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CN117420732B - Negative photosensitive resin composition and application thereof - Google Patents

Negative photosensitive resin composition and application thereof Download PDF

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Publication number
CN117420732B
CN117420732B CN202311752051.5A CN202311752051A CN117420732B CN 117420732 B CN117420732 B CN 117420732B CN 202311752051 A CN202311752051 A CN 202311752051A CN 117420732 B CN117420732 B CN 117420732B
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photosensitive resin
resin composition
formula
negative photosensitive
parts
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CN117420732A (en
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杜亚琳
贾斌
李涛
左立辉
宗文敏
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Minseoa Beijing Advanced Materials Development Co Ltd
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Minseoa Beijing Advanced Materials Development Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention discloses a negative photosensitive resin composition and application thereof. The negative photosensitive resin composition is prepared from the components of photosensitive resin, a modified silane coupling agent shown in a formula I, a photoinitiator, a photocrosslinking agent and an organic solvent; the photosensitive resin is selected from polyimide, polyimide precursor or a mixture thereof with a double bond structure capable of undergoing free radical polymerization; in the formula I, A represents a divalent organic group with more than 2 carbon atoms; r is R 1 Represents methyl or ethyl. Further, the negative photosensitive resin composition further comprises a nitrogen-containing heterocyclic compound shown in a formula IV or a formula V. The addition of the modified silane coupling agent can improve the adhesiveness between the photosensitive resin composition curing film and the metal copper-based material while ensuring the storage stability; the adhesion between the film and the metal copper is further enhanced through the synergistic effect of the modified coupling agent and the nitrogen heterocyclic compound, and the effect of inhibiting oxidative discoloration of the copper can be achieved.

Description

Negative photosensitive resin composition and application thereof
Technical Field
The invention belongs to the field of high polymer materials for semiconductors, and particularly relates to a negative photosensitive resin composition and application thereof.
Background
The film material prepared from polyimide resin has excellent mechanical property, heat resistance, electrical insulation and lower dielectric constant, and is widely applied to the fields of surface protection, interlayer insulation, electromagnetic shielding and the like of semiconductor elements. The prepared film material can be permanently remained in the electronic device as a component of the semiconductor element, and in order to ensure long-term use of the semiconductor element, the compatibility and adhesiveness of the film material and other materials of the semiconductor device are important in addition to the better tolerance of the cured film.
In order to improve the adhesion between a cured film obtained from the photosensitive resin composition and a substrate, there are conventionally used methods: pretreating the surface of a substrate by using a dilute solution of a silane coupling agent; adding a silane coupling agent into the photosensitive resin composition system; the organosilicon compound which can participate in the polymerization is introduced during the polyimide resin synthesis stage. The method of pretreating the substrate surface with a dilute solution of a silane coupling agent complicates the production process, which is not preferable. With the method of introducing a silane-containing compound into a resin structure, the silane group cannot sufficiently exert the tackifying effect because the movement of the macromolecule to which the silane group belongs is limited. The method of adding a silane coupling agent to a resin composition to achieve increased adhesion does not have the above-described problems, and is the most economically viable method.
The silane coupling agent is an organic silicon compound with a special structure, has a group capable of being combined with inorganic materials (such as silicon-based, glass-based, metal-based, ceramic-based and the like) in the molecular structure, and also has a reactive group capable of being combined with organic materials (such as resin), and the silane coupling agent plays a role of a molecular bridge to connect the inorganic materials and the organic polymer materials and plays an effect of increasing the adhesion between the two phases. The industrial production and application of the coupling agent have been in recent century, the commercialized coupling agent has various kinds, the application field and application scene are also more and more extensive, and the currently mainstream coupling agent is divided into the following kinds according to the structure: aminosilanes, epoxysilanes, acylsilanes, sulfur/mercapto silanes, isocyanate silanes, ureido silanes, alkenyl alkynyl silanes, phenyl silanes, fluorine-containing silanes, and the like, and depending on the different substrates and objects of treatment, researchers and industrial producers may choose the appropriate type of coupling agent depending on the mechanism of action of the coupling agent.
The photosensitive resin composition prepared from the polyimide resin needs to take into consideration the storage stability and the adhesion to a substrate of the prepared resin composition when selecting an appropriate coupling agent. It was found through a series of experiments that the addition of the resin composition having amino groups, epoxy groups and isocyanate silane was inferior in storage stability. The addition of phenyl, vinyl, ethynyl, sulfur/mercapto silane, acyl silane is better in terms of storage stability, curing the resin composition into a film, and the adhesion after aging experiments is not ideal, especially the adhesion with metallic copper is poor.
For the above reasons, research and development workers develop various modified silane coupling agents based on the structures of the existing silane coupling agents. Patent CN109762131B mentions that modified end-capping coupling agents are prepared by epoxy ring-opening reaction of vinyl-and amino-containing monomers with epoxy-containing silane coupling agents. Patent CN105916910a teaches that a symmetrical structure bis-silane coupling agent is prepared by reacting a dianhydride compound with an amino group-containing silane coupling agent, and the modified coupling agent has an amide bond and good compatibility with a resin, but the coupling agent of the structure has an unstable phenomenon of self-hydrolysis due to the presence of a carboxyl group at the ortho position of the amide bond. Patent CN107407869a provides a modified silane coupling agent having a urea structure which is easily interacted with a metallic copper base surface and can obtain a high adhesion effect even at a low curing temperature, but after an aging test, there is a phenomenon that a copper-based material is oxidized and discolored, which is caused by weak basicity of nitrogen in the urea structure and weak adhesion of a film to copper under a high-temperature and high-humidity environment, resulting in the occurrence of the phenomenon.
Disclosure of Invention
The present invention is also based on the above, and provides a negative photosensitive resin composition prepared from a polyimide resin, wherein a polyfunctional modified silane coupling agent having a biurea structure and an aza compound are added to the composition, and the adhesiveness between the cured film of the photosensitive resin composition and a base material such as metallic copper or gold is sufficiently ensured by a synergistic effect of the modified coupling agent and the aza compound after curing the film, and the occurrence of copper discoloration can be prevented by aging experiments. The modified coupling agent is specifically a polyfunctional silane coupling agent containing a biurea structure, can improve the adhesiveness between a film prepared by curing a photosensitive resin composition prepared from polyimide or precursor resin thereof and a substrate, particularly a metal copper-based material, while ensuring the storage stability; furthermore, the nitrogen-containing heterocyclic compound is added into the composition, and the adhesion between the film and the metallic copper is further enhanced through the synergistic effect of the modified coupling agent and the nitrogen-containing heterocyclic compound, and meanwhile, the effect of inhibiting oxidative discoloration of the copper can be achieved.
In a first aspect, the present invention provides a negative photosensitive resin composition made of components including a photosensitive resin, a modified silane coupling agent represented by formula i, a photoinitiator, a photocrosslinking agent, and an organic solvent;
the photosensitive resin is selected from polyimide, polyimide precursor or a mixture thereof with a double bond structure capable of undergoing free radical polymerization;
in the formula I, A represents a divalent organic group with more than 2 carbon atoms; r is R 1 Represents methyl or ethyl.
In the negative photosensitive resin composition, the structure of the photosensitive resin is shown as a formula II:
in the formula II, R 2 A 4-valent organic group having 6 to 36 carbon atoms; r is R 3 R is R 4 Each independently represents a hydrogen atom or a monovalent organic group having an unsaturated double bond structure represented by the following formula III; r is R 5 A 2-valent organic group having 2 to 36 carbon atoms; m and n are each independently integers of 0 to 6000 and are not 0 at the same time, and m is more than n;
in the formula III, p is an integer of 2 to 6, R 6 、R 7 、R 8 Independently of each other is a hydrogen atomOr methyl, ethyl, propyl monovalent organic groups.
In the negative photosensitive resin composition, in the formula I, A represents a linear alkyl group having 2 to 12 carbon atoms, a phenyl group, a diphenyl ether group, a biphenyl group or a cyclohexyl group.
In the negative photosensitive resin composition, the weight part of the modified silane coupling agent is 0.1 to 8 parts based on 100 parts of the photosensitive resin.
Further, in the negative photosensitive resin composition, the negative photosensitive resin composition further comprises a nitrogen-containing heterocyclic compound represented by formula iv or formula v:
in the formulas IV and V, X represents a carbon atom or a nitrogen atom, and Y represents a hydrogen atom or an alkyl group, an amino group, a mercapto group, a hydroxyl group, a carboxyl group or a higher organic group formed by bonding these groups to other organic groups by chemical reaction.
In the negative photosensitive resin composition, the higher organic group is any one of the following groups:
1) An organic group having an amide bond or an imine ring formed based on the reaction of an amino group and an acid anhydride;
2) Organic groups having urethane structures based on the reaction of hydroxyl groups with isocyanates.
In the negative photosensitive resin composition, the weight part of the nitrogen-containing heterocyclic compound shown in the formula IV or the formula V is 0.1-3 parts based on 100 parts of the photosensitive resin.
In the negative photosensitive resin composition, the photoinitiator is selected from benzophenone or derivatives, acetophenone derivatives, oximes or oxime esters photopolymerization initiators;
in the negative photosensitive resin composition, the weight part of the photoinitiator is 0.5-15 parts based on 100 parts of the weight of the photosensitive resin;
the photocrosslinker is an acrylic compound which is subjected to free radical polymerization reaction by utilizing the photoinitiator;
in the negative photosensitive resin composition, the weight part of the photocrosslinker is 2-30 parts based on 100 parts of the weight part of the photosensitive resin;
the organic solvent is one or more of aprotic polar solvent, ether solvent, ketone solvent, ester solvent or alcohol solvent;
in the negative photosensitive resin composition, the weight part of the organic solvent is 130-200 parts based on 100 parts of the photosensitive resin.
Further, the benzophenone or its derivative may be benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4' -methyldiphenyl ketone, dibenzyl ketone or fluorenone;
the acetophenone derivative may be 2, 2' -diethoxyacetophenone, 2-hydroxy-2-methylpropenyl acetone or 1-hydroxycyclohexyl phenyl ketone;
The oxime initiator may be 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-benzoyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime or 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl) oxime.
Further, the photocrosslinker may be any of the following:
1) Mono-, di-or methacrylates of ethylene glycol or polyethylene glycol (e.g. diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate);
2) Monoacrylates, diacrylates or methacrylates of propylene glycol or polypropylene glycol;
3) Mono-, di-, or triacrylates or methacrylates of glycerol.
Further, in the organic solvent, the aprotic solvent may be N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide; the ether solvent can be tetrahydrofuran or propylene glycol monomethyl ether; the ketone solvent may be acetone, diisobutyl ketone or methyl ethyl ketone; the lipid solvent can be gamma-butyrolactone, ethyl lactate, ethyl acetate or propylene glycol monomethyl ether acetate; the alcohol solvent can be ethanol, propanol or isopropanol.
In a second aspect, the invention provides an application of the negative photosensitive resin composition in preparing a cured film, wherein a base material for preparing the cured film is a copper-plated silicon wafer.
In a third aspect, the present invention provides an electronic component comprising the negative photosensitive cured film of any one of the above negative photosensitive resin compositions, wherein the substrate is a copper-plated silicon wafer.
The invention has the following beneficial effects:
(1) The negative photosensitive resin composition adopts a polyfunctional silane coupling agent containing a biurea structure,
not only has good storage stability, but also can improve the adhesiveness between the film and the substrate, especially the metal copper-based material, after the photosensitive resin composition prepared from polyimide or the precursor resin thereof is cured.
(2) According to the negative photosensitive resin composition, the prepared cured film has excellent adhesion with a metal copper-based material after an aging experiment through the synergistic effect of the modified coupling agent and the nitrogen heterocyclic compound, and the occurrence of oxidative corrosion discoloration phenomenon of the copper material can be avoided.
Detailed Description
As described in the background art, the existing negative photosensitive resin composition has the problems of large viscosity fluctuation, poor stability, poor adhesion with a substrate, particularly a metal copper-based material after curing to form a film, easy oxidation discoloration of the substrate and the like. Based on this, in a first aspect, the present invention provides a negative photosensitive resin composition made of components including a photosensitive resin (a), a modified silane coupling agent (B) represented by formula i, a photoinitiator (C), a photocrosslinking agent (D), and an organic solvent (E);
The photosensitive resin is selected from polyimide, polyimide precursor or a mixture thereof with a double bond structure capable of undergoing free radical polymerization;
in the formula I, A represents a divalent organic group with more than 2 carbon atoms; r is R 1 Represents methyl or ethyl.
Based on the technical scheme, the negative photosensitive resin composition adopts the polyfunctional silane coupling agent containing the biurea structure shown in the formula I, has good storage stability, and can improve the adhesiveness between a film prepared by curing the photosensitive resin composition prepared by polyimide or the precursor resin thereof and a substrate, particularly a metal copper-based substrate.
Hereinafter, each component of the photosensitive resin composition will be described in detail.
According to the present invention, the polyimide is a resin having an imide ring structure in a main chain structure, and the polyimide and a precursor thereof may be prepared by any one of various synthetic methods well known to those skilled in the art. The polyimide precursor is polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, etc. The photosensitive polyimide precursor resin may be esterified or ionically bonded to impart photosensitivity thereto. Esterification means that an olefinic compound having a double bond structure capable of undergoing radical polymerization is introduced into a side chain of a polyimide precursor through an ester bond, and ionic bonding means that a carboxyl group of the polyimide precursor reacts with an acrylic compound having an amino group, thereby imparting photosensitivity thereto. For example, the photosensitive resin has a structure shown in formula II:
In the formula II, R 2 Represents a C6-36 compoundA 4-valent organic group; r is R 3 R is R 4 Each independently represents a hydrogen atom or a monovalent organic group having an unsaturated double bond structure represented by the following formula III; r is R 5 A 2-valent organic group having 2 to 36 carbon atoms; m and n are each independently integers of 0 to 6000 and are not 0 at the same time, and m is more than n;
in the formula III, p is an integer of 2 to 6, R 6 、R 7 、R 8 Are respectively and independently hydrogen atoms or methyl, ethyl and propyl monovalent organic groups.
In an alternative embodiment of the present invention, in formula II, m and n represent the number of repetitions of the corresponding structural unit, where (m+n) is understood to mean the polymerization degree of the resin, preferably 5 to 10000, more preferably 10 to 5000, and in this range, the cured film obtained after curing the photosensitive resin composition through the coating film is excellent in heat resistance and mechanical properties without causing problems in solubility upon development. Wherein n may be 0 or other than 0.
In the formula II, R 2 The structure of the tetracarboxylic acid is exemplified by a tetracarboxylic acid compound which is a 4-valent organic group having 6 to 36 carbon atoms: aromatic tetracarboxylic acids such as pyromellitic acid, 2',3, 3' -biphenyltetracarboxylic acid, 3, 3',4, 4' -biphenyltetracarboxylic acid, 2, 3, 3',4' -biphenyltetracarboxylic acid, 2',3, 3' -benzophenone tetracarboxylic acid, 3, 3',4, 4' -benzophenone tetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane, bis (3, 4-dicarboxyphenyl) ether, bis (3, 4-dicarboxyphenyl) sulfone, and aliphatic tetracarboxylic acids such as pyromellitic acid, cyclopentane tetracarboxylic acid, cyclobutane tetracarboxylic acid. The above tetracarboxylic acids may also be used in the form of anhydrides or corresponding ester compounds. The above tetracarboxylic dianhydride compounds may be used alone or in combination of two or more compounds. For the tetracarboxylic dianhydride, one of bis (3, 4-dicarboxyphenyl) ether, 3',4, 4' -biphenyl tetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane is preferably used. That is to say, Preferably, R 2 Represents diphenyl ether group, biphenyl group and diphenyl hexafluoropropane group, and has the following corresponding structural formula:
to impart photosensitivity to the resin, R is as follows 2 The tetracarboxylic dianhydride having a 4-valent organic group represented by the formula (I) is reacted with an alcohol having a photoinitiated polymerizable unsaturated double bond, for example, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy3-propanol, 2-isobutylamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like to give a partially esterified tetracarboxylic acid. Namely, R 3 R is R 4 Identical or different, preferably R 3 R is R 4 Each independently represents a hydrogen atom or a monovalent organic group having an unsaturated double bond structure represented by the following formula III;
P is an integer of 2 to 6, R 6 、R 7 、R 8 Are respectively and independently hydrogen atoms or methyl, ethyl and propyl monovalent organic groups. As alcohols having photoinitiated polymerizable unsaturated double bonds, preference is given to those in which p is from 2 to 3, preferably R 6 、R 7 、R 8 Independently of each other, is a hydrogen atom or a methyl group, e.g. R 6 、R 7 Is hydrogen and R 8 Is methyl.
In the formula II, R 5 A diamine compound is shown, and examples of the diamine include p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3, 4' -diaminodiphenyl sulfone, 4, 4' -diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfide, 4' -diaminobenzophenone, 3' -diaminobenzophenone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [ 4- (4-aminophenoxy) phenyl ] sulfone, bis [ 4- (3-aminophenoxy) phenyl ] sulfone, 4-bis (4-aminophenoxy) biphenyl, 4-bis (3-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl ] ether, bis [ 4- (3-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 9, 10-bis (4-aminophenyl) anthracene, 2, aromatic diamines such as 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [ 4- (4-aminophenoxy) phenyl) propane, 2-bis [ 4- (4-aminophenoxy) phenyl) hexafluoropropane, or diamine compounds wherein a part of hydrogen atoms of the aromatic ring of the above-mentioned compounds is substituted with an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or the like. As the diamine compound, one of p-phenylenediamine, m-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane is preferable. That is, preferably, R 5 Represents phenyl, diphenyl ether, diphenyl methane, preferably para-substituted divalent organic radicals, corresponding to the following structural formula:
in order to improve the storage stability of the photosensitive resin composition, it is necessary to cap the polyimide and its precursor, and it is preferable to use a mono-active compound such as monoamine or acid anhydride as a capping agent. As monoamines, aniline, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenylthiophenol, 4-aminophenylthiophenol, 2-aminotrifluorotoluene, 3-aminotrifluorotoluene, 2-aminotoluene, 4-phenylethynyl aniline, 3-phenylethynyl aniline, norborneneamine, butylamine, propargylamine and the like can be cited. Examples of the acid anhydride include at least one of phthalic anhydride, maleic anhydride, cyclohexanedicarboxylic anhydride, norbornenedicarboxylic anhydride 3-methylphthalic anhydride, 4-methylphthalic anhydride, acetic anhydride, propionic anhydride, hydrogenated phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-methylphthalic anhydride, ethynylphthalic anhydride, trimellitic anhydride, and phenylsuccinic anhydride.
In one embodiment of the invention, the photosensitive resin has a structure as shown in formula II-a:
formula II-a, R is the following group:
。
in another embodiment of the present invention, the photosensitive resin has a structure represented by formula II-b:
in formula ii-b, R is the following group:
。
in an alternative embodiment of the present invention, the modified coupling agent is prepared by reacting a compound having an amino group with a compound containing an isocyanate, and by containing a urea group structure, the adhesion of a film after curing of a photosensitive resin composition prepared from a polyimide or a precursor resin thereof to a substrate, particularly a metallic copper-based material, can be improved. The modified coupling agent is prepared based on the reaction of amino groups with isocyanate, and the raw materials and reaction conditions required for the preparation are prepared by any one of publicly known methods by a person skilled in the art. When the diamine compound is prepared from an isocyanatopropyl trimethoxysilane or isocyanatopropyl triethoxysilane, examples of the diamine compound include ethylenediamine, propylenediamine, 1, 4-diaminobutane, 1, 5-diaminopentane, hexamethylenediamine, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, phenylenediamine, m-phenylenediamine, biphenylenediamine, 3, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3, 4 '-diaminodiphenyl methane, 4' -diaminodiphenyl methane, and the like. When the urethane composition is prepared from a diisocyanate compound and aminopropyl trimethoxysilane or aminopropyl triethoxysilane, examples of the diisocyanate compound include 1, 6-hexamethylene diisocyanate, 1, 4-cyclohexyl diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, 4' -diisocyanate dicyclohexylmethane, 4' -diisocyanate diphenyl ether, 4' -diisocyanate diphenylmethane and the like.
Further, in the formula I, A represents a straight-chain alkyl group, phenyl group, diphenyl ether group, biphenyl group or cyclohexyl alkyl group with 2-12 carbon atoms, preferably a para-substituted divalent organic group, and the corresponding structural formula is as follows:
。
for example, as examples of the compound represented by the general formula I, there may be mentioned compounds having the following structure, but not limited to any one of the following formulas Ia to Ij:
。
the comparison result shows that when A is an aliphatic bridging group such as a linear alkyl group having 2 to 12 carbon atoms, the adhesion performance is better, and the linear alkyl group having 2 to 12 carbon atoms means a linear alkyl group having 2 to 12 carbon atoms, for example, including "C2-4 alkyl group" such as ethyl, n-propyl, n-butyl, and the like, and further includes n-pentyl, n-hexyl, and the like. C2-C12 alkyl also includes C2-C6 alkyl having 2 or more and 6 or less carbon atoms.
In an alternative embodiment of the present invention, the modified silane coupling agent represented by formula i in the negative photosensitive resin composition provided by the present invention is preferably 0.1 to 8 parts by weight, more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the photosensitive resin. When the amount of the resin composition is 1 part by weight or less, the cured film prepared from the composition has poor adhesion to metallic copper, and when the adhesion test is performed, the film is peeled off, and when the amount of the resin composition is 8 parts by weight or more, the stability of the resin composition is lowered. In the case of structure selection, an aliphatic bridge structure is preferred, and the amount added is more preferably 2 to 5 parts by weight, such as 3 parts by weight.
In a further preferred embodiment of the present invention, the negative photosensitive resin composition further comprises a nitrogen-containing heterocyclic compound (F) represented by formula iv or formula v:
in the formulas IV and V, X represents a carbon atom or a nitrogen atom, and Y represents a hydrogen atom or an alkyl group, an amino group, a mercapto group, a hydroxyl group, a carboxyl group or a higher organic group formed by bonding these groups to other organic groups by chemical reaction.
For example, the higher organic group is any one of the following:
1) An organic group having an amide bond or an imine ring formed based on the reaction of an amino group and an acid anhydride;
2) Organic groups having urethane structures based on the reaction of hydroxyl groups with isocyanates.
The polyfunctional modified silane coupling agent containing a bisureido structure and the nitrogen-containing heterocyclic compound, specifically imidazole or benzimidazole, triazole or benzotriazole and derivatives thereof, are added into the negative photosensitive resin composition, and the adhesion between the cured film of the photosensitive resin composition and a base material such as metallic copper, gold and the like can be fully ensured after aging experiments by utilizing the synergistic effect of the modified coupling agent and the nitrogen-containing heterocyclic compound, and the occurrence of copper discoloration can be prevented. The addition of the aza compound can act to prevent oxidative discoloration of the copper. The nitrogen heterocyclic structure can form covalent bond and coordination bond with copper atom, and can be mutually alternated into chain polymer, and a layer of molecular protection film is formed on the surface of copper, so that the surface of copper does not produce oxidation-reduction reaction, and has the function of preventing discoloration. Meanwhile, the two-phase interaction is enhanced at the interface of the solidified film and the metallic copper by the synergistic effect of the component (B), so that the effect of enhancing the adhesion is achieved.
Specifically, the nitrogen-containing heterocyclic compound shown in the formula IV is any one of the following:
。
the nitrogen-containing heterocyclic compound shown in the formula V is any one of the following:
。
the inventor finds out through series experiments that when the added nitrogenous heterocyclic compound is a compound with smaller molecular weight such as imidazole, benzimidazole or mercaptoimidazole, after aging experiments, the peeling phenomenon of copper and a substrate silicon wafer is found, because the small molecular nitrogenous heterocyclic compound with a simple structure has good water solubility, the molecular movement is intense under a high-heat and high-humidity environment, the formed molecular protection film can be damaged, the possibility that the surface of copper migrates to a copper-silicon interface exists, copper is corroded under a long-time high-heat and high-humidity environment, copper base is damaged, and the protection meaning of a solidified film on copper is lost. When the added nitrogen heterocyclic compound is a compound with a polar structure such as an amide bond, a urethane bond, a ureido and the like, the molecular weight is increased, the water solubility is reduced, and the molecular movement is limited in a high-heat and high-humidity environment, so that the damage of a molecular protection film caused by excessive migration can not occur, and the conversion of the nitrogen heterocyclic compound from a protector to a destructor is avoided.
The nitrogen heterocyclic compound can be prepared by a person skilled in the art through the disclosed technical data, and the nitrogen heterocyclic compound has the advantages of readily available raw materials, simple preparation method and low comprehensive cost.
In an alternative embodiment of the present invention, the amount of the nitrogen-containing heterocyclic compound represented by formula iv or formula v added to the negative photosensitive resin composition provided in the present invention is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the photosensitive resin. As an example, the mass ratio of the modified silane coupling agent to the nitrogen-containing heterocyclic compound is 3:1.
According to the present invention, the photoinitiator is a compound used as an ultraviolet light polymerization initiator, such as benzophenone and its derivatives, acetophenone derivatives, oxime and oxime ester type photopolymerization initiators, and the like. Examples of the benzophenone and its derivatives include benzophenone derivatives such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4' -methyldiphenyl ketone, dibenzyl ketone and fluorenone. Acetophenone derivatives such as 2, 2' -diethoxyacetophenone, 2-hydroxy-2-methylpropenone, and 1-hydroxycyclohexyl phenyl ketone. Examples of the oxime initiator include oxime compounds such as 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-benzoyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, and 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), and the photoinitiator "irgacureoxane 01" (manufactured by basf). The amount of the photoinitiator to be added is preferably 0.5 to 15 parts by weight, more preferably 1 to 5 parts by weight, for example 2 parts by weight, relative to 100 parts by weight of the resin, and within this range, not only a certain sensitivity and sensitivity can be imparted to the resin composition, but also the development time of the resin composition can be made reasonable.
In order to improve the resolution of the photolithographic pattern, the photocrosslinker is a compound having a photopolymerizable unsaturated bond. The acrylic compound preferably undergoes radical polymerization using a photopolymerization initiator, but not limited thereto, and examples thereof include monoacrylates or diacrylates and methacrylates of ethylene glycol or polyethylene glycol typified by diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and the like; monoacrylate or diacrylate esters and methacrylates of propylene glycol or polypropylene glycol; mono-, di-, or triacrylates of glycerol, methacrylates, and the like. The amount of the photocrosslinker (E) to be added is preferably 2 to 30 parts by weight, more preferably 5 to 20 parts by weight, such as 15 parts by weight, relative to 100 parts by weight of the resin.
According to the present invention, examples of the organic solvent include aprotic polar solvents such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), ether solvents such as Tetrahydrofuran (THF), propylene Glycol Monomethyl Ether (PGME), ketone solvents such as acetone, diisobutylketone, and methyl ethyl ketone, ester solvents such as γ -butyrolactone (GBL), ethyl lactate, ethyl acetate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA), and alcohols such as ethanol, propanol, and isopropanol. One or more of the above solvents may be selected. The amount of the organic solvent to be added is preferably 130 to 200 parts by weight based on 100 parts by weight of the resin, and may be appropriately adjusted according to the viscosity requirement of the composition.
That is, in the present invention, the negative photosensitive resin composition is 1) or 2) below:
1) The composite material is prepared from the following components in parts by weight:
100 parts of photosensitive resin, 0.1 to 8 parts of modified silane coupling agent shown in formula I, 0.5 to 15 parts of photoinitiator, 2 to 30 parts of photocrosslinking agent and 130 to 200 parts of organic solvent;
2) The composite material is prepared from the following components in parts by weight:
100 parts of photosensitive resin, 0.1 to 8 parts of modified silane coupling agent shown in formula I, 0.1 to 3 parts of nitrogenous heterocyclic compound, 0.5 to 15 parts of photoinitiator, 2 to 30 parts of photocrosslinker and 130 to 200 parts of organic solvent;
preferably, the negative photosensitive resin composition is prepared from the following components in parts by weight:
100 parts of photosensitive resin, 1-5 parts of modified silane coupling agent shown in formula I, 1-5 parts of photoinitiator, 5-20 parts of photocrosslinker and 130-200 parts of organic solvent; or alternatively, the first and second heat exchangers may be,
the negative photosensitive resin composition is prepared from the following components in parts by weight:
100 parts of photosensitive resin, 1-5 parts of modified silane coupling agent shown in formula I, 0.5-2 parts of nitrogenous heterocyclic compound, 1-5 parts of photoinitiator, 5-20 parts of photocrosslinker and 130-200 parts of organic solvent;
As an example, the negative photosensitive resin composition is made of components including, by weight:
100 parts of photosensitive resin, 3 parts of modified silane coupling agent shown in formula I, 2 parts of photoinitiator, 15 parts of photocrosslinker and 150 parts of organic solvent; or alternatively, the first and second heat exchangers may be,
the negative photosensitive resin composition is prepared from the following components in parts by weight:
100 parts of photosensitive resin, 3 parts of modified silane coupling agent shown in formula I, 1 part of nitrogen-containing heterocyclic compound, 2 parts of photoinitiator, 15 parts of photocrosslinker and 150 parts of organic solvent.
The preparation method of the negative photosensitive resin composition provided by the invention comprises the following steps:
under the protection of nitrogen, adding additives into the organic solvent, adding the photosensitive resin after the additives are completely dissolved, and performing pressure filtration by using a PTFE filter membrane with the aperture of 0.22 mu m after the resin is completely dissolved to obtain a photosensitive resin composition with the viscosity of 3000-3500 cP;
the additive includes the modified silane coupling agent, the photoinitiator, and the photocrosslinking agent.
Further, the additive further comprises the nitrogen-containing heterocyclic compound.
The photosensitive resin composition after filtration is subjected to a pressure reduction defoaming treatment so as to eliminate bubbles of a minute size and to avoid defects in the cured film.
In a second aspect, the present invention provides an application of the negative photosensitive resin composition in preparing a cured film, wherein a substrate for preparing the cured film is a copper-plated silicon wafer.
In a third aspect, the present invention provides an electronic component comprising the negative photosensitive cured film of any one of the above negative photosensitive resin compositions, wherein the substrate is a copper-plated silicon wafer.
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The methods used in the examples described below, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the specifications of the product. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Synthesis example 1: synthesis of polyimide precursor resin A1
62.04g (0.2 mol) of 4,4' -biphenylene Oxide Dianhydride (ODPA), 52.06g (0.4 mol) of hydroxyethyl methacrylate (HEMA), 11.08g (0.14 mol) of pyridine and 120g of NMP solvent are added into a 1000ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel under dry nitrogen flow, stirring is started, the temperature is raised to 60 ℃ until the dissolution is complete, the reaction is continued for 2 hours, then the ice bath is cooled to below 0 ℃, and 47.85g (0.4 mol) of SOCl is slowly added dropwise 2 The reaction temperature is controlled below 0 ℃, the ice bath reaction is kept for 1h after the dripping is finished, a mixed solution of 36.04g (0.18 mol) of 4,4' -diaminodiphenyl ether (ODA), 4.36g (0.04 mol) of 4-aminophenol as a blocking agent and 120g of NMP solvent is dripped after the dripping is finished, the reaction temperature is controlled below 10 ℃, the temperature is raised to 25 ℃ after the dripping is finished, and the reaction is continued for 5h. After the reaction, pouring the reaction liquid into 3L deionized water and ethanol in a trickle state, wherein the mass ratio of the deionized water to the ethanol is 2:1 to obtain a white resin polymer precipitate. Filtering the resin, continuously soaking the resin in deionized water for 2 hours, repeating the steps for three times to obtain washed resin, putting the washed resin into a vacuum drying oven, and drying the resin at 70 ℃ for 72 hours to obtain the dried polyimide precursor resin A1.
The structural formula of the polyimide precursor resin A1 of this synthesis example is as follows:
wherein R is the following group:
。
molecular weight testing: the measurement conditions of the weight average molecular weight based on the GPC method are as follows:
LiBr (0.03 mol/L) and H were used 3 PO 4 As a eluent, an NMP solution (0.06 mol/L) was used to determine a resin concentration of 0.5mg/ml, and molecular weight calibration was performed using a Waters 2695 GPC apparatus and a PS standard.
The number average molecular weight Mn of the polyimide precursor resin A1 was measured to be in the range of 11000 to 12000, the weight average molecular weight Mw was measured to be in the range of 18000 to 24000, and the molecular weight distribution coefficient PDI was measured to be in the range of 1.6 to 2.0.
Synthesis example 2: synthesis of polyimide precursor resin A2
58.85g (0.2 mol) of 4,4' -biphenyltetracarboxylic dianhydride (BPDA), 52.06g (0.4 mol) of hydroxyethyl methacrylate (HEMA), 11.08g (0.14 mol) of pyridine and 120g of NMP solvent are added into a 1000ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel under dry nitrogen flow, stirring is started, the temperature is raised to 60 ℃ until the dissolution is complete, the reaction is continued for 2 hours, then the ice bath is cooled to below 0 ℃, and 47.85g (0.4 mol) of SOCl is slowly added dropwise 2 The reaction temperature is controlled below 0 ℃, the ice bath reaction is kept for 1h after the dripping is finished, a mixed solution of 36.04g (0.18 mol) of 4,4' -diaminodiphenyl ether (ODA), 4.36g (0.04 mol) of 4-aminophenol as a blocking agent and 120g of NMP solvent is dripped after the dripping is finished, the reaction temperature is controlled below 10 ℃, the temperature is raised to 25 ℃ after the dripping is finished, and the reaction is continued for 5h. After the reaction, pouring the reaction liquid into 3L deionized water and ethanol in a trickle state, wherein the mass ratio of the deionized water to the ethanol is 2:1 to obtain a white resin polymer precipitate. Filtering the resin, continuously soaking the resin in deionized water for 2 hours, repeating the steps for three times to obtain washed resin, putting the washed resin into a vacuum drying oven, and drying the resin at 70 ℃ for 72 hours to obtain the dried polyimide precursor resin A2.
The structural formula of the polyimide precursor resin A2 of this synthesis example is as follows:
wherein R is the following group:
。
the same molecular weight test method as that of the resin A1 was used.
The number average molecular weight Mn of the polyimide precursor resin A2 was measured to be in the range of 9500 to 11000, the weight average molecular weight Mw was measured to be in the range of 15000 to 22000, and the molecular weight distribution coefficient PDI was measured to be in the range of 1.7 to 2.0.
The modified silane coupling agents used in the examples were as follows:
the structural formula of the modified silane coupling agent B1 is shown as follows:
the structural formula of the modified silane coupling agent B2 is shown as follows:
the structural formula of the modified silane coupling agent B3 is shown as follows:
the structural formula of the modified silane coupling agent B4 is shown as follows:
。
the preparation method of the modified silane coupling agent comprises the following steps:
synthesis of modified silane coupling agent B1:
under the flow of dry nitrogen, 10.81g (0.1 mol) of p-phenylenediamine and 50g of tetrahydrofuran (THF for short) solvent are added into a 250ml four-mouth bottle equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel, the mixture is stirred at room temperature until the mixture is completely dissolved, the temperature of the ice bath is reduced to below 0 ℃, 49.40g (0.2 mol) of propyltriethoxysilane isocyanate is slowly added dropwise, the system temperature is controlled to below 10 ℃, the temperature is increased to 35 ℃ after the dropwise addition is finished, the reaction is continued for 8 hours, and after the reaction is finished, the reaction solution is distilled under reduced pressure, and the solvent is removed, so that a light yellow viscous liquid, namely the modified silane coupling agent B1, is obtained.
Synthesis of modified silane coupling agent B2:
20.02g (0.1 mol) of 4,4' -diaminodiphenyl ether (ODA) and 100g of THF solvent are added into a 250ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel under a dry nitrogen flow, stirred at room temperature until the mixture is completely dissolved, cooled to below 0 ℃ by an ice bath, 49.40g (0.2 mol) of propyltriethoxysilane isocyanate is slowly added dropwise, the system temperature is controlled below 10 ℃, the temperature is raised to 35 ℃ after the dropwise addition is finished, the reaction is continued for 8 hours, and after the reaction is finished, the reaction solution is distilled under reduced pressure, and the solvent is removed, so that a light yellow viscous liquid, namely the modified silane coupling agent B2, is obtained.
Synthesis of modified silane coupling agent B3:
6.01g (0.1 mol) of ethylenediamine and 50g of THF solvent are added into a 250ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel under the flow of dry nitrogen, stirred at room temperature until the mixture is completely dissolved, cooled to below 0 ℃ by an ice bath, 41.04g (0.2 mol) of propyltrimethoxysilane isocyanate is slowly added dropwise, the system temperature is controlled below 10 ℃, the temperature is raised to 35 ℃ after the dropwise addition is finished, the reaction is continued for 8 hours, the reaction solution is distilled under reduced pressure after the reaction is finished, and the solvent is removed, thus obtaining a light yellow liquid, namely the modified silane coupling agent B3.
Synthesis of modified silane coupling agent B4:
synthesis of modified silane coupling agent B3 was conducted in the same manner as in the above example except that 41.04g (0.2 mol) of propyltrimethoxysilane isocyanate was changed to 49.40g (0.2 mol) of propyltriethoxysilane isocyanate.
The nitrogen-containing heterocyclic compounds used in the examples were as follows:
the structural formula of the nitrogen-containing heterocyclic compound C1 is as follows:
the structural formula of the nitrogen-containing heterocyclic compound C2 is as follows:
the structural formula of the nitrogen-containing heterocyclic compound C3 is as follows:
the synthesis method of the nitrogen-containing heterocyclic compound comprises the following steps:
synthesis of nitrogen-containing heterocyclic compound C1:
under a dry nitrogen flow, 13.41g (0.1 mol) of 5-aminobenzotriazole and 100g of THF solvent are added into a 250ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel, stirred at room temperature until the mixture is completely dissolved, cooled to below 0 ℃ by an ice bath, a mixed solution of 8.31g (0.1 mol) of 2-aminoimidazole, 10.11 (0.1 mol) of triethylamine and 50g of THF solvent is slowly dropped, the temperature of the system is controlled below 10 ℃, the temperature is raised to 25 ℃ after the dropping is finished, the reaction is continued for 8 hours, triethylamine hydrochloride is filtered after the reaction is finished, the filtrate is distilled under reduced pressure, redundant solvent and reactant are removed, 100g of pure water is added for soaking and cleaning the prepared compound, the compound is filtered, the compound is poured into 100g of pure water again for stirring and soaking, then filtered, the residual solvent is removed repeatedly three times, and the purified nitrogen-containing heterocyclic compound C1 is obtained.
Synthesis of nitrogen-containing heterocyclic compound C2:
under dry nitrogen flow, 7.85g (0.1 mol) of acetyl chloride and 50g of THF solvent are added into a 250ml four-mouth bottle equipped with a tetrafluoro stirring slurry, a thermometer and a constant pressure dropping funnel, the mixture is stirred at room temperature until the mixture is completely and uniformly mixed, the temperature is reduced to below 0 ℃ by an ice bath, a mixed solution of 8.41g (0.1 mol) of 3-amino-1, 2, 4-triazole, 10.11 g (0.1 mol) of triethylamine and 50g of THF solvent is slowly added dropwise, the system temperature is controlled below 10 ℃, the temperature is raised to 25 ℃ after the dropwise addition is finished, the reaction is continued for 8 hours, triethylamine hydrochloride is filtered after the reaction is finished, the filtrate is distilled under reduced pressure, redundant solvent and reactant are removed, 100g of pure water is added for soaking and cleaning the prepared compound, the compound is filtered, the compound is poured into 100g of pure water again for stirring and soaking, then the filtering is repeated three times, and the residual solvent is removed, and the purified nitrogen-containing heterocyclic compound C2 is obtained.
Synthesis of nitrogen-containing heterocyclic compound C3:
5.71g (0.1 mol) of methyl isocyanate and 50g of THF solvent are added into a 250ml four-necked flask equipped with a tetrafluoro stirring paddle, a thermometer and a constant pressure dropping funnel under the flow of dry nitrogen, stirred at room temperature until the mixture is completely and uniformly mixed, cooled to below 0 ℃ by an ice bath, a mixed solution of 8.41g (0.1 mol) of 3-amino-1, 2, 4-triazole and 50g of THF solvent is slowly added dropwise, the temperature of the system is controlled below 10 ℃, the temperature is raised to 25 ℃ after the dropwise addition is finished, the reaction is continued for 8 hours, and after the reaction is finished, the filtrate is distilled under reduced pressure to remove the solvent, thus obtaining the nitrogen-containing heterocyclic compound C3.
The photoinitiators used in the examples are: irgacure OXE01 (manufactured by BASF corporation, trade name).
The photocrosslinkers used in the examples were: diethylene glycol dimethacrylate.
The solvent used in the examples was N-methylpyrrolidone (NMP).
Example 1
15. 15g N-methylpyrrolidone (NMP), 0.2g of a photoinitiator (OXE 01), 1.5g of a photocrosslinking agent (diethylene glycol dimethacrylate), and 0.3g of a modified silane coupling agent B1 were added to a three-necked flask under nitrogen flow, stirring was started, 10g of the resin A1 obtained in Synthesis example 1 was added after mixing uniformly, and after the resin was completely dissolved, the mixture was filtered by a pressure filtration apparatus using a filter membrane having a pore size of 0.22. Mu.m, to obtain a negative photosensitive resin composition.
Example 2
The procedure of example 1 was repeated except that the modified silane coupling agent B1 was changed to B2.
Example 3
The procedure of example 1 was repeated except that the modified silane coupling agent B1 was changed to B3.
Example 4
The procedure of example 1 was repeated except that the modified silane coupling agent B1 was changed to B4.
Example 5
The procedure of example 4 was repeated except that the resin A1 obtained in Synthesis example 1 was changed to the resin A2 obtained in Synthesis example 2.
Example 6
Based on example 4, 0.1g of nitrogen-containing heterocyclic compound C1 was added.
Example 7
Based on example 4, 0.1g of nitrogen-containing heterocyclic compound C2 was added.
Example 8
Based on example 4, 0.1g of nitrogen-containing heterocyclic compound C3 was added.
Example 9
The procedure of example 4 was repeated except that the amount of the modified silane coupling agent B4 added was changed to 0.1 g.
Example 10
The procedure of example 4 was repeated except that the amount of the modified silane coupling agent B4 added was changed to 0.2 g.
Example 11
The procedure of example 4 was repeated except that the amount of the modified silane coupling agent B4 added was changed to 0.4 g.
Example 12
Based on example 5, 0.1g of nitrogen-containing heterocyclic compound C1 was added.
Example 13
Based on example 4, 0.1g of the compound benzodiazole was added.
Comparative example 1
15. 15g N-methylpyrrolidone (NMP), 0.2g of a photoinitiator (OXE 01) and 1.5g of a photocrosslinking agent (diethylene glycol dimethacrylate) were added to a three-necked flask under a nitrogen flow, stirring was started, 10g of the resin A1 obtained in Synthesis example 1 was added after mixing uniformly, and after the resin was completely dissolved, the mixture was filtered by a pressure filter device using a filter membrane having a pore size of 0.22. Mu.m, to obtain a negative photosensitive resin composition.
Comparative example 2
Based on comparative example 1, 0.3g of 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH 560, believed to be chemical Co., ltd.) was added.
Comparative example 3
Based on comparative example 1, 0.3g of 3- (methacryloyloxy) propyl trimethoxysilane (KH 570, believed to be chemical Co., ltd.) was added.
Comparative example 4
Based on comparative example 1, 0.3g of gamma-mercaptopropyl triethoxysilane (KH 580, believed to be chemical Co., ltd.) was added.
Comparative example 5
Based on comparative example 1, 0.3g of propyltrimethoxysilane (Aba Ding Chan) was added.
Comparative example 6
Based on comparative example 1, 0.3g of 3-ureidopropyltrimethoxysilane (Aba Ding Chan) was added.
Comparative example 7
Based on comparative example 6, 0.1g of nitrogen-containing heterocyclic compound C2 was added.
Performance testing
(1) Storage stability
The storage stability of the negative photosensitive resin composition is characterized by viscosity change, specifically the viscosity change value of the negative photosensitive resin composition after being stored for a certain period of time in an isothermal environment such as freezing (-18 ℃), refrigerating (4 ℃) and normal temperature (23-25 ℃), specifically the viscosity change of the composition on the 3 rd day, 5 th day, 7 th day, 14 th day, 21 st day and 28 th day, the viscosity change on the 28 th day is used for judging whether the storage stability of the composition is good or not, the viscosity change rate is defined by Rv (viscoside), the Rv% is less than or equal to 10%, and the Rv% is less than or equal to 10% or less than or equal to 10% is judged as bad.
The viscosity test method is as follows:
1.5-2 ml of the photosensitive resin composition is taken and put into a sample cell of a cone-plate viscometer (model PC2TRVCJ 0), a proper rotor is selected, and the test is carried out at the sample temperature of 25+/-0.1.
(2) Adhesion to a substrate
The preparation method of the cured film comprises the following steps: using a spin coater, selecting a proper rotating speed, coating the prepared photosensitive resin composition on a 6-inch copper-plated silicon wafer to obtain a composition adhesive film, baking the adhesive film on a heat table at 100-130 ℃ for 2-5 min to obtain a pre-baked film, and heating and curing the pre-baked film in a nitrogen-filled oven under the following curing conditions: curing at 150℃for 1 hour, and then heating to 320℃for 1 hour, thereby producing a cured film. When the resin is cured by heating, the oxygen content is controlled to be 10ppm or less.
The 6-inch copper-plated silicon crystal after curing was uniformly divided into A, B parts, and adhesion test before and after aging was performed, respectively.
The adhesion test method of the cured film and the substrate is specifically as follows:
the cured film on the A part copper-plated silicon wafer is cut into 10 multiplied by 10 small squares (the square size is 1mm multiplied by 1 mm) by a hundred grid knife, cleaned by a hairbrush, peeled off by a special transparent 3M adhesive tape according to national standard GB/T9286-1998 'cross-cut test of color paint and clear paint film', and the peeled off condition is observed by a magnifying glass.
According to the same method as above, the cured film on the B part copper-plated silicon wafer was diced into 10×10 (square size of about 1mm×1 mm) squares by using a hundred grid knife, cleaned with a brush, then placed in a HAST aging oven, and subjected to aging experiments at 130 ℃, 85% humidity, and 96 hours. After the completion of the experiment, the peeling test was performed by using an adhesive tape in the same manner as described above, and the peeling was observed with a magnifying glass.
Adhesion evaluation criteria: the 0 level is good, the 1 level is good, and the 2-5 level is bad.
The evaluation criteria for the degree of discoloration of the substrate were: the sample piece before aging is used as a reference for comparison,
the identification of no obvious difference is no color change, and the grade I is adopted;
grade ii, a slight discoloration;
the obvious color change is identified as class III;
the severe discoloration is grade IV.
The adhesion properties and copper discoloration were measured and the results are shown in Table 2.
Table 2 results of the test for the properties of the example and comparative resin compositions
The experimental results of the examples and comparative examples are described below:
the above examples confirm that the photosensitive resin compositions prepared from the modified silane coupling agent provided by the present invention are excellent in storage stability, and that the modified bis-ureido silane coupling agents of different structures are added to the resin compositions of examples 1 to 4, and that the aliphatic phase aromatic is better in improving the adhesion of copper groups when the same parts by weight are added, because the aromatic structure compound is stronger in rigidity and the molecular bond rotation is limited, and the interaction between the ureido structure and the copper groups cannot be fully exerted, and therefore, the modified coupling agent having a bridging group as a flexible group is preferable; in example 5, the effect of the modified coupling agent was the same as that of the resin prepared with ODPA dianhydride in the adhesive solution system prepared with the resin prepared with BPDA dianhydride, and the effect of improving the adhesion of the film to the copper base was the same; in examples 6 to 8, imidazole derivatives, triazole derivatives, benzotriazole derivatives and benzodiazole were added separately on the basis of addition of the modified coupling agent, and in terms of prevention of copper discoloration, triazole derivatives were superior to benzotriazol derivatives, imidazole derivatives or diazole derivatives, and in example 13, the addition of an unmodified benzodiazole compound was more serious in discoloration of the substrate than the aging of the sample to which the modified nitrogen heterocyclic derivative was added, and therefore, the nitrogen heterocyclic compound was preferably a triazole derivative; examples 9 to 11 and example 1 are control experiments of different addition amounts of the modified coupling agent, and the addition amount is preferably 2 parts by mass or more to ensure adhesion of the film to the copper base, and preferably 5 parts by mass or less to ensure stability of the dope.
In comparative example 1, the resin composition is not added with a coupling agent and an aza-cycle compound, the prepared film has poor adhesion with copper, the film has large-area serious shedding phenomenon without aging experiments, and after aging experiments, the film is peeled off by itself without tape peeling test because of static electricity, the film loses the protection meaning on copper, and has serious color change and is dark green; in comparative examples 2 to 6, the coupling agents having epoxy group, acrylamide group, mercapto group, propyl group, and ureido group were added, respectively, the prepared resin compound was poor in adhesion to copper after curing, and the photosensitive composition prepared from the coupling agent having active epoxy group and semicarbazide group was poor in storage stability, which was caused by the fact that the resin composition system contained a large amount of active hydroxyl groups, and in addition, the cured film prepared by adding the resin composition having mercapto group coupling agent was observed by electron microscopy to have a small amount of dot-like foreign matters generated at the interface with copper, and it was suspected that the mercapto group caused corrosion to copper; the ureido structure coupling agent has a certain effect in the aspect of increasing the adhesiveness between a film and copper, but the amino group of the ureido structure coupling agent can lead to the reduction of the stability of the glue solution when the glue solution is stored for a long time, reduce the sensitivity of the glue solution and cause the gelation phenomenon, so the ureido structure coupling agent is not applicable; in comparative example 7, the addition of the aza ring compound on the basis of the addition of the ureido coupling agent, but the improvement of the adhesiveness is slightly inferior to that of the bis-ureido modified coupling agent, the synergistic effect of the ureido group and the aza ring group cannot be fully exerted, the effect of avoiding the copper discoloration after aging is limited, and the storage stability is poor.
The experiment shows that compared with the conventional structural coupling agent, the modified bis-ureido silane coupling agent can effectively improve the adhesiveness between a film and copper, and can also ensure the storage stability of the photosensitive resin composition. The derivative of the nitrogen heterocyclic compound, particularly the triazole compound, has ideal effect in preventing copper from changing color after aging experiments, and is an effective reference for a BTA protection method of a copper ware.
The modified silane coupling agent provided by the invention has the advantages of simple preparation process, convenient and easily available raw materials and certain economic applicability.
The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention may be practiced in a wide variety of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.

Claims (7)

1. A negative photosensitive resin composition is characterized by comprising photosensitive resin, a modified silane coupling agent shown in a formula I, a photoinitiator, a photocrosslinking agent and an organic solvent;
The photosensitive resin is selected from polyimide, polyimide precursor or a mixture thereof with a double bond structure capable of undergoing free radical polymerization;
the structure of the photosensitive resin is shown as a formula II:
II type
In the formula II, R 2 A 4-valent organic group having 6 to 36 carbon atoms; r is R 3 R is R 4 Each independently represents a hydrogen atom or a monovalent organic group having an unsaturated double bond structure represented by the following formula III; r is R 5 A 2-valent organic group having 2 to 36 carbon atoms; m and n are each independently integers of 0 to 6000 and are not 0 at the same time, and m is more than n;
III
In the formula III, p is an integer of 2 to 6, R 6 、R 7 、R 8 Independently of each other is a hydrogen atomOr methyl, ethyl, propyl monovalent organic groups;
i
In the formula I, A represents a divalent organic group with more than 2 carbon atoms; r is R 1 Represents methyl or ethyl;
the negative photosensitive resin composition further comprises a nitrogen-containing heterocyclic compound shown in formula IV or formula V:
in the formulas IV and V, X represents a carbon atom or a nitrogen atom, and Y represents any one of the following:
1) An organic group having an amide bond formed based on the reaction of an amino group and an acid anhydride;
2) Organic groups having urethane structures based on the reaction of hydroxyl groups with isocyanates.
2. The negative photosensitive resin composition according to claim 1, wherein: in the formula I, A represents a straight-chain alkyl group, phenyl group, diphenyl ether group, biphenyl group or cyclohexyl alkyl group with 2-12 carbon atoms.
3. The negative photosensitive resin composition according to claim 1, wherein: in the negative photosensitive resin composition, the weight part of the modified silane coupling agent is 0.1-8 parts based on 100 parts of the photosensitive resin.
4. The negative photosensitive resin composition according to claim 1, wherein: in the negative photosensitive resin composition, the weight part of the nitrogen-containing heterocyclic compound shown in the formula IV or the formula V is 0.1-3 parts based on 100 parts of the weight part of the photosensitive resin.
5. The negative photosensitive resin composition according to claim 1, wherein: the photoinitiator is selected from benzophenone or derivatives thereof, acetophenone derivatives, oximes or oxime esters photopolymerization initiators;
in the negative photosensitive resin composition, the weight part of the photoinitiator is 0.5-15 parts based on 100 parts of the weight of the photosensitive resin;
the photocrosslinker is an acrylic compound which is subjected to free radical polymerization reaction by utilizing the photoinitiator;
In the negative photosensitive resin composition, the weight part of the photocrosslinker is 2-30 parts based on 100 parts of the weight part of the photosensitive resin;
the organic solvent is one or more of aprotic polar solvent, ether solvent, ketone solvent, ester solvent or alcohol solvent;
in the negative photosensitive resin composition, the weight part of the organic solvent is 130-200 parts based on 100 parts of the photosensitive resin.
6. Use of the negative photosensitive resin composition according to any one of claims 1 to 5 for producing a cured film, wherein a substrate for producing the cured film is a copper-plated silicon wafer.
7. An electronic component comprising a substrate made of the negative photosensitive resin composition according to any one of claims 1 to 5, which is a negative photosensitive cured film of a copper-plated silicon wafer.
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