CN117304225A - Alkynyl-containing compound, positive photosensitive resin composition, and preparation methods and applications thereof - Google Patents

Alkynyl-containing compound, positive photosensitive resin composition, and preparation methods and applications thereof Download PDF

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Publication number
CN117304225A
CN117304225A CN202311174891.8A CN202311174891A CN117304225A CN 117304225 A CN117304225 A CN 117304225A CN 202311174891 A CN202311174891 A CN 202311174891A CN 117304225 A CN117304225 A CN 117304225A
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alkynyl
component
resin composition
containing compound
photosensitive resin
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CN202311174891.8A
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CN117304225B (en
Inventor
王珂
李铭新
盛泽东
陈存浩
张义腾
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Bomi Technology Co ltd
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Bomi Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • 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
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The application discloses an alkynyl-containing compound, a positive photosensitive resin composition, and a preparation method and application thereof, and belongs to the field of high polymer materials. An alkynyl-containing compound specifically has a structure represented by formula (1):the alkynyl compound has amino ester structure or hydroxy ether structure, has better compatibility with resin with hydroxy, forms hydrogen bond with the resin, and can crosslink and polymerize alkynyl in the heat treatment process, and can be added into the resin composition to improve the adhesiveness of the cured film and the substrate and improve the adhesiveness of the cured film and the substrateThe film forming property is improved, and the mechanical property and the thermal stability of the cured film are improved, so that the overall performance of the cured film is improved, and the reliability is higher.

Description

Alkynyl-containing compound, positive photosensitive resin composition, and preparation methods and applications thereof
Technical Field
The application relates to an alkynyl-containing compound, a positive photosensitive resin composition, and a preparation method and application thereof, and belongs to the field of high 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 development of miniaturization of semiconductor devices, exposure sensitivity and development resolution of photosensitive polyimide resin compositions are increasingly demanded.
In addition, the film after heat curing exists as a permanent film in the device, and therefore, the performance of the cured film is very important. In order to ensure the reliability of the semiconductor package, the bonding force between the cured film and the surface material of the semiconductor chip is critical, and the bonding force between the resin and the substrate (especially the metal substrate) is greatly improved because the resin structure does not have strong adhesive force to the substrate. In addition, the cured film should have excellent electrical properties, mechanical properties, thermal stability, chemical resistance, and the like.
In the prior art, various silane coupling agents with different groups are generally introduced to increase the adhesion of a cured film and a base material, but the problems of poor compatibility of some silane coupling agents with a resin system, poor storage stability of a resin composition caused by high reaction activity, reduced photosensitivity and the like exist; to increase the chemical and heat resistance of the cured film, thermal crosslinking agents are typically incorporated into the composition, such as: a compound containing an epoxy group, a phenolic hydroxyl group, a hydroxymethyl group or an alkoxymethyl group, but it is difficult to achieve low stress. In order to improve the comprehensive performance of the cured film, various additives are generally introduced into the resin composition, but the content of the additives is excessive, and the film retention rate of the cured film is low after high-temperature heat treatment, so that the material performance is affected. In addition, the presence of various additives is prone to problems such as improvement in performance on the one hand, degradation in other performances, and the like.
Disclosure of Invention
According to one aspect of the present application, an alkynyl-containing compound having a good compatibility with a resin having a hydroxyl group is provided, and by introducing the alkynyl-containing compound into a photosensitive resin composition, not only the adhesiveness between a cured film and a substrate is improved, but also the film forming property is improved, and at the same time, the mechanical properties, thermal stability, chemical resistance and electrical properties of the cured film are enhanced, thereby greatly improving the reliability of semiconductor packaging. The positive photosensitive resin composition obtained by using the alkynyl-containing compound has good storage stability and excellent photosensitivity, and is suitable for the fields of semiconductor manufacturing, packaging and the like.
The alkynyl-containing compound has a structure represented by a specific formula (1):
wherein X is any one of the structures shown in the general formulas (2) and (3), and the dotted line is an access site:
y is an organic group containing a benzene ring and/or a pyridine ring; r is R 1 Is a hydrocarbon group of 1 to 10 carbon atoms, R 2 、R 3 Are respectively and independently selected from R 1 At least one of O, a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms; n is any integer from 1 to 3.
The structure of X in the formula (1) is controlled, so that the alkynyl-containing compound contains an amino ester structure or a hydroxyl ether structure, has better compatibility with resin with hydroxyl groups, forms hydrogen bonds with the resin, can crosslink and polymerize the alkynyl in the heat treatment process, and is added into a resin composition, so that not only can the cohesiveness of a cured film and a base material be improved, but also the film forming property can be improved, and meanwhile, the mechanical property, the thermal stability, the chemical resistance and the electrical property of the cured film are improved, so that the overall performance of the cured film is improved, and the reliability is higher.
In one embodiment, the hydrocarbon group having 1 to 10 carbon atoms in the present invention includes any one of a substituted or unsubstituted alkyl group, cycloalkyl group, and aryl group. Specifically, examples of the alkyl group having 1 to 10 carbon atoms in the present invention include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aromatic groups such as phenyl and tolyl, and aralkyl groups such as benzyl, phenethyl and phenylpropyl. Preferably a hydrocarbon group of 1 to 4, more preferably an alkyl group of 1 to 4, and still more preferably a methyl group or an ethyl group.
R in the invention 2 、R 3 Independent of each other, not affecting each other, i.e. R 2 Selected from R 1 At least one of O, hydrogen atom and hydrocarbon group having 1 to 10 carbon atoms, R 3 Selected from R 1 At least one of O, a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms.
Preferably, R 1 Is a hydrocarbon group having 1 to 4 carbon atoms, more preferably R 1 Is alkyl with 1-4 carbon atoms; more preferably, R 1 Is methyl or ethyl.
Further preferably, R 2 、R 3 Are respectively and independently selected from R 1 At least one of O, a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms; further preferably, R 2 、R 3 Are respectively and independently selected from R 1 At least one of O, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; further preferably, R 2 、R 3 Are respectively and independently selected from R 1 At least one of O, a hydrogen atom and an alkyl group having 1 to 2 carbon atoms; further preferably, R 2 、R 3 R is independently R 1 O; more preferably, R 2 、R 3 R is independently R 1 O, and R 1 Is methyl or ethyl.
In one embodiment, Y is a structure of any one of formulas (4) to (6), and the dashed line is an access site:
in one embodiment, the alkynyl-containing compound has a structure according to any one of formulas (I) to (vi):
r in the general formulae (I) to (VI) 1 、R 2 、R 3 As above.
In yet another aspect, the present invention provides a method for preparing the alkynyl-containing compound, comprising: in the inert gas atmosphere, the raw material (a) and the raw material (b) undergo tertiary amination or ring opening reaction to obtain the catalyst;
the raw material (b) is alkyne containing benzene ring and/or pyridine ring substituted by hydroxyl;
the raw material (a) has a structure shown in the following formula (7-1) and/or formula (7-2);
r in the formulae (7-1), (7-2) of the present invention 1 、R 2 、R 3 Is as defined above.
Preferably, the raw material (b) is selected from one or more of the following formulas (8-1), (8-2) and (8-3),
preferably, the feedstock (a) and feedstock (b) are reacted in an aprotic solvent under the catalysis of a basic catalyst.
Preferably, the reaction temperature is 60-120 ℃ and the reaction time is 6-12 h.
In one embodiment, the method of preparing the alkynyl containing compound comprises the steps of:
(1) Under the protection of inactive gas, adding a certain amount of raw material (a) and aprotic polar solvent into a reaction container, and uniformly mixing;
(2) Adding a certain amount of raw material (b) into the solution, adding an alkaline catalyst, and reacting for 6-12 h at 60-160 ℃.
In one embodiment, the process for preparing an alkynyl-containing compound further comprises performing reduced pressure distillation purification after the reaction is completed.
In one embodiment, the raw material (a) is selected from at least one of isocyanatomethyl trimethoxysilane, isocyanatoethyl trimethoxysilane, isocyanatopropyl trimethoxysilane, isocyanatomethyl triethoxysilane, isocyanatoethyl triethoxysilane, isocyanatopropyl triethoxysilane, 3- (2, 3-glycidoxy) propyl trimethoxysilane, 3- (2, 3-glycidoxy) propyl triethoxysilane.
In one embodiment, the molar ratio of feedstock (a) to feedstock (b) is 1: (0.5-2), preferably in a molar ratio of 1:1.
The basic catalyst of the present invention is not particularly limited, and those skilled in the art can make routine selections, and preferably, the basic catalyst is at least one selected from the group consisting of triethylamine, potassium hydroxide, sodium carbonate, tetrabutylammonium hydroxide, tetrabutylammonium bromide.
The aprotic polar solvent of the present invention is not particularly limited, and a person skilled in the art may select, and preferably, the aprotic polar solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and γ -butyrolactone.
The amounts of the basic catalyst and aprotic polar solvent involved in the present invention are not particularly limited herein, and those skilled in the art may make routine selections.
In still another aspect of the present invention, there is provided a positive photosensitive resin composition comprising:
component (a): polyimide having a hydroxyl structure or a precursor resin thereof;
component (b): alkynyl-containing compounds;
component (c): a sensitizer;
component (e): and (3) a solvent.
In one embodiment, component (a) is a polyimide precursor having a hydroxyl structure, preferably a polyamic acid or polyamic acid ester, as shown in formula (9).
Wherein A represents a 4-valent organic group having 4 to 40 carbon atoms; b represents a 2-valent organic group having 2 to 40 carbon atoms; r is R 4 And R is 5 Each independently represents a hydrogen atom or a saturated aliphatic group having 1 to 10 carbon atoms; m is an integer greater than or equal to 1, and the groups in brackets are optionally the same or different.
Among them, a is preferably an aromatic organic group having 6 or more carbon atoms, and more preferably a structure represented by the following formula (10), but is not limited thereto. Further, 1 kind or 2 kinds or more may be combined.
B is preferably an aromatic organic group having 6 or more carbon atoms and having a hydroxyl structure, and more preferably a structure represented by the following formula (11), but is not limited thereto. Further, 1 kind or 2 kinds or more may be combined.
In order to improve the stability of the resin, a blocking agent is introduced during the resin synthesis process, preferably, the blocking agent is one or more of monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, and monoacid ester compound. The type and amount of the capping agent selected may be adjusted as desired. The capping agents are generally used in a manner that can be divided into: adding a blocking agent and diamine and dianhydride simultaneously; adding a blocking agent after the diamine reacts with the dianhydride; the diamine or dianhydride is added after reacting the capping agent with the dianhydride or diamine.
The polyamic acid and the polyamic acid ester can be self-made or can be directly purchased.
In one embodiment, the method for preparing the polyamic acid comprises the steps of: the dianhydride and the diamine are subjected to polymerization reaction, then a blocking agent is added for continuous reaction, and a polyamic acid solution is obtained after the reaction is finished.
In one embodiment, the method of preparing the polyamic acid ester comprises: the polyamic acid is heated in an esterification reagent during which the 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.
Wherein, the esterification rate of the polyamic acid is 40 to 90 percent; the temperature of the esterification reaction is 40-100 ℃ and 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), N, N-dimethylformamide dimethyl acetal (DMADAE) and the like, 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.
In one embodiment, the component (b) is at least one of the alkynyl-containing compounds represented by any of the above general formulae (I) to (VI), and may be used alone or in a mixture of 2 or more.
In one embodiment, the weight ratio of the alkynyl-containing compound of the component (b) to the polyimide having a hydroxyl structure of the component (a) or the precursor resin thereof is (0.1 to 20): 100, preferably (1-10): 100, there may be mentioned 1:100, 2.5:100, 5:100, 10: 100. 15: 100. 20: 100. 25: 100. 30:100, etc.
In a specific embodiment, the weight ratio of the alkynyl-containing compound of the component (b) to the polyimide having a hydroxyl structure of the component (a) or the precursor resin thereof is (1 to 2.5): 100. (1-5): 100. (1-10): 100. (1-15): 100. (1-20): 100. (1-25): 100. (1-30): 100. (2.5-5): 100. (2.5-10): 100. (2.5-15): 100. (2.5-20): 100. (2.5-25): 100. (2.5-30): 100. (5-10): 100. (5-15): 100. (5-20): 100. (5-25): 100. (5-30): 100. (10-15): 100. (10-20): 100. (15-20): 100. (15-25): 100. (20-25): 100. (20-30): 100. (25-30): 100.
in one embodiment, the positive photosensitive resin composition of the present invention may further include a sensitizer, for example, an organic compound containing a phenolic hydroxyl group, a hydroxyl group, or a carboxyl group, in order to enhance photosensitivity.
The phenolic hydroxyl group-containing compound includes BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name above, available from Asahi organic materials industries, ltd.), bis-Z, bisP-EZ, trisP-HAP, trisP-PA, trisP-SA, bisP-MZ, bisP-PZ, bisP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisRS-26X (trade name above, available from Ben 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', 4' -trihydroxy triphenylmethane, 1' -tris (4-hydroxyphenyl) ethane, 2,3, 4-trihydroxy benzophenone, methyl 3,4, 5-trihydroxybenzoate, and the like, and mixtures thereof in any ratio.
The organic compound containing hydroxyl refers to 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, neopentyl alcohol and a mixture thereof in any proportion.
The organic compound containing carboxyl refers to carboxylic acid compounds containing 2-16 carbon atoms, including 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, laurenic acid and mixtures thereof in any proportion.
The sensitizer is preferably used in an amount of 1 to 20% by mass, preferably 5 to 15% by mass, of the polyimide having a hydroxyl structure or a precursor resin thereof, for example, 1%, 5%,10%, 15%, 20% by mass, and the like.
The sensitizer of the present invention is not particularly limited, and those skilled in the art can make routine selections, such as photoacid generator, photobase generator, etc.
From the viewpoint of dissolution contrast, photoacid generators are preferable. Photoacid generators are compounds that generate acid by irradiation with ultraviolet light, visible light, or the like, for example: quinone diazide compounds, iodonium salt compounds, sulfonium salt compounds, and the like. Further, from the viewpoints of photosensitivity and stability, a quinone diazide compound, and a sulfonate compound formed from naphthoquinone diazide sulfonyl chloride and a low-molecular polyhydric phenol compound are preferable. 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 invention 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-oxo-1-naphthalene sulfonic acid) (manufactured by Japanese synthetic Co., ltd.) and the like can be purchased directly. 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 positive photosensitive resin composition having high sensitivity.
The photosensitive agent is preferably used in an amount of 5 to 40% by mass, for example, 5%,10%,20%,30%,40% by mass, preferably 10 to 30% by mass, more preferably 20% by mass, of the polyimide having a hydroxyl group structure or the precursor resin thereof.
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' -dihydroxyphenylsulfone, 4-hexafluoroisopropylidenediphenol, 2, 6-dimethoxymethyl-4-tert-butylphenol, 2, 6-dimethoxy-p-cresol, 2, 6-diacetoxymethyl-p-cresol, 4', 4' -Trihydroxytriphenylmethane, 1', any one or a mixture 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.
In one embodiment, the solvent is selected from one or more of polar aprotic solvents, ethers, ketones, esters, alcohols, aromatic hydrocarbons.
Preferably, the polar aprotic solvent includes, but is not limited to, one or more of the following compounds: n-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
Preferably, the ethers include, but are not limited to, one or more of the following compounds: tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
Preferably, the ketones include, but are not limited to, one or more of the following compounds: acetone, methyl ethyl ketone, diisobutyl ketone.
Preferably, the esters include, but are not limited to, one or more of the following compounds: ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate.
Preferably, the alcohols include, but are not limited to, one or more of the following compounds: diacetone alcohol, 3-methyl-3-methoxybutanol.
Preferably, the aromatic hydrocarbons include, but are not limited to, one or more of the following compounds: toluene, xylene.
Preferably, the weight ratio of the component (e) solvent to the polyimide having a hydroxyl structure of the component (a) or the precursor resin thereof is (100 to 2000): as 100, there may be mentioned 100: 100. 150: 100. 200:100, 500:100, 800:100, 1000:100, 1500: 100. 2000:100.
in a specific embodiment, the weight ratio of the solvent of the component (e) to the polyimide having a hydroxyl structure of the component (a) or the precursor resin thereof is (100 to 150): 100. (100-200): 100. (100-500): 100. (100-800): 100. (100-1000): 100. (100-1500): 100. (150-500): 100. (150-800): 100. (150-1500): 100. (150-2000): 100. (1500-2000): 100.
in one embodiment, the positive photosensitive resin composition further comprises component (d): and (3) a surfactant.
Preferably, the surfactant is an acrylic copolymer, for example, a surfactant of the POLYFLOW series and a surfactant of the SKB-FLOW series, and examples of the surfactant of the POLYFLOW series include POLYFLOW No.7, POLYFLOW No. 36, POLYFLOW No. 56, POLYFLOW No.77,POLYFLOW No 90, POLYFLOW WS-314 (trade name, kyoto chemical Co., ltd.). Examples of the SKB-FLOW series surfactants include SKB-FLOW SD, SKB-FLOW SL, SKB-FLOW P90, SKB-FLOW 1358, SKB-FLOW 1392, SKB-FLOW 1460D, SKB-FLOW 90D (trade name, korean SKB), and the like.
Further preferably, the acrylic copolymer is POLYFLOW No 77.PolyFLOW No.77 has good compatibility with the system, can improve the leveling property of the glue solution, and prevent bubbles or stripes from being generated during coating, thereby obtaining a resin film with uniform film thickness, and avoiding influencing the film performance after curing.
Preferably, the weight ratio of the component (d) surfactant to the polyimide having a hydroxyl structure of the component (a) or the precursor resin thereof is (0.01 to 5): 100, there may be mentioned 0.01: 100. 0.05: 100. 0.1: 100. 0.5:100, 1: 100. 3: 100. 5:100, etc.
In a specific embodiment, the weight ratio of the component (d) surfactant to the polyimide having a hydroxyl structure of the component (a) or the precursor resin thereof is (0.01 to 0.05): 100. (0.01-0.1): 100. (0.01-1): 100. (0.05-0.1): 100. (0.05-1): 100. (0.05-3): 100. (0.1-1): 100. (0.1-3): 100. (1-3): 100. (1-5): 100. (3-5): 100.
in still another aspect, the present invention provides a method for preparing a positive photosensitive resin composition, comprising: and (3) dissolving and dispersing each component in the component (e) uniformly, and filtering to obtain the product.
In one embodiment, the method for preparing the positive photosensitive resin composition includes: adding polyimide with a hydroxyl structure of the component (a) or precursor resin thereof and a solvent of the component (e) into a three-neck flask, and stirring; after the component (a) is fully dissolved, adding the component (c) photosensitizer, after the component (b) containing alkynyl compound and the component (d) surfactant are dissolved, and continuously stirring until the components are completely and uniformly dispersed; the mixture was press-filtered through a 1.0 μm polytetrafluoroethylene filter membrane to obtain a positive photosensitive resin composition.
In yet another aspect, the present invention provides a polyimide film prepared from the positive photosensitive resin composition, preferably having a cured relief pattern.
In still another aspect, the present invention provides a method for preparing a polyimide film, comprising: and (3) coating the positive photosensitive resin composition on a substrate, and drying, exposing, developing and curing to obtain the polyimide film.
In the above-mentioned polyimide film production method, the coated substrate is not particularly limited, and those skilled in the art can make routine selections, and there may be mentioned 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.
In the above-mentioned polyimide film production method, the drying method may be a baking operation, and specifically, baking may be performed by using an oven, a heating stage, an infrared lamp, or the like, preferably, baking by using a heating stage. Further preferably, the drying temperature is 80-150 ℃, the drying time is 1-10min, further preferably, the drying temperature is 100-130 ℃, and the drying time is 2-5min. After the drying operation was completed, the thickness of the photosensitive resin film was measured after naturally cooling to 25 ℃.
In the above-mentioned method for producing a polyimide film, the exposure step is performed by exposing the dried photosensitive resin film layer to light through a patterned mask plate by an exposure device. Typical active rays include ultraviolet rays, X-rays, electron beams, etc., and in the present invention, 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 above-mentioned polyimide film production method, the development is completed by removing the exposed portion with a developer to form a pattern. 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.
In one specific embodiment, the specific operation of the development is: pouring developing solution and rinsing solution into the two glass culture dishes respectively, controlling the temperature of the developing solution to be 25+/-1 ℃, immersing the exposed resin film into the developing solution, starting timing immediately, finishing development after the exposed part is completely exposed out of the substrate, stopping timing, and recording the time required by the whole process. The resin film may be baked at 60 to 150℃and preferably 60 to 120℃for 5s to 60 minutes, if necessary, before development. After the rinsing is finished, the resin film is heated and dried at the temperature of 60-200 ℃ for 1-60 min.
In the above-mentioned method for producing a polyimide film, the curing operation is carried out at a temperature of 300 to 400℃and 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 150℃and 250℃and 350℃is carried out for 30 minutes, a method in which the temperature is continuously raised from room temperature to 350℃or the like is carried out. 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.
The polyimide film formed by the positive photosensitive resin composition provided by the invention has high heat resistance and high mechanical strength, and can be used for surface protection films, interlayer dielectrics or insulating layers of semiconductor elements and insulating layers for protecting circuit board circuits. An electronic device including a surface protective layer, an interlayer insulating layer, and the like, which are obtained using the positive photosensitive resin composition provided in the present application, includes: magnetoresistive memory, polymer memory, phase change memory, etc.
In yet another aspect, the present invention provides a semiconductor element comprising a polyimide film.
The semiconductor element of the present invention preferably comprises a polyimide film having a cured relief pattern.
The beneficial effects that this application can produce include:
1. the alkynyl compound has an amino ester structure or a hydroxy ether structure, has better compatibility with resin with hydroxy, forms hydrogen bonds with the resin, can crosslink and polymerize in the heat treatment process, is added into the resin composition, not only improves the cohesiveness of a cured film and a base material, but also improves the film forming property, and simultaneously improves the mechanical property and the thermal stability of the cured film, so that the integral property of the cured film is improved, and the reliability is higher.
2. The positive photosensitive resin composition provided by the application does not contain silane coupling agents with different groups, has good storage stability and excellent photosensitivity, and a cured film prepared from the positive photosensitive resin composition has the advantages of high cohesiveness, high toughness, high heat resistance, excellent chemical resistance, excellent electric performance and the like, and is suitable for the fields of semiconductor manufacturing, packaging and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of an alkynyl-containing compound C-1;
FIG. 2 is an infrared spectrum of alkynyl-containing compound C-1.
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.
The structural formulas and names of the raw materials P-1, P-2, Q-1, Q-2, Q-3, ODPA and HFHA referred to below are shown in Table 1 below.
TABLE 1
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Example 1
Alkynyl-containing compound C-1 has the following structure:
the synthesis method of the alkynyl-containing compound C-1 specifically comprises the following steps:
into a 250ml three-necked flask, 20.53g (0.1 mol) of P-1 and 150g of N-methylpyrrolidone (NMP) were charged under nitrogen atmosphere and mixed uniformly. To the above solution, 11.91g (0.1 mol) of Q-1 was added, followed by stirring, 1.01g (0.01 mol) of triethylamine was added, and the mixture was stirred and heated to 60℃to react for 6 hours. After the reaction, the reaction solution is distilled and purified under reduced pressure to obtain the compound C-1.
The nuclear magnetic resonance hydrogen spectrum of the compound C-1 is shown in figure 1, and nuclear magnetic information is as follows:
1HNMR(DMSO,300MHz):δ:0.58(t,2H),1.52(m,2H),3.19(t,2H),3.55(s,9H),4.10(s,1H),6.76(s,1H),6.91(d,1H),8.15(d,1H),8.74(s,1H)。
example 2
Alkynyl-containing compound C-2 has the following structure:
the synthesis method of the alkyne-containing compound C-2 comprises the following steps:
into a 250ml three-necked flask, 20.53g (0.1 mol) of P-1 and 150g of N-methylpyrrolidone (NMP) were charged under nitrogen atmosphere and mixed uniformly. To the above solution, 11.81g (0.1 mol) of Q-2 was added, followed by stirring, 1.01g (0.01 mol) of triethylamine was added, and the mixture was stirred and heated to 60℃to react for 6 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure distillation and purification to obtain the compound C-2.
The nuclear magnetic information of compound C-2 is as follows:
1HNMR(DMSO,300MHz):δ:0.58(t,2H),1.52(m,2H),3.19(t,2H),3.55(s,9H),4.08(s,1H),6.76(s,1H),7.3～7.35(m,3H),7.82(s,1H)。
example 3
Alkynyl-containing compound C-3 has the following structure:
into a 250ml three-necked flask, 20.53g (0.1 mol) of P-1 and 150g of N-methylpyrrolidone (NMP) were charged under nitrogen atmosphere and mixed uniformly. To the above solution, 16.82g (0.1 mol) of Q-3 was added, followed by stirring, 1.01g (0.01 mol) of triethylamine was added, and the mixture was stirred and heated to 60℃to react for 6 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure distillation and purification to obtain the compound C-3.
The nuclear magnetic information of compound C-3 is as follows:
1HNMR(DMSO,300MHz):δ:0.58(t,2H),1.52(m,2H),3.19(t,2H),3.55(s,9H),4.01(s,1H),6.76(s,1H),6.89(m,1H),7.34～7.36(m,2H),7.67(m,1H),7.76(d,1H),8.30(m,1H)。
example 4
Alkynyl-containing compound C-4 has the following structure:
the synthesis method of the alkynyl-containing compound C-4 specifically comprises the following steps:
23.64g (0.1 mol) of P-2 and 150g of N-methylpyrrolidone (NMP) were added to a 250ml three-necked flask and uniformly mixed under the protection of nitrogen. To the above solution, 11.91g (0.1 mol) of Q-1 was added, and after stirring uniformly, 0.56g (0.01 mol) of potassium hydroxide was added, and the mixture was stirred and heated to 120℃for reaction for 10 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure distillation and purification to obtain the compound C-4.
The nuclear magnetic information of compound C-4 is as follows:
1HNMR(DMSO,300MHz):δ:0.56(t,2H),1.42(m,2H),3.35(m,2H),3.38(m,1H),3.55(s,9H),3.62(m,1H),3.95(m,1H),4.08(s,1H),4.20(m,1H),4.30(m,1H),5.78(s,1H),6.79(d,1H),8.18(d,1H),8.77(s,1H)。
example 5
Alkynyl-containing compound C-5 has the following structure:
the synthesis method of the alkynyl-containing compound C-5 specifically comprises the following steps:
23.64g (0.1 mol) of P-2 and 150g of N-methylpyrrolidone (NMP) were added to a 250ml three-necked flask and uniformly mixed under the protection of nitrogen. To the above solution, 11.81g (0.1 mol) of Q-2 was added, and after stirring uniformly, 0.56g (0.01 mol) of potassium hydroxide was added, and the mixture was stirred and heated to 120℃for reaction for 10 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure distillation and purification to obtain the compound C-5.
The nuclear magnetic information of compound C-5 is as follows:
1HNMR(DMSO,300MHz):δ:0.56(t,2H),1.42(m,2H),3.35(m,2H),3.39(m,1H),3.55(s,9H),3.62(m,1H),3.95(m,1H),4.08(s,1H),4.20(m,1H),4.30(m,1H),5.77(s,1H),6.92(d,1H),7.21(d,1H),7.32(t,1H),7.63(s,1H)。
example 6
Alkynyl-containing compound C-6 has the following structure:
the synthesis method of the alkynyl-containing compound C-6 specifically comprises the following steps:
23.64g (0.1 mol) of P-2 and 150g of N-methylpyrrolidone (NMP) were added to a 250ml three-necked flask and uniformly mixed under the protection of nitrogen. 16.82g (0.1 mol) of Q-3 was added to the above solution, followed by stirring, 0.56g (0.01 mol) of potassium hydroxide was added thereto, and the mixture was stirred and heated to 120℃for reaction for 10 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure distillation and purification to obtain a compound C-6.
The nuclear magnetic information of compound C-6 is as follows:
1HNMR(DMSO,300MHz):δ:0.56(t,2H),1.41(m,2H),3.35(m,2H),3.38(m,1H),3.55(s,9H),3.62(m,1H),4.01(s,1H),4.05(m,1H),4.30(m,2H),5.78(s,1H),6.89(d,1H),7.30～7.4(m,2H),7.63(d,1H),7.85(d,1H),8.30(d,1H)。
the synthesized alkynyl-containing compounds C1 to C6 were respectively tested by KBr tabletting method using infrared spectrometer (shimadzu, iraaffinity-1S) to determine whether the alkynyl-containing compounds of the present invention were successfully prepared.
The synthesized alkynyl-containing compound is qualitatively analyzed through infrared spectrogram, and the alkynyl-containing compounds C-1 to C-3 are in 1540cm -1 Near the bending vibration peak of N-H in urethane bond, at 1740cm -1 The successful synthesis of the target compound can be proved by the occurrence of an extension vibration peak of C=O in the urethane bond nearby; the alkynyl-containing compound C-4 to C-6 is 3330 to 3400cm -1 The nearby alcohol hydroxyl O-H stretching vibration peak appears at 1000-1100 cm -1 Near the C-OH stretching vibration peak appears, at the same time at 1240cm -1 (C-O extension attached to aromatic ring) and 1040cm -1 The successful synthesis of the target compound can be demonstrated by the occurrence of an extension vibration peak of the aromatic ether near (C-O extension linked to the alkyl group).
The infrared spectrum data of the alkynyl-containing compounds C-1 to C-6 are shown in Table 2, and the infrared spectrum of the alkynyl-containing compound C-1 is shown in FIG. 2.
TABLE 2
Example 7
Synthesis of polyimide precursor resin:
31.02g (0.1 mol) of ODPA and 100.00g of NMP were successively added to a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and stirred and dissolved at room temperature to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was taken, and 54.41g (0.09 mol) of HFHA and 100.00g of NMP were successively added thereto and stirred for dissolution 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 2 hours of reaction at 50℃a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and after 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. And washing the polyimide precursor resin with deionized water for three times after filtering, and putting the polyimide precursor resin into a vacuum oven for drying 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 measured to be 2.1 to 2.5 ten thousand.
The preparation method of the positive photosensitive resin composition specifically comprises the following steps:
10.0g of the synthesized polyimide precursor resin and 20g of N-methylpyrrolidone (NMP) solvent were put into a three-necked flask, after the resin was sufficiently dissolved, 0.5g of an alkynyl group-containing compound C-1,2.0g of a sensitizer quinone diazide compound NT-300 (manufactured by Toyo Seisakusho Kogyo Co., ltd.) and 0.1gPOLYFLOW NO.77 (Kyowa Kagaku Co., ltd.) were added, and after the mixture was continuously stirred until the mixture was sufficiently dissolved, the mixture was press-filtered through a 1.0 μm polytetrafluoroethylene filter membrane to obtain a positive photosensitive resin composition D-1.
Examples 8 to 16 and comparative examples 1 to 5 positive photosensitive resin compositions were prepared according to the preparation method of example 7 and the addition ratio in table 3.
The effect evaluation of the positive photosensitive resin composition was performed by the following method, and the specific test results are shown in table 4.
(1) Photosensitivity test
Coating the resin composition glue solution on a 4-inch substrate by using a spin coater, and placing the substrate on a heating table for soft drying at 120 ℃ for 3min to obtain a resin film with the film thickness of 7-8 mu m. Measuring film thickness to be a by using a step instrument (P-7, KLA-Tencor, U.S.), placing the silicon wafer on an exposure machine (BG-401A, manufactured by forty-five research institute of China electronics and technology group Co., ltd.), placing a mask, selecting 365nm light (i-line), and using 250mJ/cm 2 The photosensitive resin film is exposed to the energy of (a). The exposed silicon wafer is put into alkaline developer (2.38 percent TMAH, 25+/-1 ℃) for development, and the time for recording the complete display of the graph (the display of the base material) is T 1 The time for completely dissolving the coating adhesive in the non-exposure area is T 2 。
The dissolution rate of the exposed area was calculated by the following formula (unit: μm/s):
exposure area dissolution rate = a/T 1
The dissolution rate of the non-exposed areas was calculated by the following formula (unit: μm/s):
non-exposed area dissolution rate = a/T 2
Contrast = dissolution rate of exposed areas/dissolution rate of unexposed areas, contrast greater than 5 can meet photosensitive application requirements.
(2) Adhesion test
Coating the resin composition glue solution on a 4-inch substrate by using a spin coater, and placing the resin composition glue solution on a heating table for soft drying at 120 ℃ for 3min to obtain a resin film with the film thickness of 10-20 mu m. The resin film was patterned into 10 rows by 10 columns of squares using a dicer (BYK-Gardner A-5125) and then placed in a vacuum anaerobic oven (MOLZK-32D 1, duckweed family technology Co., ltd.) for heat treatment.
The specific process of the heat treatment is as follows: firstly, carrying out heat treatment at 150 ℃ for 30min, then carrying out heat treatment at the temperature of 350 ℃ for 1h, and then cooling to room temperature to finally obtain the resin cured film.
The obtained cured film was subjected to a PCT test (121 ℃ C., 2 atm saturated steam) for 200 hours in a high-pressure accelerated aging tester (PCT-30, dongguan, inc.), and after the PCT test was completed, a peeling test was performed with a 3M dedicated adhesive tape with reference to a cross-cut test of national standards GB/T9286-1998 paint and varnish film, and the number of peeled sheets was recorded as the peeling condition after the PCT test.
The specific evaluation criteria are as follows:
"best": the number of the stripped grids is less than 5;
"Jia": the number of the grids under stripping is less than or equal to 5 and less than 10;
"slightly good": the number of the grids under stripping is less than or equal to 10 and less than 30;
"difference": the number of the stripped grids is more than or equal to 30.
The substrate selected in the embodiment of the invention is a silicon, silver or copper substrate.
(3) Film Forming test
The low-temperature curing resin composition glue solution is coated on a 4 inch silicon substrate by using a spin coater, and is placed on a heating table for soft drying at 120 ℃ for 3 minutes, so as to obtain a resin film with the film thickness of 10-20 mu m.
Then, it was placed in a vacuum anaerobic oven (MOLZK-32D 1, duckweed family technology Co., ltd.) for heat treatment. The specific process of the heat treatment is as follows: the resin curing film is finally obtained by performing heat treatment at 150 ℃ for 30min, then performing heat treatment at 350 ℃ for 1h by programming, and then cooling to room temperature.
And (3) placing the silicon wafer with the resin cured film in hydrofluoric acid solution, and carrying out corrosion stripping on the silicon wafer.
The specific evaluation criteria are as follows:
"you": film forming, folding without breaking;
"good": forming a film, and breaking the folded part;
"difference": cannot form a film and is crushed into pieces.
In addition, when the film formability is "poor", the tensile strength and the electrical property cannot be tested.
(4) Heat resistance test
The heat resistance of a material is typically measured by a 5% thermal weight loss temperature.
10mg of the resin cured film obtained in the film forming property test (3) above was filled into an aluminum standard container, and measured by a thermogravimetric analyzer (model: TGA55, manufacturer: TA).
Test conditions: the temperature was raised from room temperature to 600℃at a heating rate of 10℃per minute.
(5) Tensile Strength test
Cutting the resin cured film obtained in the film forming property test (3) into sample strips (length <3cm, width <8 mm) meeting the test requirements by using a die, and carrying out tensile strength test on the sample strips by using a dynamic thermo-mechanical analyzer (model: DMA850, manufacturer: TA company), wherein the tensile force range is 0-18N, and the speed is: 3N/min; temperature range: 30-400 ℃, the rate is: 3 ℃/min.
(6) Chemical resistance
The cured film was immersed in 10wt% aqueous sodium hydroxide (NaOH), 10vol% aqueous sulfuric acid, and N-methylpyrrolidone (NMP) at 25 ℃ for 15 minutes, rinsed with deionized water for 10 minutes, and air-dried, and then observed under an optical microscope for abnormalities such as cracks.
(7) Electrical performance testing
And (5) performing breakdown voltage resistance electrical performance test by referring to national standard GB/T1408.2-2006.
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from the test data in table 4, the present invention provides an alkynyl-containing compound which is applied to a photosensitive resin composition to improve not only the adhesion between a cured film and a substrate but also the film forming property, and to enhance the mechanical properties, thermal stability, chemical resistance and electrical properties of the cured film, and the effect is not ideal when a silane compound and an alkyne compound are not added or only added in a direct mixing manner. In addition, the alkynyl-containing compound is applied to the photosensitive resin composition, and the photosensitive resin composition obtained at the moment has large solubility difference between an exposed part and an unexposed part in an alkaline developing solution after an exposure process, has excellent contrast and can meet the requirement of a positive photosensitive resin composition.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (10)

1. An alkynyl-containing compound characterized by having a structure represented by formula (1):
wherein X is any one of the structures shown in the general formulas (2) and (3), and the dotted line is an access site:
y is an organic group containing a benzene ring and/or a pyridine ring;
R 1 is a hydrocarbon group having 1 to 10 carbon atoms;
R 2 、R 3 are respectively and independently selected from R 1 O, hydrogen atom, C1At least one of hydrocarbon groups of 10;
n is any integer from 1 to 3.
2. The alkynyl-containing compound of claim 1, wherein R 1 Is a hydrocarbon group having 1 to 4 carbon atoms;
preferably, R 1 Is alkyl with 1-4 carbon atoms;
preferably, R 1 Methyl or ethyl;
preferably, R 2 、R 3 Independently is a hydrocarbon group having 1 to 4 carbon atoms;
preferably, R 2 、R 3 Independently is alkyl with 1-4 carbon atoms;
preferably, R 2 、R 3 Independently methyl or ethyl.
3. The alkynyl-containing compound of claim 1, wherein Y is any of the structures of formulae (4) to (6), and the dotted line is the access site:
4. a process for producing an alkynyl-containing compound according to any one of claims 1 to 3, wherein the raw materials (a) and (b) undergo tertiary amination or ring opening reaction under an inert gas atmosphere;
the raw material (b) is alkyne containing benzene ring and/or pyridine ring substituted by hydroxyl;
the raw material (a) has a structure shown in the following formula (7-1) and/or formula (7-2);
r in the formulae (7-1), (7-2) 1 、R 2 、R 3 Is defined in claim 1Consistent;
preferably, the raw material (b) is selected from one or more of the following formulas (8-1), (8-2) and (8-3),
preferably, the molar ratio of raw material (a) to raw material (b) is 1: (0.5-2);
preferably, feedstock (a) and feedstock (b) are reacted in an aprotic solvent under the catalysis of a basic catalyst;
preferably, the reaction temperature is 60-120 ℃ and the reaction time is 6-12 h.
5. A positive photosensitive resin composition is characterized by comprising the following components:
component (a): polyimide having a hydroxyl structure or a precursor resin thereof;
component (b): an alkynyl-containing compound according to any of claims 1 to 3;
component (c): a sensitizer;
component (e): a solvent;
preferably, the photosensitizer is a photoacid generator;
preferably, the sensitizer is a quinone diazide compound;
preferably, the positive photosensitive resin composition further comprises component (d): a surfactant;
preferably, the surfactant is an acrylic copolymer;
preferably, the surfactant is POLYFLOW No 77.
6. The positive photosensitive resin composition according to claim 5, wherein the polyimide having a hydroxyl structure or a precursor resin thereof is blocked with a blocking agent;
preferably, the end-capping agent is one or more of monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, and monoacid ester compound.
7. The positive photosensitive resin composition according to claim 5, wherein the weight ratio of the component (b) to the component (a) is (0.1 to 20): 100;
preferably, the weight ratio of the component (b) to the component (a) is (1 to 10): 100.
8. a method for producing the positive photosensitive resin composition according to any one of claims 5 to 7, comprising: and (3) dissolving and dispersing each component in the component (e) uniformly, and filtering to obtain the product.
9. A polyimide film prepared from the positive photosensitive resin composition according to any one of claims 5 to 7;
preferably, the polyimide film has a cured relief pattern.
10. A semiconductor device comprising the polyimide film according to claim 9.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007156243A (en) * 2005-12-07 2007-06-21 Nissan Chem Ind Ltd Positive photosensitive resin composition and its cured film
WO2008123507A1 (en) * 2007-04-02 2008-10-16 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition, cured film thereof, and display element
US20120251949A1 (en) * 2009-12-28 2012-10-04 Toray Industries, Inc. Positive type photosensitive resin composition
CN109313387A (en) * 2016-06-15 2019-02-05 东丽株式会社 Photosensitive polymer combination
CN111830786A (en) * 2020-07-17 2020-10-27 波米科技有限公司 Photosensitive resin composition containing silane coupling agent
CN114315686A (en) * 2021-09-23 2022-04-12 波米科技有限公司 Alkynyl-containing diamine, preparation method thereof and application thereof in preparation of photosensitive resin composition
CN114755883A (en) * 2021-11-24 2022-07-15 波米科技有限公司 Photosensitive resin composition, and preparation method and application thereof
CN114989433A (en) * 2022-08-08 2022-09-02 烟台三月科技有限责任公司 Resin, positive photosensitive resin composition and application
CN115974762A (en) * 2022-12-12 2023-04-18 波米科技有限公司 Diamine monomer with bulky alkynyl side group, polybenzoxazole precursor, photosensitive resin composition and application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007156243A (en) * 2005-12-07 2007-06-21 Nissan Chem Ind Ltd Positive photosensitive resin composition and its cured film
WO2008123507A1 (en) * 2007-04-02 2008-10-16 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition, cured film thereof, and display element
US20120251949A1 (en) * 2009-12-28 2012-10-04 Toray Industries, Inc. Positive type photosensitive resin composition
CN109313387A (en) * 2016-06-15 2019-02-05 东丽株式会社 Photosensitive polymer combination
CN111830786A (en) * 2020-07-17 2020-10-27 波米科技有限公司 Photosensitive resin composition containing silane coupling agent
CN114315686A (en) * 2021-09-23 2022-04-12 波米科技有限公司 Alkynyl-containing diamine, preparation method thereof and application thereof in preparation of photosensitive resin composition
CN114755883A (en) * 2021-11-24 2022-07-15 波米科技有限公司 Photosensitive resin composition, and preparation method and application thereof
CN114989433A (en) * 2022-08-08 2022-09-02 烟台三月科技有限责任公司 Resin, positive photosensitive resin composition and application
CN115974762A (en) * 2022-12-12 2023-04-18 波米科技有限公司 Diamine monomer with bulky alkynyl side group, polybenzoxazole precursor, photosensitive resin composition and application thereof

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