Hot-melt type polyimide transparent tape, semiconductor packaging laminate, and semiconductor packaging structure

Abstract

The present application provides a hot-melt type polyimide transparent adhesive tape, a semiconductor packaging laminate and a semiconductor packaging structure. The hot-melt type polyimide transparent adhesive tape comprises a transparent base film, a polyimide adhesive layer and an optional release layer; wherein the polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition comprises an aromatic diamine, a siloxane diamine, an aromatic dianhydride and an optional alkoxysilane, wherein the catalyst comprises an imidazole catalyst. The hot-melt type polyimide transparent adhesive tape of the present application can effectively reduce the heat treatment temperature of the polyimide adhesive layer by adding a catalyst in the polyimide adhesive layer.

Description

Technical Field

[0001] This invention relates to the field of polyimide technology, specifically to a hot-melt polyimide transparent tape, a semiconductor encapsulation layer, and a semiconductor encapsulation structure. Background Technology

[0002] Through-Silicon Via (TSV) technology is a core technology for achieving vertical interconnection of chips in advanced packaging. It achieves three-dimensional electrical connections between chips by creating micron-sized vertical vias inside a silicon wafer and filling them with conductive materials (such as copper), thus overcoming the physical limitations of traditional two-dimensional packaging. TSV semiconductor packaging substrates, with their ultra-high wiring density and micron-sized vertical interconnection capabilities, have become the core carrier for 2.5D / 3D advanced packaging. It can be manufactured by coating one side of a substrate film with a heat-resistant, hot-melt polyimide that can bond to the carrier glass, and coating the other side with an adhesive layer thicker than the bump height. When the adhesive layer thickness exceeds the bump height (50-100 microns), an acrylic photocurable coating can be used. To achieve photocuring of the acrylic adhesive layer, ultraviolet light must be irradiated along the direction of the substrate film. If the substrate film is an opaque material with low light transmittance, such as polyimide film, ultraviolet light cannot penetrate, making it difficult for the acrylic adhesive layer to cure.

[0003] To address the aforementioned UV transmission issue, transparent polymer films are typically used instead of polyimide films as the substrate film. However, the high-temperature heat treatment (approximately 350°C) required after hot-melt bonding of the polyimide coating can cause thermal deformation of the substrate film, thus affecting the manufacturing process. Summary of the Invention

[0004] The purpose of this invention is to overcome the disadvantage of high heat treatment temperature of polyimide adhesive layers in the prior art, and to provide a hot melt polyimide transparent tape, a semiconductor encapsulation layer assembly, and a semiconductor encapsulation structure.

[0005] In a first aspect, the present invention provides a hot-melt polyimide transparent tape, comprising a transparent substrate film, a polyimide adhesive layer, and optionally a release layer; wherein the polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane, wherein the catalyst comprises an imidazole catalyst.

[0006] Furthermore, the catalyst comprises substituted or unsubstituted imidazole compounds, wherein the substituents are selected from halogens, nitro groups, carbonyl groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, and combinations thereof.

[0007] Furthermore, the substituents are selected from chlorine, nitro, carbonyl, methyl, ethyl, isopropyl, propyl, phenyl, benzyl, cyanoethyl, and vinyl.

[0008] Further, the catalyst is selected from one or more of 1,2-dimethylimidazolium, 2,4,5-triphenylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-ethylimidazolium, 1-methylimidazolium, 1-vinylimidazolium, 2-ethylimidazolium, 2-isopropylimidazolium, 2-propylimidazolium, 2-methyl-5-nitroimidazolium, 2-chloro-4-nitroimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-ethyl-4-methylimidazolium, 2,4-dinitroimidazolium, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, 4-nitroimidazolium, imidazolium, and N,N'-carbonyldiimidazolium.

[0009] Furthermore, the monomer composition further includes a first organic solvent and / or a second organic solvent.

[0010] Further, the first organic solvent is selected from one or more of N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N,N-diethylformamide, N-ethyl-2-pyrrolidone, N,N-diethylacetamide, and N,N-dimethylpropionamide.

[0011] Further, the second organic solvent is selected from one or more of xylene, benzene, toluene, cyclohexanone, diethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane.

[0012] Further, the aromatic diamine includes p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(3-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, trimethylene bis(4-aminobenzoate), 1,5-diaminonaphthalene, bis[4-(3-aminophenoxy)phenyl]sulfone, 4-(4-aminophenoxy)phenyl]sulfone, and 2,5-dimethyl-1,4-phenylenediamine. The following are some of the following: 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 4-aminophenyl-4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzoylaniline, 3,5-diaminobenzoic acid, 4,4'-diamino-(1,1'-biphenyl)-2,2'-dicarboxylic acid, m-xylenediamine, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0013] Further, the aromatic dianhydride includes one or more of the following: phenyl dianhydride (PMDA), biphenyl dianhydride (BPDA), bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylphenylene diphenoxy) bisphthalic anhydride: BPADA), hexafluoroisopropylidene dianhydride (4,4'-(hexafluoroisopropylphenylene) bisphthalic anhydride: 6FDA), 4,4'-oxodiphenyl dianhydride (4,4'-oxodiphthalic anhydride: ODPA), benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride: BTDA), ethylene glycol bis(4-trimethoate) (TMEG), diphenyl sulfone tetracarboxylic dianhydride (4,4'-sulfonyldiphthalic anhydride: DSDA), and naphthalene-2,3,6,7-tetracarboxylic dianhydride (2,3,6,7-NTDA).

[0014] Furthermore, the siloxane diamine is a polydimethylsiloxane with diamino-terminated ends having the following formula: Where R is C 1-20 Alkylene (e.g., C10) 2-10 Alkylenes, such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, etc.), where n is an integer from 1 to 20.

[0015] Furthermore, the siloxane diamine includes one or more of bis(γ-aminopropyl)polydimethyldisiloxane and bis(aminoethyl)polydimethylsiloxane.

[0016] Furthermore, the weight-average molecular weight of the siloxane diamine is 500-1200.

[0017] Furthermore, the siloxane diamine is a bis(γ-aminopropyl)polydimethyldisiloxane with a weight-average molecular weight (Mw) of 500-1200.

[0018] Furthermore, the alkoxysilane includes one or more of tetraethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, or methyltrimethoxysilane.

[0019] Furthermore, the glass transition temperature of the polyimide adhesive layer is 30~100℃.

[0020] Furthermore, the thickness of the transparent substrate film is 10~100μm; and / or the thickness of the polyimide adhesive layer is 2~10μm; and / or the thickness of the release layer is 10~100μm.

[0021] Furthermore, the transparent substrate film is selected from one or more of polyethylene terephthalate, polyamide, polyethylene naphthalate, polyphenylene sulfide, cyclic olefin polymer, polycarbonate, and transparent polyimide.

[0022] In a second aspect, the present invention provides a method for preparing the hot-melt polyimide transparent tape described in the first aspect, comprising the following steps: S1. To form a polyamic acid from a monomer composition, said monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane; S2. Add a catalyst to the polyamic acid, the catalyst comprising an imidazole catalyst; S3. The polyamic acid containing the catalyst is coated on one surface of a transparent substrate film, followed by heat treatment to form the hot-melt polyimide transparent tape.

[0023] Furthermore, the temperature of the heat treatment is 60~240℃; and / or the total time of the heat treatment is 10~180 minutes.

[0024] Furthermore, the heat treatment is a multi-stage heat treatment.

[0025] Furthermore, S1 includes: An aromatic diamine, a first organic solvent, a siloxane diamine, a second organic solvent, an aromatic dianhydride, and optionally an alkoxysilane are mixed to obtain a mixture; the mixture is then reacted to obtain the polyamic acid.

[0026] Furthermore, the reaction temperature is 0~60℃; and / or the reaction time is 24-72h.

[0027] Furthermore, the molar ratio of the aromatic diamine to the siloxane diamine is 1.5:8.5 to 5:5.

[0028] Furthermore, the molar ratio of total diamine to total dianhydride compounds is 1.1~0.9:0.9~1.1.

[0029] Furthermore, the content of alkoxysilane does not exceed 80 mol% of the total moles of diamine and dianhydride, preferably 20-80 mol%, more preferably 20-50 mol%.

[0030] Furthermore, the amount of the catalyst used is 0.1 to 10% of the total weight of the diamine and dianhydride.

[0031] Thirdly, the present invention provides a semiconductor packaging composite comprising a substrate, a polyimide adhesive layer, a UV-transparent polymer film, and a photocurable adhesive layer; wherein the polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane, wherein the catalyst comprises an imidazole catalyst.

[0032] Furthermore, the substrate is selected from carrier glass and / or lead frame.

[0033] Furthermore, the catalyst comprises substituted or unsubstituted imidazole compounds, wherein the substituents are selected from halogens, nitro groups, carbonyl groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, and combinations thereof.

[0034] Furthermore, the substituents are selected from chlorine, nitro, carbonyl, methyl, ethyl, isopropyl, propyl, phenyl, benzyl, cyanoethyl, and vinyl.

[0035] Further, the catalyst is selected from one or more of 1,2-dimethylimidazolium, 2,4,5-triphenylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-ethylimidazolium, 1-methylimidazolium, 1-vinylimidazolium, 2-ethylimidazolium, 2-isopropylimidazolium, 2-propylimidazolium, 2-methyl-5-nitroimidazolium, 2-chloro-4-nitroimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-ethyl-4-methylimidazolium, 2,4-dinitroimidazolium, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, 4-nitroimidazolium, imidazolium, and N,N'-carbonyldiimidazolium.

[0036] Furthermore, the monomer composition further includes a first organic solvent and / or a second organic solvent.

[0037] Further, the first organic solvent is selected from one or more of N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N,N-diethylformamide, N-ethyl-2-pyrrolidone, N,N-diethylacetamide, and N,N-dimethylpropionamide.

[0038] Further, the second organic solvent is selected from one or more of xylene, benzene, toluene, cyclohexanone, diethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane.

[0039] Further, the aromatic diamine includes p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(3-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, trimethylene bis(4-aminobenzoate), 1,5-diaminonaphthalene, bis[4-(3-aminophenoxy)phenyl]sulfone, 4-(4-aminophenoxy)phenyl]sulfone, and 2,5-dimethyl-1,4-phenylenediamine. The following are some of the following: 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 4-aminophenyl-4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzoylaniline, 3,5-diaminobenzoic acid, 4,4'-diamino-(1,1'-biphenyl)-2,2'-dicarboxylic acid, m-xylenediamine, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0040] Further, the aromatic dianhydride includes one or more of the following: phenyl dianhydride (PMDA), biphenyl dianhydride (BPDA), bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylphenylene diphenoxy) bisphthalic anhydride: BPADA), hexafluoroisopropylidene dianhydride (4,4'-(hexafluoroisopropylphenylene) bisphthalic anhydride: 6FDA), 4,4'-oxodiphenyl dianhydride (4,4'-oxodiphthalic anhydride: ODPA), benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride: BTDA), ethylene glycol bis(4-trimethoate) (TMEG), diphenyl sulfone tetracarboxylic dianhydride (4,4'-sulfonyldiphthalic anhydride: DSDA), and naphthalene-2,3,6,7-tetracarboxylic dianhydride (2,3,6,7-NTDA).

[0041] Furthermore, the siloxane diamine is a polydimethylsiloxane with diamino-terminated ends having the following formula: Where R is C 1-20 Alkylene (e.g., C10) 2-10 Alkylenes, such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, etc.), where n is an integer from 1 to 20; Furthermore, the siloxane diamine includes one or more of bis(γ-aminopropyl)polydimethyldisiloxane and bis(aminoethyl)polydimethylsiloxane.

[0042] Furthermore, the weight-average molecular weight of the siloxane diamine is 500-1200.

[0043] Furthermore, the siloxane diamine is a bis(γ-aminopropyl)polydimethyldisiloxane with a weight-average molecular weight (Mw) of 500-1200.

[0044] Furthermore, the alkoxysilane includes one or more of tetraethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, or methyltrimethoxysilane.

[0045] Furthermore, the glass transition temperature of the polyimide adhesive layer is 30~100℃.

[0046] Furthermore, the method for preparing the polyimide adhesive layer includes: S1. To form a polyamic acid from a monomer composition, said monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane; S2. Add a catalyst to the polyamic acid, the catalyst comprising an imidazole catalyst.

[0047] Further, S1 comprises: mixing an aromatic diamine, a first organic solvent, a siloxane diamine, a second organic solvent, an aromatic dianhydride, and optionally an alkoxysilane to obtain a mixture; reacting the mixture to obtain the polyamic acid; Furthermore, the reaction temperature is 0~60℃; and / or the reaction time is 24-72h.

[0048] Furthermore, the molar ratio of the aromatic diamine to the siloxane diamine is 1.5:8.5 to 5:5.

[0049] Furthermore, the molar ratio of total diamine to total dianhydride compounds is 1.1~0.9:0.9~1.1.

[0050] Furthermore, the content of alkoxysilane does not exceed 80 mol% of the total molar amount of diamine and diamine, preferably 20-80 mol%, more preferably 20-50 mol%.

[0051] Furthermore, the amount of the catalyst used is 0.1 to 10% of the total weight of the diamine and dianhydride.

[0052] Fourthly, the present invention provides a semiconductor packaging structure comprising the semiconductor packaging layer assembly described in the third aspect and a semiconductor wafer with solder bumps on its surface, wherein the solder bumps on the surface of the semiconductor wafer are accommodated within a photocurable adhesive layer of the semiconductor packaging layer assembly.

[0053] The present invention has the following beneficial effects: The hot-melt polyimide transparent tape of the present invention can effectively reduce the heat treatment temperature of the polyimide adhesive layer by adding a catalyst to the polyimide adhesive layer. Attached Figure Description

[0054] Figure 1 This is a schematic diagram of a semiconductor packaging structure in one embodiment. Detailed Implementation

[0055] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way.

[0056] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0057] Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art. Unless otherwise specified, the reagents used in the following embodiments are conventional biochemical reagents; the raw materials, instruments, and equipment used in the following embodiments can all be obtained commercially or by existing methods; unless otherwise specified, the reagent dosages are those used in routine experimental operations; unless otherwise specified, the experimental methods are conventional methods.

[0058] In a first aspect, this application provides a hot-melt polyimide transparent tape, comprising a transparent substrate film, a polyimide adhesive layer, and optionally a release layer; wherein the polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane, wherein the catalyst comprises an imidazole catalyst.

[0059] As described in the background section, transparent substrate films require high-temperature heat treatment after coating with an adhesive layer, which can lead to thermal deformation of the film. However, the inventors of this application have creatively discovered that the polyimide adhesive layer is formed by polymerizing a monomer composition in the presence of a catalyst. The catalyst can effectively reduce the heat treatment temperature of the polyimide adhesive layer, thus avoiding the problem of film thermal deformation.

[0060] In some embodiments, the catalyst comprises a substituted or unsubstituted imidazole compound, wherein the substituent is selected from halogens, nitro groups, carbonyl groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, and combinations thereof.

[0061] In some embodiments, the substituents are selected from chlorine, nitro, carbonyl, methyl, ethyl, isopropyl, propyl, phenyl, benzyl, cyanoethyl, and vinyl.

[0062] In some embodiments, the catalyst is selected from one or more of 1,2-dimethylimidazolium, 2,4,5-triphenylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-ethylimidazolium, 1-methylimidazolium, 1-vinylimidazolium, 2-ethylimidazolium, 2-isopropylimidazolium, 2-propylimidazolium, 2-methyl-5-nitroimidazolium, 2-chloro-4-nitroimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-ethyl-4-methylimidazolium, 2,4-dinitroimidazolium, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, 4-nitroimidazolium, imidazolium, and N,N'-carbonyldiimidazolium.

[0063] In some embodiments, the monomer composition further includes a first organic solvent and / or a second organic solvent.

[0064] In some embodiments, the monomer composition includes a first organic solvent and a second organic solvent. In some embodiments, the mass ratio of the first organic solvent to the second organic solvent is (5-7):4. If too much of the first organic solvent is used, the polymerization reaction may be difficult to proceed; conversely, if too little is used, gelation may occur.

[0065] Since siloxane diamines require the use of low-polarity solvents, the first organic solvent is preferably a low-polarity solvent. The first organic solvent is selected from one or more of N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), N,N-diethylformamide (DEF), N-ethyl-2-pyrrolidone (NEP), N,N-diethylacetamide (DEAc), and N,N-dimethylpropionamide (DMPA).

[0066] In some embodiments, the second organic solvent is selected from one or more of xylene, benzene, toluene, cyclohexanone, diethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane.

[0067] In some embodiments, the aromatic diamine includes p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4′-diaminodiphenyl ether (ODA), 3,4′-diaminodiphenyl ether (3,4-ODA), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[4-(3-aminophenoxy)phenyl]propane (BAPP), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene (TPE-R), bis(3-aminophenyl)sulfone (3-SDA), bis(4-aminophenyl)sulfone (4-SDA), trimethylene bis(4-aminobenzoic acid ester) (TMAB), 1,5-diaminonaphthalene (1,5-DAN), bis[4-(3-aminophenyl)sulfone [m-BAPS](xyl)phenyl]sulfone, [p-BAPS](xyl)phenyl]sulfone, 2,5-dimethyl-1,4-phenylenediamine (DMPDA), 2,2'-dimethylbenzidine (m-Tolidine), 3,3'-dimethylbenzidine (o-Tolidine), 4-aminophenyl-4-aminobenzoate (APAB), 1,3-bis(3-aminophenoxy)benzene (BPTP), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 4,4'-diaminobenzoyl aniline (DABA), 3,5-diaminobenzoic acid (DABA), 4,4'-diamino-(1,1'-biphenyl)-2,2'-dicarboxylic acid (4,4-APC), m-xylenediamine (MXDA), 4,4'- One or more of the following: bis(4-aminophenoxy)benzophenone (4BABP), 4,4′-bis(4-aminophenoxy)biphenyl (BAPB), 2,2′-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether (6FODA), and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP).

[0068] The following is a list of the names and CAS numbers of these aromatic diamines:

[0069] In some embodiments, the aromatic dianhydride includes one or more of the following: phenyl dianhydride (PMDA), biphenyl dianhydride (BPDA), bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylphenylene diphenoxy)bisphthalic anhydride: BPADA), hexafluoroisopropylidene dianhydride (4,4'-(hexafluoroisopropylphenylene)bisphthalic anhydride: 6FDA), 4,4'-oxodiphenyl dianhydride (4,4'-oxodiphthalic anhydride: ODPA), benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride: BTDA), ethylene glycol bis(4-trimethoate) (TMEG), diphenyl sulfone tetracarboxylic dianhydride (4,4'-sulfonyldiphthalic anhydride: DSDA), and naphthalene-2,3,6,7-tetracarboxylic dianhydride (2,3,6,7-NTDA).

[0070] In some embodiments, the siloxane diamine is a polydimethylsiloxane (PSX) with diamino-terminated ends having the following formula. Where R is C 1-20 Alkylene (e.g., C10) 2-10 Alkylenes, such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, etc.), where n is an integer from 1 to 20.

[0071] The siloxane diamine includes one or more of bis(γ-aminopropyl)polydimethyldisiloxane (PSX) and bis(aminoethyl)polydimethylsiloxane.

[0072] In some embodiments, the weight-average molecular weight of the siloxane diamine is 500 to 1200; for example, 500, 600, 700, 800, 900, 1000, 1100, 1200 or any value between them.

[0073] In some embodiments, the siloxane diamine is a bis(γ-aminopropyl)polydimethyldisiloxane (i.e., R is 1,3-propylidene) with a weight-average molecular weight (Mw) of 500 to 1200 (e.g., 500, 600, 700, 800, 900, 1000, 1100, 1200 or any value therebetween).

[0074] In some embodiments, the alkoxysilane includes one or more of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), phenyltrimethoxysilane (PTMOS), or methyltrimethoxysilane (MTMOS). Alkoxysilanes are added as additives and can be selectively included or excluded. For products used in lead frames, since no residue must be left after debonding, alkoxysilanes are added to impart release properties, thereby preventing residue formation. For TSV glass substrates, alkoxysilanes may not be added.

[0075] In some embodiments, the glass transition temperature of the polyimide adhesive layer is 30~100°C, for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any value between them. If the glass transition temperature is too high, the adhesion of the polyimide adhesive layer will decrease; if the glass transition temperature is too low, the heat resistance of the polyimide adhesive layer will decrease.

[0076] In some embodiments, the thickness of the transparent substrate film is 10 to 100 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or any value between them.

[0077] In some embodiments, the thickness of the polyimide adhesive layer is 2 to 10 μm, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or any value between them.

[0078] In some embodiments, the thickness of the release layer is 10 to 100 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or any value between them.

[0079] In some implementations, the release layer is made of a release-treated polymer film and is used to protect the adhesive surface. The release layer must be removed before using the tape.

[0080] In some embodiments, the transparent substrate film is selected from one or more of polyethylene terephthalate, polyamide, polyethylene naphthalate, polyphenylene sulfide, cyclic olefin polymers, polycarbonate, and transparent polyimide.

[0081] In some embodiments, the initial SUS adhesion strength of the polyimide adhesive layer is 5-20 gf / cm, for example, 5 gf / cm, 6 gf / cm, 7 gf / cm, 8 gf / cm, 9 gf / cm, 10 gf / cm, 11 gf / cm, 12 gf / cm, 13 gf / cm, 14 gf / cm, 15 gf / cm, 16 gf / cm, 17 gf / cm, 18 gf / cm, 19 gf / cm, 20 gf / cm, or any value between them. In some embodiments, the initial SUS adhesion strength of the polyimide adhesive layer is 5-10 gf / cm.

[0082] In some embodiments, the SUS adhesive strength of the polyimide adhesive layer after heat treatment is 150-200 gf / cm, for example, 150 gf / cm, 160 gf / cm, 170 gf / cm, 180 gf / cm, 190 gf / cm, 200 gf / cm, or any value between them. In some embodiments, the SUS adhesive strength of the polyimide adhesive layer after heat treatment is 170-175 gf / cm.

[0083] In some embodiments, the initial glass adhesion strength of the polyimide adhesive layer is 1-15 gf / cm, for example, 1 gf / cm, 2 gf / cm, 3 gf / cm, 4 gf / cm, 5 gf / cm, 6 gf / cm, 7 gf / cm, 8 gf / cm, 9 gf / cm, 10 gf / cm, 11 gf / cm, 12 gf / cm, 13 gf / cm, 14 gf / cm, 15 gf / cm, or any value between them. In some embodiments, the initial glass adhesion strength of the polyimide adhesive layer is 3-6 gf / cm.

[0084] In some embodiments, the glass adhesion strength of the polyimide adhesive layer after heat treatment is 120-200 gf / cm, for example, 120 gf / cm, 130 gf / cm, 140 gf / cm, 150 gf / cm, 160 gf / cm, 170 gf / cm, 180 gf / cm, 190 gf / cm, 200 gf / cm, or any value between them. In some embodiments, the glass adhesion strength of the polyimide adhesive layer after heat treatment is 150-155 gf / cm. Secondly, this application provides a method for preparing the hot-melt polyimide transparent tape described in the first aspect, comprising the following steps: S1. To form a polyamic acid from a monomer composition, said monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane; S2. Add a catalyst to the polyamic acid, the catalyst comprising an imidazole catalyst; S3. The polyamic acid containing the catalyst is coated on one surface of a transparent substrate film, followed by heat treatment to form the hot-melt polyimide transparent tape.

[0085] In some embodiments, the heat treatment temperature is 60~240°C, for example 60°C, 100°C, 150°C, 200°C, 240°C or any value between them.

[0086] In some embodiments, the total time of the heat treatment is 10 to 180 minutes; for example, 10 minutes, 50 minutes, 100 minutes, 150 minutes, 180 minutes or any value between them.

[0087] In some embodiments, the heat treatment is a multi-stage heat treatment. The multi-stage heat treatment includes gradually increasing the temperature from 60°C to 240°C (e.g., 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, or any value between them), with a treatment time of 1 to 30 minutes at each temperature. In some embodiments, the multi-stage heat treatment may include gradually increasing the temperature from 60°C to 130°C, 200°C, 220°C, and 240°C, with a treatment time of 5 minutes at each temperature.

[0088] In some implementations, S1 includes: An aromatic diamine, a first organic solvent, a siloxane diamine, a second organic solvent, an aromatic dianhydride, and optionally an alkoxysilane are mixed to obtain a mixture; the mixture is then reacted to obtain the polyamic acid.

[0089] In some embodiments, the reaction temperature is 0 to 60°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C or any value between them.

[0090] In some embodiments, the reaction time is 24-72 h, for example, 24 h, 30 h, 35 h, 40 h, 45 h, 50 h, 55 h, 60 h, 65 h, 70 h, 72 h or any value between them.

[0091] In some embodiments, the molar ratio of the aromatic diamine to the siloxane diamine is 1.5:8.5 to 5:5, for example, 1:5, 1:4, 1:3, 1:2, 1:1 or any value between them. The ratio between the aromatic diamine and the siloxane diamine can control the glass transition temperature of the polyimide.

[0092] In some embodiments, the molar ratio of total diamine to total dianhydride is 1.1 to 0.9: 0.9 to 1.1, for example, 0.9:1, 0.9:1.1, 1:1, 1.1:0.9 or any value between them.

[0093] In some embodiments, the content of alkoxysilane does not exceed 80 mol% of the total moles of diamine and dianhydride. In some embodiments, the content of alkoxysilane is 20-80 mol% of the total moles of diamine and dianhydride, for example, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 80 mol%, or any value between therewith. In some embodiments, the content of alkoxysilane is 20-50 mol% of the total moles of diamine and dianhydride.

[0094] In some embodiments, the catalyst is used in an amount of 0.1% to 10% of the total weight of the diamine and dianhydride, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any value between them. If the amount of catalyst is too high, the material will undergo a gelation reaction, and an effective coating cannot be formed; while if the amount is too low, the adjustment margin for the heat treatment temperature will become very limited.

[0095] Thirdly, this application provides a semiconductor packaging composite, comprising a substrate, a polyimide adhesive layer, a UV-transparent polymer film, and a photocurable adhesive layer; wherein the polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane, wherein the catalyst comprises an imidazole catalyst.

[0096] In some embodiments, the substrate is selected from carrier glass and / or lead frame.

[0097] In some embodiments, the photocurable adhesive layer may include an acrylic adhesive.

[0098] In some embodiments, the catalyst comprises a substituted or unsubstituted imidazole compound, wherein the substituent is selected from halogens, nitro groups, carbonyl groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, and combinations thereof.

[0099] In some embodiments, the substituents are selected from chlorine, nitro, carbonyl, methyl, ethyl, isopropyl, propyl, phenyl, benzyl, cyanoethyl, and vinyl.

[0100] In some embodiments, the catalyst is selected from one or more of 1,2-dimethylimidazolium, 2,4,5-triphenylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-ethylimidazolium, 1-methylimidazolium, 1-vinylimidazolium, 2-ethylimidazolium, 2-isopropylimidazolium, 2-propylimidazolium, 2-methyl-5-nitroimidazolium, 2-chloro-4-nitroimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-ethyl-4-methylimidazolium, 2,4-dinitroimidazolium, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, 4-nitroimidazolium, imidazolium, and N,N'-carbonyldiimidazolium.

[0101] In some embodiments, the monomer composition further includes a first organic solvent and / or a second organic solvent.

[0102] In some embodiments, the monomer composition includes a first organic solvent and a second organic solvent. In some embodiments, the mass ratio of the first organic solvent to the second organic solvent is (5-7):4. If too much of the first organic solvent is used, the polymerization reaction may be difficult to proceed; conversely, if too little is used, gelation may occur.

[0103] Since siloxane diamines require the use of low-polarity solvents, the first organic solvent is preferably a low-polarity solvent. The first organic solvent is selected from one or more of N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), N,N-diethylformamide (DEF), N-ethyl-2-pyrrolidone (NEP), N,N-diethylacetamide (DEAc), and N,N-dimethylpropionamide (DMPA).

[0104] In some embodiments, the second organic solvent is selected from one or more of xylene, benzene, toluene, cyclohexanone, diethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane.

[0105] In some embodiments, the aromatic diamine includes p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4′-diaminodiphenyl ether (ODA), 3,4′-diaminodiphenyl ether (3,4-ODA), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[4-(3-aminophenoxy)phenyl]propane (BAPP), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene (TPE-R), bis(3-aminophenyl)sulfone (3-SDA), bis(4-aminophenyl)sulfone (4-SDA), trimethylene bis(4-aminobenzoic acid ester) (TMAB), 1,5-diaminonaphthalene (1,5-DAN), bis[4-(3-aminophenyl)sulfone [m-BAPS](xyl)phenyl]sulfone, [p-BAPS](xyl)phenyl]sulfone, 2,5-dimethyl-1,4-phenylenediamine (DMPDA), 2,2'-dimethylbenzidine (m-Tolidine), 3,3'-dimethylbenzidine (o-Tolidine), 4-aminophenyl-4-aminobenzoate (APAB), 1,3-bis(3-aminophenoxy)benzene (BPTP), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 4,4'-diaminobenzoyl aniline (DABA), 3,5-diaminobenzoic acid (DABA), 4,4'-diamino-(1,1'-biphenyl)-2,2'-dicarboxylic acid (4,4-APC), m-xylenediamine (MXDA), 4,4'- One or more of the following: bis(4-aminophenoxy)benzophenone (4BABP), 4,4′-bis(4-aminophenoxy)biphenyl (BAPB), 2,2′-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether (6FODA), and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP).

[0106] In some embodiments, the aromatic dianhydride includes one or more of the following: phenyl dianhydride (PMDA), biphenyl dianhydride (BPDA), bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylphenylene diphenoxy)bisphthalic anhydride: BPADA), hexafluoroisopropylidene dianhydride (4,4'-(hexafluoroisopropylphenylene)bisphthalic anhydride: 6FDA), 4,4'-oxobinanhydride (4,4'-oxodiphthalic anhydride: ODPA), benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride: BTDA), ethylene glycol bis(4-trimethoate) (TMEG), diphenyl sulfone tetracarboxylic dianhydride (4,4'-sulfonyldiphthalic anhydride: DSDA), and naphthalene-2,3,6,7-tetracarboxylic dianhydride (2,3,6,7-NTDA).

[0107] In some embodiments, the siloxane diamine is a polydimethylsiloxane (PSX) with diamino-terminated ends having the following formula. Where R is C 1-20 Alkylene (e.g., C10) 2-10 Alkylenes, such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, etc.), where n is an integer from 1 to 20.

[0108] The siloxane diamine includes one or more of bis(γ-aminopropyl)polydimethyldisiloxane and bis(aminoethyl)polydimethylsiloxane.

[0109] In some embodiments, the weight-average molecular weight of the siloxane diamine is 500 to 1200; for example, 500, 600, 700, 800, 900, 1000, 1100, 1200 or any value between them.

[0110] In some embodiments, the siloxane diamine is a bis(γ-aminopropyl)polydimethyldisiloxane (i.e., R is 1,3-propylidene) with a weight-average molecular weight (Mw) of 500 to 1200 (e.g., 500, 600, 700, 800, 900, 1000, 1100, 1200 or any value therebetween).

[0111] In some embodiments, the alkoxysilane includes one or more of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), phenyltrimethoxysilane (PTMOS), or methyltrimethoxysilane (MTMOS). Alkoxysilanes are added as additives and can be selectively included or excluded. For products used in lead frames, since no residue must be left after debonding, alkoxysilanes are added to impart release properties, thereby preventing residue formation. For TSV glass substrates, alkoxysilanes may not be added.

[0112] In some embodiments, the glass transition temperature of the polyimide adhesive layer is 30~100°C, for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any value between them. If the glass transition temperature is too high, the adhesion of the polyimide adhesive layer will decrease; if the glass transition temperature is too low, the heat resistance of the polyimide adhesive layer will decrease.

[0113] In some embodiments, the method for preparing the polyimide adhesive layer includes: S1. To form a polyamic acid from a monomer composition, said monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane; S2. Add a catalyst to the polyamic acid, the catalyst comprising an imidazole catalyst.

[0114] In some implementations, S1 includes: An aromatic diamine, a first organic solvent, a siloxane diamine, a second organic solvent, an aromatic dianhydride, and optionally an alkoxysilane are mixed to obtain a mixture; the mixture is then reacted to obtain the polyamic acid.

[0115] In some embodiments, the polyamic acid has a solid content of 10-30 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any value between them.

[0116] In some embodiments, the reaction temperature is 0 to 60°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C or any value between them.

[0117] In some embodiments, the reaction time is 24-72 h, for example, 24 h, 30 h, 35 h, 40 h, 45 h, 50 h, 55 h, 60 h, 65 h, 70 h, 72 h, or any value between them. The ratio between the aromatic diamine and the siloxane diamine can control the glass transition temperature of the polyimide.

[0118] In some embodiments, the molar ratio of the aromatic diamine to the siloxane diamine is 1.5:8.5 to 5:5, for example, 1:5, 1:4, 1:3, 1:2, 1:1 or any value between them.

[0119] In some embodiments, the molar ratio of total diamine to total dianhydride is 1.1 to 0.9: 0.9 to 1.1, for example, 0.9:1, 0.9:1.1, 1:1, 1.1:0.9 or any value between them.

[0120] In some embodiments, the content of alkoxysilane does not exceed 80 mol% of the total molar amount of diamine and dianhydride. In some embodiments, the content of alkoxysilane is 20-80 mol% of the total molar amount of diamine and dianhydride, for example, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 80 mol%, or any value between them. In some embodiments, the content of alkoxysilane is 20-50 mol% of the total molar amount of diamine and dianhydride. In some embodiments, the amount of catalyst is 0.1-10% of the total weight of diamine and dianhydride, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any value between them. If the amount of catalyst is too high, the material will undergo a gelation reaction, and an effective coating cannot be formed; while if the amount is too low, the adjustment margin for the heat treatment temperature will become very limited.

[0121] In some implementations, the release layer is made of a release-treated polymer film and is used to protect the adhesive surface. The release layer must be removed before using the tape.

[0122] In some embodiments, the UV-transparent polymer film is selected from one or more of polyethylene terephthalate, polyamide, polyethylene naphthalate, polyphenylene sulfide, cyclic olefin polymers, polycarbonate, and transparent polyimide.

[0123] Fourthly, the present invention provides a semiconductor packaging structure, comprising the semiconductor packaging layer assembly described in the third aspect of the present invention and a semiconductor wafer with solder bumps on its surface, wherein the solder bumps on the surface of the semiconductor wafer are accommodated within a photocurable adhesive layer of the semiconductor packaging layer assembly.

[0124] In some embodiments, a schematic diagram of a semiconductor package structure is shown below. Figure 1 As shown.

[0125] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples.

[0126] Comparative Example 1 p-phenylenediamine (p-PDA) was added to DMAc and dissolved by stirring at 40°C. Then, bis(γ-aminopropyl)polydimethyldisiloxane (PSX) and xylene, with the weight-average molecular weights shown in Table 1, were added. The molar ratio of PSX to p-phenylenediamine (p-PDA) was as shown in Table 1, and the weight ratio of DMAc to xylene was 6:4. Subsequently, BPDA and TEOS were added, where TEOS was 50 mol% of the total molars of diamine and dianhydride, and the molar ratio of total dianhydride to total diamine was 1:1. The reaction was carried out at 25°C for 24 hours to prepare polyamic acid. The solid content of the polyamic acid was 18 wt%.

[0127] The polyamide film was coated with the above-mentioned polyamic acid, and then subjected to gradient heating at 130℃, 200℃, 250℃ and 285℃ for 5 minutes respectively, to finally prepare a 4μm thick hot melt polyimide adhesive layer.

[0128] Comparative Example 2 The difference from Comparative Example 1 is that the molar ratio of PSX to p-PDA is 5:5.

[0129] Comparative Example 3 The difference from Comparative Example 1 is that the weight-average molecular weight of PSX is 1600.

[0130] Comparative Example 4 The difference from Comparative Example 1 is that TEOS is not added.

[0131] Comparative Example 5 The difference from Comparative Example 1 is that the amount of TEOS added is 100 mol.

[0132] Comparative Example 6 The difference from Comparative Example 1 is that the molar ratio of PSX to p-PDA is 9:1.

[0133] Comparative Example 7 The difference from Comparative Example 1 is that the molar ratio of PSX to p-PDA is 2:8.

[0134] Table 1

[0135] In Table 1, PSX:p-PDA refers to the molar ratio of PSX and p-PDA. The amount of TEOS added represents the molar percentage of TEOS in the total moles of diamine and dianhydride. X indicates that there is no adhesive residue on the surface of the adhered material, which is a qualified state; O indicates that there is adhesive residue on the surface of the adhered material, which is a non-qualified state.

[0136] Among them, Comparative Example 6 had a lower Tg and reduced heat resistance, which led to the problem of residues during the desizing process.

[0137] Example 1 p-phenylenediamine (p-PDA) was added to DMAc and dissolved by stirring at 40°C. Then, bis(γ-aminopropyl)polydimethyldisiloxane (PSX) and xylene, with the weight-average molecular weights shown in Table 2, were added. The molar ratio of PSX to p-phenylenediamine (p-PDA) was as shown in Table 2, and the weight ratio of DMAc to xylene was 6:4. Subsequently, BPDA and TEOS were added, where TEOS was 50 mol% of the total molars of diamine and dianhydride, and the molar ratio of total dianhydride to total diamine was 1:1. The reaction was carried out at 25°C for 24 hours to prepare polyamic acid. The solid content of the polyamic acid was 18 wt%.

[0138] The polymerized polyamic acid (PAA) was mixed with a catalyst (1,2-dimethylimidazole) and stirred for more than 4 hours, wherein the amount of catalyst was 2% of the total weight of the diamine and dianhydride.

[0139] Subsequently, the polyamic acid was coated on the surface of the polyamide film, and the film was subjected to gradient heating at 130°C, 200°C and 220°C for 5 minutes respectively, to finally prepare a 4μm thick hot melt polyimide adhesive layer.

[0140] Example 2 The difference from Example 1 is that the above-mentioned polyamic acid was coated on the surface of the polyamide film, and the film was subjected to gradient heating, and heat treatment was carried out at 130°C, 200°C and 240°C for 5 minutes respectively.

[0141] Example 3 The difference from Example 1 is that the polymerized polyamic acid (PAA) was mixed and stirred with the catalyst (2,4,5-triphenylimidazolium) for more than 4 hours.

[0142] Example 4 The difference from Example 1 is that the polymerized polyamic acid (PAA) was mixed and stirred with the catalyst (N,N'-carbonyldiimidazole) for more than 4 hours.

[0143] Comparative Example 8 The difference from Example 1 is that the above-mentioned polyamic acid was coated on the surface of the polyamide film, and the film was subjected to gradient heating, and heat treatment was carried out at 130°C, 200°C and 285°C for 5 minutes respectively.

[0144] Comparative Example 9 The difference from Example 1 is that the above-mentioned polyamic acid was coated on the surface of the polyamide film, and the film was subjected to gradient heating, and heat treatment was carried out at 130°C, 200°C and 240°C for 5 minutes respectively.

[0145] Comparative Example 10 The difference from Example 1 is that the above-mentioned polyamic acid was coated on the surface of the polyamide film, and the film was subjected to gradient heating, and heat treatment was carried out at 130°C, 200°C and 220°C for 5 minutes respectively.

[0146] Table 2

[0147] Table 2 examines the effects of catalyst and heat treatment temperature on the degree of imidization (the process of converting polyamic acid to polyimide, i.e., the degree of curing) through chemical resistance testing. If imidization proceeds normally, the mass loss rate in the chemical resistance test (immersion in NMP) will be low.

[0148] As can be seen from Examples 1 and 2, even when heat-treated at relatively low temperatures such as 220°C and 240°C, the samples still exhibit excellent chemical resistance, indicating that imidization has been fully completed.

[0149] Examples 3-4 used other catalysts, but their catalytic effect was not as good as that of 1,2-dimethylimidazole.

[0150] In Comparative Example 8, the heat treatment temperature needs to reach 285°C to ensure sufficient imidization, which will cause thermal deformation of the polyamide film.

[0151] Comparisons of Comparative Examples 9 and 10 with Examples 1-2 show that the imidization reaction is complete when 1,2-dimethylimidazole is added; however, the high mass loss rate in the chemical resistance test indicates that imidization is not fully carried out when 1,2-dimethylimidazole is not added. Therefore, it is evident that adding a catalyst can effectively reduce the heat treatment temperature of the polyimide adhesive layer.

[0152] The test methods used in the above embodiments and comparative examples are as follows: (1) SUS adhesive strength test method The hot-melt polyimide adhesive films prepared in the above examples and comparative examples were cut into 30mm (width) × 150mm (length) pieces and then bonded to an SUS board using a hot press (temperature: 90℃, pressure: 10MPa, time: 5 seconds). A 90° peel test was then performed using a UTM to measure the initial adhesive force. Next, the bonded samples were subjected to heat treatment at 190℃ for 90 minutes (simulating chip bonding process) and at 200℃ for 60 minutes (simulating wire bonding process), followed by another 90° peel test to measure the adhesive force after heat treatment (chip bonding and wire bonding process temperatures).

[0153] (2) Glass adhesion test method The hot-melt polyimide adhesive films prepared in the above examples and comparative examples were cut into 30mm (width) × 150mm (length) pieces, and then bonded to glass using a roller laminator (temperature: 100℃). The initial adhesion was then measured by a 90° peel test. The laminated samples were then heat-treated using a hot plate at 150℃ / 5 minutes and 250℃ / 60 minutes (simulating the TSV process), and the adhesion after heat treatment was measured by a 90° peel test.

[0154] (3) Test method for residues after degumming To evaluate residues on the heat-sealed polyimide adhesive film, the film was bonded to a leadframe (SUS board) using a hot press (temperature: 90°C, pressure: 10 MPa, time: 5 seconds). The bonded samples were then heat-treated using a hot plate at temperatures of 190°C / 90 minutes (simulating chip mounting), 200°C / 60 minutes (simulating wire bonding), and 175°C / 360 minutes (simulating PMC). Afterward, the heat-sealed polyimide adhesive film adhered to the other side of the leadframe was removed by peeling off the tape, and the residues remaining on the leadframe surface were examined using a microscope.

[0155] (4) Test methods for chemical resistance At room temperature, the polyimide film was immersed in NMP for 24 hours, and its mass loss rate was tested.

[0156] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hot-melt polyimide transparent tape, comprising a transparent substrate film, a polyimide adhesive layer, and optionally a release layer; wherein, The polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition including aromatic diamines, siloxane diamines, aromatic dianhydrides and optionally alkoxysilanes, wherein the catalyst includes an imidazole catalyst.

2. The hot-melt polyimide transparent tape according to claim 1, characterized in that, The catalyst comprises substituted or unsubstituted imidazole compounds, wherein the substituents are selected from halogens, nitro groups, carbonyl groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, and combinations thereof; Preferably, the substituent is selected from chlorine, nitro, carbonyl, methyl, ethyl, isopropyl, propyl, phenyl, benzyl, cyanoethyl, and vinyl; Preferably, the catalyst is selected from one or more of 1,2-dimethylimidazole, 2,4,5-triphenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-ethylimidazole, 1-methylimidazole, 1-vinylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-methyl-5-nitroimidazole, 2-chloro-4-nitroimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2,4-dinitroimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 4-nitroimidazole, imidazole, and N,N'-carbonyldiimidazole.

3. The hot-melt polyimide transparent tape according to claim 1 or 2, characterized in that, The monomer composition further includes a first organic solvent and / or a second organic solvent; Preferably, the first organic solvent is selected from one or more of N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N,N-diethylformamide, N-ethyl-2-pyrrolidone, N,N-diethylacetamide, and N,N-dimethylpropionamide; Preferably, the second organic solvent is selected from one or more of xylene, benzene, toluene, cyclohexanone, diethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane.

4. The hot-melt polyimide transparent tape according to any one of claims 1-3, characterized in that, The aromatic diamines include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(3-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, trimethylene bis(4-aminobenzoic acid ester), 1,5-diaminonaphthalene, bis[4-(3-aminophenoxy)phenyl]sulfone, 4-(4-aminophenoxy)phenyl]sulfone, 2,5-dimethyl-1,4-phenylenediamine, 2 One or more of the following: 2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 4-aminophenyl-4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzoyl aniline, 3,5-diaminobenzoic acid, 4,4'-diamino-(1,1'-biphenyl)-2,2'-dicarboxylic acid, m-xylenediamine, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; and / or The aromatic dianhydride includes one or more of the following: phenyltetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, bisphenol A diether dianhydride, hexafluoroisopropylidene dianhydride, 4,4′-oxodiphthalic anhydride (4,4'-oxophthalic anhydride: ODPA), benzophenone tetracarboxylic dianhydride, ethylene glycol bis(4-triphenyltriacyl anhydride), diphenyl sulfone tetracarboxylic dianhydride, and naphthalene-2,3,6,7-tetracarboxylic dianhydride; and / or The siloxane diamine is a polydimethylsiloxane with diamino-terminated ends having the following formula: Where R is C 1-20 Alkylene (e.g., C10) 2-10 Alkylenes, such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, etc.), where n is an integer from 1 to 20; Preferably, the siloxane diamine comprises one or more of bis(γ-aminopropyl)polydimethyldisiloxane and bis(aminoethyl)polydimethylsiloxane; Preferably, the siloxane diamine has a weight-average molecular weight of 500-1200; preferably, the siloxane diamine is bis(γ-aminopropyl)polydimethyldisiloxane with a weight-average molecular weight (Mw) of 500-1200; and / or The alkoxysilane includes one or more of tetraethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, or methyltrimethoxysilane; Preferably, the glass transition temperature of the polyimide adhesive layer is 30~100℃.

5. The hot-melt polyimide transparent tape according to any one of claims 1-4, characterized in that, The thickness of the transparent substrate film is 10~100μm; and / or the thickness of the polyimide adhesive layer is 2~10μm; and / or the thickness of the release layer is 10~100μm; Preferably, the transparent substrate film is selected from one or more of polyethylene terephthalate, polyamide, polyethylene naphthalate, polyphenylene sulfide, cyclic olefin polymers, polycarbonate, and transparent polyimide.

6. A method for preparing a hot-melt polyimide transparent tape according to any one of claims 1-5, comprising the following steps: S1. To form a polyamic acid from a monomer composition, said monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane; S2. Add a catalyst to the polyamic acid, the catalyst comprising an imidazole catalyst; S3. The polyamic acid containing the catalyst is coated on one surface of a transparent substrate film, followed by heat treatment to form the hot-melt polyimide transparent tape; Preferably, the temperature of the heat treatment is 60~240℃; and / or the total time of the heat treatment is 10~180 minutes; Preferably, the heat treatment is a multi-stage heat treatment.

7. The preparation method according to claim 6, characterized in that, S1 includes: An aromatic diamine, a first organic solvent, a siloxane diamine, a second organic solvent, an aromatic dianhydride, and optionally an alkoxysilane are mixed to obtain a mixture; the mixture is then reacted to obtain the polyamic acid. Preferably, the reaction temperature is 0~60℃; and / or the reaction time is 24-72h; Preferably, the molar ratio of the aromatic diamine to the siloxane diamine is 1.5:8.5 to 5:5; and / or the molar ratio of the total diamine to the total dianhydride compound is 1.1 to 0.9:0.9 to 1.1; and / or the content of alkoxysilane does not exceed 80 mol% of the total molar amount of diamine and dianhydride; preferably 20-80 mol%, more preferably 20-50 mol%.

8. The preparation method according to claim 6, characterized in that, The amount of catalyst used is 0.1-10% of the total weight of diamine and dianhydride.

9. A semiconductor packaging composite, comprising a substrate, a polyimide adhesive layer, a UV-transparent polymer film, and a photocurable adhesive layer; wherein, The polyimide adhesive layer is polymerized from a monomer composition in the presence of a catalyst, the monomer composition including aromatic diamines, siloxane diamines, aromatic dianhydrides and optionally alkoxysilanes, wherein the catalyst includes an imidazole catalyst; Preferably, the substrate is selected from carrier glass and / or lead frame.

10. The semiconductor packaging composite according to claim 9, characterized in that, The catalyst comprises substituted or unsubstituted imidazole compounds, wherein the substituents are selected from halogens, nitro groups, carbonyl groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, and combinations thereof; Preferably, the substituent is selected from chlorine, nitro, carbonyl, methyl, ethyl, isopropyl, propyl, phenyl, benzyl, cyanoethyl, and vinyl; Preferably, the catalyst is selected from one or more of 1,2-dimethylimidazolium, 2,4,5-triphenylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-ethylimidazolium, 1-methylimidazolium, 1-vinylimidazolium, 2-ethylimidazolium, 2-isopropylimidazolium, 2-propylimidazolium, 2-methyl-5-nitroimidazolium, 2-chloro-4-nitroimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-ethyl-4-methylimidazolium, 2,4-dinitroimidazolium, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, 4-nitroimidazolium, imidazolium, and N,N'-carbonyldiimidazolium; and / or The monomer composition further includes a first organic solvent and / or a second organic solvent; Preferably, the first organic solvent is selected from one or more of N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N,N-diethylformamide, N-ethyl-2-pyrrolidone, N,N-diethylacetamide, and N,N-dimethylpropionamide; The second organic solvent is selected from one or more of xylene, benzene, toluene, cyclohexanone, diethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane; and / or The aromatic diamines include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(3-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, trimethylene bis(4-aminobenzoic acid ester), 1,5-diaminonaphthalene, bis[4-(3-aminophenoxy)phenyl]sulfone, 4-(4-aminophenoxy)phenyl]sulfone, 2,5-dimethyl-1,4-phenylenediamine, 2 One or more of the following: 2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 4-aminophenyl-4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzoyl aniline, 3,5-diaminobenzoic acid, 4,4'-diamino-(1,1'-biphenyl)-2,2'-dicarboxylic acid, m-xylenediamine, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; and / or The aromatic dianhydride comprises one or more of the following: phenyl dianhydride (PMDA), biphenyl dianhydride (BPDA), bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylphenylene diphenoxy)bisphthalic anhydride: BPADA), hexafluoroisopropylidene dianhydride (4,4'-(hexafluoroisopropylphenylene)bisphthalic anhydride: 6FDA), 4,4'-oxobinanhydride (4,4'-oxophthalic anhydride: ODPA), benzophenone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride: BTDA), ethylene glycol bis(4-triphenylene oxide) (TMEG), diphenyl sulfone tetracarboxylic dianhydride (4,4'-sulfonyl phthalic anhydride: DSDA), and naphthalene-2,3,6,7-tetracarboxylic dianhydride (2,3,6,7-NTDA); and / or The siloxane diamine is a polydimethylsiloxane with diamino-terminated ends having the following formula: Where R is C 1-20 Alkylene (e.g., C10) 2-10 Alkylenes, such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, etc.), where n is an integer from 1 to 20; Preferably, the siloxane diamine comprises one or more of bis(γ-aminopropyl)polydimethyldisiloxane and bis(aminoethyl)polydimethylsiloxane; Preferably, the siloxane diamine has a weight-average molecular weight of 500-1200; preferably, the siloxane diamine is bis(γ-aminopropyl)polydimethyldisiloxane with a weight-average molecular weight (Mw) of 500-1200; and / or The alkoxysilane includes one or more of tetraethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, or methyltrimethoxysilane; Preferably, the glass transition temperature of the polyimide adhesive layer is 30~100℃; Preferably, the method for preparing the polyimide adhesive layer includes: S1. To form a polyamic acid from a monomer composition, said monomer composition comprising an aromatic diamine, a siloxane diamine, an aromatic dianhydride, and optionally an alkoxysilane; S2. Add a catalyst to the polyamic acid, the catalyst comprising an imidazole catalyst; Preferably, S1 comprises: mixing an aromatic diamine, a first organic solvent, a siloxane diamine, a second organic solvent, an aromatic dianhydride, and optionally an alkoxysilane to obtain a mixture; reacting the mixture to obtain the polyamic acid; Preferably, the reaction temperature is 0~60℃; and / or the reaction time is 24-72h; Preferably, the molar ratio of the aromatic diamine to the siloxane diamine is 1.5:8.5 to 5:5; and / or the molar ratio of total diamine to total dianhydride compounds is 1.1 to 0.9:0.9 to 1.1; and / or the content of alkoxysilane does not exceed 80 mol% of the total molar amount of diamine and diamine, preferably 20-80 mol%, more preferably 20-50 mol%; Preferably, the amount of catalyst used is 0.1-10% of the total weight of diamine and dianhydride.

11. A semiconductor package structure, comprising the semiconductor package composite of claim 10 and a semiconductor wafer with solder bumps on its surface, wherein, The solder bumps on the surface of the semiconductor wafer are housed within the photocurable adhesive layer of the semiconductor package assembly.

Images