WO2021232248A1 - Polysulfonamide polymer, negative photosensitive composition containing polysulfonamide polymer and application thereof - Google Patents

Polysulfonamide polymer, negative photosensitive composition containing polysulfonamide polymer and application thereof Download PDF

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WO2021232248A1
WO2021232248A1 PCT/CN2020/091094 CN2020091094W WO2021232248A1 WO 2021232248 A1 WO2021232248 A1 WO 2021232248A1 CN 2020091094 W CN2020091094 W CN 2020091094W WO 2021232248 A1 WO2021232248 A1 WO 2021232248A1
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polymer
polysulfonamide
mass
parts
film
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PCT/CN2020/091094
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French (fr)
Chinese (zh)
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崔庆洲
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崔国英
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Priority to CN202080100667.2A priority Critical patent/CN115581120A/en
Priority to PCT/CN2020/091094 priority patent/WO2021232248A1/en
Publication of WO2021232248A1 publication Critical patent/WO2021232248A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/30—Polysulfonamides; Polysulfonimides
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

Definitions

  • the present invention relates to a photosensitive dielectric material used in the semiconductor field, in particular to a negative photosensitive composition containing a polysulfonamide polymer, a cured product prepared therefrom, and its application in semiconductor packaging.
  • Advanced packaging is considered to be the new technology most likely to achieve this technological breakthrough. Advanced packaging connects multiple chips or packages together through direct chip connection chip, chip connection package, package connection package and other means.
  • This optimized system integration not only realizes short-distance and rapid transmission between signals, but also effectively The energy consumption and heat generation of functional devices are reduced. In addition, the most important thing is that this system integration can also reduce a large number of functions to a smaller area, thereby providing unlimited innovation possibilities for the current mobile computing innovation based on smart phones.
  • the redistribution layer material is generally composed of copper leads wrapped in an insulating dielectric material. These copper leads introduce or export signals to the chip to realize signal transmission between the chip and the outside world. These micron-sized copper leads have been difficult to efficiently prepare with traditional mechanical methods. At this stage, electrochemical deposition methods have gradually become the mainstream method for preparing copper leads with the assistance of photosensitive dielectric materials. In addition, these photosensitive dielectric materials will remain in the device after the preparation process is completed and become permanent insulating materials that wrap the copper leads.
  • this application requires insulating materials not only to have excellent lithography performance, but also to have good insulation performance, mechanical properties, adhesion, high temperature stability, low water absorption, high chemical resistance, etc. It is precisely due to the aforementioned comprehensive requirements that photosensitive polyimide (PI), polybenzobisoxazole (PBO), benzocyclobutene (BCB) and other materials are due to their excellent resistance
  • PI photosensitive polyimide
  • PBO polybenzobisoxazole
  • BCB benzocyclobutene
  • the properties of high-temperature materials have gradually become the main materials in this field.
  • these new high-performance insulating materials also have great prospects in other applications such as interlayer insulating buffer films, cover coatings or surface protection films.
  • the main purpose of the present invention is to overcome the shortcomings of the existing photosensitive photosensitive optical dielectric materials, and provide a new type of polysulfonamide polymer mainly used for negative photosensitive photosensitive optical dielectric materials, the polysulfonamide polymer
  • the material not only has excellent mechanical properties, but also has good insulation properties, adhesion, high temperature stability, low water absorption, high chemical resistance and other advantages.
  • Another main purpose of the present invention is to provide a negative photosensitive composition containing polysulfonamide polymer.
  • the technical problem to be solved is to enable these compositions to be heat-treated at a lower temperature (less than or equal to 250°C). It has effective cross-linking ability and excellent photolithography performance, so that cured products with embossed microstructure can be prepared.
  • Another object of the present invention is to provide a patterned cured product prepared by using the above-mentioned novel photosensitive polysulfonamide polymer composition.
  • Another object of the present invention is to provide the application of the above-mentioned cured product in the redistribution layer, the interlayer insulation buffer film, the cover coating or the surface protection film.
  • Another object of the present invention is to use the above-mentioned cured product in related electronic products.
  • the polysulfonamide polymer has the following repeating unit structural formula, where m and n represent the number of structural units in the polymer, which are integers from 1 to 99.
  • X1 and X2 in the general formula (1) are divalent aromatic linking groups, which may be different or the same and have the following general formulas (2), (3), Or the group shown in (4);
  • R 1 , R 2 , R 3 , and R 4 respectively represent a hydrogen atom or a monovalent organic group
  • the Q is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene;
  • the T is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -met, -p-phenylene, Wherein R 5 to R 12 are the same or different monovalent organic groups, selected from H, CH 3 , or CF 3 ;
  • Y in the polysulfonamide polymer of the general formula (1) is a divalent aromatic group selected from structural units represented by the following formula (5) or (6):
  • U in the general formula (6) is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -between , -P-phenylene.
  • the polysulfonamide polymer is a block copolymer or a random copolymer, and its weight average molecular weight ranges from 5,000 to 200,000.
  • the negative photosensitive composition containing polysulfonamide polymer proposed according to the present invention includes:
  • Photoacid generator The content in the composition is preferably 0.1-20 parts by mass, and more preferably 1-10 parts by mass relative to 100 parts by mass of component (A);
  • (C) Crosslinking agent The content in the composition is preferably 2-50 parts by mass, more preferably 8-40 parts by mass relative to 100 parts by mass of component (A);
  • (D) Solvent The content in the composition relative to 100 parts by mass of the component (A) is preferably 50 to 800 parts by mass, more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass.
  • the component (B) is at least one photoacid generator.
  • the photoacid generator is selected from but not limited to ionic compounds including sulfur salts, phosphonium salts or iodonium salts; non-ionic compounds include oxime sulfonate, sulfonate compound or quinone diazide compound; or mixtures thereof . From the viewpoint of sensitivity and imaging properties, oxime sulfonate compounds are preferred; and/or
  • the component (C) contains at least one alkoxy compound/hydroxy compound having -CH 2 OR (R is a hydrogen atom or a monovalent organic group); epoxy compound; oxetanyl Compounds or vinyl ether-based compounds, preferably compounds having alkoxyalkyl groups such as hydroxymethyl and alkoxymethyl; and/or
  • the components of the composition are dissolved in a solvent (D), and the solvent includes at least one compound selected from the following solvents: ester, ether, ether-ester, ketone, ketone-ester, aromatic compound , And/or halogenated hydrocarbon solvents.
  • the cured product with embossed pattern prepared from the negative photosensitive composition containing polysulfonamide polymer according to the present invention is prepared by a method including the following steps:
  • the temperature of the heat treatment is less than or equal to 250°C.
  • the aforementioned cured product with embossed patterns is a cured product film with micro-structured embossed patterns.
  • the purpose of the present invention and the solution of its technical problems are also achieved by adopting the following technical solutions.
  • the cured product with embossed patterns proposed according to the present invention is applied to a redistribution layer, an interlayer insulation buffer film, a cover coating or a surface protection film.
  • An electronic device includes the redistribution layer, the interlayer insulation buffer film, the cover coating or the surface protection film.
  • the present invention discloses a polysulfonamide polymer, a negative photosensitive composition containing the polysulfonamide polymer, and applications thereof.
  • the negative photosensitive composition containing polysulfonamide polymer is composed of the following raw materials in a certain weight ratio: polysulfonamide polymer, photoacid generator, crosslinking agent, solvent and some other components.
  • the composition prepares a polysulfonamide cured film under relatively low curing temperature conditions ( ⁇ 250°C), and the cured film can be used as a redistribution layer, an interlayer insulation buffer film, a covering coating or a surface protection film material.
  • the negative photosensitive composition containing polysulfonamide polymer, the cured product prepared therefrom, and the application in semiconductor packaging of the present invention have at least the following advantages:
  • a novel polysulfonamide composition is used in the present invention.
  • this kind of film can prepare a film with embossed microstructure under lower temperature (less than or equal to 250°C) heat treatment conditions.
  • the various components of the composition and the heat treatment conditions By adjusting the ratio of various monomers in the film, the various components of the composition and the heat treatment conditions, the dissolution rate and mechanical properties of the film and various other material properties can be well controlled and optimized.
  • this resin composition maintains the general advantage that most negative photosensitive materials have excellent adhesion to the substrate.
  • monomers containing fluorine atoms in the polymer synthesis process these new materials will significantly improve their performance in reducing material water absorption, so that the cured film prepared from the composition is more suitable for the current advanced Packaging process requirements.
  • the technical solution of the present invention has many of the above-mentioned advantages and practical value, and there is no similar design published or used in similar products, and it is indeed innovative. It has both formula and function. Larger improvements have made great progress in technology, and have produced easy-to-use and practical effects, and have improved multiple functions compared with existing products, so they are more suitable for practical use and have a wide range of industrial use values , Sincerely a novel, progressive and practical new design.
  • Figure 1 is an embodiment of the present invention, which involves the manufacture of a redistribution layer.
  • the polysulfonamide polymer having the above formula (1) is characterized in that the polymer has the structural formula of the repeating unit depicted in the general formula (1), where m and n represent the number of structural units in the polymer, and are 1 to An integer of 99. It is preferable from the viewpoint of film-forming properties and control of the dissolution rate, and m and n are preferably integers of 5 to 99.
  • X1 and X2 in the general formula (1) are divalent aromatic linking groups, and they may be different or the same and have groups represented by the following general formulas (2), (3), or (4).
  • the R 1 , R 2 , R 3 , and R 4 respectively represent a hydrogen atom or a monovalent organic group, such as a methyl group.
  • the Q in it represents a direct bond or other divalent organic groups, such as O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene.
  • divalent organic groups such as O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene.
  • the T mentioned here represents a direct bond or other divalent organic groups, such as O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene.
  • R 5 to R 12 are the same or different monovalent organic groups, such as H, CH 3 , or CF 3 .
  • Y in the general formula (1) is a divalent aromatic group selected from structural units represented by the following formula (5) or (6):
  • U in the general formula (6) is a direct bond or other divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH ), (CH 2 ) p (1 ⁇ p ⁇ 10), (CF 2 ) q (1 ⁇ q ⁇ 10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted-ortho, -M, -p-phenylene.
  • the method for synthesizing the above-mentioned polysulfonamide polymer is as follows: in an inert atmosphere, dissolve the diamine mixture and 2-methylpyridine in N-methylpyrrolidone, and then add dropwise an equimolar amount of sulfonate to the diamine monomer.
  • the acid chloride monomer (dissolved in N-methylpyrrolidone) was reacted in an ice bath at 0-5°C for 1 hour.
  • the resulting polymer solution was settled in a deionized water medium, filtered, and dried in vacuum at 80-120°C to obtain a polymer solution.
  • Sulfonamide polymer Sulfonamide polymer.
  • the above-mentioned polysulfonamide polymer may have a weight average molecular weight of 5,000 to 200,000. It is preferably a weight average molecular weight of 10,000 to 120,000 in molecular weight.
  • the molecular weight is measured by a gel permeation chromatography (GPC) method and calculated using a standard polystyrene calibration curve.
  • the above-mentioned polysulfonamide polymer may be a block copolymer or a random copolymer.
  • the end of the main chain can also be blocked with a blocking agent such as a monoamine or a monochloride compound.
  • the introduction ratio of the monoamine used as the blocking agent is preferably 0.5 mol to 30 mol% with respect to all amine components.
  • aniline, 2-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene can be selected , 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene; as mono-acid chloride compounds: you can choose 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and other monocarboxylic acids and their carboxyl generating acid chloride
  • the monoacid chloride compound obtained by chemical conversion can also choose terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7 -Dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and other dicarboxylic acid monoch
  • the above-mentioned polysulfonamide polymer is usually developed using an alkaline aqueous solution. Therefore, polysulfonamide polymers that are soluble in alkali solvents are preferred.
  • a substrate such as a silicon wafer and heated to dry to remove the solvent to form a resin film with a thickness of about 10 microns; then it is immersed in tetramethylammonium hydroxide at 20 ⁇ 25°C In an aqueous solution; the difficulty of dissolving the component (A) in an alkaline aqueous solution is judged based on the time required for the complete dissolution of the film.
  • the transmittance of the i-line directly affects the resolution of the photosensitive composition during the process.
  • the polysulfonamide polymer preferably has a monomer structure containing fluorine atoms with better light transmittance.
  • the fluorine-containing composition is also beneficial to reduce the immersion and swelling effect of the solution on the film during development, thereby inhibiting the exudation from the surface, and can also reduce the water absorption of the composition after curing.
  • the stress of the cured film obtained by coating the composition containing the polysulfonamide polymer represented by the formula (1) on the substrate and heat curing is preferably 30 MPa or less. If the stress is less than or equal to 30 MPa, after curing into a film, the warpage of the wafer can be effectively suppressed, which is suitable for the application of the wafer reconstitution (wafer reconstitution) process which is widely used in the current advanced packaging process.
  • the polysulfonamide polymer from the comprehensive perspective of light transmittance, water absorption, alkali solubility and stress, X1 and X2 in the general formula (1) are divalent aromatic linking groups, and they At least one of them is preferably a trifluoromethyl group-containing structural unit represented by the following general formula (7) and/or a phenyl ether group-containing structural unit represented by the following general formula (8).
  • Y in the polysulfonamide polymer general formula (1) also preferably has a phenyl ether-based structural unit represented by the general formula (8).
  • the synthesis methods of polymer-2 and polymer-3 refer to Synthesis Example 1, except that the mole fraction of the diamine monomer is adjusted to: 2,2'-bis(trifluoromethyl)diaminobiphenyl (75mmol), 4 ,4'-Diaminodiphenyl ether (25mmol) (Synthesis Example 2) and 2,2'-bis(trifluoromethyl)diaminodiphenyl (25mmol), 4,4'-Diaminodiphenyl ether (75mmol) ) (Synthesis Example 3). Other conditions/processes are exactly the same as in Synthesis Example 1.
  • the synthesis methods of polymer-5 and polymer-6 refer to Synthesis Example 4, except that the mole fraction of the diamine monomer is adjusted to: 2,2'-bis(trifluoromethyl)diaminobiphenyl (71.25mmol), 4,4'-diaminodiphenyl ether (23.75mmol) (synthesis example 5) and 2,2'-bis(trifluoromethyl)diaminodiphenyl (23.75mmol), 4,4'-diaminodiphenyl Ether (71.25 mmol) (Synthesis Example 6). Other conditions/processes are exactly the same as in Synthesis Example 4.
  • the synthesis methods of polymer-8 and polymer-9 refer to Synthesis Example 7, except that the mole fraction of the diamine monomer is adjusted to: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (75mmol ), 4,4'-diaminodiphenyl ether (25mmol) (Synthesis Example 8) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (25mmol), 4,4'-bis Aminodiphenyl ether (75 mmol) (Synthesis Example 9).
  • the other conditions/processes are exactly the same as in Synthesis Example 7.
  • polymer-11 and polymer-12 refer to Synthesis Example 10, except that the mole fraction of the diamine monomer is adjusted to: 2,2-bis[4-(4-aminophenoxy)phenyl]-1 ,1,1,3,3,3-hexafluoropropane (75mmol), 4,4'-diaminodiphenyl ether (25mmol) (synthesis example 11) and 2,2-bis[4-(4-aminobenzene) (Oxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (25 mmol), 4,4'-diaminodiphenyl ether (75 mmol) (Synthesis Example 12).
  • the synthetic methods of polymer-14 and polymer-15 refer to Synthesis Example 13, except that the mole fraction of the diamine monomer is adjusted to: 2,2'-bis(trifluoromethyl)diaminobiphenyl (75mmol), 2 ,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (25mmol) (Synthesis Example 14) and 2,2'-bis( Trifluoromethyl)diaminobiphenyl (25mmol), 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (75mmol) ) (Synthesis Example 15).
  • the synthesis methods of polymer-17 and polymer-18 refer to Synthesis Example 16, except that the mole fraction of the diamine monomer is adjusted to: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (75mmol ), 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (25mmol) (Synthesis Example 17) and 2,2- Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (25mmol), 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3 -Hexafluoropropane (75 mmol) (Synthesis Example 18).
  • the mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C.
  • the obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product.
  • the synthetic methods of polymer-20 and polymer-21 refer to Synthesis Example 19, except that the mole fraction of the diamine monomer is adjusted to: p-phenylenediamine (75mmol), 4,4'-diaminodiphenyl ether (25mmol) (Synthesis Example 20) and p-phenylenediamine (25 mmol) and 4,4'-diaminodiphenyl ether (75 mmol) (Synthesis Example 21).
  • the other conditions/processes are exactly the same as in Synthesis Example 19.
  • Synthesis examples 22 to 25 are not mixed polymers, but are also included in the claims of the present invention.
  • X1 and X2 expressed in the general formula (1) of the component (A) according to claim 1 may be the same or different divalent aromatic linking groups.
  • the following polymers 22-25 (the structural formula is as follows) can still be synthesized by the method of the aforementioned Synthesis Example 1.
  • the negative photosensitive composition of the present invention contains at least (A) a polysulfonamide polymer (structure such as general formula (1)), (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent .
  • A a polysulfonamide polymer (structure such as general formula (1))
  • B a photoacid generator
  • C a crosslinking agent
  • D a solvent
  • each component used in the composition of the present invention will be described in detail.
  • the polysulfonamide polymer, performance and synthesis of component A refer to the introduction in the first part above.
  • the photoacid generator as the component (B) in the present invention is a compound that generates an acid when irradiated with light.
  • the photoacid generated by exposure will cause the polymer in the film to crosslink, thereby significantly reducing the solubility of the exposed part.
  • these photoacid generators do not undergo a chemical reaction and thus maintain good solubility in the developer. As a result, the dissolution rate of the exposed area and the non-exposed area (dark area) will be quite different (contrast), and a film with a microstructure relief pattern will be obtained after the development step.
  • the photoacid generator is selected from but not limited to ionic compounds including sulfur salts, phosphonium salts or iodonium salts; non-ionic compounds include oxime sulfonate, sulfonate compound or quinone diazide compound; or mixtures thereof . From the viewpoint of sensitivity and imageability, oxime sulfonate compounds are preferred.
  • the oxime sulfonate compound can obtain a photoacid compound having good sensitivity to the i-line (wavelength of 365 nm), h-line (wavelength of 405 nm), and g-line (wavelength of 436 nm) of a mercury lamp which is a normal ultraviolet light. Many oxime sulfonate compounds can be purchased through commercial channels.
  • the following formula (9) represents several common oxime ester compounds.
  • the content of the oxime ester compound is preferably 0.1 to 20 parts by mass, and more preferably 1.0 to 10.0 parts by mass relative to 100 parts by mass of the component (A).
  • the exposed part of the polymer will have a better degree of cross-linking to obtain a practical relief pattern.
  • component (B) component can be used alone or in combination of two or more
  • the (C) crosslinking agent component in the photosensitive polysulfonamide composition of the present invention is capable of interacting with the component (A) polysulfonamide polymer in the steps of exposing and heating and curing the negative photosensitive composition. Compounds that undergo cross-linking reactions. Due to these effective crosslinking reactions, the cured film obtained from the polysulfonamide polymer will have excellent photosensitive resolution and achieve excellent adhesion, mechanical properties, and Corrosion resistance to chemical reagents, thus avoiding the use of high post-curing temperatures in the process.
  • the crosslinking agent preferably contains at least one alkoxy compound/hydroxyl group having -CH 2 OR (R is a hydrogen atom or a monovalent organic group) Compounds; epoxy compounds; oxetanyl compounds or vinyl ether-based compounds. From the viewpoint of the mechanical properties of the cured film and the high reactivity during low-temperature curing, it is preferably one having a hydroxyalkyl group such as a hydroxyl group and a hydroxymethyl group, or an alkoxyalkyl group such as an alkoxymethyl group, as shown in the following formula (10) The compound represented.
  • the content of the crosslinking agent (C) is preferably 2-50 parts by mass, and more preferably 8-40 parts by mass relative to 100 parts by mass of the component (A). If the cross-linking agent is less than 2 parts by mass, it will not achieve significant cross-linking and improve the corrosion resistance of chemical reagents; if the cross-linking agent is more than 50 parts by mass, it may reduce the mechanical properties of the material.
  • the component (C) may be used singly or in combination of two or more of the above-mentioned crosslinking agents.
  • the component (D) A component is used as a solvent, and the said (A)-(C) component is melt
  • the component (D) may include at least one compound selected from the following solvents: ester, ether, ether-ester, ketone, ketone-ester, aromatic compound, and/or halogenated hydrocarbon solvent. Generally, as long as it can fully dissolve other components in the negative photosensitive composition and is suitable for the photolithography process, there is no particular limitation.
  • Some common solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -caprolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide , 2-Methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate Ester, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, 1,3-butanediol acetate, cyclohexanone, tetrahydrofuran, etc.
  • a solvent system mainly composed of ⁇ -butyrolactone, N-methyl-2-pyrrolidone, and cyclopentanone from the viewpoint of excellent solubility and coating properties of the
  • the content of the component (D) is not particularly limited, but mainly from the viewpoint of controlling the film thickness, it is preferably 50 to 800 parts by mass relative to 100 parts by mass of the component (A), more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass
  • the resin composition of the present invention may also contain other components as necessary, such as an anticorrosive agent, a thickener, a softening agent, a dissolution accelerator, a leveling agent, and the like.
  • an anticorrosive agent such as sodium sulfate, sodium sulfate, sodium sulfate, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium
  • azole compound for example, 1H-triazole, 1H-benzotriazole, 2-(2H-benzotriazol-2-yl)p-cresol, 1,5-dimethyltriazole, 4 ,5-Diethyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole , 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole , 5-benzyl-1H-triazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethyl Benzyl)phenyl)-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxy
  • the content of the anti-corrosion agent is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the component (A).
  • Tackifiers can be selected from organosilane compounds and aluminum-based adhesive additives including tris(ethylacetoacetate) aluminum, tris(acetylacetonate) aluminum, and ethyl aluminum diisopropyl acetoacetate. It is preferable to use an organosilane compound from the viewpoint of improving the adhesion to a substrate such as copper.
  • Organosilane compounds include: 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane, vinyl triethoxy Silane, vinyl trimethoxy silane, ⁇ -ureidopropyl triethoxy silane, ⁇ -glycidoxy propyl triethoxy silane, ⁇ -glycidoxy propyl trimethoxy silane, ⁇ -Methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, amino Triethoxysilylpropyl ethyl formate, 3-(triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane,
  • the content of the thickener component in the composition is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the component (A) from the viewpoint of improving the adhesion to the substrate.
  • the softener can improve the flexibility of the cured film prepared therefrom to increase the elongation when the material breaks.
  • a softener compounds such as polyols, polyesters, and polyhydroxy esters with different molecular weights can be selected. These softeners can be used alone or in combination of two or more. If the softener component is selected, its content in the composition is preferably 1 to 40 parts by mass relative to 100 parts by mass of the component (A).
  • the dissolution accelerator can increase the dissolution speed of the unexposed part to improve the resolution and development contrast of the micropattern.
  • the dissolution accelerator for example, a compound having a hydroxyl group or a carboxyl group, etc. can be cited. Examples of compounds having a hydroxyl group include p-cumyl phenol, resorcinols, bisphenols, other linear or non-linear phenolic compounds, and 2 to 5 diphenylmethanes. Phenolic substituents, 1 to 5 phenolic substituents of 3,3-diphenylpropane, etc. These dissolution accelerators can be used alone or in combination of two or more.
  • the content of the dissolution accelerator component in the composition is preferably 1 to 50 parts by mass relative to 100 parts by mass of the component (A).
  • a surfactant can be added to the composition as a leveling agent.
  • surfactants include polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, and polyoxyethylene lauryl ether. Oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, etc.
  • Some examples that can be purchased directly from the market include Megafac F171, F173 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.); organosiloxane KP341, KBM303, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.); and some containing fluorine Surfactants PolyFox PF-6320 (Omnova Solutions), Fluorad FC430, FC171 (manufactured by Sumitomo 3M Co., Ltd.), etc.
  • the content of the surfactant to be used is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the component (A).
  • Example 1 Polymer-1 (100 parts by mass) obtained in Synthesis Example 1, B-1 as a photoacid (3 parts by mass relative to polymer-1), and C-1 as a crosslinking agent (20 parts by mass) was dissolved in cyclopentanone (D-1, 180 parts), and E-1 (1.5 parts by mass) as an anticorrosive agent, F-1 (2 parts by mass) as a thickener, as H-1 (0.05 parts by mass) of the leveling agent to obtain the negative photosensitive resin composition of the present invention.
  • H-1 Leveling agent: PolyFox PF-6320 (OMNOVA Solutions Inc.)
  • NA It means that there is no such component in the composition.
  • the photosensitive resin composition (also called varnish) obtained from the above examples/comparative examples was filtered through a polytetrafluoroethylene filter membrane to obtain the final negative photosensitive resin composition.
  • a polytetrafluoroethylene filter membrane with a pore size of 0.45-3 microns can be selected.
  • the above varnish is made into a polysulfonamide resin film with a thickness of about 10 micrometers coated on the substrate material according to the method described in claim 6 above.
  • these polysulfonamide resin films and the cured product films with embossed patterns prepared therefrom will be further described.
  • the manufacturing method of a patterned cured product prepared from the polysulfonamide composition of the present invention includes the following steps:
  • Resin film forming step a step of applying the polysulfonamide polymer composition according to claims 1 to 5 on a substrate and heating and drying to remove the solvent to form a photosensitive resin film.
  • the substrate include semiconductor substrates such as Si substrates (silicon wafers), ceramic substrates, metal substrates (including copper substrates, aluminum substrates, copper alloy substrates, etc.), silicon nitride substrates, and the like.
  • the coating method may be a spin coating method, a spray method, a dipping method, etc., and from the viewpoint of controlling the film thickness, a spin coating method using a spin coater is preferred.
  • a hot plate, oven, etc. can be used for heating and drying.
  • the heating and drying temperature is preferably 90 to 150°C, more preferably 90 to 130°C.
  • the thickness of the resin film is preferably 1 to 50 ⁇ m, more preferably 1 to 30 ⁇ m.
  • Exposure step a step of patterning the photosensitive resin film using a mask.
  • the pattern exposure is exposed in a predetermined pattern through a photomask, for example.
  • the active light rays to be irradiated include ultraviolet rays such as i-rays, visible light rays, and radiation rays, and i-rays are preferred.
  • a scanning exposure machine, a projection exposure machine, a stepping exposure machine, etc. can be used as the exposure device.
  • development step By performing the development step, a resin film with a microstructure relief pattern can be obtained.
  • development is performed by methods such as a dipping method and a rotary spray method.
  • the developer can remove the unexposed part of the film to obtain a relief pattern.
  • the development time is generally 10 seconds to 15 minutes, and from the viewpoint of productivity improvement and process control, it is preferably 20 seconds to 5 minutes.
  • inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia can be used; organic amines such as ethylamine, triethanolamine, and diethylamine can also be used; and tetramethylammonium hydroxide can also be used (TMAH), aqueous solutions of quaternary ammonium salts such as tetrabutylammonium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • water-soluble organic solvents such as methanol and ethanol or surfactants can be added in an appropriate amount as needed to enhance the effect.
  • tetramethylammonium hydroxide aqueous solution is preferable.
  • TMAH aqueous solution of TMAH with a concentration of 2.38%.
  • concentration of TMAH in the alkaline developer can be appropriately diluted to adjust the film dissolution rate in the exposed area and the non-exposed area to obtain the optimal contrast during development.
  • washing liquid can be used to remove the developer liquid, thereby obtaining a patterned film.
  • the rinse liquid distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. can be used alone or in combination.
  • the heating treatment step is a process of heating and curing the embossed patterned resin film to obtain the optimal physical properties of the material.
  • the relief pattern obtained by the above development is heated to convert it into a cured relief pattern.
  • a method using a hot plate or an oven can be selected, and the heating temperature is preferably 250°C or less, and more preferably a temperature of 180 to 230°C.
  • the time for the heat treatment is usually 30 minutes to 4 hours, and more preferably 30 minutes to 2 hours from the time required for the crosslinking reaction.
  • the atmosphere of the heat treatment may be performed in air or in an atmosphere of inert gas such as nitrogen and argon. In view of the ability to prevent oxidation of the patterned resin film and cost considerations, it is preferable to heat and cure in a high-purity nitrogen ( ⁇ 99.999%) atmosphere.
  • the cured product of the present invention is a cured polymer resin film obtained by the above-mentioned treatment process, and this film may be the cured film with embossed patterns as described above, or it may be a cured film without a pattern.
  • a cured film it may be laminated in the semiconductor element by direct contact, or it may be laminated
  • Figure 1 (a schematic diagram of a structural section) is a construction of a redistribution layer structure using the composition of the present invention and its embodiments. It should be noted that the ratio of film thickness to device size in the graph does not represent the true ratio.
  • the signal can realize the signal input/output function between the chip (Al Pad: aluminum contact plate electrode) and the outside (Solder Bump: solder ball).
  • the two-layer wiring structure is realized by copper redistribution layer leads (Cu RDL) wrapped on the insulating material polymer layer (polymer layer 1 and polymer layer 2).
  • the copper leads connect the aluminum sheet on the chip to the pad electrode (Al Pad) and the solder ball (Solder Bump).
  • the solder balls will be connected to other packages or the motherboard in the next process after packaging to realize the connection of the package to the package or the package to the motherboard.
  • the connection between the solder balls and the copper leads here is achieved through the UBM Stud.
  • the two layers of insulating materials (polymer layer 1 and polymer layer 2) use the polysulfonamide cured film described in the present invention. Through such design and construction, rewiring and changing the position/size of the contact electrode can be realized.
  • the cured polysulfonamide film here is not only an insulating dielectric material that wraps the copper leads, but also plays a structural role in relaxing internal stress. These materials need to have good long-term stability in order to maintain excellent stability and material recovery ability during the thermal expansion and contraction cycles caused by continuous temperature changes and the accompanying stress changes.
  • the cured product film is mainly used as an insulating material for wrapping copper wires, so the good adhesion between the two materials is a very critical material parameter.
  • ASTM American Society for Testing and Materials
  • D3359 Standard Test Methods for Measuring Adhesion by Tape Test
  • the material film is cut into 10 ⁇ 10 grid-like small grids (each grid area is 1 mm * 1 mm) with a zigzag 100 grid blade in the vertical direction.
  • stick an adhesive tape manufactured by 3M
  • the appearance of the obtained cured film covering the copper metal was evaluated by an optical microscope and the naked eye. If the cured film can well maintain the original color of the underlying copper metal film after curing, it is evaluated as A: discoloration is suppressed; if the color of the copper under the cured film changes significantly to deep red/brown, it is evaluated as B: discoloration is not suppressed .
  • A discoloration is suppressed
  • B discoloration is not suppressed
  • the cured polysulfonamide film obtained by the present invention has a good protective effect on the copper substrate and inhibits the discoloration of the copper metal.
  • the polysulfonamide cured product film proposed in the present invention effectively solves the disadvantage of the poor adhesion of such materials to the copper substrate material, and has an excellent protective effect on the copper metal of the substrate.

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Abstract

A polysulfonamide polymer, a negative photosensitive composition containing a polysulfonamide polymer and an application thereof. The negative photosensitive composition containing a polysulfonamide polymer consists of the following raw materials according to a certain weight ratio: the polysulfonamide polymer, a photoacid generator, a crosslinking agent, a solvent, and other components. The composition can be used to prepare a polysulfonamide cured film under a relatively low curing temperature condition (≤250°C), and the cured film can be used as a redistribution layer, an interlayer insulation buffer film, a coating or a surface protection film material.

Description

聚磺酰胺聚合物、含有聚磺酰胺聚合物的负型光敏性组合物及其应用Polysulfonamide polymer, negative photosensitive composition containing polysulfonamide polymer and application thereof 技术领域Technical field
本发明涉及一种半导体领域中应用的光敏性介电材料，特别是涉及一种含有聚磺酰胺聚合物的负型光敏性组合物、由其制备的固化物及其在半导体封装中的应用。The present invention relates to a photosensitive dielectric material used in the semiconductor field, in particular to a negative photosensitive composition containing a polysulfonamide polymer, a cured product prepared therefrom, and its application in semiconductor packaging.
背景技术Background technique
半导体芯片是过去的六十年科学技术进步的主要推动力之一，许多技术创新都依靠半导体芯片强大的计算能力及其逐渐变小的尺寸。摩尔定律一直有效地预测并主导着半导体制程的晶体管缩小化，然而近年来在28纳米的技术结点之后晶体管小型化在成本上变得越来越昂贵。另外材料物理和化学的极限也使晶体管小型化在技术上的突破变得越来越困难。未来的技术进步需要寻找新的技术突破点。先进封装被认为是当前最有可能实现这种技术突破的新技术。先进封装通过直接的芯片连接芯片、芯片连接封装、封装连接封装等手段把多个芯片或封装连接到一起，这种优化后的系统集成不但实现了信号之间的短距离快速传输，而且有效地减少了功能器件的能耗和发热。另外最重要的是这种系统集成还能把大量的功能缩小到较小的面积从而为当前以智能手机为主的移动计算创新提供了无限创新的可能性。Semiconductor chips are one of the main driving forces of scientific and technological progress in the past sixty years. Many technological innovations rely on the powerful computing power of semiconductor chips and their gradual shrinking size. Moore's Law has been effectively predicting and leading the reduction of transistors in semiconductor manufacturing processes. However, in recent years, the miniaturization of transistors has become more and more expensive after the 28-nanometer technology junction. In addition, the physical and chemical limitations of materials have made it more and more difficult to make breakthroughs in the miniaturization of transistors. Future technological progress needs to find new technological breakthroughs. Advanced packaging is considered to be the new technology most likely to achieve this technological breakthrough. Advanced packaging connects multiple chips or packages together through direct chip connection chip, chip connection package, package connection package and other means. This optimized system integration not only realizes short-distance and rapid transmission between signals, but also effectively The energy consumption and heat generation of functional devices are reduced. In addition, the most important thing is that this system integration can also reduce a large number of functions to a smaller area, thereby providing unlimited innovation possibilities for the current mobile computing innovation based on smart phones.
现有市场中的每个先进封装技术都会有不同，但其中大部分的先进封装技术都需要一种重新分布层的构建。这些重新分布层解决了芯片、封装及主板之间连接问题。重新分布层材料一般是由铜引线包裹在绝缘介电材料中组成。这些铜引线会把信号引入或导出到芯片中从而实现芯片和外界的信号传递。这些微米尺寸的铜引线已经很难用传统的机械方法高效地制备，现阶段电化学沉积法在光敏性介电材料的辅助下逐渐成为制备铜引线 的主流方法。另外，这些光敏性介电材料在制备工艺完成之后会留在装置中成为包裹铜引线的永久性绝缘材料。所以这个应用要求绝缘材料不但具有优良的光刻性能，还要具有较好的绝缘性能、机械性能、黏贴行、高温稳定性、低吸水性、高抗化学腐蚀性等。正是由于前述的综合要求，光敏性的聚酰亚胺(polyimide,PI)、聚苯并二噁唑(polybenzobisoxazole，PBO)、苯并环丁烯(benzocyclobutene,BCB)等材料由于其优良的耐高温材料性能逐渐成了这个领域的主要材料。另外，这类新的高性能绝缘材料在其它的一些应用例如层间绝缘缓冲膜、覆盖涂层或表面保护膜等方面也有很大前景。Every advanced packaging technology in the existing market will be different, but most of the advanced packaging technologies require a redistribution layer construction. These redistribution layers solve the connection problem between the chip, the package, and the motherboard. The redistribution layer material is generally composed of copper leads wrapped in an insulating dielectric material. These copper leads introduce or export signals to the chip to realize signal transmission between the chip and the outside world. These micron-sized copper leads have been difficult to efficiently prepare with traditional mechanical methods. At this stage, electrochemical deposition methods have gradually become the mainstream method for preparing copper leads with the assistance of photosensitive dielectric materials. In addition, these photosensitive dielectric materials will remain in the device after the preparation process is completed and become permanent insulating materials that wrap the copper leads. Therefore, this application requires insulating materials not only to have excellent lithography performance, but also to have good insulation performance, mechanical properties, adhesion, high temperature stability, low water absorption, high chemical resistance, etc. It is precisely due to the aforementioned comprehensive requirements that photosensitive polyimide (PI), polybenzobisoxazole (PBO), benzocyclobutene (BCB) and other materials are due to their excellent resistance The properties of high-temperature materials have gradually become the main materials in this field. In addition, these new high-performance insulating materials also have great prospects in other applications such as interlayer insulating buffer films, cover coatings or surface protection films.
现有的先进封装技术工艺普遍结合采用环氧烷类的EMC(Epoxy Molding Compounds)和熔点较低的无铅焊锡材料(熔点≈260℃或更低)，这都要求后续处理工艺步骤必须避免采用较高的后固化温度但又要求材料拥有较好的长期稳定性。传统的光敏性聚酰亚胺、聚苯并二噁唑、苯并环丁烯往往要求≥300℃的后固化温度，因而这类传统耐高温材料在这类新应用中还有较大的局限性。另外这些传统材料还有包括吸水性大、膜厚损失大、工艺过程复杂等缺点，这都进一步限制了这类传统材料在这一新领域的应用。Existing advanced packaging technology processes generally combine the use of alkylene oxide EMC (Epoxy Molding Compounds) and low melting point lead-free solder materials (melting point ≈260°C or lower), which requires that subsequent processing steps must be avoided Higher post-curing temperature but requires the material to have better long-term stability. Traditional photosensitive polyimides, polybenzodioxazoles, and benzocyclobutenes often require post-curing temperatures of ≥300°C. Therefore, such traditional high-temperature resistant materials have significant limitations in such new applications. sex. In addition, these traditional materials have shortcomings including large water absorption, large film thickness loss, and complex process, which further limit the application of such traditional materials in this new field.
由此可见，上述现有的含有聚酰亚胺、聚苯并二噁唑、苯并环丁烯的光敏性组合物、由其制备的固化物仍存在有不便与缺陷，而亟待加以进一步改进。因而，新型的具有低温固化能力的光敏性材料还有很大的市场需求和应用前景。本发明中的新型聚磺酰胺材料就是在这个背景下开发的可以实现较低固化成型温度的一种新材料。It can be seen that the above-mentioned existing photosensitive compositions containing polyimide, polybenzodioxazole, and benzocyclobutene and cured products prepared therefrom still have inconveniences and defects, and further improvement is urgently needed. . Therefore, new photosensitive materials with low-temperature curing ability still have great market demand and application prospects. The novel polysulfonamide material in the present invention is a new material developed under this background that can achieve a lower curing and molding temperature.
发明内容Summary of the invention
本发明的主要目的在于，克服现有的光敏性感光介电材料存在的缺陷，而提供一种新的主要用于负型光敏性感光介电材料的聚磺酰胺聚合物，该聚磺酰胺聚合物不但具有优异的机械性能，还具有较好的绝缘性能、粘接性、高温稳定性、低吸水性、高抗化学腐蚀性等优点。The main purpose of the present invention is to overcome the shortcomings of the existing photosensitive photosensitive optical dielectric materials, and provide a new type of polysulfonamide polymer mainly used for negative photosensitive photosensitive optical dielectric materials, the polysulfonamide polymer The material not only has excellent mechanical properties, but also has good insulation properties, adhesion, high temperature stability, low water absorption, high chemical resistance and other advantages.
本发明的另一主要目的在于，提供一种含有聚磺酰胺聚合物的负型光敏性组合物，所要解决的技术问题是使这些组合物能在较低温度(小于或等于250℃)热处理条件下具备有效的交联能力和优异的光刻性能，从而能制备出具有浮雕微结构的固化物。Another main purpose of the present invention is to provide a negative photosensitive composition containing polysulfonamide polymer. The technical problem to be solved is to enable these compositions to be heat-treated at a lower temperature (less than or equal to 250°C). It has effective cross-linking ability and excellent photolithography performance, so that cured products with embossed microstructure can be prepared.
本发明的另一目的在于提供一种利用上述新型光敏性聚磺酰胺聚合物的组合物制备得到的图案固化物。Another object of the present invention is to provide a patterned cured product prepared by using the above-mentioned novel photosensitive polysulfonamide polymer composition.
本发明的再一目的在于提供上述固化物在重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜的应用。Another object of the present invention is to provide the application of the above-mentioned cured product in the redistribution layer, the interlayer insulation buffer film, the cover coating or the surface protection film.
本发明还有一目的在于将上述固化物用于相关电子产品中。Another object of the present invention is to use the above-mentioned cured product in related electronic products.
本发明的目的及解决其技术问题是采用以下技术方案来实现的。依据本发明提出的一种具有如下通式(1)聚磺酰胺聚合物，The purpose of the present invention and the solution of its technical problems are achieved by adopting the following technical solutions. According to the present invention, a polysulfonamide polymer with the following general formula (1) is proposed,
Figure PCTCN2020091094-appb-000001
Figure PCTCN2020091094-appb-000001
所述聚磺酰胺聚合物具有如下的重复单元结构式，其中m和n表示聚合物中的结构单元数，其为1～99的整数。The polysulfonamide polymer has the following repeating unit structural formula, where m and n represent the number of structural units in the polymer, which are integers from 1 to 99.
本发明的目的及解决其技术问题还可采用以下技术措施进一步实现。The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.
前述的的聚磺酰胺聚合物，所述通式(1)中的X1和X2是二价芳香族连接基团，其可以为不同或相同的具有下述通式(2)、(3)、或者(4)所示的基团；In the aforementioned polysulfonamide polymer, X1 and X2 in the general formula (1) are divalent aromatic linking groups, which may be different or the same and have the following general formulas (2), (3), Or the group shown in (4);
Figure PCTCN2020091094-appb-000002
Figure PCTCN2020091094-appb-000002
其中所述的R 1，R 2，R 3，R 4分别表示氢原子或者一价有机基团； Wherein said R 1 , R 2 , R 3 , and R 4 respectively represent a hydrogen atom or a monovalent organic group;
Figure PCTCN2020091094-appb-000003
Figure PCTCN2020091094-appb-000003
其中所述的Q为直接键或二价有机基团，所述有机基团选自O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻，-间，-对亚苯基； The Q is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene;
Figure PCTCN2020091094-appb-000004
Figure PCTCN2020091094-appb-000004
其中所述的T为直接键或二价有机基团，所述有机基团选自O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻，-间，-对亚苯基，其中R 5～R 12是相同的或不同的一价有机基，选自H、CH 3、或CF 3； The T is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -met, -p-phenylene, Wherein R 5 to R 12 are the same or different monovalent organic groups, selected from H, CH 3 , or CF 3 ;
其中所述通式(1)的聚磺酰胺聚合物中的Y是二价芳香族基团，选自从下述式(5)或者(6)所代表的结构单元：Wherein, Y in the polysulfonamide polymer of the general formula (1) is a divalent aromatic group selected from structural units represented by the following formula (5) or (6):
Figure PCTCN2020091094-appb-000005
Figure PCTCN2020091094-appb-000005
其中通式(6)中所述的U为直接键或二价有机基团，所述的有机基团选自O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻、-间、-对亚苯基。 Wherein U in the general formula (6) is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -between , -P-phenylene.
前述的聚磺酰胺聚合物，所述聚磺酰胺聚合物为嵌段共聚物或者无规共聚物，其重均分子量范围为5,000到200,000。In the aforementioned polysulfonamide polymer, the polysulfonamide polymer is a block copolymer or a random copolymer, and its weight average molecular weight ranges from 5,000 to 200,000.
本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的含有聚磺酰胺聚合物的负型光敏性组合物，其包括：The purpose of the present invention and the solution of its technical problems are also achieved by adopting the following technical solutions. The negative photosensitive composition containing polysulfonamide polymer proposed according to the present invention includes:
(A)聚磺酰胺聚合物；(A) Polysulfonamide polymer;
(B)光酸产生剂：其在组合物中的含量相对于(A)成分100质量份而言优选为0.1～20质量份，更优选为1～10质量份；(B) Photoacid generator: The content in the composition is preferably 0.1-20 parts by mass, and more preferably 1-10 parts by mass relative to 100 parts by mass of component (A);
(C)交联剂：其在组合物中的含量相对于(A)成分100质量份而言优选为2～50质量份，进一步优选为8～40质量份；(C) Crosslinking agent: The content in the composition is preferably 2-50 parts by mass, more preferably 8-40 parts by mass relative to 100 parts by mass of component (A);
(D)溶剂：其在组合物中的含量相对于(A)成分100质量份优选为50～800质量份，更优选为60～300质量份，进一步优选为80～220质量份。(D) Solvent: The content in the composition relative to 100 parts by mass of the component (A) is preferably 50 to 800 parts by mass, more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass.
本发明的目的及解决其技术问题还可采用以下技术措施进一步实现。The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.
前述的含有聚磺酰胺聚合物的负型光敏性组合物，其中的组分(B)的成分为至少一种光酸产生剂。所述光酸产生剂选自但不限于离子型化合物包括硫盐、鏻盐或碘鎓盐；非离子型化合物包括肟磺酸酯、磺酸酯化合物或醌二叠氮化物化合物；或其混合物。从灵敏度和成像性的角度考虑，优选肟磺酸酯化合物；和/或In the aforementioned negative photosensitive composition containing polysulfonamide polymer, the component (B) is at least one photoacid generator. The photoacid generator is selected from but not limited to ionic compounds including sulfur salts, phosphonium salts or iodonium salts; non-ionic compounds include oxime sulfonate, sulfonate compound or quinone diazide compound; or mixtures thereof . From the viewpoint of sensitivity and imaging properties, oxime sulfonate compounds are preferred; and/or
其中的组分(C)的成分包含至少一种具有-CH 2OR(R是氢原子或1价有机基团)的烷氧基化合物/羟基化合物；环氧基化合物；氧杂环丁烷基化合物或乙烯基醚基化合物，优选具有羟甲基、烷氧基甲基等烷氧基烷基的化合物；和/或 Among them, the component (C) contains at least one alkoxy compound/hydroxy compound having -CH 2 OR (R is a hydrogen atom or a monovalent organic group); epoxy compound; oxetanyl Compounds or vinyl ether-based compounds, preferably compounds having alkoxyalkyl groups such as hydroxymethyl and alkoxymethyl; and/or
其中所述的组合物的成分溶解在一种溶剂(D)中，所述溶剂包括至少一 种从如下溶剂所选的化合物：酯、醚、醚-酯、酮、酮-酯、芳香族化合物，和/或卤代烃类溶剂。The components of the composition are dissolved in a solvent (D), and the solvent includes at least one compound selected from the following solvents: ester, ether, ether-ester, ketone, ketone-ester, aromatic compound , And/or halogenated hydrocarbon solvents.
本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的含有聚磺酰胺聚合物的负型光敏性组合物制备的具有浮雕图案的固化物，由包括以下步骤的方法制备：The purpose of the present invention and the solution of its technical problems are also achieved by adopting the following technical solutions. The cured product with embossed pattern prepared from the negative photosensitive composition containing polysulfonamide polymer according to the present invention is prepared by a method including the following steps:
(a)将所述的聚磺酰胺聚合物组合物涂布于基板上并加热去除溶剂而形成感光性树脂膜的步骤；(a) The step of coating the polysulfonamide polymer composition on a substrate and heating to remove the solvent to form a photosensitive resin film;
(b)利用掩模版对所述感光性树脂膜进行图案曝光的步骤；(b) A step of patterning the photosensitive resin film using a mask;
(c)去除涂层未曝光的区域，从而得到具有浮雕图案的树脂固化物膜的步骤，以及(c) the step of removing unexposed areas of the coating to obtain a cured resin film with embossed patterns, and
(d)对所述浮雕图案树脂膜进行加热固化处理的步骤。(d) A step of heating and curing the relief pattern resin film.
本发明的目的及解决其技术问题还可采用以下技术措施进一步实现。The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.
前述的具有浮雕图案的固化物，其中所述加热处理的温度小于或等于250℃。In the aforementioned cured product with embossed patterns, the temperature of the heat treatment is less than or equal to 250°C.
前述的具有浮雕图案的固化物，其为具有微结构浮雕图案的固化物膜。The aforementioned cured product with embossed patterns is a cured product film with micro-structured embossed patterns.
本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的具有浮雕图案的固化物应用于重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜。The purpose of the present invention and the solution of its technical problems are also achieved by adopting the following technical solutions. The cured product with embossed patterns proposed according to the present invention is applied to a redistribution layer, an interlayer insulation buffer film, a cover coating or a surface protection film.
本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的一种电子器件，其包含所述的重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜。The purpose of the present invention and the solution of its technical problems are also achieved by adopting the following technical solutions. An electronic device according to the present invention includes the redistribution layer, the interlayer insulation buffer film, the cover coating or the surface protection film.
经由上述可知，本发明公开了一种聚磺酰胺聚合物、含有聚磺酰胺聚合物的负型光敏性组合物及其应用。其中所述的含有聚磺酰胺聚合物的负型光敏性组合物由下述原料按照一定重量比例组成：聚磺酰胺聚合物、光 酸产生剂、交联剂、溶剂以及一些其它组分。该组合物在较低固化温度条件下(≤250℃)制备出聚磺酰胺固化物膜，该固化物膜可用做重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜材料。Based on the above knowledge, the present invention discloses a polysulfonamide polymer, a negative photosensitive composition containing the polysulfonamide polymer, and applications thereof. The negative photosensitive composition containing polysulfonamide polymer is composed of the following raw materials in a certain weight ratio: polysulfonamide polymer, photoacid generator, crosslinking agent, solvent and some other components. The composition prepares a polysulfonamide cured film under relatively low curing temperature conditions (≤250°C), and the cured film can be used as a redistribution layer, an interlayer insulation buffer film, a covering coating or a surface protection film material.
借由上述技术方案，本发明含有聚磺酰胺聚合物的负型光敏性组合物、由其制备的固化物及其在半导体封装中的应用至少具有下列优点：With the above technical solutions, the negative photosensitive composition containing polysulfonamide polymer, the cured product prepared therefrom, and the application in semiconductor packaging of the present invention have at least the following advantages:
鉴于传统感光介电材料要求的固化温度比较高，在本发明使用了新型的聚磺酰胺组合物。结果发现，这种膜可以在较低温度(小于或等于250℃)热处理条件下制备出具有浮雕微结构的薄膜。通过调节各种单体在薄膜中的比例、组合物的各个成分和热处理条件，膜的溶解速度和机械性能以及各种其它材料性能可以得到很好的调控和优化。另外，这种树脂组合物保持了大多数负型光敏性材料对基板有优异的粘接性的普遍优点。最后，通过在聚合物合成过程中使用含氟原子的单体，这些新材料会在降低材料吸水性方面性能方面有显著提高，从而使从本组合物制备的固化物膜更加适于当前的先进封装工艺要求。In view of the relatively high curing temperature required for traditional photosensitive dielectric materials, a novel polysulfonamide composition is used in the present invention. As a result, it was found that this kind of film can prepare a film with embossed microstructure under lower temperature (less than or equal to 250°C) heat treatment conditions. By adjusting the ratio of various monomers in the film, the various components of the composition and the heat treatment conditions, the dissolution rate and mechanical properties of the film and various other material properties can be well controlled and optimized. In addition, this resin composition maintains the general advantage that most negative photosensitive materials have excellent adhesion to the substrate. Finally, by using monomers containing fluorine atoms in the polymer synthesis process, these new materials will significantly improve their performance in reducing material water absorption, so that the cured film prepared from the composition is more suitable for the current advanced Packaging process requirements.
综上所述，本发明的技术方案其具有上述诸多的优点及实用价值，并在同类产品中未见有类似的设计公开发表或使用而确属创新，其不论在配方上或功能上皆有较大的改进，在技术上有较大的进步，并产生了好用及实用的效果，且较现有的产品具有增进的多项功效，从而更加适于实用，而具有产业的广泛利用价值，诚为一新颖、进步、实用的新设计。In summary, the technical solution of the present invention has many of the above-mentioned advantages and practical value, and there is no similar design published or used in similar products, and it is indeed innovative. It has both formula and function. Larger improvements have made great progress in technology, and have produced easy-to-use and practical effects, and have improved multiple functions compared with existing products, so they are more suitable for practical use and have a wide range of industrial use values , Sincerely a novel, progressive and practical new design.
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。The above description is only an overview of the technical solution of the present invention. In order to understand the technical means of the present invention more clearly and implement it in accordance with the content of the description, the preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings.
附图说明Description of the drawings
图1是本发明的一个实施方式，其中涉及重新分布层的制造。Figure 1 is an embodiment of the present invention, which involves the manufacture of a redistribution layer.
具体实施方式Detailed ways
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,以下结合附图及较佳实施例，对依据本发明提出的聚磺酰胺聚合物、含有聚磺酰胺聚合物的负型光敏性组合物、由其制备的固化物及其在半导体封装中的应用其具体实施方式详细说明如后。In order to further explain the technical means and effects of the present invention to achieve the intended purpose of the invention, in conjunction with the accompanying drawings and preferred embodiments, the following is a comparison of the polysulfonamide polymer and the negative type containing polysulfonamide polymer according to the present invention. The specific embodiments of the photosensitive composition, the cured product prepared therefrom, and its application in semiconductor packaging are described in detail below.
以下，通过聚磺酰胺聚合物的合成例和实施例/比较例对本发明进行进一步的具体说明。需要说明的是，本发明不受这些聚合物合成例和实施例/比较例的限定，在本领域中具有通常知识的人员能够在本发明的技术思想内进行多种变形。Hereinafter, the present invention will be further specifically described through synthesis examples and examples/comparative examples of polysulfonamide polymers. It should be noted that the present invention is not limited by these polymer synthesis examples and examples/comparative examples, and a person with ordinary knowledge in the art can make various modifications within the technical idea of the present invention.
一、(A)：聚磺酰胺聚合物1. (A): Polysulfonamide polymer
合成例1～25制备的聚磺酰胺聚合物的性能说明如下。The properties of the polysulfonamide polymers prepared in Synthesis Examples 1-25 are described as follows.
Figure PCTCN2020091094-appb-000006
Figure PCTCN2020091094-appb-000006
具有如上式(1)的聚磺酰胺聚合物，其特征在于，聚合物具有如通式(1)所描绘的重复单元的结构式，其中m和n表示聚合物中的结构单元数，是1～99的整数。从成膜性和控制溶解速度的角度优选，m和n优选5～99的整数。The polysulfonamide polymer having the above formula (1) is characterized in that the polymer has the structural formula of the repeating unit depicted in the general formula (1), where m and n represent the number of structural units in the polymer, and are 1 to An integer of 99. It is preferable from the viewpoint of film-forming properties and control of the dissolution rate, and m and n are preferably integers of 5 to 99.
所述通式(1)中的X1和X2是二价芳香族连接基团，它们可以为不同或相同的具有下述通式(2)、(3)、或者(4)所示基团。X1 and X2 in the general formula (1) are divalent aromatic linking groups, and they may be different or the same and have groups represented by the following general formulas (2), (3), or (4).
Figure PCTCN2020091094-appb-000007
Figure PCTCN2020091094-appb-000007
其中所述的R 1，R 2，R 3，R 4分别表示氢原子或者一价有机基团，例如甲基。 The R 1 , R 2 , R 3 , and R 4 respectively represent a hydrogen atom or a monovalent organic group, such as a methyl group.
Figure PCTCN2020091094-appb-000008
Figure PCTCN2020091094-appb-000008
其中所述的Q，表示直接键或其他2价的有机基团，例如O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻，-间，-对亚苯基。 The Q in it represents a direct bond or other divalent organic groups, such as O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1≤p≤ 10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene.
Figure PCTCN2020091094-appb-000009
Figure PCTCN2020091094-appb-000009
其中所述的T，表示直接键或其他2价的有机基团，例如O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻，-间，-对亚苯基。其中R 5～R 12是相同的或不同的一价有机基，例如H、CH 3、或CF 3。 The T mentioned here represents a direct bond or other divalent organic groups, such as O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1≤p≤ 10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene. Wherein R 5 to R 12 are the same or different monovalent organic groups, such as H, CH 3 , or CF 3 .
上述的聚磺酰胺聚合物，所述通式(1)中的Y是二价芳香族基团，选自从下述式(5)或者(6)所代表的结构单元：In the above-mentioned polysulfonamide polymer, Y in the general formula (1) is a divalent aromatic group selected from structural units represented by the following formula (5) or (6):
Figure PCTCN2020091094-appb-000010
Figure PCTCN2020091094-appb-000010
其中通式(6)中所述的U为直接键或其他2价的有机基团，所述的有机基团选自O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻、-间、-对亚苯基。 Wherein U in the general formula (6) is a direct bond or other divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH ), (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted-ortho, -M, -p-phenylene.
上述的聚磺酰胺聚合物的合成方法如下：在惰性气氛中，将二胺混合物和2-甲基吡啶溶解于N－甲基吡咯烷酮中，然后再滴加与二胺单体等摩尔量的磺酰氯单体(溶于N－甲基吡咯烷酮)于0～5℃冰浴中反应1小时，将所得聚合物溶液在去离子水介质中沉降，经过过滤后，于80～120℃真空干燥得到聚磺酰胺聚合物。The method for synthesizing the above-mentioned polysulfonamide polymer is as follows: in an inert atmosphere, dissolve the diamine mixture and 2-methylpyridine in N-methylpyrrolidone, and then add dropwise an equimolar amount of sulfonate to the diamine monomer. The acid chloride monomer (dissolved in N-methylpyrrolidone) was reacted in an ice bath at 0-5°C for 1 hour. The resulting polymer solution was settled in a deionized water medium, filtered, and dried in vacuum at 80-120°C to obtain a polymer solution. Sulfonamide polymer.
上述的聚磺酰胺聚合物可以有5,000到200,000的重均分子量。优选为分子量10,000到120,000的重均分子量。在这里，该分子量是由凝胶渗透色谱(GPC)法进行测定，并用标准聚苯乙烯标准曲线算出。The above-mentioned polysulfonamide polymer may have a weight average molecular weight of 5,000 to 200,000. It is preferably a weight average molecular weight of 10,000 to 120,000 in molecular weight. Here, the molecular weight is measured by a gel permeation chromatography (GPC) method and calculated using a standard polystyrene calibration curve.
上述的聚磺酰胺聚合物可以是嵌段共聚物或者无规共聚物。为了提高组合物的稳定性，也可将其主链末端利用单胺或单酰氯化合物等封端剂进行封端。用作封端剂的单胺的导入比例相对于全部胺成分而言优选为0.5摩尔～30摩尔％。作为单胺：可以选择苯胺、2-乙炔基苯胺、5-氨基-8-羟基喹啉、1-羟基-7-氨基萘、1-羟基-6-氨基萘、1-羟基-5-氨基萘、1-羟基-4-氨基萘、2-羟基-7-氨基萘；作为单酰氯化合物：可以选择3-羧基苯磺酸、4-羧基苯磺酸等单羧酸类及它们的羧基发生酰氯化而得到的单酰氯化合物，也可选择对苯二甲酸、邻苯二甲酸、马来酸、环己烷二甲酸、1,5-二羧基萘、1,6-二羧基萘、1,7-二羧基萘、2，6-二羧基萘等二羧酸类的仅一 个羧基发生酰氯化反应后而得到的单酰氯化合物，通过单酰氯化合物与N-羟基苯并三唑、N-羟基-5-降冰片烯-2,3-二羧基酰亚胺的反应而得到的活性酯化合物等。封端剂可以使用前述化合物中的一种或一种以上的化合物。The above-mentioned polysulfonamide polymer may be a block copolymer or a random copolymer. In order to improve the stability of the composition, the end of the main chain can also be blocked with a blocking agent such as a monoamine or a monochloride compound. The introduction ratio of the monoamine used as the blocking agent is preferably 0.5 mol to 30 mol% with respect to all amine components. As a monoamine: aniline, 2-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene can be selected , 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene; as mono-acid chloride compounds: you can choose 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and other monocarboxylic acids and their carboxyl generating acid chloride The monoacid chloride compound obtained by chemical conversion can also choose terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7 -Dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and other dicarboxylic acid monochloride compounds obtained after only one carboxyl group undergoes acid chlorination reaction, through the monoacid chloride compound and N-hydroxybenzotriazole, N-hydroxy- Active ester compound etc. obtained by reaction of 5-norbornene-2,3-dicarboxyimide. One or more of the aforementioned compounds can be used as the blocking agent.
上述聚磺酰胺聚合物通常使用碱性水溶液进行显影。因此，优选可溶于碱溶剂的聚磺酰胺聚合物。聚磺酰胺聚合物制成溶液后，旋涂于硅晶片等基板上加热干燥去溶剂后而形成膜厚10微米左右的树脂膜；然后在20～25℃将其浸渍于四甲基氢氧化铵水溶液中；根据膜完全溶解所需的时间判断(A)成分溶于碱性水溶液的难易程度。The above-mentioned polysulfonamide polymer is usually developed using an alkaline aqueous solution. Therefore, polysulfonamide polymers that are soluble in alkali solvents are preferred. After the polysulfonamide polymer is made into a solution, it is spin-coated on a substrate such as a silicon wafer and heated to dry to remove the solvent to form a resin film with a thickness of about 10 microns; then it is immersed in tetramethylammonium hydroxide at 20～25℃ In an aqueous solution; the difficulty of dissolving the component (A) in an alkaline aqueous solution is judged based on the time required for the complete dissolution of the film.
另外，i线的透过率直接影响光敏组合物在工艺过程中的分辨率。为了在相同膜厚条件得到分辨率最佳的微结构浮雕图案，聚磺酰胺聚合物优选透光率较好的含有氟原子的单体结构。含有氟的组合物也有利于在显影时减少溶液对膜的浸渍肿胀影响从而抑制从表面的渗出，还能减小组合物固化后的吸水性。In addition, the transmittance of the i-line directly affects the resolution of the photosensitive composition during the process. In order to obtain the microstructure relief pattern with the best resolution under the same film thickness condition, the polysulfonamide polymer preferably has a monomer structure containing fluorine atoms with better light transmittance. The fluorine-containing composition is also beneficial to reduce the immersion and swelling effect of the solution on the film during development, thereby inhibiting the exudation from the surface, and can also reduce the water absorption of the composition after curing.
最后，将含有式(1)所表示的聚磺酰胺聚合物的组合物涂布于基材并进行加热固化而得的固化膜的应力优选小于或等于30MPa。如果应力小于或等于30MPa，则在固化成膜后，能够有效地抑制晶圆的翘曲，从而适合应用在当前先进封装工艺中被广泛采用的晶圆重建(wafer reconstitution)工艺过程。Finally, the stress of the cured film obtained by coating the composition containing the polysulfonamide polymer represented by the formula (1) on the substrate and heat curing is preferably 30 MPa or less. If the stress is less than or equal to 30 MPa, after curing into a film, the warpage of the wafer can be effectively suppressed, which is suitable for the application of the wafer reconstitution (wafer reconstitution) process which is widely used in the current advanced packaging process.
因此，所述的聚磺酰胺聚合物，从透光率、吸水性、碱溶性和应力的综合角度考虑，所述通式(1)中的X1和X2是二价芳香族连接基团，它们中的至少一个优选为含有三氟甲基的具有下述通式(7)和/或含有苯醚基的具有下述通式(8)所表示的结构单元。Therefore, the polysulfonamide polymer, from the comprehensive perspective of light transmittance, water absorption, alkali solubility and stress, X1 and X2 in the general formula (1) are divalent aromatic linking groups, and they At least one of them is preferably a trifluoromethyl group-containing structural unit represented by the following general formula (7) and/or a phenyl ether group-containing structural unit represented by the following general formula (8).
Figure PCTCN2020091094-appb-000011
Figure PCTCN2020091094-appb-000011
所述聚磺酰胺聚合物通式(1)中的Y，从应力和碱溶性的角度进一步考虑，也优选具有上述通式(8)所表示的苯醚基结构单元。From the viewpoint of stress and alkali solubility, Y in the polysulfonamide polymer general formula (1) also preferably has a phenyl ether-based structural unit represented by the general formula (8).
以下是本发明中聚磺酰胺聚合物较优的合成实施例。The following are the preferred synthesis examples of the polysulfonamide polymer in the present invention.
合成例1：Synthesis Example 1:
在具有机械搅拌器、温度计以及高纯氮气氛围下的四口烧瓶中，加入2,2'-二(三氟甲基)二氨基联苯(50mmol)、4,4'-二氨基二苯醚(50mmol)、2-甲基吡啶(300mmol)以及无水N-甲基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-1,其结构式如下。m和n是相应重复单元数，结构单元的 摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。In a four-necked flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, add 2,2'-bis(trifluoromethyl)diaminobiphenyl (50mmol), 4,4'-diaminodiphenyl ether (50mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25g), stir until completely dissolved (the solution becomes clear), and cool to -10°C. Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The random copolymer obtained was named Polymer-1, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-1)(Polymer-1)
Figure PCTCN2020091094-appb-000012
Figure PCTCN2020091094-appb-000012
合成例2～3：Synthesis example 2～3:
聚合物-2和聚合物-3的合成方法参照合成例1，只是二胺单体的摩尔分数分别调整为：2,2'-二(三氟甲基)二氨基联苯(75mmol)、4,4'-二氨基二苯醚(25mmol)(合成例2)和2,2'-二(三氟甲基)二氨基联苯(25mmol)、4,4'-二氨基二苯醚(75mmol)(合成例3)。其它条件/过程与合成例1完全相同。因而聚合物-2和聚合物-3的化学式和聚合物-1完全相同，只是摩尔分数m/(m+n)有所改变：分别为3：1(合成例2：聚合物-2)和1：3(合成例3：聚合物-3)。The synthesis methods of polymer-2 and polymer-3 refer to Synthesis Example 1, except that the mole fraction of the diamine monomer is adjusted to: 2,2'-bis(trifluoromethyl)diaminobiphenyl (75mmol), 4 ,4'-Diaminodiphenyl ether (25mmol) (Synthesis Example 2) and 2,2'-bis(trifluoromethyl)diaminodiphenyl (25mmol), 4,4'-Diaminodiphenyl ether (75mmol) ) (Synthesis Example 3). Other conditions/processes are exactly the same as in Synthesis Example 1. Therefore, the chemical formulas of polymer-2 and polymer-3 are exactly the same as those of polymer-1, except that the mole fraction m/(m+n) is changed: 3:1 (synthesis example 2: polymer-2) and 1:3 (Synthesis Example 3: Polymer-3).
合成例4Synthesis Example 4
在具有机械搅拌器、温度计以及高纯氮气气氛下的四口烧瓶中，装入2,2'-二(三氟甲基)二氨基联苯(47.5mmol)、4,4'-二氨基二苯醚(47.5mmol)、间氨基苯酚(10mmol)、2-甲基吡啶(300mmol)以及无水N-甲基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中 干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-4，其结构式如下。m和n是相应重复单元数，结构单元的摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。In a four-necked flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, charge 2,2'-bis(trifluoromethyl)diaminobiphenyl (47.5mmol), 4,4'-diaminodiphenyl Phenyl ether (47.5mmol), m-aminophenol (10mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25g), stir until completely dissolved (the solution becomes clear) , Cool to -10°C. Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The random copolymer obtained was named Polymer-4, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-4)(Polymer-4)
Figure PCTCN2020091094-appb-000013
Figure PCTCN2020091094-appb-000013
合成例5～6：Synthesis example 5～6:
聚合物-5和聚合物-6的合成方法参照合成例4，只是二胺单体的摩尔分数分别调整为：2,2'-二(三氟甲基)二氨基联苯(71.25mmol)、4,4'-二氨基二苯醚(23.75mmol)(合成例5)和2,2'-二(三氟甲基)二氨基联苯(23.75mmol)、4,4'-二氨基二苯醚(71.25mmol)(合成例6)。其它条件/过程与合成例4完全相同。因而聚合物-5和聚合物-6的化学式和聚合物-4完全相同，只是摩尔分数m/(m+n)有所改变，分别为3：1(合成例5：聚合物-5)和1：3(合成例6：聚合物-6)。The synthesis methods of polymer-5 and polymer-6 refer to Synthesis Example 4, except that the mole fraction of the diamine monomer is adjusted to: 2,2'-bis(trifluoromethyl)diaminobiphenyl (71.25mmol), 4,4'-diaminodiphenyl ether (23.75mmol) (synthesis example 5) and 2,2'-bis(trifluoromethyl)diaminodiphenyl (23.75mmol), 4,4'-diaminodiphenyl Ether (71.25 mmol) (Synthesis Example 6). Other conditions/processes are exactly the same as in Synthesis Example 4. Therefore, the chemical formulas of polymer-5 and polymer-6 are exactly the same as those of polymer-4, except that the mole fraction m/(m+n) is changed to 3:1 (synthesis example 5: polymer-5) and 1:3 (Synthesis Example 6: Polymer-6).
合成例7Synthesis Example 7
在具有机械搅拌器、温度计以及高纯氮气气氛下的四口烧瓶中，装入2,2-双(3-氨基-4-羟基苯基)六氟丙烷(50mmol)、4,4'-二氨基二苯醚(50mmol)、2-甲基吡啶(300mmol)以及无水N-甲基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应 溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-7，其结构式如下。m和n是相应重复单元数，结构单元的摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。In a four-necked flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, charge 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (50mmol), 4,4'-two Aminodiphenyl ether (50mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25g), stir until completely dissolved (the solution becomes clear), and cool to -10°C . Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water three times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The obtained random copolymer was named Polymer-7, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-7)(Polymer-7)
Figure PCTCN2020091094-appb-000014
Figure PCTCN2020091094-appb-000014
合成例8～9：Synthesis examples 8-9:
聚合物-8和聚合物-9的合成方法参照合成例7，只是二胺单体的摩尔分数分别调整为：2,2-双(3-氨基-4-羟基苯基)六氟丙烷(75mmol)、4,4'-二氨基二苯醚(25mmol)(合成例8)和2,2-双(3-氨基-4-羟基苯基)六氟丙烷(25mmol)、4,4'-二氨基二苯醚(75mmol)(合成例9)。其它条件/过程与合成例7完全相同。因而聚合物-8和聚合物-9的化学式和聚合物-7完全相同，只是摩尔分数m/(m+n)有所改变，分别为3：1(合成例8：聚合物-8)和1：3(合成例9：聚合物-9)。The synthesis methods of polymer-8 and polymer-9 refer to Synthesis Example 7, except that the mole fraction of the diamine monomer is adjusted to: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (75mmol ), 4,4'-diaminodiphenyl ether (25mmol) (Synthesis Example 8) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (25mmol), 4,4'-bis Aminodiphenyl ether (75 mmol) (Synthesis Example 9). The other conditions/processes are exactly the same as in Synthesis Example 7. Therefore, the chemical formulas of polymer-8 and polymer-9 are exactly the same as those of polymer-7, except that the mole fraction m/(m+n) is changed to 3:1 (synthesis example 8: polymer-8) and 1:3 (Synthesis Example 9: Polymer-9).
合成例10：Synthesis Example 10:
在具有机械搅拌器、温度计以及高纯氮气气氛下的四口烧瓶中，装入2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(50mmol)、4,4'-二氨基二苯醚(50mmol)、2-甲基吡啶(300mmol)以及无水N-甲基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约 半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-10，其结构式如下。m和n是相应重复单元数，结构单元的摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。Put 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3 into a four-necked flask with mechanical stirrer, thermometer and high-purity nitrogen atmosphere. ,3-hexafluoropropane (50mmol), 4,4'-diaminodiphenyl ether (50mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25g) , Stir until completely dissolved (the solution becomes clear), and cool to -10°C. Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The obtained random copolymer was named Polymer-10, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-10)(Polymer-10)
Figure PCTCN2020091094-appb-000015
Figure PCTCN2020091094-appb-000015
合成例11～12：Synthesis examples 11-12:
聚合物-11和聚合物-12的合成方法参照合成例10，只是二胺单体的摩尔分数分别调整为：2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(75mmol)、4,4'-二氨基二苯醚(25mmol)(合成例11)和2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(25mmol)、4,4'-二氨基二苯醚(75mmol)(合成例12)。其它条件/过程与合成例10完全相同。因而聚合物-11和聚合物-12的化学式和聚合物-10完全相同，只是摩尔分数m/(m+n)有所改变，分别为3：1(合成例11：聚合物-11)和1：3(合成例12：聚合物-12)。The synthesis methods of polymer-11 and polymer-12 refer to Synthesis Example 10, except that the mole fraction of the diamine monomer is adjusted to: 2,2-bis[4-(4-aminophenoxy)phenyl]-1 ,1,1,3,3,3-hexafluoropropane (75mmol), 4,4'-diaminodiphenyl ether (25mmol) (synthesis example 11) and 2,2-bis[4-(4-aminobenzene) (Oxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (25 mmol), 4,4'-diaminodiphenyl ether (75 mmol) (Synthesis Example 12). Other conditions/processes are exactly the same as in Synthesis Example 10. Therefore, the chemical formulas of polymer-11 and polymer-12 are exactly the same as those of polymer-10, except that the mole fraction m/(m+n) is changed to 3:1 (Synthesis Example 11: Polymer-11) and 1:3 (Synthesis Example 12: Polymer-12).
合成例13：Synthesis Example 13:
在具有机械搅拌器、温度计以及高纯氮气气氛下的四口烧瓶中，装入2,2'-二(三氟甲基)二氨基联苯(50mmol)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(50mmol)、2-甲基吡啶(300mmol)以及无水N-甲 基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-13，其结构式如下。m和n是相应重复单元数，结构单元的摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。In a four-necked flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, charge 2,2'-bis(trifluoromethyl)diaminobiphenyl (50mmol), 2,2-bis[4-( 4-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane (50mmol), 2-picoline (300mmol) and anhydrous N-methyl-2-pyrrolidone ( NMP) (47.25g), stir until completely dissolved (the solution becomes clear), and cool to -10°C. Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The random copolymer obtained was named Polymer-13, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-13)(Polymer-13)
Figure PCTCN2020091094-appb-000016
Figure PCTCN2020091094-appb-000016
合成例14～15：Synthesis examples 14-15:
聚合物-14和聚合物-15的合成方法参照合成例13，只是二胺单体的摩尔分数分别调整为：2,2'-二(三氟甲基)二氨基联苯(75mmol)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(25mmol)(合成例14)和2,2'-二(三氟甲基)二氨基联苯(25mmol)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(75mmol)(合成例15)。其它条件/过程与合成例13完全相同。因而聚合物-14和聚合物-15的化学式和聚合物-13完全相同，只是摩尔分数m/(m+n)有所改变，分别为3：1(合成例14：聚合物-14)和1：3(合成例15：聚合物-15)。The synthetic methods of polymer-14 and polymer-15 refer to Synthesis Example 13, except that the mole fraction of the diamine monomer is adjusted to: 2,2'-bis(trifluoromethyl)diaminobiphenyl (75mmol), 2 ,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (25mmol) (Synthesis Example 14) and 2,2'-bis( Trifluoromethyl)diaminobiphenyl (25mmol), 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (75mmol) ) (Synthesis Example 15). The other conditions/processes are exactly the same as in Synthesis Example 13. Therefore, the chemical formulas of polymer-14 and polymer-15 are exactly the same as those of polymer-13, except that the mole fraction m/(m+n) is changed to 3:1 (Synthesis Example 14: Polymer-14) and 1:3 (Synthesis Example 15: Polymer-15).
合成例16：Synthesis Example 16:
在具有机械搅拌器、温度计以及高纯氮气气氛下的四口烧瓶中，装入 2,2-双(3-氨基-4-羟基苯基)六氟丙烷(50mmol)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(50mmol)、2-甲基吡啶(300mmol)以及无水N-甲基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-16，其结构式如下。m和n是相应重复单元数，结构单元的摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。In a four-necked flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, charge 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (50mmol), 2,2-bis[ 4-(4-Aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane (50mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2 -Pyrrolidone (NMP) (47.25g), stir until completely dissolved (the solution becomes clear), and cool to -10°C. Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The random copolymer obtained was named Polymer-16, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-16)(Polymer-16)
Figure PCTCN2020091094-appb-000017
Figure PCTCN2020091094-appb-000017
合成例17～18：Synthesis examples 17-18:
聚合物-17和聚合物-18的合成方法参照合成例16，只是二胺单体的摩尔分数分别调整为：2,2-双(3-氨基-4-羟基苯基)六氟丙烷(75mmol)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(25mmol)(合成例17)和2,2-双(3-氨基-4-羟基苯基)六氟丙烷(25mmol)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(75mmol)(合成例18)。其它条件/过程与合成例16完全相同。因而聚合物-17和聚合物-18的化学式和聚合物-16完全相同，只是摩尔分数m/(m+n)有所改变，分别为3：1(合成例17：聚合物-17)和1：3(合成例18：聚合物-18)。The synthesis methods of polymer-17 and polymer-18 refer to Synthesis Example 16, except that the mole fraction of the diamine monomer is adjusted to: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (75mmol ), 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (25mmol) (Synthesis Example 17) and 2,2- Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (25mmol), 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3 -Hexafluoropropane (75 mmol) (Synthesis Example 18). Other conditions/processes are exactly the same as in Synthesis Example 16. Therefore, the chemical formulas of polymer-17 and polymer-18 are exactly the same as those of polymer-16, except that the mole fraction m/(m+n) is changed to 3:1 (Synthesis Example 17: Polymer-17) and 1:3 (Synthesis Example 18: Polymer-18).
合成例19：Synthesis Example 19:
在具有机械搅拌器、温度计以及高纯氮气气氛下的四口烧瓶中，装入对苯二胺(50mmol)、4,4'-二氨基二苯醚(50mmol)、2-甲基吡啶(300mmol)以及无水N-甲基-2-吡咯烷酮(NMP)(47.25克)，搅拌至完全溶解(溶液变清)，冷却至-10℃。保持上述溶液在-10至-5℃的温度区间内向其滴加已经溶解好的4,4'-双(磺酰氯)二苯醚(100mmol)和无水N-甲基-2-吡咯烷酮(42.00克)的混合液，约半个小时滴毕，然后在使溶液温度保持在0至5℃的同时继续搅拌1小时。将得到的反应溶液缓慢滴流至约8升的水中，沉降并过滤回收析出物并重复相同过程用纯水清洗3次后，得到湿品。并于80℃真空烘箱中干燥24h以上得到终产物。将得到的无规共聚物命名为聚合物-19，其结构式如下。m和n是相应重复单元数，结构单元的摩尔分数分别为m/(m+n)＝0.5和n/(m+n)＝0.5。In a four-necked flask with a mechanical stirrer, a thermometer and a high-purity nitrogen atmosphere, p-phenylenediamine (50mmol), 4,4'-diaminodiphenyl ether (50mmol), 2-methylpyridine (300mmol) ) And anhydrous N-methyl-2-pyrrolidone (NMP) (47.25g), stir until completely dissolved (the solution becomes clear), and cool to -10°C. Keep the above solution in the temperature range of -10 to -5°C and add dropwise the dissolved 4,4'-bis(sulfonyl chloride) diphenyl ether (100mmol) and anhydrous N-methyl-2-pyrrolidone (42.00). The mixture of g) is dripped in about half an hour, and then stirring is continued for 1 hour while keeping the temperature of the solution at 0 to 5°C. The obtained reaction solution was slowly trickled into about 8 liters of water, settled and filtered to recover the precipitate, and the same process was repeated and washed with pure water 3 times to obtain a wet product. And dried in a vacuum oven at 80°C for more than 24 hours to obtain the final product. The random copolymer obtained was named Polymer-19, and its structural formula is as follows. m and n are the corresponding numbers of repeating units, and the mole fractions of structural units are m/(m+n)=0.5 and n/(m+n)=0.5, respectively.
(聚合物-19)(Polymer-19)
Figure PCTCN2020091094-appb-000018
Figure PCTCN2020091094-appb-000018
合成例20～21：Synthesis example 20-21:
聚合物-20和聚合物-21的合成方法参照合成例19，只是二胺单体的摩尔分数分别调整为：对苯二胺(75mmol)、4,4'-二氨基二苯醚(25mmol)(合成例20)和对苯二胺(25mmol)、4,4'-二氨基二苯醚(75mmol)(合成例21)。其它条件/过程与合成例19完全相同。因而聚合物-20和聚合物-21的化学式和聚合物-19完全相同，只是摩尔分数m/(m+n)有所改变，分别为3：1(合成例20：聚合物-20)和1：3(合成例21：聚合物-21)。The synthetic methods of polymer-20 and polymer-21 refer to Synthesis Example 19, except that the mole fraction of the diamine monomer is adjusted to: p-phenylenediamine (75mmol), 4,4'-diaminodiphenyl ether (25mmol) (Synthesis Example 20) and p-phenylenediamine (25 mmol) and 4,4'-diaminodiphenyl ether (75 mmol) (Synthesis Example 21). The other conditions/processes are exactly the same as in Synthesis Example 19. Therefore, the chemical formulas of polymer-20 and polymer-21 are exactly the same as those of polymer-19, except that the mole fraction m/(m+n) is changed to 3:1 (synthesis example 20: polymer-20) and 1:3 (Synthesis Example 21: Polymer-21).
合成例22～25不是混聚物，但也包括在本发明的权利要求书中。如权利要求1所述(A)成分的通式(1)中所表述的X1和X2可以是相同或不同的二 价芳香族连接基团。当X1和X2是相同的芳香族连接基团，如下聚合物22～25(结构式如下)仍然可以用前述合成例1的方法合成。只是合成例1中的2,2'-二(三氟甲基)二氨基联苯(50mmol)和4,4'-二氨基二苯醚(50mmol)组分分别由如下化合物替代：2,2'-二(三氟甲基)二氨基联苯(100mmol)(合成例22：聚合物-22)；2,2-双(3-氨基-4-羟基苯基)六氟丙烷(100mmol)(合成例23：聚合物-23)；2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(100mmol)(合成例24：聚合物-24)；4,4'-二氨基二苯醚(100mmol)(合成例25：聚合物-25)。Synthesis examples 22 to 25 are not mixed polymers, but are also included in the claims of the present invention. X1 and X2 expressed in the general formula (1) of the component (A) according to claim 1 may be the same or different divalent aromatic linking groups. When X1 and X2 are the same aromatic linking group, the following polymers 22-25 (the structural formula is as follows) can still be synthesized by the method of the aforementioned Synthesis Example 1. Only the 2,2'-bis(trifluoromethyl)diaminobiphenyl (50mmol) and 4,4'-diaminodiphenyl ether (50mmol) components in Synthesis Example 1 were replaced by the following compounds: 2,2 '-Bis(trifluoromethyl)diaminobiphenyl (100mmol) (Synthesis Example 22: Polymer-22); 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (100mmol) ( Synthesis Example 23: Polymer-23); 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (100mmol) (synthesis Example 24: Polymer-24); 4,4'-diaminodiphenyl ether (100 mmol) (Synthesis Example 25: Polymer-25).
合成例22：Synthesis Example 22:
(聚合物-22)(Polymer-22)
Figure PCTCN2020091094-appb-000019
Figure PCTCN2020091094-appb-000019
合成例23：Synthesis Example 23:
(聚合物-23)(Polymer-23)
Figure PCTCN2020091094-appb-000020
Figure PCTCN2020091094-appb-000020
合成例24Synthesis example 24
(聚合物-24)(Polymer-24)
Figure PCTCN2020091094-appb-000021
Figure PCTCN2020091094-appb-000021
合成例25：Synthesis Example 25:
(聚合物-25)(Polymer-25)
Figure PCTCN2020091094-appb-000022
Figure PCTCN2020091094-appb-000022
以下，对本发明的负型光敏性组合物、图案固化物的制造方法、固化物、重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜以及电子器件的实施方式进行详细说明。需要说明的是，本发明不受以下的实施方式的限定。另外，在本说明书中，所谓“A或B”，只要包含A和B中的任一者即可，也可以两者均包含。还有，使用“～”表示的数值范围表示包含“～”前后所记载的数值分别作为最小值和最大值的范围。Hereinafter, embodiments of the negative photosensitive composition, pattern cured product, cured product, redistribution layer, interlayer insulating buffer film, cover coat or surface protective film, and electronic devices of the present invention will be described in detail. In addition, this invention is not limited by the following embodiment. In addition, in this specification, the so-called "A or B" should just include any one of A and B, or both may be included. In addition, the numerical range indicated by "-" means a range that includes the numerical values described before and after "-" as the minimum and maximum values, respectively.
本发明的负型光敏性组合物含有至少(A)一种聚磺酰胺聚合物(结构如通式(1))、(B)光酸产生剂、(C)交联剂、(D)溶剂。以下，对本发明组合物中使用的各成分进行详细说明，其中A组分聚磺酰胺聚合物、性能和合成参见上述第一部分的介绍。The negative photosensitive composition of the present invention contains at least (A) a polysulfonamide polymer (structure such as general formula (1)), (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent . Hereinafter, each component used in the composition of the present invention will be described in detail. Among them, the polysulfonamide polymer, performance and synthesis of component A, refer to the introduction in the first part above.
二、(B)：光酸产生剂2. (B): Photoacid generator
本发明中作为(B)成分的光酸产生剂是受到光线的照射而产生酸的化合物。这里的含有聚磺酰胺聚合物的负型光敏性组合物在成膜后，曝光产生的光酸会导致膜中的聚合物交联从而使曝光部分的溶解度显著降低。在非曝光部分，这些光酸产生剂不会发生化学反应因而保持在显影液中的良好溶解性。由此，曝光区域和非曝光区域(暗区)的溶解速度会有较大差别(contrast)，进而在显影步骤后会得到具有微结构浮雕图案的膜。The photoacid generator as the component (B) in the present invention is a compound that generates an acid when irradiated with light. After the negative photosensitive composition containing the polysulfonamide polymer is formed into a film, the photoacid generated by exposure will cause the polymer in the film to crosslink, thereby significantly reducing the solubility of the exposed part. In the non-exposed part, these photoacid generators do not undergo a chemical reaction and thus maintain good solubility in the developer. As a result, the dissolution rate of the exposed area and the non-exposed area (dark area) will be quite different (contrast), and a film with a microstructure relief pattern will be obtained after the development step.
所述光酸产生剂选自但不限于离子型化合物包括硫盐、鏻盐或碘鎓盐；非离子型化合物包括肟磺酸酯、磺酸酯化合物或醌二叠氮化物化合物；或其混合物。从灵敏度和成像性的角度考虑，优选肟磺酸酯化合物。肟磺 酸酯类化合物，能够得到对于作为通常的紫外线的汞灯的i线(波长365nm)、h线(波长405nm)、g线(波长436nm)具有较好敏感度的光酸化合物。很多肟磺酸酯类化合物可以通过商业渠道购得。下面的式(9)代表几个常见的肟酯类化合物。The photoacid generator is selected from but not limited to ionic compounds including sulfur salts, phosphonium salts or iodonium salts; non-ionic compounds include oxime sulfonate, sulfonate compound or quinone diazide compound; or mixtures thereof . From the viewpoint of sensitivity and imageability, oxime sulfonate compounds are preferred. The oxime sulfonate compound can obtain a photoacid compound having good sensitivity to the i-line (wavelength of 365 nm), h-line (wavelength of 405 nm), and g-line (wavelength of 436 nm) of a mercury lamp which is a normal ultraviolet light. Many oxime sulfonate compounds can be purchased through commercial channels. The following formula (9) represents several common oxime ester compounds.
Figure PCTCN2020091094-appb-000023
Figure PCTCN2020091094-appb-000023
为了得到最优分辨率和提高图案对比度，肟酯类化合物的含量相对于(A)成分100质量份而言优选为0.1～20质量份，更优选为1.0～10.0质量份。在上述范围内，曝光部分聚合物会有较好程度的交联从而得到实用的浮雕图案。另外，这里(B)成分可以单独使用一种，也可以组合两种以上使用In order to obtain the optimal resolution and improve the pattern contrast, the content of the oxime ester compound is preferably 0.1 to 20 parts by mass, and more preferably 1.0 to 10.0 parts by mass relative to 100 parts by mass of the component (A). Within the above range, the exposed part of the polymer will have a better degree of cross-linking to obtain a practical relief pattern. In addition, here (B) component can be used alone or in combination of two or more
三、(C)：交联剂成分3. (C): Crosslinking agent components
本发明中的光敏性聚磺酰胺组合物中所述(C)交联剂成分是在对负型光敏性组合物进行曝光和加热固化的步骤中能与组分(A)聚磺酰胺聚合物进行交联反应的化合物。由于这些有效的交联反应，由聚磺酰胺聚合物得到的固化膜会具有优良的光敏分辨率和在较低的后固化温度(通常≤250℃)达到优良的粘接性、机械性能、和耐化学试剂腐蚀性，从而避免了在工艺流程中采用很高的后固化温度。从固化物膜的机械性能和低温固化时的交联性考虑，交联剂优选为至少含有一种具有-CH 2OR(R是氢原子或1价有机基团)的烷氧基化合物/羟基化合物；环氧基化合物；氧杂环丁烷基化合物或乙烯基醚基化合物。从固化物膜的机械特性和低温固化时的反应性高的观点考虑，优选为具有羟基、羟甲基等羟基烷基或烷氧基甲基等烷氧基烷基的如下述式(10)所代表的化合物。 The (C) crosslinking agent component in the photosensitive polysulfonamide composition of the present invention is capable of interacting with the component (A) polysulfonamide polymer in the steps of exposing and heating and curing the negative photosensitive composition. Compounds that undergo cross-linking reactions. Due to these effective crosslinking reactions, the cured film obtained from the polysulfonamide polymer will have excellent photosensitive resolution and achieve excellent adhesion, mechanical properties, and Corrosion resistance to chemical reagents, thus avoiding the use of high post-curing temperatures in the process. In view of the mechanical properties of the cured film and the crosslinkability during low-temperature curing, the crosslinking agent preferably contains at least one alkoxy compound/hydroxyl group having -CH 2 OR (R is a hydrogen atom or a monovalent organic group) Compounds; epoxy compounds; oxetanyl compounds or vinyl ether-based compounds. From the viewpoint of the mechanical properties of the cured film and the high reactivity during low-temperature curing, it is preferably one having a hydroxyalkyl group such as a hydroxyl group and a hydroxymethyl group, or an alkoxyalkyl group such as an alkoxymethyl group, as shown in the following formula (10) The compound represented.
Figure PCTCN2020091094-appb-000024
Figure PCTCN2020091094-appb-000024
为了得到最优的抗化学试剂腐蚀性效果，交联剂(C)含量相对于(A)成分100质量份而言，优选为2～50质量份，进一步优选为8～40质量份。如果交联剂低于2质量份，会起不到显著交联和改善抗化学试剂腐蚀性的效果；如果交联剂高于50质量份，则可能会降低材料的各项机械性能。这里(C)成分可以单独使用一种，也可以组合两种以上所述的交联剂共同使用。In order to obtain the best anti-corrosion effect of chemical reagents, the content of the crosslinking agent (C) is preferably 2-50 parts by mass, and more preferably 8-40 parts by mass relative to 100 parts by mass of the component (A). If the cross-linking agent is less than 2 parts by mass, it will not achieve significant cross-linking and improve the corrosion resistance of chemical reagents; if the cross-linking agent is more than 50 parts by mass, it may reduce the mechanical properties of the material. Here, the component (C) may be used singly or in combination of two or more of the above-mentioned crosslinking agents.
四、(D)成分：溶剂Fourth, (D) component: solvent
(D)成分作为溶剂，将上述(A)～(C)成分溶解而使组合物形成清漆。(D)成分可采用包括至少一种从如下溶剂所选的化合物：酯、醚、醚-酯、酮、酮-酯、芳香族化合物，和/或卤代烃类溶剂。通常，只要能够充分溶解负型光敏性组合物中的其他成分并适合光刻工艺过程就没有特别限制。一些常用溶剂包括N-甲基-2-吡咯烷酮、γ-丁内酯、ε-己内酯、N，N－二 甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、2-甲氧基乙醇、二乙二醇二乙基醚、二乙二醇二丁基醚、丙二醇单甲基醚、二丙二醇单甲基醚、丙二醇单甲基醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲基-1,3-丁二醇乙酸酯、1,3-丁二醇乙酸酯、环己酮、四氢呋喃等。在这些溶剂中，从溶解性和树脂膜的涂布性优异的观点考虑，优选使用γ-丁内酯、N-甲基-2-吡咯烷酮、环戊酮为主体的溶剂体系。(D) A component is used as a solvent, and the said (A)-(C) component is melt|dissolved, and a composition becomes a varnish. The component (D) may include at least one compound selected from the following solvents: ester, ether, ether-ester, ketone, ketone-ester, aromatic compound, and/or halogenated hydrocarbon solvent. Generally, as long as it can fully dissolve other components in the negative photosensitive composition and is suitable for the photolithography process, there is no particular limitation. Some common solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, ε-caprolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide , 2-Methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate Ester, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, 1,3-butanediol acetate, cyclohexanone, tetrahydrofuran, etc. Among these solvents, it is preferable to use a solvent system mainly composed of γ-butyrolactone, N-methyl-2-pyrrolidone, and cyclopentanone from the viewpoint of excellent solubility and coating properties of the resin film.
(D)成分的含量没有特别限制，主要从调控膜厚的角度考虑，优选相对于(A)成分100质量份为50～800质量份，更优选为60～300质量份，进一步优选为80～220质量份The content of the component (D) is not particularly limited, but mainly from the viewpoint of controlling the film thickness, it is preferably 50 to 800 parts by mass relative to 100 parts by mass of the component (A), more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass
五、组合物其它成分Five, other components of the composition
本发明的树脂组合物除了上述(A)～(D)成分以外，也可以根据需要含有其它成分，例如抗腐蚀剂、增粘剂、柔顺剂、溶解促进剂、流平剂等。加入这些添加剂的原则是不会实质上损害本发明的最终固化物膜的基本特性。通常这些成分会改善材料的某些性质从而使其更加适用于一些针对具体客户的工艺和应用。下面对这些成分及作用一一详述。In addition to the above-mentioned (A) to (D) components, the resin composition of the present invention may also contain other components as necessary, such as an anticorrosive agent, a thickener, a softening agent, a dissolution accelerator, a leveling agent, and the like. The principle of adding these additives is not to substantially impair the basic characteristics of the final cured film of the present invention. Usually these ingredients will improve certain properties of the material to make it more suitable for certain customer-specific processes and applications. These ingredients and their effects are described in detail below.
抗腐蚀剂-将本发明的感光性树脂组合物涂于基板铜或铜合金上时，为了抑制由于铜腐蚀而导致的变色和稳定性降低，可以在组合物中加入至少一个包含碳原子和氮原子的如通式(11)所示的含有三唑环、咪唑环以及噻唑环骨架的化合物。作为唑化合物，例如可列举出1H-三唑、1H-苯并三唑、2-(2H-苯并三氮唑-2-基)对甲苯酚、1,5-二甲基三唑、4,5-二乙基-1H-三唑、4-叔丁基-5-苯基-1H-三唑、5-乙基-1H-三唑、4,5-二甲基-1H-三唑、5-苯基-1H-三唑、5-羟基苯基-1H-三唑、对乙氧基苯基三唑、5-苯基-1-(2-二甲基氨基乙基)三唑、5-苄基-1H-三唑、2-(5-甲基-2-羟基苯基)苯并三 唑、2-[2-羟基-3,5-双(α,α-二甲基苄基)苯基]-苯并三唑、2-(3,5-二叔丁基-2-羟基苯基)苯并三唑、2-(3-叔丁基-5-甲基-2-羟基苯基)-苯并三唑、2-(3,5-二叔戊基-2-羟基苯基)苯并三唑、2-(2’-羟基-5’-叔辛基苯基)苯并三唑、羟基苯基苯并三唑、甲苯基三唑、4-甲基-1H-苯并三唑、4-羧基-1H-苯并三唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-氨基-1H-四唑、1-甲基-1H-四唑等。优选含有苯环的苯并三唑化合物例如甲苯基三唑、5-甲基-1H-苯并三唑的1种或一种以上的混合物。Anti-corrosion agent-When the photosensitive resin composition of the present invention is applied to the substrate copper or copper alloy, in order to suppress the discoloration and stability reduction due to copper corrosion, at least one containing carbon atoms and nitrogen atoms may be added to the composition The compound containing triazole ring, imidazole ring and thiazole ring skeleton as represented by general formula (11). As the azole compound, for example, 1H-triazole, 1H-benzotriazole, 2-(2H-benzotriazol-2-yl)p-cresol, 1,5-dimethyltriazole, 4 ,5-Diethyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole , 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole , 5-benzyl-1H-triazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethyl Benzyl)phenyl)-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2 -Hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl) ) Benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-methyl-1H-tetrazole Azole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Preferably, a benzene ring-containing benzotriazole compound such as tolyltriazole and 5-methyl-1H-benzotriazole is a mixture of one or more kinds.
Figure PCTCN2020091094-appb-000025
Figure PCTCN2020091094-appb-000025
为了得到最优的抗金属腐蚀效果，抗腐蚀剂含量相对于(A)成分100质量份而言优选为0.1～10质量份，更优选为0.5～8质量份。In order to obtain the optimal anti-metal corrosion effect, the content of the anti-corrosion agent is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the component (A).
增粘剂-为了提高由本发明的感光性树脂组合物制成的固化物膜与基板的粘接性，可以在该感光性树脂组合物中配混增粘剂成分。增粘剂可选有机硅烷化合物和包括三(乙基乙酰乙酸基)铝、三(乙酰丙酮)铝、乙酰乙酸乙基铝二异丙酯等铝系粘接助剂等。从提高在铜等基板的粘接力考虑，优选使用有机硅烷化合物。有机硅烷化合物包括：3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-[双(2-羟乙基)氨基]丙烷-三乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-脲基丙基三乙氧基硅烷、γ-缩水甘油氧基丙基三乙氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三甲氧基硅烷、3-异氰酸酯基丙基三乙氧基硅烷、氨基甲酸三乙氧基甲硅烷基丙基乙酯、3-(三乙氧基甲硅烷基)丙基琥珀酸酐、苯基三乙氧基硅 烷、苯基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷等。这些有机硅烷化合物可以单独使用，也可以组合2种以上使用。增粘剂成分在组合物中的含量，从改善对基板的粘贴行的角度考虑，相对于(A)成分100质量份优选为0.1～10质量份，更优选为0.5～8质量份。Tackifier-In order to improve the adhesiveness of the cured product film made of the photosensitive resin composition of the present invention to the substrate, a tackifier component may be blended in the photosensitive resin composition. Tackifiers can be selected from organosilane compounds and aluminum-based adhesive additives including tris(ethylacetoacetate) aluminum, tris(acetylacetonate) aluminum, and ethyl aluminum diisopropyl acetoacetate. It is preferable to use an organosilane compound from the viewpoint of improving the adhesion to a substrate such as copper. Organosilane compounds include: 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane, vinyl triethoxy Silane, vinyl trimethoxy silane, γ-ureidopropyl triethoxy silane, γ-glycidoxy propyl triethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ -Methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, amino Triethoxysilylpropyl ethyl formate, 3-(triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3 -Aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. These organosilane compounds may be used alone or in combination of two or more kinds. The content of the thickener component in the composition is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the component (A) from the viewpoint of improving the adhesion to the substrate.
柔顺剂-在这里的负型聚磺酰胺组合物中，柔顺剂可以提高由其制备的固化物膜的柔韧性从而增大材料断裂时的拉伸长度参数(elongation)。作为柔顺剂，可选择具有不同分子量的多元醇、聚酯、多羟基酯等化合物。这些柔顺剂可单独使用或将两种以上组合使用。如果选用柔顺剂成分，其在组合物中的含量，相对于(A)成分100质量份优选为1～40质量份。Softener-In the negative polysulfonamide composition here, the softener can improve the flexibility of the cured film prepared therefrom to increase the elongation when the material breaks. As a softener, compounds such as polyols, polyesters, and polyhydroxy esters with different molecular weights can be selected. These softeners can be used alone or in combination of two or more. If the softener component is selected, its content in the composition is preferably 1 to 40 parts by mass relative to 100 parts by mass of the component (A).
溶解促进剂-在这里的负型聚磺酰胺组合物中，溶解促进剂可以提高未曝光部分的溶解速度从而提高微图形的分辨率和显影对比度。作为溶解促进剂，可列举出例如具有羟基或羧基的化合物等。作为具有羟基的化合物的例子，可列举对异丙苯基苯酚、间苯二酚类、双酚类、其它直链状或非直链状酚类化合物、二苯基甲烷的2～5个的酚类取代物、3,3-二苯基丙烷的1～5个的酚类取代物等。这些溶解促进剂可单独使用或将两种以上组合使用。溶解促进剂成分在组合物中的含量，相对于(A)成分100质量份优选为1～50质量份。Dissolution accelerator-In the negative polysulfonamide composition herein, the dissolution accelerator can increase the dissolution speed of the unexposed part to improve the resolution and development contrast of the micropattern. As the dissolution accelerator, for example, a compound having a hydroxyl group or a carboxyl group, etc. can be cited. Examples of compounds having a hydroxyl group include p-cumyl phenol, resorcinols, bisphenols, other linear or non-linear phenolic compounds, and 2 to 5 diphenylmethanes. Phenolic substituents, 1 to 5 phenolic substituents of 3,3-diphenylpropane, etc. These dissolution accelerators can be used alone or in combination of two or more. The content of the dissolution accelerator component in the composition is preferably 1 to 50 parts by mass relative to 100 parts by mass of the component (A).
流平剂-为了在旋涂制膜时提高涂布性以及表面光滑性，可以在组合物中加入表面活性剂作为流平剂，可以举出的表面活性剂包括聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯酚醚等。一些可以直接从市场购买得到的例子，包括MegafacF171、F173(大日本油墨化学工业株式会社制造)；有机硅氧烷类的KP341、KBM303、KBM803(信越化学工业株式会社制造)；还有一些含氟的表面活性剂PolyFox PF-6320 (Omnova Solutions)，Fluorad FC430、FC171(住友3M株式会社制造)等。关于使用表面活性剂的含量，相对于(A)成分100质量份优选为0.01～5质量份，进一步优选为0.05～3质量份。Leveling agent-In order to improve the coating properties and surface smoothness during spin coating film formation, a surfactant can be added to the composition as a leveling agent. Examples of surfactants include polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, and polyoxyethylene lauryl ether. Oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, etc. Some examples that can be purchased directly from the market include Megafac F171, F173 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.); organosiloxane KP341, KBM303, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.); and some containing fluorine Surfactants PolyFox PF-6320 (Omnova Solutions), Fluorad FC430, FC171 (manufactured by Sumitomo 3M Co., Ltd.), etc. The content of the surfactant to be used is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the component (A).
以下是本发明含有聚磺酰胺聚合物的负型光敏性组合物的较优实施例。The following are preferred examples of the negative photosensitive composition containing polysulfonamide polymer of the present invention.
实施例1：将在合成例1中得到的聚合物-1(100质量份)、作为光酸的B-1(3质量份，相对于聚合物-1)、作为交联剂的C-1(20质量份)溶解于环戊酮(D-1，180份)中，并添加作为抗腐蚀剂的E-1(1.5质量份)、作为增粘剂的F-1(2质量份)、作为流平剂的H-1(0.05质量份)而得到本发明所述的负型光敏性树脂组合物。除聚合物组分(A)以外的其它组分信息参照如下：Example 1: Polymer-1 (100 parts by mass) obtained in Synthesis Example 1, B-1 as a photoacid (3 parts by mass relative to polymer-1), and C-1 as a crosslinking agent (20 parts by mass) was dissolved in cyclopentanone (D-1, 180 parts), and E-1 (1.5 parts by mass) as an anticorrosive agent, F-1 (2 parts by mass) as a thickener, as H-1 (0.05 parts by mass) of the leveling agent to obtain the negative photosensitive resin composition of the present invention. Please refer to the following for information on other components except polymer component (A):
Figure PCTCN2020091094-appb-000026
Figure PCTCN2020091094-appb-000026
(D-1):环戊酮(D-1): Cyclopentanone
(D-2):90％环戊酮/10％甲基戊基酮(D-2): 90% cyclopentanone/10% methyl amyl ketone
(E-1):1H-苯并三唑(E-1): 1H-Benzotriazole
(E-2):2-(2H-苯并三氮唑-2-基)对甲苯酚(E-2): 2-(2H-benzotriazol-2-yl)p-cresol
(E-3):5-甲基-1H-苯并三唑(E-3): 5-methyl-1H-benzotriazole
(F-1):Z-6040 Silane(Dow Corning)(F-1):Z-6040 Silane(Dow Corning)
(F-2):3-(2,3-环氧丙氧)丙基三甲氧基硅烷(F-2): 3-(2,3-glycidoxy)propyltrimethoxysilane
(F-3)：3-[双(2-羟乙基)氨基]丙烷-三乙氧基硅烷(F-3): 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane
(G-1)(柔顺剂):K-PURE CDR-3314(King Industries，Inc)(G-1) (Softener): K-PURE CDR-3314 (King Industries, Inc)
(H-1)(流平剂):PolyFox PF-6320(OMNOVA Solutions Inc.)(H-1) (Leveling agent): PolyFox PF-6320 (OMNOVA Solutions Inc.)
实施例2～25和比较例1～5的制备方法与实施例1完全相同，只是其中所用各个组分或含量有所不同。这些实施例/比较例所述的组合物组分及其各组分相对于聚合物(A)(100质量份)的含量(括号中的质量份)详见下表-1。The preparation methods of Examples 2-25 and Comparative Examples 1-5 are exactly the same as those of Example 1, except that the various components or contents used therein are different. The composition components described in these examples/comparative examples and the content of each component relative to the polymer (A) (100 parts by mass) (parts by mass in parentheses) are shown in Table-1 below.
表-1Table 1
Figure PCTCN2020091094-appb-000027
Figure PCTCN2020091094-appb-000027
Figure PCTCN2020091094-appb-000028
Figure PCTCN2020091094-appb-000028
NA：代表组合物中不含该类组分。NA: It means that there is no such component in the composition.
由上面实施例/对比例所获的感光性树脂组合物(又称清漆)，经过聚四氟乙烯的过滤膜进行过滤，从而得到最终的负型感光性树脂组合物。根据组合物中的聚合物浓度和清漆粘度，可以选择0.45-3微米孔径的聚四氟乙烯过滤膜。The photosensitive resin composition (also called varnish) obtained from the above examples/comparative examples was filtered through a polytetrafluoroethylene filter membrane to obtain the final negative photosensitive resin composition. According to the polymer concentration and varnish viscosity in the composition, a polytetrafluoroethylene filter membrane with a pore size of 0.45-3 microns can be selected.
然后把以上清漆按前述权利要求6所述方法制成涂在基板材料上的10微米厚左右的聚磺酰胺树脂膜。以下对这些聚磺酰胺树脂膜及由制备的具有浮雕图案的固化物膜进行进一步说明。Then, the above varnish is made into a polysulfonamide resin film with a thickness of about 10 micrometers coated on the substrate material according to the method described in claim 6 above. Hereinafter, these polysulfonamide resin films and the cured product films with embossed patterns prepared therefrom will be further described.
由本发明中聚磺酰胺组合物制备的一种图案固化物的制造方法包含如下步骤：The manufacturing method of a patterned cured product prepared from the polysulfonamide composition of the present invention includes the following steps:
(a)树脂膜形成步骤：将权利要求1～5中所述的聚磺酰胺聚合物组合物涂布于基板上并加热干燥去除溶剂而形成感光性树脂膜的步骤。作为基板，可列举Si基板(硅晶片)等半导体基板、陶瓷基板类、金属基板(包括铜基板、铝基板、铜合金基板等)、氮化硅基板等。涂布方法可以采用可以举出旋转涂布法、喷涂法、浸渍法等，从控制膜厚的角度，优选依靠旋涂器的旋涂法。加热干燥可以使用热板、烘箱等。加热干燥温度优选为90～150℃，更优选为90～130℃。树脂膜的膜厚优选为1～50μm，进一步优选为1～30μm。(a) Resin film forming step: a step of applying the polysulfonamide polymer composition according to claims 1 to 5 on a substrate and heating and drying to remove the solvent to form a photosensitive resin film. Examples of the substrate include semiconductor substrates such as Si substrates (silicon wafers), ceramic substrates, metal substrates (including copper substrates, aluminum substrates, copper alloy substrates, etc.), silicon nitride substrates, and the like. The coating method may be a spin coating method, a spray method, a dipping method, etc., and from the viewpoint of controlling the film thickness, a spin coating method using a spin coater is preferred. A hot plate, oven, etc. can be used for heating and drying. The heating and drying temperature is preferably 90 to 150°C, more preferably 90 to 130°C. The thickness of the resin film is preferably 1 to 50 μm, more preferably 1 to 30 μm.
(b)曝光步骤：利用掩模版对所述感光性树脂膜进行图案曝光的步骤。图案曝光例如隔着光掩模曝光成预定图案。所照射的活性光线可列举i线等 紫外线、可见光线、放射线等，优选为i线。作为曝光装置，可以使用扫描曝光机、投影曝光机、步进曝光机等。(b) Exposure step: a step of patterning the photosensitive resin film using a mask. The pattern exposure is exposed in a predetermined pattern through a photomask, for example. The active light rays to be irradiated include ultraviolet rays such as i-rays, visible light rays, and radiation rays, and i-rays are preferred. As the exposure device, a scanning exposure machine, a projection exposure machine, a stepping exposure machine, etc. can be used.
(c)显影步骤：通过进行显影步骤，能够得到具有微结构浮雕图案的树脂膜。一般而言，通过浸渍法、旋转喷雾法等方法进行显影。在本发明使用负型感光性树脂组合物的情况下，显影液可以除去膜的未曝光部分从而可以得到浮雕图案。显影时间一般为10秒钟～15分钟，从提高生产率和过程控制的观点考虑，优选为20秒钟～5分钟。作为显影液，可以使用氢氧化钠、碳酸钠、硅酸钠、氨水等无机碱类；亦可以使用乙胺、三乙醇胺、二乙胺等有机胺类；还可以使用四甲基氢氧化铵(TMAH)、四丁基氢氧化铵等季铵盐类等的水溶液。在前述的各类显影液中，可以根据需要添加适当量的甲醇、乙醇等水溶性有机溶剂或表面活性剂而加强效果。这些显影液中，优选为四甲基氢氧化铵水溶液。一般而言，优选使用浓度为2.38％的TMAH水溶液。需要说明的是，根据(A)成分溶解速度，碱性显影液中TMAH的浓度可以适当稀释以调节曝光区域和非曝光区域的膜溶解速度从而在显影时得到最优的对比度。显影后，可以使用冲洗液进行清洗以去除显影液，由此可以得到图案薄膜。作为冲洗液，可以将蒸馏水、甲醇、乙醇、异丙醇、丙二醇单甲醚、丙二醇单甲醚乙酸酯等单独使用或混合使用。(c) Development step: By performing the development step, a resin film with a microstructure relief pattern can be obtained. In general, development is performed by methods such as a dipping method and a rotary spray method. In the case where the negative photosensitive resin composition is used in the present invention, the developer can remove the unexposed part of the film to obtain a relief pattern. The development time is generally 10 seconds to 15 minutes, and from the viewpoint of productivity improvement and process control, it is preferably 20 seconds to 5 minutes. As the developer, inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia can be used; organic amines such as ethylamine, triethanolamine, and diethylamine can also be used; and tetramethylammonium hydroxide can also be used ( TMAH), aqueous solutions of quaternary ammonium salts such as tetrabutylammonium hydroxide. In the aforementioned various developing solutions, water-soluble organic solvents such as methanol and ethanol or surfactants can be added in an appropriate amount as needed to enhance the effect. Among these developing solutions, tetramethylammonium hydroxide aqueous solution is preferable. In general, it is preferable to use an aqueous solution of TMAH with a concentration of 2.38%. It should be noted that, according to the dissolution rate of component (A), the concentration of TMAH in the alkaline developer can be appropriately diluted to adjust the film dissolution rate in the exposed area and the non-exposed area to obtain the optimal contrast during development. After development, washing liquid can be used to remove the developer liquid, thereby obtaining a patterned film. As the rinse liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. can be used alone or in combination.
(d)加热固化步骤:加热处理步骤是对所述浮雕图案树脂膜进行加热固化从而获得材料最优物性的过程。本步骤中，对通过上述显影而得到的浮雕图案进行加热，从而使其转变为固化浮雕图案。可以选择利用热板或烘箱的方法，加热温度优选为250℃以下，更优选为180～230℃的温度。加热处理的时间从交联反应需要的时间考虑通常需要30分钟到4小时，更优选为30分钟～2小时。加热处理的气氛可以在空气中进行，也可以在氮气、氩气等惰性气体的氛围中进行。从能够防止图案树脂膜的氧化和成本考虑，优 选在高纯氮气(≥99.999％)氛围中加热固化。(d) Heating and curing step: The heating treatment step is a process of heating and curing the embossed patterned resin film to obtain the optimal physical properties of the material. In this step, the relief pattern obtained by the above development is heated to convert it into a cured relief pattern. A method using a hot plate or an oven can be selected, and the heating temperature is preferably 250°C or less, and more preferably a temperature of 180 to 230°C. The time for the heat treatment is usually 30 minutes to 4 hours, and more preferably 30 minutes to 2 hours from the time required for the crosslinking reaction. The atmosphere of the heat treatment may be performed in air or in an atmosphere of inert gas such as nitrogen and argon. In view of the ability to prevent oxidation of the patterned resin film and cost considerations, it is preferable to heat and cure in a high-purity nitrogen (≥99.999%) atmosphere.
本发明的固化物即为采用上述处理工序得到的聚合树脂固化膜，这种膜既可以为上述的具有浮雕图案的固化膜，也可以为无图案的固化膜。The cured product of the present invention is a cured polymer resin film obtained by the above-mentioned treatment process, and this film may be the cured film with embossed patterns as described above, or it may be a cured film without a pattern.
作为固化膜，可以通过直接接触的方式层叠于半导体元件之中，或者也可以之间夹着其它的层来层叠。它们还可以用来包裹其它材料例如金属导线从而起到绝缘介质的作用。可列举出的应用包括重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜材料等。As a cured film, it may be laminated in the semiconductor element by direct contact, or it may be laminated|stacked by sandwiching another layer in between. They can also be used to wrap other materials such as metal wires to act as an insulating medium. Examples of applications include redistribution layers, interlayer insulation buffer films, cover coatings or surface protection film materials.
下面结合附图1对本发明所述的一例重新分布层的制造方法进行说明。In the following, an example of a method for manufacturing a redistribution layer according to the present invention will be described with reference to FIG. 1.
图1(结构剖面的概略示意图)是采用本发明组合物及其实施方式的重新分布层结构的构建。需要说明的是图形中的膜厚和器件尺寸比例不代表真实比例。在本实施方式中，通过两层配线结构的设计，信号可以实现在芯片(Al Pad：铝接触板电极)和外界(Solder Bump：焊锡球)之间的信号输入/输出功能。两层配线结构是由包裹在绝缘材料聚合物层(聚合物层1和聚合物层2)上的铜重新分布层引线(Cu RDL)实现的。如图所示，铜引线连接芯片上的铝片接触板电极(Al Pad)和焊锡球(Solder Bump)。焊锡小球在封装之后的下一步工艺中会连接到其它封装或主板上从而实现封装对封装或者封装对主板的连接。这里的焊锡小球和铜引线的连接是通过球下金属层(UBM Stud)实现的。这两层绝缘材料(聚合物层1和聚合物层2)采用本发明所述的聚磺酰胺固化物膜。通过这样的设计和构建可以实现重新布线并实现改变接触电极位置/尺寸的目的。另外，在这里的聚磺酰胺固化物膜不仅是包裹铜引线的绝缘介电材料，还会起到缓和内部应力的结构性作用。这些材料需要具备较好的长期稳定性从而在温度不断变化而带来的热胀冷缩循环中及其伴随的应力变化中维持优良的稳定性和材料复原能力。Figure 1 (a schematic diagram of a structural section) is a construction of a redistribution layer structure using the composition of the present invention and its embodiments. It should be noted that the ratio of film thickness to device size in the graph does not represent the true ratio. In this embodiment, through the design of the two-layer wiring structure, the signal can realize the signal input/output function between the chip (Al Pad: aluminum contact plate electrode) and the outside (Solder Bump: solder ball). The two-layer wiring structure is realized by copper redistribution layer leads (Cu RDL) wrapped on the insulating material polymer layer (polymer layer 1 and polymer layer 2). As shown in the figure, the copper leads connect the aluminum sheet on the chip to the pad electrode (Al Pad) and the solder ball (Solder Bump). The solder balls will be connected to other packages or the motherboard in the next process after packaging to realize the connection of the package to the package or the package to the motherboard. The connection between the solder balls and the copper leads here is achieved through the UBM Stud. The two layers of insulating materials (polymer layer 1 and polymer layer 2) use the polysulfonamide cured film described in the present invention. Through such design and construction, rewiring and changing the position/size of the contact electrode can be realized. In addition, the cured polysulfonamide film here is not only an insulating dielectric material that wraps the copper leads, but also plays a structural role in relaxing internal stress. These materials need to have good long-term stability in order to maintain excellent stability and material recovery ability during the thermal expansion and contraction cycles caused by continuous temperature changes and the accompanying stress changes.
使用选自由上述重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜材料等中的一种或一种以上，能够制造可靠性高稳定性好的半导体装置、多层线路板等电子部件。Using one or more selected from the above-mentioned redistribution layer, interlayer insulation buffer film, cover coating or surface protection film materials, etc., it is possible to manufacture semiconductor devices with high reliability and good stability, multilayer circuit boards and other electronics part.
八、粘接性的评价8. Evaluation of adhesion
本发明中固化物膜主要用来做为包裹铜导线的绝缘材料，因而这两种材料之间的良好粘贴性是一个很关键的材料参数。根据美国材料与试验协会(American Society for Testing and Materials，ASTM)的一个标准粘贴性测试方法：D3359用胶带测试粘贴行的标准方法(Standard Test Methods for Measuring Adhesion by Tape Test)，对所得到的固化物膜，用锯齿形百格刀片在垂直方向切割成10×10的格状的小格子(每格面积为1毫米*1毫米)。根据ASTM D3359所述方法，在固化物膜的这些小片上贴附粘性胶带(3M生产),并剥掉粘着带。根据剥掉粘着带时从基板剥离的固化膜的小片数量判断材料的粘贴行。在本发明中，如下的标准A或B用来判断材料膜对铜基板的粘贴性。详细结果列出在表-2中。In the present invention, the cured product film is mainly used as an insulating material for wrapping copper wires, so the good adhesion between the two materials is a very critical material parameter. According to a standard adhesive test method of the American Society for Testing and Materials (ASTM): D3359 Standard Test Methods for Measuring Adhesion by Tape Test, the obtained curing The material film is cut into 10×10 grid-like small grids (each grid area is 1 mm * 1 mm) with a zigzag 100 grid blade in the vertical direction. According to the method described in ASTM D3359, stick an adhesive tape (manufactured by 3M) on these small pieces of the cured film, and peel off the adhesive tape. Judge the sticking line of the material based on the number of small pieces of the cured film peeled off the substrate when the adhesive tape is peeled off. In the present invention, the following criteria A or B are used to judge the adhesion of the material film to the copper substrate. The detailed results are listed in Table-2.
A：没有剥离的格子A: No stripped grid
B:剥离格子数至少为1B: The number of stripped grids is at least 1
从下表-2可见，由本发明得到的聚磺酰胺固化物膜总体来讲对铜基板具有优良的黏着性。It can be seen from Table-2 below that the cured polysulfonamide film obtained by the present invention has excellent adhesion to the copper substrate as a whole.
九、变色抑制的评价9. Evaluation of Discoloration Inhibition
对于所得到的覆盖在铜金属上的固化膜，通过光学显微镜和肉眼来评价外观。如果固化膜能在固化后很好地保持底层铜金属膜的原色，就评价为A:抑制了变色；若固化膜下面的铜颜色明显向深红/褐色转变，就评价为B:未抑制变色。详细结果列出在下表-2中。The appearance of the obtained cured film covering the copper metal was evaluated by an optical microscope and the naked eye. If the cured film can well maintain the original color of the underlying copper metal film after curing, it is evaluated as A: discoloration is suppressed; if the color of the copper under the cured film changes significantly to deep red/brown, it is evaluated as B: discoloration is not suppressed . The detailed results are listed in Table-2 below.
A：抑制了变色A: Discoloration is suppressed
B：未抑制变色B: Discoloration is not suppressed
从下表-2可见，由本发明得到的聚磺酰胺固化物膜总体来讲对铜基板起到很好的保护作用并抑制了铜金属的变色。It can be seen from the following table-2 that the cured polysulfonamide film obtained by the present invention has a good protective effect on the copper substrate and inhibits the discoloration of the copper metal.
综上所述，本发明提出的聚磺酰胺固化物膜有效地解决了这类材料对铜基板材料粘着性不强的缺点，并且对基板铜金属起到了优良的保护作用。In summary, the polysulfonamide cured product film proposed in the present invention effectively solves the disadvantage of the poor adhesion of such materials to the copper substrate material, and has an excellent protective effect on the copper metal of the substrate.
表-2Table 2
实施例/对比例Example/Comparative Example 粘接性Adhesion 变色抑制Discoloration inhibition
实施例#1Example #1 AA AA
实施例#2Example #2 AA AA
实施例#3Example #3 AA AA
实施例#4Example #4 AA AA
实施例#5Example #5 AA BB
实施例#6Example #6 BB AA
实施例#7Example #7 AA AA
实施例#8Example #8 BB BB
实施例#9Example #9 AA AA
实施例#10Example #10 AA AA
实施例#11Example #11 BB BB
实施例#12Example #12 AA AA
实施例#13Example #13 AA AA
实施例#14Example #14 AA AA
实施例#15Example #15 AA AA
实施例#16Example #16 AA AA
实施例#17Example #17 AA AA
实施例#18Example #18 AA BB
实施例#19Example #19 AA AA
实施例#20Example #20 AA AA
实施例#21Example #21 AA AA
实施例#22Example #22 AA AA
实施例#23Example #23 AA AA
实施例#24Example #24 AA AA
实施例#25Example #25 AA AA
对比例#1 Comparative example #1 无法成膜Can not form film 无法成膜Can not form film
对比例#2Comparative example #2 无法成膜Can not form film 无法成膜Can not form film
对比例#3Comparative example #3 AA AA
对比例#4Comparative example #4 AA BB
对比例#5Comparative example #5 BB BB
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式 上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明,任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的方法及技术内容作出些许的更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。The above are only the preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed in the preferred embodiments as above, it is not intended to limit the present invention. Anyone familiar with the profession Those skilled in the art, without departing from the scope of the technical solution of the present invention, can use the methods and technical content disclosed above to make slight changes or modifications to equivalent embodiments with equivalent changes, but any content that does not depart from the technical solution of the present invention, Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solutions of the present invention.

Claims (10)

  1. 一种具有如下通式(1)聚磺酰胺聚合物，A polysulfonamide polymer with the following general formula (1),
    Figure PCTCN2020091094-appb-100001
    Figure PCTCN2020091094-appb-100001
    所述聚磺酰胺聚合物具有如下的重复单元结构式，其中m和n表示聚合物中的结构单元数，其为1～99的整数。The polysulfonamide polymer has the following repeating unit structural formula, where m and n represent the number of structural units in the polymer, which are integers from 1 to 99.
  2. 根据权利要求1所述的聚磺酰胺聚合物，所述通式(1)中的X1和X2是二价芳香族连接基团，其可以为不同或相同的具有下述通式(2)、(3)、或者(4)所示的基团；The polysulfonamide polymer according to claim 1, wherein X1 and X2 in the general formula (1) are divalent aromatic linking groups, which may be different or the same and have the following general formula (2), (3) or the group shown in (4);
    Figure PCTCN2020091094-appb-100002
    Figure PCTCN2020091094-appb-100002
    其中所述的R 1，R 2，R 3，R 4分别表示氢原子或者一价有机基团； Wherein said R 1 , R 2 , R 3 , and R 4 respectively represent a hydrogen atom or a monovalent organic group;
    Figure PCTCN2020091094-appb-100003
    Figure PCTCN2020091094-appb-100003
    其中所述的Q为直接键或二价有机基团，所述有机基团选自O、S、CO、 SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻，-间，-对亚苯基； Wherein the Q is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -meta, -p-phenylene;
    Figure PCTCN2020091094-appb-100004
    Figure PCTCN2020091094-appb-100004
    其中所述的T为直接键或二价有机基团，所述有机基团选自O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻，-间，-对亚苯基，其中R 5～R 12是相同的或不同的一价有机基，选自H、CH 3、或CF 3； The T is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1 ≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -met, -p-phenylene, Wherein R 5 to R 12 are the same or different monovalent organic groups, selected from H, CH 3 , or CF 3 ;
    其中所述通式(1)的聚磺酰胺聚合物中的Y是二价芳香族基团，选自从下述式(5)或者(6)所代表的结构单元：Wherein, Y in the polysulfonamide polymer of the general formula (1) is a divalent aromatic group selected from structural units represented by the following formula (5) or (6):
    Figure PCTCN2020091094-appb-100005
    Figure PCTCN2020091094-appb-100005
    其中通式(6)中所述的U为直接键或二价有机基团，所述的有机基团选自O、S、CO、SO 2、Si(CH 3) 2、CH(OH)、(CH 2) p(1≤p≤10)、(CF 2) q(1≤q≤10)、C(CH 3) 2、C(CF 3) 2、取代或未取代的-邻、-间、-对亚苯基。 Wherein U in the general formula (6) is a direct bond or a divalent organic group, and the organic group is selected from O, S, CO, SO 2 , Si(CH 3 ) 2 , CH(OH), (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , substituted or unsubstituted -ortho, -between , -P-phenylene.
  3. 根据权利要求1所述的聚磺酰胺聚合物，所述聚磺酰胺聚合物为嵌段共聚物或者无规共聚物，其重均分子量范围为5,000到200,000。The polysulfonamide polymer according to claim 1, wherein the polysulfonamide polymer is a block copolymer or a random copolymer with a weight average molecular weight ranging from 5,000 to 200,000.
  4. 一种含有权利要求1-3中任一权利要求所述的聚磺酰胺聚合物的负型光敏性组合物，其包括：A negative photosensitive composition containing the polysulfonamide polymer according to any one of claims 1 to 3, which comprises:
    (A)聚磺酰胺聚合物；(A) Polysulfonamide polymer;
    (B)光酸产生剂：其在组合物中的含量相对于(A)成分100质量份而言优 选为0.1～20质量份，更优选为1～10质量份；(B) Photoacid generator: The content in the composition is preferably 0.1-20 parts by mass, more preferably 1-10 parts by mass relative to 100 parts by mass of component (A);
    (C)交联剂：其在组合物中的含量相对于(A)成分100质量份而言优选为2～50质量份，进一步优选为8～40质量份；(C) Crosslinking agent: The content in the composition is preferably 2-50 parts by mass, more preferably 8-40 parts by mass relative to 100 parts by mass of component (A);
    (D)溶剂：其在组合物中的含量相对于(A)成分100质量份优选为50～800质量份，更优选为60～300质量份，进一步优选为80～220质量份。(D) Solvent: The content in the composition relative to 100 parts by mass of the component (A) is preferably 50 to 800 parts by mass, more preferably 60 to 300 parts by mass, and still more preferably 80 to 220 parts by mass.
  5. 根据权利要求4所述的含有聚磺酰胺聚合物的负型光敏性组合物，其中的组分(B)的成分为至少一种光酸产生剂。所述光酸产生剂选自但不限于离子型化合物包括硫盐、鏻盐或碘鎓盐；非离子型化合物包括肟磺酸酯、磺酸酯化合物或醌二叠氮化物化合物；或其混合物。从灵敏度和成像性的角度考虑，优选肟磺酸酯化合物；和/或The negative photosensitive composition containing polysulfonamide polymer according to claim 4, wherein the component (B) is at least one photoacid generator. The photoacid generator is selected from but not limited to ionic compounds including sulfur salts, phosphonium salts or iodonium salts; non-ionic compounds include oxime sulfonate, sulfonate compound or quinone diazide compound; or mixtures thereof . From the viewpoint of sensitivity and imaging properties, oxime sulfonate compounds are preferred; and/or
    其中的组分(C)的成分包含至少一种具有-CH 2OR(R是氢原子或1价有机基团)的烷氧基化合物/羟基化合物；环氧基化合物；氧杂环丁烷基化合物或乙烯基醚基化合物，优选具有羟甲基、烷氧基甲基等烷氧基烷基的化合物；和/或 Among them, the component (C) contains at least one alkoxy compound/hydroxy compound having -CH 2 OR (R is a hydrogen atom or a monovalent organic group); epoxy compound; oxetanyl Compounds or vinyl ether-based compounds, preferably compounds having alkoxyalkyl groups such as hydroxymethyl and alkoxymethyl; and/or
    其中所述的组合物的成分溶解在一种溶剂(D)中，所述溶剂包括至少一种从如下溶剂所选的化合物：酯、醚、醚-酯、酮、酮-酯、芳香族化合物，和/或卤代烃类溶剂。The components of the composition are dissolved in a solvent (D), and the solvent includes at least one compound selected from the following solvents: ester, ether, ether-ester, ketone, ketone-ester, aromatic compound , And/or halogenated hydrocarbon solvents.
  6. 一种根据权利要求4～5任一所述的含有聚磺酰胺聚合物的负型光敏性组合物制备的具有浮雕图案的固化物，由包括以下步骤的方法制备：A cured product with embossed pattern prepared from the negative photosensitive composition containing polysulfonamide polymer according to any one of claims 4 to 5, prepared by a method comprising the following steps:
    (a)将所述的聚磺酰胺聚合物组合物涂布于基板上并加热去除溶剂而形成感光性树脂膜的步骤；(a) The step of coating the polysulfonamide polymer composition on a substrate and heating to remove the solvent to form a photosensitive resin film;
    (b)利用掩模版对所述感光性树脂膜进行图案曝光的步骤；(b) A step of patterning the photosensitive resin film using a mask;
    (c)去除涂层未曝光的区域，从而得到具有浮雕图案的树脂固化物膜的步骤，以及(c) the step of removing unexposed areas of the coating to obtain a cured resin film with embossed patterns, and
    (d)对所述浮雕图案树脂膜进行加热固化处理的步骤。(d) A step of heating and curing the relief pattern resin film.
  7. 根据权利要求6所述的具有浮雕图案的固化物，其中所述加热处理的温度小于或等于250℃。The cured product with embossed patterns according to claim 6, wherein the temperature of the heat treatment is less than or equal to 250°C.
  8. 根据权利要求6所述的具有浮雕图案的固化物，其为具有微结构浮雕图案的固化物膜。The cured product with embossed patterns according to claim 6, which is a cured product film with micro-structured embossed patterns.
  9. 权利要求6～8中任一项所述的具有浮雕图案的固化物应用于重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜。The cured product with embossed patterns according to any one of claims 6 to 8 is applied to a redistribution layer, an interlayer insulation buffer film, a cover coating or a surface protection film.
  10. 一种电子器件，其包含权利要求9所述的重新分布层、层间绝缘缓冲膜、覆盖涂层或表面保护膜。An electronic device comprising the redistribution layer, an interlayer insulation buffer film, a cover coating or a surface protection film according to claim 9.
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