CN118666819B - A compound, a photosensitive resin composition, and a preparation method and application thereof - Google Patents
A compound, a photosensitive resin composition, and a preparation method and application thereofInfo
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- CN118666819B CN118666819B CN202410650552.0A CN202410650552A CN118666819B CN 118666819 B CN118666819 B CN 118666819B CN 202410650552 A CN202410650552 A CN 202410650552A CN 118666819 B CN118666819 B CN 118666819B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- H10W20/48—
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本申请公开了本申请提供了一种化合物、感光性树脂组合物及其制备方法和应用，属于功能性高分子材料技术领域，该化合物同时具有氮杂环和环氧结构，通过在感光树脂组合物中引入该化合物，与树脂和同种分子进行缩合反应从而形成交联结构体，从而在应用中提高固化膜的成膜性、耐化学品性、机械性能及热稳定性能，并利用杂环N原子的存在降低固化膜的介电常数、抑制铜或铜合金基材变色问题。
The present application discloses a compound, a photosensitive resin composition, a preparation method and an application thereof, belonging to the technical field of functional polymer materials. The compound has both nitrogen heterocycle and epoxy structure. By introducing the compound into the photosensitive resin composition, a condensation reaction is carried out with the resin and the same molecules to form a cross-linked structure, thereby improving the film-forming property, chemical resistance, mechanical properties and thermal stability of the cured film in application, and utilizing the presence of heterocyclic N atoms to reduce the dielectric constant of the cured film and suppress the discoloration problem of the copper or copper alloy substrate.
Description
Technical Field
The application relates to a compound, a photosensitive resin composition, a preparation method and application thereof, and belongs to the technical field of functional polymer materials.
Background
The photosensitive polyimide (PSPI) is a polymer composite material with excellent thermal performance, mechanical performance, electrical performance and chemical performance and photosensitive property, and is subjected to ultraviolet exposure and development to obtain a three-dimensional figure with a fine structure, so that the photoetching drawing process is obviously simplified, and the photosensitive polyimide is an ideal insulating material in the fields of microelectronics and semiconductor packaging. With the light weight, high performance and multifunction of electronic products, higher requirements are put on PSPI packaging materials.
At present, the dielectric constant of some common PSPI packaging materials is higher (generally more than 3), and the performance requirements of low dielectric constant and low dielectric loss of the new generation of communication technology cannot be met. On the other hand, with the progress of integration and chip size miniaturization of semiconductor devices, wiring patterns and mounting methods of semiconductor devices have changed. The conventional gold or aluminum wiring is changed to copper or copper alloy wiring with lower resistance, and the conventional lead-tin eutectic soldering is changed to ball grid array and chip size mounting with higher density. The cured resin film is in direct contact with copper or copper alloy and solder bumps, which requires excellent heat resistance and chemical resistance of the resin cured film, good adhesion to copper or copper alloy substrates, and no discoloration of the copper or copper alloy substrates.
In the prior art, various additives are typically added to improve the overall properties of the cured film. In patent JP5446203B2, the addition of a heterocyclic compound reduces corrosion of copper or copper alloy by the resin, and increases adhesion. In CN102375336B, a purine derivative, a crosslinking agent, and an organic titanium compound are added to increase adhesion, heat resistance, and chemical resistance, thereby suppressing discoloration of a copper or copper alloy substrate. In order to realize comprehensive performance, various additives are added in the prior art, so that the content of the additives is often excessive, and the performance of the resin material is reduced. In addition, there is a problem that whether or not the compounding properties of the various additives match, and it is easy to cause improvement in one property while causing another property to be lowered.
Disclosure of Invention
In order to solve the problem that the resin performance is reduced due to excessive additives in order to realize the comprehensiveness in the prior art of photosensitive polyimide (PSPI) packaging materials, the application provides a compound, a photosensitive resin composition and a preparation method thereof, wherein the compound has an azacyclic ring and an epoxy structure at the same time, by introducing the compound into the photosensitive resin composition, the condensation reaction with the resin and the same molecule to form a cross-linked structure, thereby improving the film forming property, chemical resistance, mechanical property and thermal stability of the cured film in application, reducing the dielectric constant of the cured film and inhibiting the discoloration problem of the copper or copper alloy substrate by utilizing the existence of the heterocyclic N atom.
The application adopts the following technical scheme:
According to a first aspect of the present application there is provided a compound having the structure of formula I:
in the formula I, W is an organic group containing nitrogen heterocycle.
Optionally, W is selected from any one of the groups of formula II-a:
wherein the dashed line represents the access site.
Optionally, the compound is at least one compound having a structure represented by formula I-1 to formula I-5:
according to a second aspect of the present application, there is provided a process for the preparation of the above compound, comprising the steps of:
s1, heating a mixed solution containing a triamine compound and a solvent I, and then dropwise adding a material containing epoxy chlorinated alkane and a solvent II into the mixed solution for ring-opening reaction;
s2, dropwise adding an alkali solution into the product of the reaction in the step S1, performing cyclization reaction, and separating and purifying to obtain the compound.
Optionally, the dropping rate of the material of the epoxy chloroalkane and the solvent II and the dropping rate of the strong alkali solution are independently 1-5 mL/min.
Optionally, the dropping rate of the material of the epoxy chloroalkane and the solvent II, the dropping rate of the strong base solution are independently selected from any value of 1mL/min, 1.5mL/min, 2mL/min, 2.5mL/min, 3mL/min, 3.5mL/min, 4mL/min, 4.5mL/min, 5mL/min, or a range of values therebetween.
Optionally, in the step S1, the molar ratio of the triamine compound to the epoxy chlorinated alkane is 1:6-10.
Optionally, in step S1, the molar ratio of the triamine compound to the epichlorohydrin is selected from any value of 1:6, 1:7, 1:8, 1:9, 1:10, or a range of values therebetween.
Optionally, in the step S1, the heating condition comprises heating to 35-60 ℃.
Optionally, in the step S1, the condition of the ring-opening reaction comprises the reaction temperature of 35-60 ℃ and the reaction time of 3-6 h.
Optionally, the molar ratio of the triamine compound to the strong base is 1:6-10.
Alternatively, the molar ratio of the triamine compound to the strong base is selected from any of 1:6, 1:7, 1:8, 1:9, 1:10, or a range of values therebetween.
Optionally, in the step S2, the cyclization reaction condition comprises a reaction temperature of 35-60 ℃ and a reaction time of 1-5 h.
Alternatively, the solvent I and the solvent II are independently selected from at least one of ethanol, ethylene glycol, glycerol, ethylene glycol butyl ether.
Optionally, the concentration of the alkali in the strong alkali solution is 20-50wt%.
Optionally, the strong base solution is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
Optionally, the separation and purification comprises at least one of extraction, washing, rotary steaming and drying.
Optionally, the triamine compound is selected from at least one of compounds with a structure shown in a formula II-b:
Alternatively, the epichlorohydrin is selected from epichlorohydrin or epibromohydrin.
According to a third aspect of the present application, there is provided a photosensitive resin composition obtained by uniformly mixing raw materials comprising:
Polyimide with hydroxyl structure or its precursor resin, the compound shown in the formula I, photosensitizer and solvent III.
Optionally, the photosensitive resin composition is obtained by mixing the above raw materials and filtering.
Optionally, the weight ratio of polyimide or precursor resin thereof with hydroxyl structure to the compound is 1:0.001-0.2, preferably 1:0.01-0.1.
Optionally, the weight ratio of polyimide having a hydroxyl structure or a precursor resin thereof to the compound is selected from any value or range of values between any two of 1:0.001, 1:0.01, 1:0.05, 1:0.1, 1:0.2.
Optionally, the solvent III is selected from at least one of methyl pyrrolidone, methyl ethyl ketone, acetone, gamma-butyrolactone, ethyl acetate, ethyl lactate, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
Optionally, the weight ratio of polyimide or precursor resin thereof with a hydroxyl structure to the solvent III is 1:1-20.
Optionally, the weight ratio of polyimide having a hydroxyl structure or a precursor resin thereof to solvent III is selected from any of 1:1, 1:1.5, 1:2, 1:5, 1:8, 1:15, 1:20, or a range of values therebetween.
Alternatively, the preparation of the polyimide precursor having a hydroxyl structure is described with reference to the technical solution of the applicant in the publication No. CN 117304225A.
Optionally, the polyimide precursor with a hydroxyl structure is a polyamic acid or polyamic acid ester, as shown in formula III:
In the formula III, A represents a 4-valent organic group with 4-40 carbon atoms, B represents a 2-valent organic group with 2-40 carbon atoms, R 1 and R 2 respectively and independently represent a hydrogen atom or a saturated aliphatic group with 1-10 carbon atoms, m is an integer more than or equal to 1, and groups in brackets are optionally the same or different.
Optionally, in formula III, A is preferably an aromatic organic group having 6 or more carbon atoms, and more preferably at least one compound having a structure represented by formula III-a:
in formula III, B is preferably an aromatic organic group having 6 or more carbon atoms and having a hydroxyl structure, and more preferably at least one compound having a structure represented by formula III-B:
optionally, the polyimide precursor with the hydroxyl structure further comprises a blocking agent, wherein the blocking agent is introduced in the resin synthesis process for improving the stability of the resin, and the blocking agent is used in a mode of adding the blocking agent and diamine and dianhydride simultaneously, or adding the blocking agent after the diamine reacts with the dianhydride, or adding diamine or dianhydride after the blocking agent reacts with the dianhydride or the diamine.
Optionally, the end-capping agent is selected from at least one of monoamines, anhydrides, monocarboxylic acids, monoacylchloride compounds, and monoacylester compounds. The type and amount of capping agent can be adjusted as desired by those skilled in the art.
Optionally, the preparation method of the polyamic acid comprises the following steps of firstly carrying out polymerization reaction on dianhydride and diamine, then adding a blocking agent for continuous reaction, and obtaining the polyamic acid solution after the reaction is finished.
Alternatively, the polyamic acid ester is prepared by heating the polyamic acid in an esterification reagent, during which process carboxylic acid functionality in the polyamic acid is converted to carboxylate groups by an esterification reaction. The esterification reaction can be further performed on the polyamic acid solution.
The esterification reaction temperature is 40-100 ℃, the reaction time is 1-12 hours, the esterification reagent comprises alcohol compounds such as methanol, ethanol and N-butanol, acetal compounds such as N, N-dimethylformamide dimethyl methylal (DMFDMA) and N, N-dimethylformamide dimethyl acetal (DMADEA), and the molar ratio of the polyamic acid to the esterification reagent is 1:1-10.
The polymer obtained by the above method is put into a large amount of water or methanol solution, precipitated, filtered, and dried to be separated. By the above operation, the unreacted monomer, dimer, trimer and other oligomer components can be removed, and the film characteristics after heat curing can be improved.
Optionally, the compound shown in the formula I in the photosensitive resin composition is at least one compound shown in the structures shown in the formulas I-1 to I-5.
Optionally, the dosage of the photosensitizer is 5-40% of the mass of polyimide or precursor resin thereof with a hydroxyl structure.
Optionally, the photosensitive agent is used in an amount of 10-30% or any value selected from 5%, 10%, 20%, 30% and 40% or any range between any two of the polyimide with hydroxyl structure or the precursor resin thereof.
Alternatively, the photosensitive agent in the photosensitive resin composition is not strictly limited in the present application, and one skilled in the art can select among the prior art, such as photoacid generator and photobase generator, as needed. The photoacid generator is preferably a photoacid generator which generates an acid by irradiation with ultraviolet light, visible light or the like, for example, a quinone diazide compound, an iodonium salt compound or a sulfonium salt compound, and the photoacid generator is preferably a quinone diazide compound from the viewpoint of photosensitivity and stability, and is preferably a sulfonate compound composed of naphthoquinone diazide sulfonyl chloride and a low-molecular polyhydric phenol compound. The diazonaphthoquinone compound has a dissolution inhibiting effect on the resin before exposure, and can generate indenic acid in the ultraviolet exposure region after exposure, and the solubility of the exposed portion in an alkaline aqueous solution is increased, so that the exposed portion can be removed, leaving an unexposed portion, and finally the desired pattern can be obtained. Among them, the difference in dissolution rate of the exposed portion and the unexposed portion in an alkaline developer is a key to obtaining an excellent pattern.
The quinone diazide compound of the present application can be prepared from naphthoquinone diazide sulfonyl chloride and a low molecular polyhydric phenol compound, and commercial products, preferably commercial quinone diazide compounds such as NT-300 (esterification reaction product of 2,3, 4-tetrahydroxybenzophenone and 6-diazonium-5, 6-dihydroxy-5-oxy-1-naphthalene sulfonic acid), 4NT-300 (esterification reaction product of 2,3, 4-tetrahydroxybenzophenone and 6-diazonium-5, 6-dihydroxy-5-oxy-1-naphthalene sulfonic acid), HP-190 (esterification reaction product of tris (4-hydroxyphenyl) ethane and 6-diazonium-5, 6-dihydroxy-5-oxy-1-naphthalene sulfonic acid) (manufactured by Tokyo Co., ltd.), etc. can be directly purchased. The use of two or more kinds of the quinone diazide compounds can further increase the dissolution rate ratio of the exposed portion to the unexposed portion, and can further provide a photosensitive resin composition having high sensitivity. The naphthoquinone diazide sulfonyl chloride is selected from any one or two of 1, 2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1, 2-naphthoquinone-2-diazide-5-sulfonyl chloride, and the structural formulas of the 1, 2-naphthoquinone-2-diazide-4-sulfonyl chloride and the 1, 2-naphthoquinone-2-diazide-5-sulfonyl chloride are respectively as follows:
The low molecular polyphenol compound is selected from bisphenol A, triphenol A, 4 '-isopropylidenediphenol, 1' -bis 4- (hydroxyphenyl) cyclohexane, 4 '-dihydroxyphenyl sulfone, 4-hexafluoroisopropylidenediphenol, 2, 6-dimethoxymethyl-4-tert-butylphenol, 2, 6-dimethoxy-p-cresol, 2, 6-diacetoxymethyl-p-cresol, 4',4 '-Trihydroxytriphenylmethane, 1', at least one of 1 "-tris (4-hydroxyphenyl) ethane, 4'- [1- [4- [1- (4-hydroxyphenyl) 1-methylethyl ] phenyl ] ethylene ] bisphenol, methyl 3,4, 5-trihydroxybenzoate, propyl 3,4, 5-trihydroxybenzoate, isoamyl 3,4, 5-trihydroxybenzoate, 2-ethylbutyl 3,4, 5-trihydroxybenzoate, 2, 4-dihydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 2',4 '-tetrahydroxybenzophenone, 2,3, 4' -tetrahydroxybenzophenone, 2,3,4,2',4' -pentahydroxybenzophenone.
Optionally, the photosensitive resin composition further comprises a sensitizer.
Optionally, the amount of the sensitizer is 1-20% of the mass of polyimide or precursor resin thereof with a hydroxyl structure, and preferably 5-15%.
Optionally, the sensitizer is used in an amount such that the mass ratio of polyimide having a hydroxyl structure or a precursor resin thereof is selected from any value of 1%, 5%, 10%, 15%, 20% or a range between any two.
The addition of a sensitizer may enhance photosensitivity, and typical sensitizers suitable for use in the present application include, for example, phenolic hydroxyl group, hydroxyl group or carboxyl group-containing organic compounds, etc.:
The compound containing phenolic hydroxyl group includes BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name is above, trade name is above ),Bis-Z、BisP-EZ、TrisP-HAP、TrisP-PA、TrisP-SA、BisP-MZ、BisP-PZ、BisP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisRS-26X( available from Asahi organic materials industries, ltd., available from Benzhou chemical industries, ltd.), 2, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxydiphenyl sulfone, 2-bis (4-hydroxyphenyl) hexafluoropropane, 9-bis (4-hydroxyphenyl) fluorene, 4' -dihydroxydiphenyl cyclohexane, bis (4-hydroxyphenyl) sulfide, 1, 4-naphthalene diphenol, 2, 3-naphthalene diphenol, 4', at least one of 4' -trihydroxy triphenylmethane, 1' -tris (4-hydroxyphenyl) ethane, 2,3, 4-trihydroxybenzophenone, and methyl 3,4, 5-trihydroxybenzoate.
The organic compound containing hydroxyl is at least one of saturated or unsaturated aliphatic alcohols containing 2-16 carbons, including ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, amyl alcohol, n-hexanol, cyclopropylmethanol, cyclohexylmethanol, 4-methyl-1-cyclohexylmethanol, 3, 4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-tert-butylcyclohexanol, heptanol, octanol, cyclooctanol, 1-cyclohexyl-1-pentanol, 3, 5-trimethylcyclohexanol, norbornene-2-methanol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 2, 7-octadienol, 2, 4-methyl-2-pentanol, cyclohexylmethanol, cis-2-hexen-1-ol, n-hexanol, isoamyl alcohol, 3-methyl-2-butanol, 4-methyl-2-pentanol, isobutanol and neopentanol.
The organic compound containing carboxyl refers to a carboxylic acid compound containing 2-16 carbon atoms, and comprises at least one of acetic acid, propionic acid, butyric acid, valeric acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, n-decanoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecenoic acid, p-methoxybenzoic acid, m-methylbenzoic acid, benzoic acid, mandelic acid, trans-2-hexenoic acid, 3, 7-dimethyl-6-octanoic acid, sorbic acid, 3, 5-trimethylhexanoic acid, lauric acid and laurenic acid.
Optionally, the photosensitive resin composition further comprises a surfactant.
Optionally, the weight ratio of the surfactant to the polyimide with a hydroxyl structure or the precursor resin thereof is 0.0001-0.05:1.
Optionally, the weight ratio of the surfactant to polyimide having a hydroxyl structure or precursor resin thereof is selected from any value or range of values between any two of 0.0001:1, 0.0005:1, 0.001:1, 0.005:1, 0.01:1, 0.03:1, 0.05:1.
Alternatively, the surfactant is an acrylic copolymer selected from POLYFLOW series surfactants or SKB-FLOW series surfactants, and exemplary POLYFLOW series surfactants may be selected from at least one of POLYFLOW No7, POLYFLOW No, POLYFLOW No, POLYFLOW No77, POLYFLOW No, POLYFLOW WS, POLYFLOW WS-314 (trade name, co-available from chemical company, inc.), and SKB-FLOW series surfactants may be selected from at least one of SKB-FLOWSD, SKB-FLOW SL, SKB-FLOW P90, SKB-FLOW 1358, SKB-FLOW 1392, SKB-FLOW 1460D, SKB-FLOW 90D (trade name, korea). The acrylic ester copolymer is preferably POLYFLOW No to 77, because POLYFLOW NO.77 has good compatibility with a system, the leveling property of glue solution can be improved, and bubbles or stripes are prevented from being generated during coating, so that a resin film with uniform film thickness is obtained, and the influence on the film performance after curing is avoided.
Alternatively, the photosensitive resin composition is obtained by uniformly mixing raw materials including polyimide or precursor resin thereof with a hydroxyl structure, a compound shown in the formula I, a photosensitizer and a solvent III and filtering.
Optionally, the photosensitive resin composition is prepared by uniformly mixing raw materials including polyimide with a hydroxyl structure or precursor resin thereof, a compound shown in the formula I, a photosensitizer, a solvent III, a photosensitizer and a surfactant, and filtering;
The mixing process comprises the steps of mixing polyimide or precursor resin thereof with a hydroxyl structure and a solvent III, stirring, adding a photosensitizer after the polyimide or precursor resin thereof with the hydroxyl structure is fully dissolved, adding a compound shown in the formula I and a surfactant after the polyimide or precursor resin thereof with the hydroxyl structure is dissolved, continuously stirring until the polyimide or precursor resin is fully and uniformly dispersed, and then performing filter pressing by using a polytetrafluoroethylene filter membrane with the diameter of 1.0 mu m to obtain the photosensitive resin composition.
According to a fourth aspect of the present application, there is provided a polyimide film obtained by coating and curing the photosensitive resin composition.
In the preparation process of the polyimide film of the present application, the coated substrate is not particularly limited, and those skilled in the art can make routine selections, and there may be exemplified silicon wafers, aluminum sheets, silver sheets, copper alloy sheets, ceramic sheets, etc., preferably silicon wafers (e.g., 4 inch silicon wafers), aluminum sheets, silver sheets, copper sheets, etc. Specific coating methods are not particularly limited, and examples thereof include a spray coating method, a spin coating method, a doctor blade method, and the like, and film thickness varies depending on the coating method, the rotation speed, the viscosity, the composition component, and the like during actual coating operation. The coating method is preferably spin coating.
Optionally, the polyimide film has a cured relief pattern.
Optionally, the preparation method of the polyimide film with the cured relief pattern comprises the steps of coating the photosensitive resin composition on a substrate, and drying, exposing, developing and curing to obtain the polyimide film.
In the preparation process of the polyimide film with the cured relief pattern, the drying method can adopt baking operation, and particularly can adopt baking by adopting an oven, a heating table, an infrared lamp and the like, and the baking is preferably carried out by adopting the heating table. Further preferably, the drying temperature is 80-150 ℃, the drying time is 1-10 min, further preferably, the drying temperature is 100-130 ℃, and the drying time is 2-5 min. After the drying operation was completed, the thickness of the photosensitive resin film layer was measured after naturally cooling to 25 ℃.
In the process of producing a polyimide film having a cured relief pattern according to the present application, the exposure operation is performed by exposing the dried photosensitive resin film layer to light through a patterned reticle using an exposure device. Typical active rays include ultraviolet rays, X-rays, electron beams, etc., and in the present application, exposure treatment using a mercury lamp is preferable, wherein the exposure treatment includes three light sources of i-line (365 nm), h-line (405 nm), g-line (436 nm).
In the preparation process of the polyimide film with the cured relief pattern, the development is completed by removing the exposed part to form the pattern by adopting the developing solution. Selection of the developer the person skilled in the art can make routine selections such as aqueous solutions of tetramethyl ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like, aqueous solutions of compounds exhibiting basicity, and the like. The specific operation of developing is that the developing solution and the rinsing solution are respectively poured into two glass culture dishes, the temperature of the developing solution is controlled to be 25+/-1 ℃, the exposed resin film is immersed into the developing solution, timing is started immediately, after the exposed part is completely exposed out of the substrate, the developing is finished, the timing is stopped, and the time required by the whole process is recorded. The resin film may be baked at 60 to 150 ℃, preferably 60 to 120 ℃ for 5s to 60min, if necessary, before development. And after the rinsing is finished, heating and drying the resin film at the temperature of 60-200 ℃ for 1-60 min.
In the preparation process of the polyimide film or the polyimide film with the cured relief pattern, the curing operation temperature is 300-400 ℃, preferably 350 ℃. The pattern obtained after the development and rinsing is subjected to thermal imidization to be converted into a cured film. The heating treatment is usually carried out by a stepwise heating, and a continuous heating at different temperatures for a certain period of time or a certain temperature range. For example, a heat treatment method in which the temperature is raised from room temperature to 350 ℃ continuously or the like is performed at 150 ℃, 250 ℃ and 350 ℃ for 30 minutes, respectively. Inert gases such as nitrogen and argon are often used for curing. As a specific application example, firstly controlling the oxygen content in the oven cavity to be reduced to below 50ppm, then starting to heat to 150 ℃ and keeping the temperature for 30 minutes, then heating to 250 ℃ and keeping the temperature for 30 minutes, then heating to 350 ℃ and keeping the temperature for 1 hour, and cooling to room temperature, thus finally obtaining the cured relief pattern.
According to a fifth aspect of the present application, there is provided use of at least one of the above compound, the above photosensitive resin composition, and the above polyimide film for manufacturing a semiconductor element.
Optionally, the semiconductor element comprises the polyimide film or the polyimide film with the cured relief pattern.
Since the polyimide film obtained by curing the above photosensitive resin composition of the present application has high heat resistance and high mechanical strength, the application includes the use of the polyimide film obtained by curing the above photosensitive resin composition of the present application for a surface protective film, an interlayer dielectric or an insulating layer of a semiconductor element and an insulating layer for protecting a circuit board wiring. An electronic device such as a surface protective layer and an interlayer insulating layer obtained by using the photosensitive resin composition provided by the application is, for example, a magnetoresistive memory, a polymer memory, a phase change memory, or the like.
The application has the beneficial effects that:
The compound provided by the application has an azacyclic ring and an epoxy structure, and is introduced into a photosensitive resin composition to perform condensation reaction with resin and the same molecule to form a crosslinked structure, so that the film forming property, chemical resistance, mechanical property and thermal stability of a cured film are improved. In addition, the existence of the heterocyclic N atoms can also reduce the dielectric constant of the cured film, inhibit the problem of color change of the copper or copper alloy base material, improve the overall performance of the cured film and improve the reliability.
Drawings
FIG. 1 is a comparison of the chemical resistance micrographs of the cured films of inventive example 1 and comparative examples 1, 2.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
If not specified, the test methods are all conventional methods, and the instrument settings are all recommended by manufacturers.
The structural formulas and names of the raw materials P-1, P-2, P-3, P-4, P-5, P-6, ODPA and HFHA related in the specific embodiment of the application are shown in the following table 1, wherein the raw materials P-1 to P-5 are synthesized by synthesis examples 1-5.
TABLE 1
Synthesis example 1
Compound C-1, has the structure:
the synthesis method of the compound C-1 specifically comprises the following steps:
Adding 57.06g (0.5 mol) of P-1 and a proper amount of absolute ethyl alcohol into a three-neck flask provided with a stirring device, a constant pressure dropping funnel and a reflux condenser, heating to 60 ℃, adding 323.89g (3.5 mol) of mixed solution of epichlorohydrin and absolute ethyl alcohol into the constant pressure dropping funnel, slowly dripping, reacting for 6 hours after the dripping of epichlorohydrin is finished, slowly dripping 450g of 30% sodium hydroxide aqueous solution with a mass fraction by using the constant pressure dropping funnel after the completion of the P-1 reaction, controlling the dripping speed at 3mL/min, maintaining the temperature at 50 ℃ for 3 hours after the dripping, extracting by using toluene, standing for layering after stirring, adding a proper amount of deionized water into an oil phase for washing to be neutral in pH, and decompressing and distilling the oil phase to remove redundant epichlorohydrin and solvent to obtain colorless transparent liquid.
1HNMR(DMSO):δ:2.36(m,6H),2.49(m,6H),2.54(m,6H),2.60(m,6H),2.79(m,6H),3.04(m,6H),3.29(m,6H)。
Synthesis example 2
Compound C-2 has the structure:
The synthesis method of the compound C-2 specifically comprises the following steps:
Adding 62.57g (0.5 mol) of P-2 and a proper amount of absolute ethyl alcohol into a three-neck flask provided with a stirring device, a constant pressure dropping funnel and a reflux condenser, heating to 60 ℃, adding 323.89g (3.5 mol) of mixed solution of epichlorohydrin and absolute ethyl alcohol into the constant pressure dropping funnel, slowly dropwise adding, reacting for 6 hours after the completion of the dropwise addition of the epichlorohydrin, slowly dropwise adding 450g of 30% sodium hydroxide aqueous solution with the mass fraction by using the constant pressure dropping funnel after the completion of the reaction of P-1, controlling the dropwise addition speed at 3mL/min, maintaining the temperature at 50 ℃ for 3 hours after the completion of the dropwise addition, extracting by using toluene, standing for layering after stirring, adding a proper amount of deionized water into an oil phase, washing the oil phase to be neutral with PH, and decompressing and distilling the oil phase to remove redundant epichlorohydrin and solvent to obtain colorless transparent liquid.
1HNMR(DMSO):δ:2.36(m,6H),2.49(m,6H),2.60(m,6H),3.04(m,6H),3.29(m,6H),4.74(s,1H)。
Synthesis example 3
Compound C-3, having the structure:
the synthesis method of the compound C-3 specifically comprises the following steps:
Adding 63.06g (0.5 mol) of P-3 and a proper amount of absolute ethyl alcohol into a three-neck flask provided with a stirring device, a constant pressure dropping funnel and a reflux condenser, heating to 60 ℃, adding 323.89g (3.5 mol) of mixed solution of epoxy chloropropane and absolute ethyl alcohol into the constant pressure dropping funnel, slowly dripping, reacting for 6 hours after the epoxy chloropropane is dripped, slowly dripping 450g of 30% sodium hydroxide aqueous solution with mass fraction by using the constant pressure dropping funnel after the P-1 reaction is confirmed by HPLC, controlling the dripping speed to be 3mL/min, maintaining the temperature to be 50 ℃ after the dripping is finished, performing ring-closure reaction for 3 hours, extracting by toluene, standing for layering after stirring, adding a proper amount of deionized water into the oil phase, washing the oil phase to be neutral with PH, and decompressing and distilling the oil phase to remove redundant epoxy chloropropane and solvent to obtain colorless transparent liquid.
1HNMR(DMSO):δ:2.36(m,6H),2.49(m,6H),2.60(m,6H),3.04(m,6H),3.29(m,6H),4.74(s,1H)。
Synthesis example 4
Compound C-4, having the structure:
The synthesis method of the compound C-4 specifically comprises the following steps:
Adding 177.21g (0.5 mol) of P-4 and a proper amount of absolute ethyl alcohol into a three-neck flask provided with a stirring device, a constant pressure dropping funnel and a reflux condenser, heating to 60 ℃, adding 323.89g (3.5 mol) of mixed solution of epichlorohydrin and absolute ethyl alcohol into the constant pressure dropping funnel, slowly dropwise adding, reacting for 6 hours after the completion of the dropwise addition of the epichlorohydrin, slowly dropwise adding 450g of 30% sodium hydroxide aqueous solution with the mass fraction by using the constant pressure dropping funnel after the completion of the reaction of P-1, controlling the dropwise addition speed at 3mL/min, maintaining the temperature at 50 ℃ for 3 hours after the completion of the dropwise addition, extracting by using toluene, standing for layering after stirring, adding a proper amount of deionized water into an oil phase, washing the oil phase to be neutral with PH, and decompressing and distilling the oil phase to remove redundant epichlorohydrin and solvent to obtain colorless transparent liquid.
1HNMR(DMSO):δ:2.36(m,6H),2.49(m,6H),2.60(m,6H),3.33(m,6H),3.58(m,6H),6.92(d,6H),7.87(d,6H)。
Synthesis example 5
Compound C-5, having the structure:
the synthesis method of the compound C-5 specifically comprises the following steps:
Adding 144.18g (0.5 mol) of P-5 and a proper amount of absolute ethyl alcohol into a three-neck flask provided with a stirring device, a constant pressure dropping funnel and a reflux condenser, heating to 60 ℃, adding 323.89g (3.5 mol) of mixed solution of epichlorohydrin and absolute ethyl alcohol into the constant pressure dropping funnel, slowly dropwise adding, reacting for 6 hours after the completion of the dropwise addition of the epichlorohydrin, slowly dropwise adding 450g of 30% sodium hydroxide aqueous solution with the constant pressure dropping funnel after the completion of the P-1 reaction by using HPLC, controlling the dropwise adding speed at 3mL/min, maintaining the temperature at 50 ℃ for 3 hours after the completion of the dropwise addition, extracting by using toluene, standing for layering after stirring, adding a proper amount of deionized water into an oil phase, washing the oil phase to be neutral with PH, and decompressing and distilling the oil phase to remove redundant epichlorohydrin and solvent to obtain colorless transparent liquid.
1HNMR(DMSO):δ：2.36(m,6H),2.49(m,6H),2.60(m,6H),3.33(m,6H),3.58(m,6H),6.03(d,1H),6.87～6.90(m,4H),7.40(d,1H),7.55～7.56(d,3H),7.76(d,1H).
Example 1
(1) Synthesis of polyimide precursor resin
To a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer were successively added 31.02g (0.1 mol) of ODPA and 100.00g of NMP under a nitrogen flow, and the mixture was stirred and dissolved at room temperature to obtain a dianhydride solution. A three-necked flask equipped with a stirrer was further charged with 54.41g (0.09 mol) of HFHA and 100.00g of NMP in this order, and stirred and dissolved to obtain a diamine solution. And (3) dropwise adding the diamine solution into the dianhydride solution, reacting for 1h at normal temperature after the dropwise adding is finished, and then reacting for 2h at 50 ℃. After completion of the reaction, 2.18g (0.02 mol) of 3-aminophenol as a blocking agent was added, and after the reaction at 50℃for 2 hours, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise, and after the completion of the dropwise addition, the reaction was carried out at 50℃for 3 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. After filtration, the polyimide precursor resin was obtained by washing three times with deionized water, and drying in a vacuum oven at 80℃for 72 hours.
The molecular weight of the polyimide precursor resin powder was measured by standard polystyrene conversion, the eluent was N-methylpyrrolidone, the column oven temperature was 40 ℃, and the weight average molecular weight (Mw) was 2.1 to 2.5 ten thousand as a result of measurement.
(2) Preparation of photosensitive resin composition
10.0G of the polyimide precursor resin synthesized in the above step and 20g of N-methylpyrrolidone (NMP) solvent were put into a three-necked flask, after the resin was sufficiently dissolved, 0.5g of Compound C-1,2.0g of sensitizer quinone diazide compound NT-300 (manufactured by Nippon Denshoku Kogyo Co., ltd.) and 0.1gPOLYFLOW NO.77 (Kyowa Kagaku Co., ltd.) were added, and after continuing stirring until the mixture was sufficiently dissolved, the mixture was press-filtered through a 1.0 μm polytetrafluoroethylene filter membrane to obtain a photosensitive resin composition, which was designated as D-1.
Examples 2 to 10 and comparative examples 1 to 2
The synthesis of the polyimide precursor resin and the preparation method of the photosensitive resin composition were the same as in example 1, except that the addition ratio of the compound in the preparation of the photosensitive resin composition was different, as shown in table 2.
TABLE 2 addition ratio of different Compounds
Test example 1 film Forming Property test
The film forming property test method comprises the steps of coating a photosensitive resin composition glue solution on a 4-inch silicon substrate by using a spin coater, and placing the glue solution on a heating table for soft drying at 120 ℃ for 3 minutes to obtain a soft drying film with the film thickness of 10-20 mu m. Then, it was placed in a vacuum anaerobic oven (Lemnaceae, technophora Co., ltd., MOLZK-32D 1) for heat treatment. The heat treatment comprises heating to 150deg.C for 30min, heating to 250deg.C for 30min, heating to 350deg.C for 1 hr, and cooling to room temperature to obtain the final product.
And (3) placing the silicon wafer with the solidified film in hydrofluoric acid solution, and carrying out corrosion stripping on the silicon wafer.
The specific evaluation criteria are as follows:
film forming, folding without breaking;
film forming and breaking the folded part;
"poor" means that film formation and flaking are impossible.
The photosensitive resin compositions synthesized in examples 1 to 10 and comparative examples 1 to 2 were each tested by the above film forming property test method, and the results are shown in table 3.
Test example 2 Heat resistance test
The heat resistance test is carried out by measuring the heat resistance of the material by using a heat loss temperature of 5%.
10Mg of each of the cured films obtained in the film forming property test of test example 1 was filled into an aluminum standard container, and measured by a thermogravimetric analyzer (model: TGA55, manufacturer: TA). Test conditions were that the temperature was raised from room temperature to 600℃at a heating rate of 10℃per minute. The results are shown in Table 3.
Test example 3 tensile Strength test
The tensile strength test method comprises the steps of cutting different cured films obtained in the film forming property test of test example 1 into sample strips (with the length of <3cm and the width of <8 mm) meeting test requirements by using a die, and carrying out the tensile strength test on the sample strips by using a dynamic thermo-mechanical analyzer (model: DMA850, manufacturer: TA company) with the tensile force ranging from 0N to 18N, the speed ranging from 3N/min, the temperature ranging from 30 ℃ to 400 ℃ and the speed ranging from 3 ℃/min. The results are shown in Table 3.
Test example 4 dielectric Property test
The dielectric property test was carried out by cutting the cured films obtained in the film forming property test of test example 1 to 2cm. Times.2 cm, respectively. The dielectric constant of the polyimide film is tested by using an Agilent vector network analyzer E5071C by adopting a resonant cavity method, and the test frequency is 1MHz. The results are shown in Table 3.
Test example 5 copper discoloration test
The copper color-changing test method comprises the steps of uniformly coating the composition on a copper substrate, then placing the copper substrate on a heating table at 120 ℃ for soft drying for 3 minutes to obtain a soft drying film with the film thickness of 10-20 mu m, and placing the soft drying film in a developing solution for dissolution after the soft drying film is placed for 12 hours at room temperature. The discoloration of the copper substrate after dissolution of the soft baked film was evaluated according to the following criteria:
"optimal". The discoloration of the copper substrate was not confirmed even when observed under visual observation with a 200-fold optical microscope;
"good" in that no discoloration of the copper substrate was visually confirmed, and a slight discoloration of the copper substrate was confirmed when observed with a 200-fold optical microscope;
slightly better, the slight discoloration of the copper substrate was confirmed visually;
"poor" the copper substrate was visually confirmed to be severely discolored.
The photosensitive resin compositions synthesized in examples 1 to 10 and comparative examples 1 to 2 were each tested by the test method of the copper discoloration test, and the results are shown in table 3.
Test example 6 chemical resistance
The chemical resistance was measured by immersing the silicon wafer with different cured films obtained in the film forming property test of test example 1 in 10wt% aqueous sodium hydroxide (NaOH), 10vol% aqueous sulfuric acid, N-methylpyrrolidone (NMP), and a stripping solution, respectively, for 15 minutes at 25 ℃, then rinsing with deionized water for 10 minutes, and observing whether or not the cured film surface developed an abnormality such as crack under an optical microscope after air-drying, and the results are shown in table 3.
TABLE 3 evaluation of film Forming Property, thermal stability, tensile Strength, dielectric Property, copper discoloration test, and chemical resistance
As can be seen from the data in table 3, the present application provides a compound having a nitrogen-containing heterocycle and epoxy structure, which is used in a photosensitive resin composition, and which not only improves the film forming property, chemical resistance, mechanical properties and thermal stability of the cured film, but also reduces the dielectric constant of the cured film, suppresses the discoloration problem of the copper or copper alloy substrate, and improves the overall performance of the cured film with higher reliability.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (17)
1. A compound, characterized in that the compound has the structure of formula I:
A formula I;
In the formula I, the compound (I),
W is selected from any one of the groups shown in the formula II-a:
formula II-a;
wherein the dashed line represents the access site.
2. A process for the preparation of a compound as claimed in claim 1, comprising the steps of:
s1, heating a mixed solution containing a triamine compound and a solvent I, and then dropwise adding a material containing epoxy chlorinated alkane and a solvent II into the mixed solution for ring-opening reaction;
s2, dropwise adding an alkali solution into the product of the reaction in the step S1, performing cyclization reaction, and separating and purifying to obtain the compound.
3. The preparation method according to claim 2, wherein the dropping rate of the material of the epichlorohydrin and the solvent II and the dropping rate of the strong alkali solution are independently 1 to 5ml/min.
4. The preparation method according to claim 2, wherein in the step S1, the molar ratio of the triamine compound to the epichlorohydrin is 1:6-10.
5. The preparation method according to claim 2, wherein in the step S1, the heating condition is that the heating temperature is 35-60 ℃.
6. The preparation method according to claim 2, wherein in the step S1, the condition of the ring-opening reaction is that the reaction temperature is 35-60 ℃ and the reaction time is 3-6 h.
7. The method according to claim 2, wherein the molar ratio of the triamine compound to the strong base is 1:6-10.
8. The preparation method according to claim 2, wherein in the step S2, the cyclization reaction is carried out at a reaction temperature of 35-60 ℃ for 1-5 hours.
9. The preparation method according to claim 2, wherein the solvent I and the solvent II are independently selected from at least one of ethanol, ethylene glycol, glycerol, ethylene glycol butyl ether.
10. The method according to claim 2, wherein the alkali concentration in the strong alkali solution is 20-50wt%.
11. The method of claim 2, wherein the epichlorohydrin is selected from epichlorohydrin or epibromohydrin.
12. A photosensitive resin composition is characterized by being obtained by uniformly mixing the following raw materials:
A polyimide having a hydroxyl group structure or a precursor resin thereof, the compound according to claim 1, a sensitizer, and a solvent III.
13. The photosensitive resin composition according to claim 12, wherein a weight ratio of the polyimide having a hydroxyl structure or a precursor resin thereof to the compound is 1:0.001 to 0.2.
14. The preparation method according to claim 12, wherein the solvent III is at least one selected from the group consisting of methyl pyrrolidone, methyl ethyl ketone, acetone, γ -butyrolactone, ethyl acetate, ethyl lactate, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
15. The method according to claim 12, wherein the weight ratio of the polyimide having a hydroxyl structure or a precursor resin thereof to the solvent III is 1:1 to 20.
16. A polyimide film obtained by coating and curing the photosensitive resin composition according to any one of claims 12 to 15.
17. Use of at least one of the compound according to claim 1, the photosensitive resin composition according to any one of claims 12 to 15, and the polyimide film according to claim 16 for manufacturing a semiconductor element.
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