaction solution was distilled under reduced pressure to remove the solvent, yielding urea-based photocrosslinking agent A-4, with the following structural formula:

[0095]

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

[0097] 1¹H NMR (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 photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, cooled to 0°C in an ice bath, and 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, keeping the reaction system temperature below 10°C. The addition was completed 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, yielding urea-based photocrosslinking agent A-5, with the following structural formula:

[0099]

[0100] The 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 photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, then cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction temperature below 10°C, over 0.5 h. After the addition was complete, the mixture was naturally warmed to room temperature and the reaction continued for 8 h. After the reaction was complete, the reaction solution was distilled under reduced pressure to remove the solvent, yielding urea-based photocrosslinking agent A-6, with the following structural formula:

[0104]

[0105] The 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 photocrosslinking agent 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 stirrer and a constant-pressure dropping funnel. The mixture was stirred at room temperature until completely dissolved, then cooled to 0°C in an ice bath. 16.62 g (0.2 mol) of allyl isocyanate was slowly added dropwise, maintaining the reaction temperature below 10°C, and the addition was completed over 0.5 h. After the addition was complete, the mixture was naturally warmed to room temperature and the reaction continued for 8 h. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove the solvent, yielding urea-based photocrosslinking agent A-7, with the following structural formula:

[0109]

[0110] The A-7 MRI 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 photocrosslinking agent A-8

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

[0114]

[0115] The 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 a nitrogen stream, 31.02 g (0.1 mol) of 4,4'-oxobisphthalic 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 sequentially to a 500 mL three-necked flask, stirred to dissolve, and reacted at 55 °C for 4 h. The mixture was then cooled to 25 °C to obtain reaction solution A.

[0119] Add 24.03 g (0.202 mol) of SOCl2 dropwise to reaction solution A, ensuring that the temperature of the reaction system is controlled below 10℃ during the dropwise addition process; after the dropwise addition is completed, continue the reaction at 0-10℃ for 2 hours to obtain reaction solution B.

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

[0121] The weight-average molecular weight (Mw) of each resin was determined by gel permeation chromatography (converted to standard polystyrene) using a Shimadzu GPC system. The weight-average molecular weight (Mw) of the polyimide precursor resins obtained in Synthesis Example 1 ranged from 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 complete dissolution, 5 g of photocrosslinking agent A-1 and 0.5 g of photoinitiator 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE-01) were added. After complete dissolution, the mixture was filtered through a 1.0 μm filter membrane to obtain a negative photosensitive resin composition.

[0124] Example 2

[0125] Except for changing the photocrosslinking agent A-1 from 5g to 2g, everything else is the same as in Example 1.

[0126] Example 3

[0127] Except for changing the photocrosslinking agent A-1 from 5g to 10g, everything else is the same as in Example 1.

[0128] Example 4

[0129] Except for changing the photocrosslinking agent A-1 from 5g to 15g, everything else is the same as in Example 1.

[0130] Example 5

[0131] Except for replacing photocrosslinker A-1 with A-2, everything else is the same as in Example 1.

[0132] Example 6

[0133] Except for replacing photocrosslinker A-1 with A-3, everything else is the same as in Example 1.

[0134] Example 7

[0135] Except for replacing photocrosslinker A-1 with A-4, everything else is the same as in Example 1.

[0136] Example 8

[0137] Except for replacing photocrosslinker A-1 with A-5, everything else is the same as in Example 1.

[0138] Example 9

[0139] Except for replacing photocrosslinker A-1 with A-6, everything else is the same as in Example 1.

[0140] Example 10

[0141] Except for replacing photocrosslinker A-1 with A-7, everything else is the same as in Example 1.

[0142] Example 11

[0143] Except for replacing the photocrosslinker A-1 with A-8, everything else is the same as in Example 1.

[0144] Example 12

[0145] Except for replacing photocrosslinker A-1 with 2.5g A-1 and 2.5g A-8, everything else is the same as in Example 1.

[0146] Example 13

[0147] Except for replacing photocrosslinker A-1 with 2.5g of bisphenol A dimethicone ethoxylate and 2.5g of A-8, everything else is the same as in Example 1.

[0148] Example 14

[0149] Except for replacing the photoinitiator with 0.5g of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), everything else is the same as in Example 12.

[0150] Example 15

[0151] Except for replacing the photoinitiator with 0.25g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE-01) and 0.25g of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), everything else is the same as in Example 12.

[0152] Comparative Example 1

[0153] Except for replacing the photocrosslinker A-1 with 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Adamas reagent, formula V), everything else is the same as in Example 1.

[0154]

[0155] Comparative Example 2

[0156] Except for replacing the photoinitiator with 0.25g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE-01) and 0.25g of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), everything else was the same as in Comparative Example 1.

[0157] Comparative Example 3

[0158] Except for replacing 5g of photocrosslinking agent 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione with 5g of bisphenol A dimethacrylate ester oxyacetate, everything else is the same as in Comparative Example 2.

[0159] Comparative Example 4

[0160] Except for the absence of photocrosslinking agent A-1, everything else is the same as 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, and the methods are as follows:

[0162] 1. Resolution

[0163] A negative-type photosensitive resin composition sample was coated onto a silicon wafer and then soft-baked at 120°C for 3 minutes using a hot stage to obtain a photosensitive composition film. The film thickness was measured using a KLA Tencor P-7 step meter, and the film thickness was found to be 15 μm. The film was then exposed to UV light (i and g lines) at an exposure dose of 400 mJ / cm². 2 Exposure was performed using a photomask. After exposure, cyclopentanone was used for spray development for 120 seconds. Unexposed areas were removed, and the sample was rinsed with water. The pattern was observed using an optical microscope (MX63-F, Olympus) at 20x magnification, and the smallest size that could be resolved to show the through-hole pattern was taken as the resolution. ("None" indicates that the photosensitive composition film was completely dissolved or completely insoluble, and no developed pattern was obtained.)

[0164] 2. Film-forming property test

[0165] A negative-type photosensitive resin composition sample was coated onto a silicon wafer and softened at 120°C for 3 minutes using a hot plate to obtain a photosensitive composition film with a thickness of 10–20 μm. This film was then placed in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. Specifically, it was first heat-treated at 150°C for 30 minutes, followed by a 20-minute warm-up to 200°C for 1 hour to obtain a polyimide film. The film was then immersed in a hydrofluoric acid solution for demolding, rinsed with deionized water, and air-dried to obtain a cured photosensitive resin composition film, which was then subjected to film-forming tests.

[0166] The standards are as follows:

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

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

[0169] "Poor": The cured film of the photosensitive resin composition cannot form a film and is fragmented.

[0170] 3. Mechanical property testing

[0171] A negative-type photosensitive resin composition sample was coated onto a silicon wafer and softened at 120°C for 3 minutes using a hot plate to obtain a photosensitive composition film with a thickness of 10-20 μm. This film was then placed in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. Specifically, it was first heat-treated at 150°C for 30 minutes, followed by a 20-minute warm-up to 200°C for 1 hour to obtain a polyimide film. The film was then immersed in a hydrofluoric acid solution for demolding, rinsed with deionized water, and air-dried to obtain a cured photosensitive resin composition film.

[0172] The cured film of the photosensitive resin composition was cut into strips 15 mm long and 3 mm wide, and the tensile strength of the film was tested using DMA (TA, DMA850). The tensile rate was 3 N / min, and 5 strips were used in each group. The highest and lowest values ​​were removed, and the remaining 3 values ​​were averaged to obtain the tensile strength.

[0173] 4. Adhesion performance test

[0174] The negative-type photosensitive resin composition was spin-coated onto a 4-inch silicon wafer and then softened at 120°C for 3 minutes using a hot plate to obtain a photosensitive composition film. This film was then placed in a vacuum oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. Specifically, it was first heat-treated at 150°C for 30 minutes, followed by a 20-minute warm-up to 200°C for 1 hour to obtain a cured film. The film thickness was measured using a step meter (KLA Tencor P-7) and found to be 15µm.

[0175] Using a cross-cut tester (model: BYK-Gardner A-5125), a grid of 10 rows and 10 columns was cut into the cured film. A peel test was then performed using tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 Cross-cut test for paint and varnish films. The number of squares peeled off was recorded as the peeling status before PCT.

[0176] Following the same method described above, a grid of 10 rows and 10 columns was used to mark the cured film with a grid cutter (model: BYK-Gardner A-5125). The cured film with the grid was first subjected to a 200-hour PCT test (121℃, 2 atmospheres of saturated steam; Dongguan Hongjin Technology PCT-30). After the PCT test was completed, a peel test was performed using tape in the same way described above. The number of grids peeled off was recorded as the peel status after PCT.

[0177] If the number of peeled off in the adhesive peel test is less than 10, it is considered to have good adhesion; if it is greater than or equal to 10, it is considered to have poor adhesion.

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

[0179] 5. Copper discoloration test

[0180] Negative photosensitive resin compositions were spin-coated onto 4-inch silicon wafers and softened at 120°C for 3 minutes using a hot plate to obtain photosensitive film. The films were then developed using cyclopentanone and rinsed with pure water to completely dissolve the coating. The dissolved copper substrate was evaluated according to the following criteria:

[0181] “Excellent” means that no discoloration of the copper substrate was detected even when observed with a 200x optical microscope.

[0182] "Good": When observed with a 200x optical microscope, a small amount of discoloration is observed on the copper substrate;

[0183] “Middle”: When observed with a 200x optical microscope, a large amount of discoloration was observed on the copper substrate;

[0184] "Poor": The copper substrate was severely discolored as observed by the naked eye.

[0185] Table 1

[0186]

[0187]

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

[0189] As can be seen from the data in Examples 1-15 and Comparative Examples 1-4 in Table 1, the negative photosensitive resin composition containing urea-based photocrosslinking agent in this application has high resolution and good film-forming properties. The cured film of the prepared negative photosensitive resin composition has high tensile strength and strong adhesion to the substrate, which can effectively improve the copper discoloration problem.

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

[0191] As can be seen from Examples 12, 14, 15 and Comparative Examples 1-4 in Table 1, the negative photosensitive resin composition of this application produces the best resolution film when OXE-01 and BAPO are used in combination.

Claims

1. A negative photosensitive resin composition, characterized by Comprising: a photosensitive resin and a photo-crosslinking agent; the photo-crosslinking agent comprises a photo-crosslinking agent A selected from at least one of the structures shown in the following formulas A-1~A-8: Formula A-1 Formula A-2 Formula A-3 Formula A-4 Formula A-5 Formula A-6 Formula A-7 Formula A-8.

2. The negative photosensitive resin composition according to claim 1, characterized by: the photosensitive resin is selected from at least one of polyimide precursors having a double bond structure.

3. The negative photosensitive resin composition according to claim 1 or 2, characterized by: the polyimide precursor contains a structure shown in the following formula II: Formula II in formula II, R3 is a 4-valent organic group with 2~16 carbon atoms; R4 is a 2-valent organic group with 2~20 carbon atoms; R5 and R6 are independently selected from one of the following: a hydrogen atom, a 1-valent organic group having a structure shown in the following formula III, and a saturated aliphatic group with 1~4 carbon atoms; Formula III In formula III, R7, R8, R9are each independently selected from a hydrogen atom or an organic group having 1 to 3 carbon atoms, denotes an access site; m is an integer of 2~10, and n is an integer of 2~200.

4. The negative photosensitive resin composition according to claim 1, characterized by: the photo-crosslinking agent A accounts for 50~100% of the total mass of the photo-crosslinking agent.

5. The negative photosensitive resin composition according to claim 1, characterized by: the weight ratio of the photosensitive resin to the photo-crosslinking agent A is 100: (20~150).

6. The negative photosensitive resin composition according to claim 1, characterized by: further comprising a photo-initiator and an organic solvent.

7. The negative photosensitive resin composition according to claim 6, characterized by: the weight ratio of the photosensitive resin to the photo-initiator is 100: (0.1-20).

8. The negative photosensitive resin composition according to claim 6, characterized by: the weight ratio of the photosensitive resin to the organic solvent is 100: (80~5000).

9. An insulating film or encapsulating film, characterized by, obtained by curing the negative photosensitive resin composition according to any one of claims 1-8.

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