WO2023246762A1 - 感光树脂组合物、膜材、含苯并环丁烯结构的环氧化合物及其应用 - Google Patents

感光树脂组合物、膜材、含苯并环丁烯结构的环氧化合物及其应用 Download PDF

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WO2023246762A1
WO2023246762A1 PCT/CN2023/101334 CN2023101334W WO2023246762A1 WO 2023246762 A1 WO2023246762 A1 WO 2023246762A1 CN 2023101334 W CN2023101334 W CN 2023101334W WO 2023246762 A1 WO2023246762 A1 WO 2023246762A1
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group
photosensitive resin
substituted
resin composition
formula
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PCT/CN2023/101334
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English (en)
French (fr)
Inventor
刘付林
唐新颖
苗杰
秦德君
贾斌
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华为技术有限公司
明士新材料有限公司
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Publication of WO2023246762A1 publication Critical patent/WO2023246762A1/zh

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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the embodiments of the present application relate to the technical field of photosensitive resin materials, and in particular to a photosensitive resin composition, a photosensitive resin film, an epoxy compound containing a benzocyclobutene structure, and their applications.
  • the resin composition is easily cured and molded into various sizes and shapes, and is widely used in the field of electronic packaging.
  • Surface Acoustic Wave (SAW) filter as a passive filter, is widely used in the field of wireless communications.
  • SAW Surface Acoustic Wave
  • Its main packaging forms include metal packaging, ceramic packaging, flip-chip soldering packaging and wafer-level packaging. Due to the increase in 5G communication frequency bands, more filters need to be embedded in mobile phones. Therefore, filter chips and packages are developing towards miniaturization, thinness, and modularization.
  • Wafer Level Package is the smallest form of packaging for surface acoustic wave filters. It uses photosensitive resin material on the surface of the wafer to be exposed, developed and solidified twice to form cavities of various sizes. The area is protected, and processes such as electroplating are used to lead the pads on the periphery of the chip to the surface of the device to complete the packaging.
  • photosensitive resin materials need to be used to build a hollow cavity for the filter chip, and then the entire module is injection molded and packaged at a high temperature of 180°C and above and a pressure of 3MPa-5MPa. Therefore, the photosensitive resin material needs to be molded at high temperatures. It has high resistance to molding and keeps the hollow cavity from collapsing. Traditional photosensitive resin materials are softened by heat at high temperatures, and their mechanical strength and modulus are greatly reduced, making it difficult to withstand the high pressure during molding, resulting in cavity collapse and module failure. In order to improve the mold resistance of photosensitive resin materials at high temperatures, a large amount of inorganic fillers and additives are usually added to photosensitive resin materials.
  • the dielectric constant and dielectric loss of the photosensitive resin cured film are very low. Difficult to keep at a low level. Therefore, it is necessary to provide a photosensitive resin material that has excellent high-temperature molding resistance and low dielectric constant and dielectric loss to better meet the packaging needs of various electronic components such as SAW filter chips. .
  • embodiments of the present application provide a photosensitive resin composition.
  • the solid film of the photosensitive resin composition has excellent high-temperature molding resistance and low dielectric constant and dielectric loss, which can better meet the requirements of filtering. packaging requirements for electronic components such as device chips.
  • the first aspect of the embodiment of the present application provides a photosensitive resin composition, including a resin, a cross-linking agent, an initiator, and an epoxy compound containing a benzocyclobutene structure.
  • the photosensitive resin composition in the embodiment of the present application can reduce the dielectric constant and dielectric loss of the cured product after curing the photosensitive resin composition by adding an epoxy compound containing a benzocyclobutene structure; and it contains benzocyclobutene.
  • the structural epoxy compound can achieve better cross-linking during the curing process, increase the cross-linking density of the final cured product, thereby improving the heat resistance and mechanical properties of the cured product, while also reducing water absorption; the photosensitive resin composition Used for packaging electronic components to improve packaging reliability.
  • the epoxy compound containing a benzocyclobutene structure based on 100 parts by weight of the resin, is 0.1-60 parts by weight.
  • the addition of an appropriate weight portion of an epoxy compound containing a benzocyclobutene structure can enable the photosensitive resin composition to obtain better comprehensive properties.
  • the epoxy compound containing a benzocyclobutene structure includes a benzocyclobutene ring and at least one epoxy group-containing substituent connected to the benzocyclobutene ring.
  • Epoxy compounds containing benzocyclobutene structures can combine the performance advantages of benzocyclobutene structures and substituents containing epoxy groups.
  • the epoxy compound containing a benzocyclobutene structure includes any one or more compounds with the structure shown in formula (I):
  • At least one group among R 1 to R 6 is the substituent of the epoxy group-containing group, and the remaining groups are independently selected from hydrogen atoms, substituted or unsubstituted C1 to C20 aliphatic hydrocarbon groups , substituted or unsubstituted C1 to C20 aliphatic hydrocarbonoxy group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C7 to C20 arylalkyl group.
  • the substituent group in the C7 to C20 arylalkyl group includes one or more of a halogen atom, a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an alkyl group, an ester group and an acyl group.
  • the epoxy group-containing substituents include groups represented by formula (1a) to formula (1d):
  • the substituent group in the substituted C1 to C20 alkylene group and the substituted C1 to C20 alkyleneoxy group includes one of a halogen atom, an aryl group, an ester group, and an acyl group.
  • a halogen atom an aryl group, an ester group, and an acyl group.
  • the benzocyclobutene structure-containing epoxy compound at least includes a benzocyclobutene structure-containing epoxy compound containing an epoxy group-containing substituent represented by formula (1d).
  • the resin includes one or more of phenolic epoxy resin, acrylic resin, polyimide precursor resin, soluble polyimide resin, and polybenzoxazole precursor resin.
  • the initiator includes a photopolymerization initiator.
  • the photopolymerization initiator is a compound that can decompose to generate free radicals under ultraviolet light.
  • the photopolymerization initiator includes benzophenone, benzophenone-derived compounds, acetophenone derivatives, thioxanthone, thioxanthone derivatives, benzil, benzoyl derivatives, benzoin, benzoin derivatives, 1-phenyl-1,2-propanedione -2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime), 1-benzene One or more of 1,2-butanedione-2-(o-methoxycarbonyl) oxime and 1,3-diphenylglycerol-2-(o-ethoxycarbonyl) oxime.
  • the initiator based on 100 parts by weight of the resin, the initiator is 0.1-20 parts by weight.
  • the cross-linking agent includes a photopolymerizable compound
  • the photopolymerizable compound is a compound that can be cross-linked by free radicals.
  • the photopolymerizable compound includes 2-hydroxymethyl methacrylate, methyl 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Ester, 2-hydroxybutyl acrylate, glycidyl acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bis One or more of ethyl ether methacrylate, ethylene glycol diethyl ether acrylate and polyethylene glycol methacrylate.
  • the inorganic filler includes one or more of silica, alumina, talc powder, barium sulfate, glass powder, and mica powder; based on 100 parts by weight of the resin, the inorganic filler The filler is 50-400 parts by weight.
  • the film material usually includes a base material, a photosensitive resin film disposed on the surface of the base material, and a cover film disposed on the photosensitive resin film. That is, the film material usually has a three-layer film structure.
  • the application of film materials in preparing electronic packaging structures includes preparing packaging substrates, protective layers, passivation layers, interlayer insulating layers, dielectric layers, buffer layers, planarization layers, and ⁇ -ray shielding layers. Or in the rewiring layer, or used to build elastic wave filters and packaging cavities in MEMS.
  • the photosensitive resin film among the film materials remains in the electronic packaging structure after being completely cured, and both the base material and the cover film are peeled off. That is, the photosensitive resin film is completely cured to form the various film layers mentioned above or to form the above package. cavity.
  • the sixth aspect of the embodiment of the present application provides an epoxy compound containing a benzocyclobutene structure.
  • the epoxy compound containing a benzocyclobutene structure has a structure represented by formula (I):
  • the epoxy compound containing a benzocyclobutene structure in the embodiment of the present application contains an epoxy group-containing substituent represented by formula (1d).
  • the substituent is a substituent containing an ester group and an epoxy group.
  • the substituted C1 to C20 aliphatic hydrocarbon group, the substituted C1 to C20 aliphatic hydrocarbon oxygen group, the substituted C6 to C20 aryl group and the substituted C7 to C20 aryl group include one or more of halogen atoms, hydroxyl groups, hydroxyalkyl groups, carboxyl groups, carboxyalkyl groups, alkyl groups, ester groups and acyl groups.
  • the substituent group in the substituted C1 to C20 alkylene group and the substituted C1 to C20 alkyleneoxy group includes one of a halogen atom, an aryl group, an ester group, and an acyl group.
  • a halogen atom an aryl group, an ester group, and an acyl group.
  • the embodiments of this application also provide the use of the benzocyclobutene structure-containing epoxy compound described in the sixth aspect of the embodiments of this application in preparing coatings, composite materials, casting materials, adhesives, curing agents, photosensitive resin compositions, and photosensitive resin films. materials, plastic encapsulation materials, molding materials and injection molding materials.
  • FIG. 2 is a schematic diagram of an electronic packaging structure 200 provided by an embodiment of the present application.
  • photosensitive resin materials are usually used to build a hollow packaging cavity for the filter chip, and then the entire module is processed at high temperatures of 180°C and above with 3MPa-5MPa Injection molding packaging is performed under high pressure, so the photosensitive resin material is required to have high mold resistance at high temperatures to keep the hollow packaging cavity from collapsing; in addition, as a packaging material for filter chips, the photosensitive resin material is also required to have a low Dielectric constant and dielectric loss.
  • a photosensitive resin material with excellent high-temperature molding resistance and low dielectric constant and dielectric loss to meet the requirements for packaging of electronic components such as filter chips, embodiments of the present application provide a photosensitive resin composition .
  • the photosensitive resin composition in the embodiment of the present application can reduce the dielectric constant and dielectric loss of the cured product after curing the photosensitive resin composition by adding an epoxy compound containing a benzocyclobutene structure; and it contains benzocyclobutene.
  • the structured epoxy compound can achieve better cross-linking during the curing process, increase the cross-linking density of the cured product, thereby improving the heat resistance and mechanical properties of the cured product, while also reducing water absorption; the photosensitive resin composition is used For the packaging of electronic components, it can improve packaging reliability.
  • the epoxy compound containing a benzocyclobutene structure includes a benzocyclobutene ring and at least one epoxy group-containing substituent connected to the benzocyclobutene ring. That is, epoxy compounds containing benzocyclobutene structures can be at the 6 substitutable carbon positions of the benzocyclobutene ring. A compound with one or more epoxy-containing substituents attached to it. Epoxy compounds containing benzocyclobutene structures can combine the performance advantages of benzocyclobutene structures and substituents containing epoxy groups.
  • R1 to R6 is a substituent containing an epoxy group, and the remaining groups are independently selected from hydrogen atoms, substituted or Unsubstituted C1 to C20 aliphatic hydrocarbon group, substituted or unsubstituted C1 to C20 aliphatic hydrocarbon oxygen group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C7 to C20 arylalkyl group base.
  • one or more (two or more) groups of R1 to R6 may be substituents containing epoxy groups.
  • one of R1 to R6 may be a substituent containing an epoxy group; in some embodiments, two of R1 to R6 may be a substituent containing an epoxy group. .
  • the remaining groups are those of R1 to R6 that are not substituents containing an epoxy group.
  • R3 is an epoxy group-containing substituent
  • the remaining groups namely R1, R2, R4, R5 and R6, are hydrogen atoms, or substituted or unsubstituted C1 to C20 aliphatic hydrocarbon groups, Or a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C7 to C20 arylalkyl group.
  • the multiple epoxy group-containing substituents can have the same structure or different structures. .
  • the substituted or unsubstituted C1 to C20 aliphatic hydrocarbon group may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a substituted or unsubstituted C2 to C20 alkynyl group.
  • the substituted or unsubstituted C1 to C20 aliphatic hydrocarbon group may specifically be substituted or unsubstituted C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14 , C15, C16, C17, C18, C19, C20 aliphatic hydrocarbon groups.
  • the substituted or unsubstituted C1 to C20 alkyl group may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, and the like.
  • the substituted or unsubstituted C2 to C20 alkenyl group may be a substituted or unsubstituted vinyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, or the like.
  • the substituted or unsubstituted C2 to C20 alkynyl group may be a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, or the like.
  • the substituted or unsubstituted C1 to C20 aliphatic hydrocarbonoxy group may be a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenoxy group, a substituted or Unsubstituted C2 to C20 alkynyloxy group.
  • the substituted or unsubstituted C1 to C20 aliphatic hydrocarbonoxy group may specifically be substituted or unsubstituted C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13 , C14, C15, C16, C17, C18, C19, C20 aliphatic hydrocarbonoxy groups.
  • the substituted or unsubstituted C1 to C20 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group.
  • the substituted or unsubstituted C6 to C20 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted condensed ring aryl group, etc.
  • the substituted or unsubstituted C7 to C20 arylalkyl group may be a substituted or unsubstituted phenylalkyl group, biphenylalkyl group, fused ring arylalkyl group, etc.
  • R1 to R6 include a substituted C1 to C20 aliphatic hydrocarbon group, a substituted C1 to C20 aliphatic hydrocarbon oxygen group, a substituted C6 to C20 aryl group, and a substituted C7 to C20 aryl group.
  • Substituent groups in the alkyl group include one or more of halogen atoms, hydroxyl groups, hydroxyalkyl groups, carboxyl groups, carboxyalkyl groups, alkyl groups, ester groups and acyl groups.
  • the halogen atom can be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
  • the C1 to C20 aliphatic hydrocarbon group substituted by a halogen atom may be a fluorine-substituted methyl group, a fluorine-substituted ethyl group, a fluorine-substituted propyl group, or the like.
  • Specific examples of the C1 to C20 aliphatic hydrocarbonoxy group substituted by a halogen atom include a fluorine-substituted methoxy group, a fluorine-substituted ethoxy group, a fluorine-substituted propoxy group, and the like.
  • hydroxyl-substituted C1 to C20 aliphatic hydrocarbon group may be hydroxymethyl (-CH2OH), hydroxyethyl (-CH2CH2OH), etc.
  • Specific examples of the hydroxyl-substituted C1 to C20 aliphatic hydrocarbonoxy group may be hydroxymethoxy (-OCH2OH), hydroxyethoxy (-OCH2CH2OH), etc.
  • Specific examples of the carboxy-substituted C1 to C20 aliphatic hydrocarbon group include carboxymethyl (-CH2COOH), carboxyethyl (-CH2CH2COOH), and the like.
  • the substituted or unsubstituted C1 to C20 alkylene group may specifically be substituted or unsubstituted C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, Alkylene group of C13, C14, C15, C16, C17, C18, C19, C20.
  • the substituted or unsubstituted C1 to C20 alkylene group may be a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, or a substituted or unsubstituted butylene group. wait.
  • the substituted or unsubstituted C1 to C20 alkyleneoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethyleneoxy group, a substituted or unsubstituted propyleneoxy group, a substituted or unsubstituted propyleneoxy group, Substituted butyleneoxy, etc.
  • the substituent group in the substituted C1 to C20 alkylene group and the substituted C1 to C20 alkyleneoxy group includes one of a halogen atom, an aryl group, an ester group, an acyl group, or Various.
  • the halogen atom can be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
  • the benzocyclobutene structure-containing epoxy compound may be an epoxy compound containing a benzocyclobutene structure that at least contains an epoxy group-containing substituent represented by formula (1d).
  • the epoxy group-containing substituent represented by formula (1d) is a substituent containing an ester group and an epoxy group, and is essentially an ester group substituted by an epoxy group.
  • the epoxy compound containing a benzocyclobutene structure contains an ester group, it has a stronger interaction with the polar groups in the resin main chain, that is, it can increase the intermolecular force, thereby better improving the resin Thermal resistance and mechanical properties of materials.
  • the resin in the photosensitive resin composition, may include, but is not limited to, phenolic epoxy resin, acrylic resin, polyimide precursor resin (polyamic acid ester resin), soluble polyimide resin, polyamide resin, One or more benzoxazole precursor resins.
  • the weight average molecular weight of the resin may be 2,000-200,000; in some embodiments, the weight average molecular weight of the resin may be 10,000-100,000; in some embodiments, the weight average molecular weight of the resin may be 10,000-50,000.
  • the photosensitive resin composition may include one or more resins. By selecting different resin systems, different photosensitive resin compositions can be obtained to meet the needs of different scenarios.
  • the initiator includes a photopolymerization initiator.
  • the photopolymerization initiator is a compound that can decompose to generate free radicals under ultraviolet light. It may include, but is not limited to, benzophenone, benzophenone derivatives, phenylbenzene, etc.
  • the initiator may be 0.1-20 parts by weight. In some embodiments, the initiator is 0.5-10 parts by weight; in some embodiments, the initiator is 1-5 parts by weight.
  • the cross-linking agent includes a photopolymerizable compound.
  • the photopolymerizable compound is a compound that can be cross-linked by free radicals, and may include, but is not limited to, 2-hydroxymethyl methacrylate, 2-hydroxymethyl methacrylate.
  • the cross-linking agent based on 100 parts by weight of the resin, is 2-50 parts by weight. In some embodiments, the cross-linking agent is 5-30 parts by weight; in some embodiments, the cross-linking agent is 10-20 parts by weight.
  • the photosensitive resin composition may also include an adhesion promoter, a polymerization inhibitor and a solvent.
  • the adhesion promoter can improve the adhesion between the photosensitive resin composition glue and the substrate.
  • the adhesion promoter can be but is not limited to including ⁇ -aminopropyltriethoxysilane, ⁇ -glycidyl ether Oxypropyltrimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane alkane, ⁇ -glycidoxypropyltriethoxysilane, 3-isocyanatotrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-urea Propyltriethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane One or more of e
  • the adhesion promoter may be 0.5-20 parts by weight; in some embodiments, the adhesion promoter may be 1-10 parts by weight; in some embodiments, the adhesion promoter may be 2-5 parts by weight share.
  • the addition of polymerization inhibitors can quench free radical compounds.
  • the polymerization inhibitors can include but are not limited to hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso - One or more of 2-naphthol, 2-nitroso-1-naphthol and 2-nitroso-5-(N-ethyl-sulfopropylamino)phenol.
  • the polymerization inhibitor Based on 100 parts by weight of the resin, the polymerization inhibitor is 0.01-10 parts by weight; in some embodiments, the polymerization inhibitor can be 0.05-5 parts by weight; in some embodiments, the polymerization inhibitor can be 0.1-2 parts by weight.
  • the solvent may include, but is not limited to, N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, tetramethyl One or more of urea, ⁇ -butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate.
  • the solvent is 100-1000 parts by weight; in some embodiments, the solvent is 150-500 parts by weight; in some embodiments, the solvent is 200-300 parts by weight.
  • the photosensitive resin composition further includes an inorganic filler.
  • the addition of inorganic fillers can improve the high-temperature molding resistance of the photosensitive resin composition.
  • the inorganic filler may be, but is not limited to, one or more of silica, alumina, talc powder, barium sulfate, glass powder, and mica powder; based on 100 parts by weight of the resin,
  • the inorganic filler is 50-400 parts by weight; in some embodiments, the inorganic filler is 75-300 parts by weight; in some embodiments, the inorganic filler is 100-200 parts by weight.
  • the photosensitive resin composition is a glue liquid, and the photosensitive resin composition is obtained by mixing various components.
  • the photosensitive resin composition can be used for packaging of various electronic components.
  • the photosensitive resin composition of the embodiment of the present application can be directly used in the packaging substrate, protective layer, passivation layer, interlayer insulating layer, dielectric layer, buffer layer, planarization layer, ⁇ -ray shielding layer and rewiring in the electronic packaging structure. Preparation of layers.
  • the film material 100 includes a photosensitive resin film 10.
  • the photosensitive resin film 10 is prepared by using the photosensitive resin composition described above in the embodiments of the present application.
  • the photosensitive resin film 10 is a solid adhesive film, which is obtained by coating the photosensitive resin composition onto the surface of the substrate 11 and then baking it.
  • the photosensitive resin film 10 is attached to the surface of the base material 11, and a cover film 12 is provided on the photosensitive resin film 10 for protection, forming a three-layer film structure. That is, the film material 100 generally includes a base material 11 , a photosensitive resin film 10 provided on the surface of the base material 11 , and a cover film 12 provided on the photosensitive resin film 10 .
  • the base material 11 may be made of polyethylene terephthalate (PET) or polypropylene (PP).
  • the cover film 12 may be a PET film or a biaxially oriented polypropylene film (BOPP film), or the like. The cover film 12 may be pressed onto the surface of the photosensitive resin film 10 under vacuum conditions, a certain temperature and pressure.
  • the coating may include any one or more of blade coating, spin coating, and spray coating.
  • the baking temperature can be 50-120°C, or 70-100°C; the baking time can be 1-60min, or 5-30min.
  • the pressing temperature can be 30-100°C, or 50-80°C; the pressing pressure can be 5-100kPa, or 30-50kPa.
  • the thickness of the photosensitive resin film 10 in the film material 100, can be prepared as needed, and the thickness of the photosensitive resin film 10 can be 10um-100um.
  • the thickness of the photosensitive resin film 10 may be 10um, 15um, 20um, 25um, 30um, 35um, 40um, 45um, 50um, 55um, 60um, 65um, 70um, 75um, 80um, 85um, 90um, 95um, 100um.
  • the film thickness of the photosensitive resin film 10 after complete curing may be 8um-100um.
  • the photosensitive resin composition and film material 100 of the embodiment of the present application can be used for packaging of various electronic components (such as various chips, transistors, LED devices, resistor-capacitor components (such as resistors, capacitors, inductors), etc.) to form Electronic packaging structures.
  • Embodiments of the present application provide applications of the photosensitive resin composition or film material 100 in preparing electronic packaging structures.
  • the application of the photosensitive resin composition in preparing electronic packaging structures may include using the photosensitive resin composition to prepare packaging substrates, protective layers, passivation layers, interlayer insulating layers, dielectric layers, buffer layers, and planarization layers. , ⁇ -ray shielding layer or rewiring layer, the photosensitive resin composition can be directly coated and then cured to form the various film layers mentioned above.
  • films material 100 in the preparation of electronic packaging structures include preparation of packaging substrates, protective layers, passivation layers, interlayer insulating layers, dielectric layers, buffer layers, planarization layers, ⁇ -ray shielding layers or rewiring layers. , or used to construct elastic wave filters and packaging cavities in micro-electromechanical systems MEMS. It should be noted that in practical applications, only the photosensitive resin film 10 of the film material 100 remains in the electronic packaging structure after being completely cured. Both the base material 11 and the cover film 12 are peeled off, that is, the photosensitive resin film 10 is completely cured to form the above various film layers or to construct the above packaging cavity.
  • the electronic packaging structure 200 includes a cured product of the photosensitive resin composition of the embodiment of the present application.
  • the electronic packaging structure 200 is specifically an elastic wave filter chip packaging structure.
  • the electronic packaging structure 200 includes a substrate 20 , an elastic wave filter chip 201 disposed on the substrate 20 , and a first film formed on the substrate 20 Layer 21, formed on the first film
  • the second film layer 22, the first film layer 21 and the second film layer 22 on the layer 21 are patterned film layers, the first film layer 21 forms a supporting wall, and the second film layer 22 is the photosensitive resin combination of the embodiment of the present application.
  • the substrate 20 , the first film layer 21 and the second film layer 22 together form a packaging cavity 1 , and the elastic wave filter chip 201 is accommodated in the packaging cavity 1 .
  • the packaging cavity 1 may accommodate one or more chips as needed. It is understandable that as the second film layer material for constructing the packaging cavity 1, it needs to have photolithographic hole opening performance to achieve patterning, low dielectric properties, and high temperature molding resistance.
  • the application method includes:
  • Step (1) Apply the film, peel off the covering film 12 of the film material 100, and combine the photosensitive resin film 10 with the base material 11 and the silicon wafer with the patterned first film layer 21 (including the base 21 and the elastic wave filter
  • the chip 201) is attached under a certain pressure and temperature; the attaching pressure of the film can be 10-100kPa or 40-70kPa; the attaching temperature can be 30-90°C or 50-70°C;
  • the first film layer 21 may be formed by completely curing the photosensitive resin film 10 of the embodiment of the present application, or may be formed by using other photosensitive resin materials;
  • Step (2) Post-baking, the combination obtained in step (1) is baked; this post-baking step is an optional step. In some embodiments, the post-baking operation may not be performed and may be performed directly after the completion of step (1). Subsequent exposure and development steps; baking temperature can be 50-100°C or 70-90°C; baking time can be 0.1-20min or 1-5min;
  • Step (4) Develop, use a developing solvent to elute the unexposed part, and then clean it with a rinse solution to obtain a pattern corresponding to the mask plate, and obtain a patterned photosensitive resin film; the developer can be a negative photosensitive resin composition A good solvent, or a combination of a good solvent and a poor solvent.
  • good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone.
  • the poor solvent can be methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, One or more types of propylene glycol methyl ether acetate.
  • the rinsing liquid can be one or more of isopropyl alcohol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclopentanone, and cyclohexanone;
  • the curing temperature can be set according to actual needs. Taking the photosensitive resin film as a polyimide film as an example, the curing temperature can be 180-400°C or 200-300°C.
  • the curing time can be 30-500min or It is 60-150min.
  • An embodiment of the present application also provides an electronic device, which includes the electronic packaging structure described above in the embodiment of the present application.
  • the embodiments of the present application also provide an epoxy compound containing a benzocyclobutene structure.
  • the epoxy compound containing a benzocyclobutene structure has a structure represented by formula (I):
  • At least one group among R 1 to R 6 is an epoxy group-containing substituent represented by formula (1d), and the remaining groups are independently selected from hydrogen atoms, substituted or unsubstituted C1 to C20 aliphatic hydrocarbon group, substituted or unsubstituted C1 to C20 aliphatic hydrocarbon oxygen group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C7 to C20 arylalkyl group, formula (1a ), an epoxy group-containing substituent represented by formula (1b), an epoxy group-containing substituent represented by formula (1c),
  • R1 to R6 may have one or more (two or more) groups of the formula ( The epoxy group-containing substituent shown in 1d), the remaining groups are independently selected from hydrogen atoms, substituted or unsubstituted C1 to C20 aliphatic hydrocarbon groups, substituted or unsubstituted C1 to C20 aliphatic hydrocarbon oxygen group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 arylalkyl group, an epoxy group-containing substituent represented by formula (1a), a substituent represented by formula (1b) The epoxy group-containing substituent, the epoxy group-containing substituent represented by formula (1c).
  • the epoxy group-containing substituent represented by formula (1d) is a substituent containing an ester group and an epoxy group, and is essentially an ester group substituted by an epoxy group.
  • the epoxy compound containing a benzocyclobutene structure contains an ester group, it has a stronger interaction with the polar groups in the resin main chain, that is, it can increase the intermolecular force, thereby better improving the resin Thermal resistance and mechanical properties of materials.
  • the embodiments of the present application also provide the use of the above-mentioned benzocyclobutene structure-containing epoxy compounds in the preparation of coatings, composite materials, casting materials, adhesives, curing agents, photosensitive resin compositions, photosensitive resin film materials, and plastic sealing materials. , molding materials and injection molding materials.
  • the hydrogen nuclear magnetic resonance spectrum results of the epoxy compound B2 containing a benzocyclobutene structure are: 1H NMR (400MHz, Chloroform-d) ⁇ : 7.21 (d, 1H, ArH), 7.07 (d, 1H, ArH), 6.95 (s,1H,ArH),4.46-4.09(m,2H,-CH2-),3.27-3.15(m,4H,-CH2-CH2-),2.94(m,1H,-CH-),2.68-2.55 (m,2H,-CH2-).
  • Thick liquid namely epoxy compound B3 containing benzocyclobutene structure.
  • the hydrogen nuclear magnetic resonance spectrum results of epoxy compound B3 containing benzocyclobutene structure are: 1H NMR (400MHz, Chloroform-d) ⁇ : 6.89 (d, 1H, ArH), 6.65 (d, 1H, ArH), 6.60 (s,1H,ArH), 3.70-3.30(m,4H,-CH2-), 3.20-3.0(m,4H,-CH2-CH2-), 2.80-2.70(m,2H,-CH-), 2.50 (s,4H,-CH2-).
  • the photosensitive resin composition solution prepared above was scraped onto the PET film to form a wet film, and then baked in a blast oven at 80°C for 20 minutes to obtain a photosensitive resin solid film.
  • the thickness of the photosensitive resin solid film was measured to be 30 ⁇ m. .
  • the BOPP film is bonded to the above-mentioned photosensitive resin solid adhesive film with PET base material film at 60°C by vacuum lamination to form a film material with a three-layer film structure.
  • Examples 2-9 and Comparative Examples 1-4 The specific components and contents of the photosensitive resin composition glue and photosensitive resin film materials of Examples 2-9 and Comparative Examples 1-4 are listed in Table 1. Refer to Example 1 for their preparation process.
  • A1, A2, and A3 are the resins prepared in Synthesis Example 1-3
  • B1, B2, and B3 are the epoxy compounds containing benzocyclobutene structures prepared in Synthesis Example 4-6
  • B4 is bisphenol A.
  • the polyimide cured film was cut into 30 mm ⁇ 5 mm ⁇ 30 ⁇ m splines to characterize the heat resistance (including glass transition temperature) and tensile properties (including tensile modulus and tensile strength). Then take an 8cm ⁇ 8cm polyimide cured film sample, and after air drying at 150°C for 2 hours, characterize the water absorption and dielectric properties of the sample at 10GHz (including dielectric constant and dielectric loss at 10GHz).
  • the film application process parameters (including the rolling temperature and film coverage during film application) of the photosensitive resin solid adhesive films in Examples 1-9 and Comparative Examples 1-4 of the present application are listed in Table 2; Examples 1-9 and Comparative Examples of the present application
  • the cured film performance evaluation results of the photosensitive resin materials in Ratios 1-4 are listed in Table 2.
  • the epoxy compound containing a benzocyclobutene structure in the photosensitive resin composition of the embodiment of the present application can be Ring-opening and solidification of cyclobutene occurs in the film stage (the heat treatment stage after development), which increases the cross-linking density, thus giving the system higher tensile modulus, tensile strength and glass compared to the photosensitive resin composition of the comparative proportion. Glass transition temperature, while also reducing dielectric constant, dielectric loss and water absorption.
  • Example 1 and Example 3 Example 4 and Example 5
  • epoxy compounds containing benzocyclobutene structures with the same number of epoxy rings contain an ester group bridged structure because they have Stronger intermolecular interactions can more significantly increase the glass transition temperature, tensile modulus and tensile strength of the cured film of the photosensitive resin composition, but will affect the dielectric constant, dielectric loss and water absorption to a certain extent. Reduce effectiveness.

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Abstract

本申请实施例提供一种感光树脂组合物，包括树脂、交联剂、引发剂和含苯并环丁烯结构的环氧化合物。本申请实施例的感光树脂组合物，通过加入含苯并环丁烯结构的环氧化合物可以降低感光树脂组合物固化后所得固化物的介电常数和介电损耗；而且含苯并环丁烯结构的环氧化合物在固化过程中可以实现更好的交联，提高最终固化物的交联密度，从而提高固化物的耐热性能和机械力学性能，同时还能降低吸水率。本申请实施例还提供了采用该感光树脂组合物制备的膜材，以及提供该感光树脂组合物和膜材的应用。

Description

感光树脂组合物、膜材、含苯并环丁烯结构的环氧化合物及其应用
本申请要求于2022年6月23日提交中国专利局、申请号为202210717092.X、申请名称为“感光树脂组合物、膜材、含苯并环丁烯结构的环氧化合物及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请实施例涉及感光树脂材料技术领域，特别是涉及一种感光树脂组合物、感光树脂膜、含苯并环丁烯结构的环氧化合物及其应用。
背景技术
树脂组合物易固化成型成各种尺寸形状，在电子封装领域得到广泛应用。声表面波(Surface Acoustic Wave,SAW)滤波器作为一种无源的滤波器，广泛应用于无线通讯领域，其主要封装形式有金属封装、陶瓷封装、倒装焊封装与晶圆级封装。由于5G通讯频段的增加，需要在手机内埋入更多的滤波器，因此滤波器芯片与封装朝着小型化、薄型化、模组化发展。目前，晶圆级封装(Wafer Level Package,WLP)是声表面波滤波器尺寸最小的一种封装形式，通过在晶元表面利用感光树脂材料两次曝光显影固化形成各种尺寸空腔，将工作区域保护起来，同时使用电镀等工艺将芯片外围的焊盘引出至器件的表面，从而完成封装。
在WLP工艺中，需要使用感光树脂材料为滤波器芯片构筑中空腔体，随后模组整体在180℃及以上的高温与3MPa-5MPa的压力下进行注塑模压封装，因此需要感光树脂材料在高温下具有高抗模压性能，保持中空腔体不塌陷。传统感光树脂材料在高温下受热软化，机械强度与模量大幅降低，难以承受模压时的高压，从而导致腔体塌陷，模组失效。为了提升感光树脂材料高温下的抗模压性能，目前通常是在感光树脂材料中添加大量无机填料和添加剂，而大量无机填料和添加剂的存在下，感光树脂硬化膜的介电常数和介电损耗很难保持在较低水平。因此，有必要提供一种兼具优异的抗高温模压性能、以及较低的介电常数和介电损耗的感光树脂材料，以更好地满足SAW滤波器芯片等各种电子元器件的封装需求。
发明内容
鉴于此，本申请实施例提供一种感光树脂组合物，该感光树脂组合物的固态膜兼具优异的抗高温模压性能、以及较低的介电常数和介电损耗，可以更好地满足滤波器芯片等电子元器件的封装需求。
具体地，本申请实施例第一方面提供一种感光树脂组合物，包括树脂、交联剂、引发剂和含苯并环丁烯结构的环氧化合物。
本申请实施例的感光树脂组合物，通过加入含苯并环丁烯结构的环氧化合物可以降低感光树脂组合物固化后所得固化物的介电常数和介电损耗；而且含苯并环丁烯结构的环氧化合物在固化过程中可以实现更好的交联，提高最终固化物的交联密度，从而提高固化物的耐热性能和机械性能，同时还能降低吸水率；该感光树脂组合物用于电子元器件的封装，可以提高封装可靠性。
本申请实施方式中，以所述树脂为100重量份计，所述含苯并环丁烯结构的环氧化合物为0.1-60重量份。适合重量份的含苯并环丁烯结构的环氧化合物的加入，可以使感光树脂组合物获得更好的综合性能。
本申请实施方式中，所述含苯并环丁烯结构的环氧化合物包括苯并环丁烯环和至少一个连接在所述苯并环丁烯环上的含环氧基团的取代基。含苯并环丁烯结构的环氧化合物可以兼具苯并环丁烯结构和含环氧基团的取代基的性能优势。
本申请实施方式中，所述含苯并环丁烯结构的环氧化合物包括式(I)所示结构的任意一种或多种化合物：
式(I)中，R1至R6中至少一个基团为所述含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基。
本申请实施方式中，所述R1至R6中，所述取代的C1至C20的脂肪族烃基、取代的C1至C20的脂肪族烃氧基、取代的C6至C20的芳基和取代的C7至C20的芳基烷基中的取代基团包括卤素原子、羟基、羟基烷基、羧基、羧基烷基、烷基、酯基和酰基中的一种或多种。
本申请实施方式中，所述含环氧基团的取代基包括式(1a)至式(1d)所示的基团：
式(1a)至式(1c)中，a为0至10的整数；式(1a)至式(1d)中，X为单键、取代或未取代的C1至C20的亚烷基、或取代或未取代的C1至C20的亚烷氧基。
本申请实施方式中，所述X中，取代的C1至C20的亚烷基、取代的C1至C20的亚烷氧基中的取代基团包括卤素原子、芳基、酯基、酰基中的一种或多种。
本申请实施方式中，所述含苯并环丁烯结构的环氧化合物至少包括含有式(1d)所示的含环氧基团的取代基的含苯并环丁烯结构的环氧化合物。
本申请实施方式中，所述树脂包括酚醛环氧树脂、丙烯酸树脂、聚酰亚胺前驱体树脂、可溶性聚酰亚胺树脂、聚苯并噁唑前驱体树脂中的一种或多种。通过选用不同树脂体系，可以获得不同体系感光树脂组合物，以满足不同场景需要。
本申请实施方式中，所述引发剂包括光聚合引发剂，光聚合引发剂为在紫外光照下可以分解产生自由基的化合物，所述光聚合引发剂包括二苯甲酮、二苯甲酮衍生物、苯乙酮衍生物、噻吨酮、噻吨酮衍生物、苯偶酰、苯偶酰衍生物、苯偶姻、苯偶姻衍生物、1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟、1-[4-(苯硫基)苯基]-1,2-辛烷二酮-2-(O-苯甲酰肟)、1-苯基-1,2-丁二酮-2-(邻甲氧基羰基)肟和1,3-二苯基丙三酮-2-(邻乙氧基羰基)肟中的一种或多种。
本申请实施方式中，以所述树脂为100重量份计，所述引发剂为0.1-20重量份。
本申请实施方式中，所述交联剂包括光聚合性化合物，光聚合性化合物为可由自由基引发交联的化合物，所述光聚合性化合物包括甲基丙烯酸-2-羟甲酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟丁酯、丙烯酸-2-羟甲酯、丙烯酸-2-羟乙酯、丙烯酸-2-羟丙酯、丙烯酸-2-羟丁酯、丙烯酸缩水甘油酯、丙烯酸环氧丙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸环氧丙酯、四乙二醇二甲基丙烯酸酯、乙二醇双乙醚甲基丙烯酸酯、乙二醇双乙醚丙烯酸酯和聚乙二醇甲基丙烯酸酯中的一种或多种。
本申请实施方式中，以所述树脂为100重量份计，所述交联剂为2-50重量份。
本申请实施方式中，所述感光树脂组合物还包括助粘剂、阻聚剂和溶剂。助粘剂可以提升感光树脂组合物胶液与基材的粘附性。阻聚剂的加入可以淬灭自由基的化合物。
本申请实施方式中，所述助粘剂包括γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲氧基甲基硅烷、γ-缩水甘油醚氧基丙基三乙氧基硅烷、3-异氰酸酯基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、3-脲基丙基三甲氧基硅烷、3-脲基丙基三乙氧基硅烷、3-异氰酸酯基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-(三乙氧基甲硅烷基)丙基琥珀酸酐、乙烯基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷中的一种或 多种；以所述树脂为100重量份计，所述助粘剂为0.5-20重量份。
本申请实施方式中，所述阻聚剂包括对苯二酚、4-甲氧基苯酚、N-亚硝基二苯基胺、对叔丁基儿茶酚、吩噻嗪、N-苯基萘基胺、2,6-二叔丁基对甲基苯酚、5-亚硝基-8-羟基喹啉、1-亚硝基-2-萘酚、2-亚硝基-1-萘酚和2-亚硝基-5-(N-乙基-磺基丙基氨基)苯酚中的一种或多种；以所述树脂为100重量份计，所述阻聚剂为0.01-10重量份。
本申请实施方式中，所述溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜、四甲基脲、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、四氢呋喃、乙酸乙酯和乙酸丁酯中的一种或多种；以所述树脂为100重量份计，所述溶剂为100-1000重量份。
本申请实施方式中，所述感光树脂组合物还包括无机填料。
本申请实施方式中，所述无机填料包括二氧化硅、氧化铝、滑石粉、硫酸钡、玻璃粉、云母粉中的一种或多种；以所述树脂为100重量份计，所述无机填料为50-400重量份。
本申请实施例的感光树脂组合物为一种胶液，感光树脂组合物通过将各种组分混合得到。该感光树脂组合物可以用于各种电子元器件的封装。
本申请实施例第二方面提供一种膜材，所述膜材包括感光树脂膜，所述感光树脂膜采用本申请实施例第一方面所述的感光树脂组合物制备得到。
本申请实施方式中，膜材通常包括基材，设置于基材表面的感光树脂膜和设置在感光树脂膜上的覆盖膜，即膜材通常为三层膜结构。
本申请实施例第三方面提供本申请实施例第一方面所述的感光树脂组合物或本申请实施例第二方面所述的膜材在制备电子封装结构中的应用。
本申请实施方式中，感光树脂组合物在制备电子封装结构中的应用包括用于制备封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层或再布线层。本申请感光树脂组合物可以直接通过涂覆后固化形成上述的各种膜层。
本申请实施方式中，膜材在制备电子封装结构中的应用包括用于制备封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层或再布线层中，或用于构建弹性波滤波器和微机电系统MEMS中的封装腔体。在实际应用中，膜材中仅感光树脂膜经完全固化后保留在电子封装结构中，基材和覆盖膜均被剥离，即感光树脂膜完全固化后形成上述各种膜层或构建形成上述封装腔体。
本申请实施例第四方面提供一种电子封装结构，所述电子封装结构包括第一方面所述的感光树脂组合物的固化物。该感光树脂组合物的固化物具有高结构强度，具有较低介电性能和吸水率，可以提高封装效果。
本申请实施例第五方面提供一种电子设备，所述电子设备包括本申请实施例第四方面提供的电子封装结构。采用本申请实施例电子封装结构，可以改善电子设备性能。
本申请实施例第六方面提供一种含苯并环丁烯结构的环氧化合物，所述含苯并环丁烯结构的环氧化合物具有式(I)所示的结构：
式(I)中，R1至R6中至少一个基团为式(1d)所示的含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基、式(1a)所示的含环氧基团的取代基、式(1b)所示的含环氧基团的取代基、式(1c)所示的含环氧基团的取代基，
式(1a)至式(1c)中，a为0至10的整数；式(1a)至式(1d)中，X为单键、取代或未取代的C1至C20的亚烷基、或取代或未取代的C1至C20的亚烷氧基。
本申请实施例含苯并环丁烯结构的环氧化合物包含式(1d)所示的含环氧基团的取代基，该取代基为含有酯基和环氧基团的取代基，其实质为环氧基团取代的酯基。当含苯并环丁烯结构的环氧化合物含有酯基时，其与树脂主链中的极性基团具有更强的相互作用，即可以提高分子间作用力，从而可更好地提高树脂材料的耐热性和力学性能。
本申请实施方式中，所述R1至R6中，所述取代的C1至C20的脂肪族烃基、取代的C1至C20的脂肪族烃氧基、取代的C6至C20的芳基和取代的C7至C20的芳基烷基中的取代基团包括卤素原子、羟基、羟基烷基、羧基、羧基烷基、烷基、酯基和酰基中的一种或多种。
本申请实施方式中，所述X中，取代的C1至C20的亚烷基、取代的C1至C20的亚烷氧基中的取代基团包括卤素原子、芳基、酯基、酰基中的一种或多种。
本申请实施例还提供本申请实施例第六方面所述的含苯并环丁烯结构的环氧化合物在制备涂料、复合材料、浇铸料、胶粘剂、固化剂、感光树脂组合物、感光树脂膜材、塑封料、模压材料和注射成型材料中的应用。
附图说明
图1为本申请实施例提供的膜材100的结构示意图；
图2为本申请实施例提供的电子封装结构200的示意图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例进行说明。
在滤波器芯片的晶圆级封装(Wafer Level Package,WLP)工艺中，通常是使用感光树脂材料为滤波器芯片构筑中空封装腔体，随后模组整体在180℃及以上的高温与3MPa-5MPa的压力下进行注塑模压封装，因此需要感光树脂材料在高温下具有高抗模压性能，能够保持中空封装腔体不塌陷；另外，作为滤波器芯片的封装材料，还需要感光树脂材料具有较低的介电常数和介电损耗。为获得兼具优异的抗高温模压性能、以及较低的介电常数和介电损耗的感光树脂材料，以满足滤波器芯片等电子元器件的封装，本申请实施例提供一种感光树脂组合物。
具体地，本申请实施例提供的感光树脂组合物，包括树脂、交联剂、引发剂和含苯并环丁烯结构的环氧化合物。
本申请实施例的感光树脂组合物，通过加入含苯并环丁烯结构的环氧化合物可以降低感光树脂组合物固化后所得固化物的介电常数和介电损耗；而且含苯并环丁烯结构的环氧化合物在固化过程中可以实现更好的交联，提高固化物的交联密度，从而提高固化物的耐热性能和机械性能，同时还能降低吸水率；该感光树脂组合物用于电子元器件的封装，可以提高封装可靠性。
本申请实施方式中，感光树脂组合物中，以所述树脂为100重量份计，含苯并环丁烯结构的环氧化合物为0.1-60重量份。本申请一些实施方式中，含苯并环丁烯结构的环氧化合物为0.5-30重量份；本申请一些实施方式中，含苯并环丁烯结构的环氧化合物为1-20重量份。示例性地，感光树脂组合物中，以树脂为100重量份计，含苯并环丁烯结构的环氧化合物可以是0.1、0.5、1、5、10、15、20、25、30、35、40、45、50、55、60重量份。适合量的含苯并环丁烯结构的环氧化合物的加入，可以使感光树脂组合物获得更好的综合性能。
本申请实施方式中，含苯并环丁烯结构的环氧化合物包括苯并环丁烯环和至少一个连接在苯并环丁烯环上的含环氧基团的取代基。即含苯并环丁烯结构的环氧化合物可以是在苯并环丁烯环的6个可取代碳位 上连接有一个或多个含环氧基团的取代基的化合物。含苯并环丁烯结构的环氧化合物可以兼具苯并环丁烯结构和含环氧基团的取代基的性能优势。
本申请实施方式中，含苯并环丁烯结构的环氧化合物包括式(I)所示结构的任意一种或多种化合物：
式(I)中，R1至R6(即R1、R2、R3、R4、R5和R6)中至少一个基团为含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基。
式(I)中，R1至R6中可以是有一个或多个(两个或两个以上)基团为含环氧基团的取代基。一些实施例中，R1至R6中可以是有一个基团为含环氧基团的取代基；一些实施例中，R1至R6中可以是有两个基团为含环氧基团的取代基。其余基团即R1至R6中不为含环氧基团的取代基的基团。例如，在一些实施例中，R3为含环氧基团的取代基，其余基团即R1、R2、R4、R5和R6为氢原子、或取代或未取代的C1至C20的脂肪族烃基、或取代或未取代的C6至C20的芳基、或取代或未取代的C7至C20的芳基烷基。当R1至R6中有多个(两个或两个以上)基团为含环氧基团的取代基，多个含环氧基团的取代基可以是具有相同结构，也可以是具有不同结构。
本申请实施方式中，取代或未取代的C1至C20的脂肪族烃基可以是取代或未取代的C1至C20的烷基、取代或未取代的C2至C20的烯基、取代或未取代的C2至C20的炔基。具体地，取代或未取代的C1至C20的脂肪族烃基具体可以是取代或未取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20的脂肪族烃基。例如，取代或未取代的C1至C20的烷基可以是取代或未取代的甲基、取代或未取代的乙基、取代或未取代的丙基、取代或未取代的丁基等。取代或未取代的C2至C20的烯基可以是取代或未取代的乙烯基、取代或未取代的丙烯基、取代或未取代的丁烯基等。取代或未取代的C2至C20的炔基可以是取代或未取代的乙炔基、取代或未取代的丙炔基、取代或未取代的丁炔基等。
本申请实施方式中，取代或未取代的C1至C20的脂肪族烃氧基可以是取代或未取代的C1至C20的烷氧基、取代或未取代的C2至C20的烯氧基、取代或未取代的C2至C20的炔氧基。具体地，取代或未取代的C1至C20的脂肪族烃氧基具体可以是取代或未取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20的脂肪族烃氧基。例如，取代或未取代的C1至C20的烷氧基可以是取代或未取代的甲氧基、取代或未取代的乙氧基、取代或未取代的丙氧基、取代或未取代的丁氧基等。取代或未取代的C2至C20的烯氧基可以是取代或未取代的乙烯氧基、取代或未取代的丙烯氧基、取代或未取代的丁烯氧基等。取代或未取代的C2至C20的炔氧基可以是取代或未取代的乙炔氧基、取代或未取代的丙炔氧基、取代或未取代的丁炔氧基等。
本申请实施方式中，取代或未取代的C6至C20的芳基可以是取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的稠环芳基等。本申请实施方式中，取代或未取代的C7至C20的芳基烷基可以是取代或未取代的苯基烷基、联苯基烷基、稠环芳基烷基等。
本申请实施方式中，R1至R6中，取代的C1至C20的脂肪族烃基、取代的C1至C20的脂肪族烃氧基、取代的C6至C20的芳基和取代的C7至C20的芳基烷基中的取代基团包括卤素原子、羟基、羟基烷基、羧基、羧基烷基、烷基、酯基和酰基中的一种或多种。其中，卤素原子可以是氟原子、氯原子、溴原子、碘原子等。示例性地，卤素原子取代的C1至C20的脂肪族烃基具体例如可以是氟取代甲基、氟取代乙基、氟取代丙基等。卤素原子取代的C1至C20的脂肪族烃氧基具体例如可以是氟取代甲氧基、氟取代乙氧基、氟取代丙氧基等。羟基取代的C1至C20的脂肪族烃基具体例如可以是羟基甲基(-CH2OH)、羟基乙基(-CH2CH2OH)等。羟基取代的C1至C20的脂肪族烃氧基具体例如可以是羟基甲氧基(-OCH2OH)、羟基乙氧基(-OCH2CH2OH)等。羧基取代的C1至C20的脂肪族烃基具体例如可以是羧基甲基(-CH2COOH)、羧基乙基(-CH2CH2COOH)等。羧基取代的C1至C20的脂肪族烃氧基具体例如可以是羧基甲氧基(-OCH2COOH)、羧基乙氧基(-OCH2CH2COOH)等。烷基取代的C1至C20的脂肪族烃 基具体可以是烷基取代的烯基，示例性地，烷基取代的烯基为甲基乙烯基等。烷基取代的C6至C20的芳基具体可以是烷基苯基，示例性地，烷基苯基为甲基苯基、乙基苯基等。酯基取代的C6至C20的芳基具体例如可以是酯基取代的苯基。
本申请实施方式中，含环氧基团的取代基可以是包括式(1a)至式(1d)所示的任意一种基团：
式(1a)至式(1c)中，a为0至10的整数；具体例如可以是a为0、1、2、3、4、5、6、7、8、9、10。
式(1a)至式(1d)中，X可以是为单键、取代或未取代的C1至C20的亚烷基、或取代或未取代的C1至C20的亚烷氧基。式(1a)和式(1c)中，两个X可以是相同基团，也可以是不同基团。
本申请实施方式中，取代或未取代的C1至C20的亚烷基具体可以是取代或未取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20的亚烷基。例如，取代或未取代的C1至C20的亚烷基可以是取代或未取代的亚甲基、取代或未取代的亚乙基、取代或未取代的亚丙基、取代或未取代的亚丁基等。
本申请实施方式中，取代或未取代的C1至C20的亚烷氧基具体可以是取代或未取代的C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20的亚烷氧基。例如，取代或未取代的C1至C20的亚烷氧基可以是取代或未取代的亚甲氧基、取代或未取代的亚乙氧基、取代或未取代的亚丙氧基、取代或未取代的亚丁氧基等。
本申请实施方式中，X中，取代的C1至C20的亚烷基、取代的C1至C20的亚烷氧基中的取代基团包括卤素原子、芳基、酯基、酰基中的一种或多种。其中，卤素原子可以是氟原子、氯原子、溴原子、碘原子等。示例性地，卤素原子取代的C1至C20的亚烷基具体例如可以是氟取代亚甲基、氟取代亚乙基、氟取代亚丙基等。卤素原子取代的C1至C20的亚烷氧基具体例如可以是氟取代亚甲氧基、氟取代亚乙氧基、氟取代亚丙氧基等。芳基取代的C1至C20的亚烷基例如可以是苯基取代的亚乙基。
本申请一些实施方式中，当式(I)所示结构的含苯并环丁烯结构的环氧化合物中，R1至R6中有一个基团为含环氧基团的取代基，该一个含环氧基团的取代基可以是具有式(1a)至式(1d)所示的任意一种结构的含环氧基团的取代基。当式(I)所示结构的含苯并环丁烯结构的环氧化合物中，R1至R6中有多个(两个或两个以上)基团为含环氧基团的取代基时，多个含环氧基团的取代基可以是具有式(1a)至式(1d)所示的任意一种或多种结构的含环氧基团的取代基。
本申请实施方式中，感光树脂组合物中可以是包含一种含苯并环丁烯结构的环氧化合物，也可以是包含多种含苯并环丁烯结构的环氧化合物。
本申请一些实施方式中，含苯并环丁烯结构的环氧化合物可以是至少包括含有式(1d)所示的含环氧基团的取代基的含苯并环丁烯结构的环氧化合物。式(1d)所示的含环氧基团的取代基为含有酯基和环氧基团的取代基，其实质为环氧基团取代的酯基。当含苯并环丁烯结构的环氧化合物含有酯基时，其与树脂主链中的极性基团具有更强的相互作用，即可以提高分子间作用力，从而可更好地提高树脂材料的耐热性和力学性能。本申请一些实施方式中，感光树脂组合物仅包括含有式(1d)所示的含环氧基团的取代基的含苯并环丁烯结构的环氧化合物；本申请另一些实施方式中，感光树脂组合物同时包括含有式(1d)所示的含环氧基团的取代基的含苯并环丁烯结构的环氧化合物和其他类型的含苯并环丁烯结构的环氧化合物。其他类型的含苯并环丁烯结构的环氧化合物可以是包括含有式(1a)、式(1b)、式(1c)所示的含环氧基团的取代基的含苯并环丁烯结构的环氧化合物。
示例性地，本申请实施方式中，含苯并环丁烯结构的环氧化合物具体可以是包括式(1)至式(19)所示的任意一种或多种化合物：
本申请实施方式中，感光树脂组合物中，树脂可以是但不限于包括酚醛环氧树脂、丙烯酸树脂、聚酰亚胺前驱体树脂(聚酰胺酸酯树脂)、可溶性聚酰亚胺树脂、聚苯并噁唑前驱体树脂中的一种或多种。感光树脂组合物中，树脂的重均分子量可以是2000-200000；一些实施例中，树脂的重均分子量可以是10000-100000；一些实施例中，树脂的重均分子量可以是10000-50000。感光树脂组合物中，可以是包括一种或多种树脂。通过选用不同树脂体系，可以获得不同体系感光树脂组合物，以满足不同场景需要。
本申请实施方式中，引发剂包括光聚合引发剂，光聚合引发剂为在紫外光照下可以分解产生自由基的化合物，可以但不限于包括二苯甲酮、二苯甲酮衍生物、苯乙酮衍生物、噻吨酮、噻吨酮衍生物、苯偶酰、苯偶酰衍生物、苯偶姻、苯偶姻衍生物、1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟、1-[4-(苯硫基)苯基]-1,2-辛烷二酮-2-(O-苯甲酰肟)、1-苯基-1,2-丁二酮-2-(邻甲氧基羰基)肟和1,3-二苯基丙三酮-2-(邻乙氧基羰基)肟中的一种或多种。
本申请实施方式中，以树脂为100重量份计，引发剂可以是为0.1-20重量份。一些实施例中，引发剂为0.5-10重量份；一些实施例中，引发剂为1-5重量份。
本申请实施方式中，交联剂包括光聚合性化合物，光聚合性化合物为可由自由基引发交联的化合物，可以但不限于包括甲基丙烯酸-2-羟甲酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟丁酯、丙烯酸-2-羟甲酯、丙烯酸-2-羟乙酯、丙烯酸-2-羟丙酯、丙烯酸-2-羟丁酯、丙烯酸缩水甘油酯、丙烯酸环氧丙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸环氧丙酯、四乙二醇二甲基丙烯酸酯、乙二醇双乙醚甲基丙烯酸酯、乙二醇双乙醚丙烯酸酯和聚乙二醇甲基丙烯酸酯中的一种或多种。聚乙二醇甲基丙烯酸酯例如可以是四乙二醇二甲基丙烯酸酯。
本申请实施方式中，以树脂为100重量份计，交联剂为2-50重量份。一些实施例中，交联剂为5-30重量份；一些实施例中，交联剂为10-20重量份。
本申请实施方式中，感光树脂组合物还可以包括助粘剂、阻聚剂和溶剂。
本申请实施方式中，助粘剂可以提升感光树脂组合物胶液与基材的粘附性，助粘剂可以是但不限于包括γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲氧基甲基硅 烷、γ-缩水甘油醚氧基丙基三乙氧基硅烷、3-异氰酸酯基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、3-脲基丙基三甲氧基硅烷、3-脲基丙基三乙氧基硅烷、3-异氰酸酯基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-(三乙氧基甲硅烷基)丙基琥珀酸酐、乙烯基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷中的一种或多种。以树脂为100重量份计，助粘剂可以是为0.5-20重量份；一些实施例中，助粘剂可以是1-10重量份；一些实施例中，助粘剂可以是2-5重量份。
本申请实施方式中，阻聚剂的加入可以淬灭自由基的化合物，阻聚剂可以是但不限于包括对苯二酚、4-甲氧基苯酚、N-亚硝基二苯基胺、对叔丁基儿茶酚、吩噻嗪、N-苯基萘基胺、2,6-二叔丁基对甲基苯酚、5-亚硝基-8-羟基喹啉、1-亚硝基-2-萘酚、2-亚硝基-1-萘酚和2-亚硝基-5-(N-乙基-磺基丙基氨基)苯酚中的一种或多种。以树脂为100重量份计，阻聚剂为0.01-10重量份；一些实施例中，阻聚剂可以是0.05-5重量份；一些实施例中，阻聚剂可以是0.1-2重量份。
本申请实施方式中，溶剂可以是但不限于包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜、四甲基脲、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、四氢呋喃、乙酸乙酯和乙酸丁酯中的一种或多种。以树脂为100重量份计，溶剂为100-1000重量份；一些实施例中，溶剂为150-500重量份；一些实施例中，溶剂为200-300重量份。
本申请实施方式中，感光树脂组合物还包括无机填料。无机填料的加入可提高感光树脂组合物的抗高温模压性能。本申请实施方式中，无机填料可以是但不限于包括二氧化硅、氧化铝、滑石粉、硫酸钡、玻璃粉、云母粉中的一种或多种；以所述树脂为100重量份计，所述无机填料为50-400重量份；一些实施例中，无机填料为75-300重量份；一些实施例中，无机填料为100-200重量份。
本申请实施方式中，感光树脂组合物为一种胶液，感光树脂组合物通过将各种组分混合得到。该感光树脂组合物可以用于各种电子元器件的封装。本申请实施例感光树脂组合物可以直接用于电子封装结构中的封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层和再布线层的制备。
参见图1，本申请实施例还提供一种膜材100，膜材100包括感光树脂膜10，感光树脂膜10采用本申请实施例上述的感光树脂组合物制备得到。感光树脂膜10为一种固态胶膜，由感光树脂组合物涂覆至基材11表面后，经烘烤得到。通常感光树脂膜10附于基材11表面，且感光树脂膜10上还设置有覆盖膜12进行保护，形成三层膜结构。即膜材100通常包括基材11，设置于基材11表面的感光树脂膜10和设置在感光树脂膜10上的覆盖膜12。其中，基材11可以是聚对苯二甲酸乙二醇酯(PET)或聚丙烯(PP)等材质。覆盖膜12可以是PET膜或双向拉伸聚丙烯薄膜(BOPP薄膜)等。覆盖膜12可以是在真空条件下，一定温度和压力下压合至感光树脂膜10表面。
其中，涂敷可以是包括刮涂法、甩涂法、喷涂法中的任意一种或多种。烘烤的温度可以是50-120℃，或70-100℃；烘烤的时间可以是1-60min，或5-30min。压合的温度可以是30-100℃，或50-80℃；压合的压力可以是5-100kPa，或30-50kPa。
本申请实施方式中，膜材100中，感光树脂膜10的厚度可以根据需要进行制备，感光树脂膜10的厚度可以是10um-100um。一些实施例中，感光树脂膜10的厚度具体可以是10um、15um、20um、25um、30um、35um、40um、45um、50um、55um、60um、65um、70um、75um、80um、85um、90um、95um、100um。感光树脂膜10在实际应用中经完全固化后的膜厚可以是8um-100um。
本申请实施例的感光树脂组合物和膜材100可以用于各种电子元器件(例如各种芯片、晶体管、LED器件、阻容感元件(如电阻、电容、电感)等)的封装，形成电子封装结构。本申请实施例提供感光树脂组合物或膜材100在制备电子封装结构中的应用。其中，感光树脂组合物在制备电子封装结构中的应用可以是包括将感光树脂组合物用于制备封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层或再布线层，感光树脂组合物可以直接通过涂覆后固化形成上述的各种膜层。膜材100在制备电子封装结构中的应用包括用于制备封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层或再布线层中，或用于构建弹性波滤波器和微机电系统MEMS中的封装腔体，需要说明的是，在实际应用中，膜材100中仅感光树脂膜10经完全固化后保留在电子封装结构中，基材11和覆盖膜12均被剥离，即感光树脂膜10完全固化后形成上述各种膜层或构建形成上述封装腔体。
参见图2，本申请实施例提供电子封装结构200，电子封装结构200包括本申请实施例的感光树脂组合物的固化物。该实施方式中，电子封装结构200具体为弹性波滤波器芯片封装结构，该电子封装结构200包括基底20、设置在基底20上的弹性波滤波器芯片201，形成在基底20上的第一膜层21，形成在第一膜 层21上的第二膜层22，第一膜层21和第二膜层22为图案化膜层，第一膜层21形成支撑墙，第二膜层22为本申请实施例的感光树脂组合物的固化物或感光树脂膜10的固化物。基底20、第一膜层21和第二膜层22一同形成封装腔体1，弹性波滤波器芯片201容置于封装腔体1中。本申请实施例的电子封装结构200中，封装腔体1中可以是根据需要容置一个或多个芯片。可以理解地，作为构建封装腔体1的第二膜层材料，需要具备光刻开孔性能实现图案化，需要具备较低的介电性能，还同时需要具备抗高温模压性能。
下面以图2所示的弹性波滤波器芯片封装结构为例，介绍本申请膜材100的应用方法，具体地，应用方法包括：
步骤(1)：贴膜，揭下膜材100的覆盖膜12，将带有基材11的感光树脂膜10与具有图案化第一膜层21的硅晶圆(包括基底21和弹性波滤波器芯片201)，在一定压力和温度下进行贴附；贴膜的贴附压力可以是10-100kPa，也可以是40-70kPa；贴附温度可以是30-90℃，也可以是50-70℃；第一膜层21可以是采用本申请实施例的感光树脂膜10经完全固化形成，也可以是采用其他感光树脂材料形成；
步骤(2)：后烘，将步骤(1)所得结合体进行烘烤；该后烘步骤为可选步骤，一些实施例中，可以不进行后烘操作，在步骤(1)完成后直接进行后续曝光显影步骤；烘烤温度可以是50-100℃，也可以是70-90℃；烘烤时间可以是0.1-20min，也可以是1-5min；
步骤(3)：曝光，将基材11与感光树脂膜10剥离，采用紫外线曝光设备通过相应的掩模板进行曝光；曝光剂量可以根据需要选择，可以是50-500mJ/cm2，也可以是100-200mJ/cm2；
步骤(4)：显影，采用显影溶剂洗脱未曝光的部分，然后采用漂洗液清洗，得到与掩模板对应的图案，得到图案化的感光树脂膜；显影液可以是负性光敏性树脂组合物的良溶剂、或良溶剂与不良溶剂的组合。良溶剂例如可以是N-甲基吡咯烷酮、N-环己基-2-吡咯烷酮、N,N-二甲基乙酰胺、环戊酮、环己酮、甲基乙基酮、甲基异丁基酮、γ-丁内酯中的一种或多种；不良溶剂可以是甲醇、乙醇、异丙醇、乳酸乙酯、乙酸乙酯、乙酸丁酯、四氢呋喃、二氧六环、丙二醇单甲醚、丙二醇甲醚乙酸酯中的一种或多种。漂洗液可以是异丙醇、乙酸乙酯、乙酸丁酯、丙二醇单甲醚、丙二醇单甲醚乙酸酯、乳酸乙酯、环戊酮、环己酮中的一种或多种；
步骤(5)：完全固化：将图案化的感光树脂膜加热固化转化成硬化膜。固化温度可以是根据实际需要设定，以感光树脂膜为聚酰亚胺膜为例，固化温度可以是180-400℃，也可以是200-300℃，固化时间可以是30-500min，也可以是60-150min。
本申请实施例还提供一种电子设备，电子设备包括本申请实施例上述的电子封装结构。
本申请实施例还提供一种含苯并环丁烯结构的环氧化合物，含苯并环丁烯结构的环氧化合物具有式(I)所示的结构：
式(I)中，R1至R6中至少一个基团为式(1d)所示的含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基、式(1a)所示的含环氧基团的取代基、式(1b)所示的含环氧基团的取代基、式(1c)所示的含环氧基团的取代基，
式(1a)至式(1c)中，a为0至10的整数；式(1a)至式(1d)中，X为单键、取代或未取代的C1至C20的亚烷基、或取代或未取代的C1至C20的亚烷氧基。
本申请实施方式中，式(I)所示的含苯并环丁烯结构的环氧化合物中，R1至R6中可以是有一个或多个(两个或两个以上)基团为式(1d)所示的含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基、式(1a)所示的含环氧基团的取代基、式(1b)所示的含环氧基团的取代基、式(1c)所示的含环氧基团的取代基。式(1d)所示的含环氧基团的取代基为含有酯基和环氧基团的取代基，其实质为环氧基团取代的酯基。当含苯并环丁烯结构的环氧化合物含有酯基时，其与树脂主链中的极性基团具有更强的相互作用，即可以提高分子间作用力，从而可更好地提高树脂材料的耐热性和力学性能。
本申请R1至R6的各种选择、式(1a)所示的含环氧基团的取代基、式(1b)所示的含环氧基团的取代基、式(1c)所示的含环氧基团的取代基的具体说明请参见本申请上文的记载，此处不再赘述。
本申请实施例还提供本申请实施例上述的含苯并环丁烯结构的环氧化合物在制备涂料、复合材料、浇铸料、胶粘剂、固化剂、感光树脂组合物、感光树脂膜材、塑封料、模压材料和注射成型材料中的应用。
本申请中，“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况，其中A,B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
下面分多个实施例对本申请实施例进行进一步的说明。
合成例一
聚酰胺酸酯(PAE)树脂A1的合成
(1)在装有机械搅拌器、温度计和氮气保护装置的三口圆底烧瓶中，依次加入4,4'-氧双邻苯二甲酸酐(ODPA，1eq)、甲基丙烯酸-2-羟乙酯(HEMA，2eq)、吡啶(2eq)和N-甲基吡咯烷酮(NMP)，调节整体固含量至30wt.％左右，室温搅拌6h生成相应的二取代酯化酸酐。随后于冰水浴中，在0-10℃的条件下加入二氯亚砜(SOCl2，2eq)，室温反应4h，生成相应的二酰氯二甲基丙烯酸酯。
(2)在装有机械搅拌器、温度计和氮气保护装置的三口圆底烧瓶中，将4,4'-二氨基-2,2'-双(三氟甲基)联苯(TFDB，0.95eq)加入到NMP中，搅拌使其溶解形成均相透明的二胺溶液，固含量约为30wt.％。采用冰水浴将二胺溶液冷却至10℃以下，并向其中缓慢滴加上述制备的二酰氯二甲基丙烯酸酯溶液，滴加完毕后在室温下反应10h，再加入对氨基苯酚(0.1eq)继续室温搅拌反应2h。最后将反应液倒入5L去离子水中，析出固体、过滤、洗涤、真空干燥，得到聚酰胺酸酯树脂A1。
合成例二
聚酰胺酸酯(PAE)树脂A2的合成
(1)在装有机械搅拌器、温度计和氮气保护装置的三口圆底烧瓶中，依次加入3,3',4,4'-联苯四羧酸二酐(BPDA，1eq)、甲基丙烯酸-2-羟乙酯(HEMA，2eq)、吡啶(2eq)和N-甲基吡咯烷酮(NMP)，调节整体固含量至30wt.％左右，室温搅拌6h生成相应的二取代酯化酸酐。随后于冰水浴中，在0-10℃的条件下加入二氯亚砜(SOCl2，2eq)，室温反应4h，生成相应的二酰氯二甲基丙烯酸酯。
(2)在装有机械搅拌器、温度计和氮气保护装置的三口圆底烧瓶中，将4,4'-二氨基二苯醚(ODA，0.95eq)加入到NMP中，搅拌使其溶解形成均相透明的二胺溶液，固含量约为30wt.％。采用冰水浴将二胺溶液冷却至10℃以下，并向其中缓慢滴加上述制备的二酰氯二甲基丙烯酸酯溶液，滴加完毕后在室温下反应10h，再加入对氨基苯酚(0.1eq)继续室温搅拌反应2h。最后将反应液倒入5L去离子水中，析出固体、过滤、洗涤、真空干燥，得到聚酰胺酸酯树脂A2。
合成例三
可溶性聚酰亚胺树脂A3的合成
(1)在装有机械搅拌器、温度计和氮气保护装置的三口圆底烧瓶中，将2,2-双(3-氨基-4-羟基苯基)六 氟丙烷(6FAP，0.95eq)搅拌溶解于NMP中，待完全溶解后加入4,4-六氟异丙基邻苯二甲酸酐(6FDA，1eq)调节固含量至30wt.％，常温反应6h，随后向反应液中加入对氨基苯酚(0.1eq)，继续室温搅拌反应2h。
(2)氮气保护下架上分水器，利用甲苯回流，180℃反应8h，降至室温后将反应液倒入5L去离子水中，析出固体、过滤、洗涤、真空干燥，得到可溶性聚酰亚胺树脂A3。
合成例四
含苯并环丁烯结构的环氧化合物B1(即本申请式(8)所示化合物)的合成
(1)向装有回流冷凝管、磁力搅拌、温度计、一氧化碳导管的四口烧瓶中依次加入正丁醇200mL、2,5-二溴双环[4.2.0]-1,3,5-辛三烯60g、三乙胺(Et3N)160mL、三苯基膦PPh35.6g，醋酸钯Pd(OAc)20.8g，一氧化碳气体置换多次，80℃反应120h。反应完成后降至室温，过滤，母液浓缩后柱层析分离产物，得淡黄色油状液体，即化合物1-a。
(2)向配有机械搅拌、温度计、冷凝管的四口烧瓶中依次加入甲醇MeOH 900mL、65g化合物1-a、80g 25％的氢氧化钠水溶液，回流反应3h。反应完成后降至室温，向反应体系中加入1L去离子水，过滤，滤液降至0℃，调节pH至4，过滤，滤饼用去离子水洗至滤液呈中性，滤饼50℃真空干燥至恒重，得白色固体，即化合物1-b。
(3)向配有磁力搅拌、温度计、冷凝管的四口烧瓶中依次加入300g环氧氯丙烷、39.5g化合物1-b、1.7g十六烷基三甲基溴化铵，90℃反应3h，然后降温至30℃，向反应体系滴加40％的氢氧化钠水溶液，30℃反应6h。反应完成后，分液，有机相用去离子水洗至中性，柱层析分离产物得白色固体，即含苯并环丁烯结构的环氧化合物B1。含苯并环丁烯结构的环氧化合物B1的核磁共振氢谱结果为：1H NMR(400MHz,Chloroform-d)δ：7.88(s,2H,ArH),4.65-4.17(m,4H,-CH2-),3.46(s,4H,-CH2-CH2-),3.33(m,2H,-CH-),2.91-2.74(m,4H,-CH2-)。
上述反应过程的反应式如下：
合成例五
含苯并环丁烯结构的环氧化合物B2(即本申请式(19)所示化合物)的合成
(1)向装有回流冷凝管、磁力搅拌、温度计、一氧化碳导管的四口烧瓶中依次加入正丁醇150mL、4-溴苯并环丁烯50g、三乙胺160mL、三苯基膦3.4g，醋酸钯0.5g，一氧化碳气体置换多次，80℃反应120h。反应完成后降至室温，过滤，母液浓缩后柱层析分离产物，得淡黄色油状液体，即化合物2-a。
(2)向配有机械搅拌、温度计、冷凝管的四口烧瓶中依次加入甲醇900mL、65g化合物2-a、60g 25％的氢氧化钠水溶液，回流反应3h。反应完成后降至室温，向反应体系中加入1L去离子水，过滤，滤液降至0℃，调节pH至4，过滤，滤饼用去离子水洗至滤液呈中性，滤饼50℃真空干燥至恒重，得白色固体，即化合物2-b。
(3)向配有磁力搅拌、温度计、冷凝管的四口烧瓶中依次加入150g环氧氯丙烷、30.4g化合物2-b、0.9g十六烷基三甲基溴化铵，90℃反应3h，然后降温至30℃，向反应体系滴加40％的氢氧化钠水溶液，30℃反应6h。反应完成后，分液，有机相用去离子水洗至中性，柱层析分离产物得白色固体，即含苯并环丁烯结构的环氧化合物B2。含苯并环丁烯结构的环氧化合物B2的核磁共振氢谱结果为：1H NMR(400MHz,Chloroform-d)δ：7.21(d,1H,ArH),7.07(d,1H,ArH),6.95(s,1H,ArH),4.46-4.09(m,2H,-CH2-),3.27-3.15(m,4H,-CH2-CH2-),2.94(m,1H,-CH-),2.68-2.55(m,2H,-CH2-)。
上述反应过程的反应式如下：
合成例六
含苯并环丁烯结构的环氧化合物B3(即本申请式(1)所示化合物)的合成
(1)在高压釜中依此加入40g 4-溴苯并环丁烯、500mL氨水、4.18g碘化亚铜，密封高压釜，搅拌升温至150℃后持续反应4h。反应后自然冷却至室温，取出反应液倒入水中，用二氯甲烷萃取三次，合并有机层，无水硫酸钠干燥，有机相旋转蒸发浓缩，200-300目Al2O3柱分离，二氯甲烷淋洗，收集浅棕色液体，即化合物3-a。
(2)向配有磁力搅拌、温度计、冷凝管的四口烧瓶中加入环氧氯丙烷10.26g，抽真空通氮气除去体系中的氧和水，搅拌反应升温至40℃，利用恒压漏斗缓慢滴加化合物3-a，滴加完后升温至60℃反应5h。停止加热并降温至30℃以下，向反应体系滴加40％的氢氧化钠水溶液搅拌6h，反应完成后，分液，有机相用去离子水洗至中性，柱层析分离产物得浅棕色粘稠状液体，即含苯并环丁烯结构的环氧化合物B3。含苯并环丁烯结构的环氧化合物B3的核磁共振氢谱结果为：1H NMR(400MHz，Chloroform-d)δ:6.89(d,1H,ArH)，6.65(d,1H,ArH),6.60(s,1H,ArH)，3.70-3.30(m,4H，-CH2-)，3.20-3.0(m，4H，-CH2-CH2-)，2.80-2.70(m,2H,-CH-)，2.50(s,4H,-CH2-)。
上述反应过程的反应式如下：
实施例1
感光树脂组合物胶液的制备：
在配有黄光灯的千级超净间内，将2.5重量份的1-[4-(苯硫基)苯基]-1,2-辛烷二酮-2-(O-苯甲酰肟)、0.15重量份的2,6-二叔丁基对甲基苯酚、3重量份的γ-缩水甘油醚氧基丙基三甲氧基硅烷、10重量份的四乙二醇二甲基丙烯酸酯以及10重量份的含有苯并环丁烯结构的环氧B1加入200重量份的NMP中，全部溶解完全后加入125重量份的二氧化硅粒子，室温搅拌2h后，加入100重量份的聚酰胺酸酯树脂A1，并补加25重量份的NMP，室温下搅拌3h，使其形成均相组合物溶液。
感光树脂膜材的制备：
将上述制备的感光树脂组合物溶液刮涂在PET膜上制成湿膜，然后放入80℃鼓风烘箱中烘烤20min后，得到感光树脂固态胶膜，测量感光树脂固态胶膜厚度为30μm。通过真空压合的方法将BOPP膜在60℃下贴合到上述带有PET基材薄膜的感光树脂固态胶膜上，形成三层膜结构的膜材。
实施例2-9和对比例1-4的感光树脂组合物胶液及感光树脂膜材的具体组成成分和含量列于表1，其制备过程参考实施例1。表1中，A1、A2、A3为合成例1-3制备的树脂，B1、B2、B3为合成例4-6制备的含苯并环丁烯结构的环氧化合物，B4为双酚A二缩水甘油醚，B5为聚丙二醇二缩水甘油醚(Mw～400)，C为1-[4-(苯硫基)苯基]-1,2-辛烷二酮-2-(O-苯甲酰肟)，D为四乙二醇二甲基丙烯酸酯，E为γ-缩水甘油醚氧基丙基三甲氧基硅烷，F为2,6-二叔丁基对甲基苯酚，G为二氧化硅粒子(粒径1um)，H为N-甲基吡咯烷酮。表1中的含量均为重量份数。
表1.各实施例与对比例的具体组成成分和含量
实施例1-9和对比例1-4的感光树脂材料性能评价
1.1揭下上述三层膜的BOPP覆盖膜，将带有PET基材薄膜的感光树脂固态胶膜贴附到具有图案化第一膜层的硅片上，感光树脂固态胶膜与具有图案的硅片构建形成空腔。贴膜过程中压力设置为60kPa。贴附后将PET基材揭下，评价感光树脂固态胶膜在硅片上的覆盖率(覆盖率越高表明胶膜在硅片上的粘合更好，其中，覆盖率100％说明在撕下PET的时候胶膜可以100％留在硅片上，不会随着PET撕掉)。随后采用紫外曝光机曝光25s(约250mJ/cm2曝光剂量)，采用环戊酮显影40s，丙二醇甲醚醋酸酯冲洗25s，并 于250℃真空固化2h，感光树脂固态胶膜完全固化得到聚酰亚胺硬化膜，聚酰亚胺固化膜用于构成支撑空腔，聚酰亚胺膜可根据需要具有开孔(开孔的孔径例如可以是60微米)。评价500um×500um空腔在固化后的空腔支撑情况，看有无塌陷开裂等现象。
1.2将感光树脂固态胶膜以与1.1相同工艺贴附到镀铜硅片上，揭下PET基材薄膜，在相同的曝光显影工艺后250℃真空固化2h，感光树脂固态胶膜完全固化得到聚酰亚胺硬化膜，将贴附有聚酰亚胺硬化膜的镀铜硅片在三氯化铁中浸泡1h，使聚酰亚胺硬化膜与硅片剥离，即可得到完整的聚酰亚胺硬化膜。将聚酰亚胺硬化膜切割成30mm×5mm×30μm的样条表征耐热性能(包括玻璃化转变温度)与拉伸性能(包括拉伸模量和拉伸强度)。再取8cm×8cm的聚酰亚胺硬化膜样品，经150℃鼓风干燥2h后，表征样品的吸水率与10GHz下介电性能(包括10GHz下的介电常数和介电损耗)。
本申请实施例1-9和对比例1-4中感光树脂固态胶膜的贴膜工艺参数(包括贴膜时的辊压温度和贴膜覆盖率)列于表2；本申请实施例1-9和对比例1-4中感光性树脂材料的固化膜性能评价结果列于表2。
表2.实施例1-9和对比例1-4的贴膜工艺参数和性能评价结果
表2中，O表示500um×500um空腔无塌陷开裂等行为；X表示500um×500um空腔塌陷。
由表2的结果可知，本申请实施例的感光树脂组合物具有与对比例1、对比例2、对比例4的含有普通环氧化合物的树脂组合物相当的良好粘附性能，可保证片状感光膜材在50℃-70℃的低温下与底层带有图案的硅片很好地粘合，实现贴膜覆盖率100％；本申请实施例感光树脂组合物膜材具有良好的抗高温模压性能，在高温固化后能够较好地支撑其构筑的空腔不塌陷；同时，本申请实施例的感光树脂组合物固化后在高频下具有较低的介电常数和介电损耗，本申请实施例感光树脂组合物具有较高的玻璃化转变温度和较低吸水率。
对比采用相同树脂体系的实施例4、实施例5、对比例1和对比例2还可以获知，本申请实施例的感光树脂组合物中的含苯并环丁烯结构的环氧化合物可在坚膜阶段(显影后的热处理阶段)发生环丁烯的开环固化，提高交联密度，从而相较对比例的感光树脂组合物，可赋予体系更高的拉伸模量、拉伸强度和玻 璃化转变温度，同时还能降低介电常数、介电损耗与吸水率。另外，对比实施例1和实施例3，实施例4和实施例5可以获知，具有相同环氧环数量的含苯并环丁烯结构的环氧化合物，其中含有酯基桥连的结构因为具有更强的分子间相互作用，可以更加显著的提高感光树脂组合物硬化膜的玻璃化转变温度、拉伸模量与拉伸强度，但会一定程度影响介电常数、介电损耗和吸水率的降低效果。

Claims (29)

  1. 一种感光树脂组合物，其特征在于，包括树脂、交联剂、引发剂和含苯并环丁烯结构的环氧化合物。
  2. 如权利要求1所述的感光树脂组合物，其特征在于，以所述树脂为100重量份计，所述含苯并环丁烯结构的环氧化合物为0.1-60重量份。
  3. 如权利要求1或2所述的感光树脂组合物，其特征在于，所述含苯并环丁烯结构的环氧化合物包括苯并环丁烯环和至少一个连接在所述苯并环丁烯环上的含环氧基团的取代基。
  4. 如权利要求3所述的感光树脂组合物，其特征在于，所述含苯并环丁烯结构的环氧化合物包括式(I)所示结构的任意一种或多种化合物：
    式(I)中，R1至R6中至少一个基团为所述含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基。
  5. 如权利要求4所述的感光树脂组合物，其特征在于，所述R1至R6中，所述取代的C1至C20的脂肪族烃基、取代的C1至C20的脂肪族烃氧基、取代的C6至C20的芳基和取代的C7至C20的芳基烷基中的取代基团包括卤素原子、羟基、羟基烷基、羧基、羧基烷基、烷基、酯基和酰基中的一种或多种。
  6. 如权利要求3-5任一项所述的感光树脂组合物，其特征在于，所述含环氧基团的取代基包括式(1a)至式(1d)所示的基团：
    式(1a)至式(1c)中，a为0至10的整数；式(1a)至式(1d)中，X为单键、取代或未取代的C1至C20的亚烷基、或取代或未取代的C1至C20的亚烷氧基。
  7. 如权利要求6所述的感光树脂组合物，其特征在于，所述X中，取代的C1至C20的亚烷基、取代的C1至C20的亚烷氧基中的取代基团包括卤素原子、芳基、酯基、酰基中的一种或多种。
  8. 如权利要求6或7所述的感光树脂组合物，其特征在于，所述含苯并环丁烯结构的环氧化合物至少包括含有式(1d)所示的含环氧基团的取代基的含苯并环丁烯结构的环氧化合物。
  9. 如权利要求1-8任一项所述的感光树脂组合物，其特征在于，所述树脂包括酚醛环氧树脂、丙烯酸树脂、聚酰亚胺前驱体树脂、可溶性聚酰亚胺树脂、聚苯并噁唑前驱体树脂中的一种或多种。
  10. 如权利要求1-9任一项所述的感光树脂组合物，其特征在于，所述引发剂包括光聚合引发剂，所述光聚合引发剂包括二苯甲酮、二苯甲酮衍生物、苯乙酮衍生物、噻吨酮、噻吨酮衍生物、苯偶酰、苯偶酰衍生物、苯偶姻、苯偶姻衍生物、1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟、1-[4-(苯硫基)苯基]-1,2-辛烷二酮-2-(O-苯甲酰肟)、1-苯基-1,2-丁二酮-2-(邻甲氧基羰基)肟和1,3-二苯基丙三酮-2-(邻乙氧基羰基)肟中的一种或多种。
  11. 如权利要求1-10任一项所述的感光树脂组合物，其特征在于，以所述树脂为100重量份计，所述引发剂为0.1-20重量份。
  12. 如权利要求1-11任一项所述的感光树脂组合物，其特征在于，所述交联剂包括光聚合性化合物，所述光聚合性化合物包括甲基丙烯酸-2-羟甲酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯 酸-2-羟丁酯、丙烯酸-2-羟甲酯、丙烯酸-2-羟乙酯、丙烯酸-2-羟丙酯、丙烯酸-2-羟丁酯、丙烯酸缩水甘油酯、丙烯酸环氧丙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸环氧丙酯、四乙二醇二甲基丙烯酸酯、乙二醇双乙醚甲基丙烯酸酯、乙二醇双乙醚丙烯酸酯和聚乙二醇甲基丙烯酸酯中的一种或多种。
  13. 如权利要求1-12任一项所述的感光树脂组合物，其特征在于，以所述树脂为100重量份计，所述交联剂为2-50重量份。
  14. 如权利要求1-13任一项所述的感光树脂组合物，其特征在于，所述感光树脂组合物还包括助粘剂、阻聚剂和溶剂。
  15. 如权利要求14所述的感光树脂组合物，其特征在于，所述助粘剂包括γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲氧基甲基硅烷、γ-缩水甘油醚氧基丙基三乙氧基硅烷、3-异氰酸酯基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、3-脲基丙基三甲氧基硅烷、3-脲基丙基三乙氧基硅烷、3-异氰酸酯基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-(三乙氧基甲硅烷基)丙基琥珀酸酐、乙烯基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷中的一种或多种；以所述树脂为100重量份计，所述助粘剂为0.5-20重量份。
  16. 如权利要求14所述的感光树脂组合物，其特征在于，所述阻聚剂包括对苯二酚、4-甲氧基苯酚、N-亚硝基二苯基胺、对叔丁基儿茶酚、吩噻嗪、N-苯基萘基胺、2,6-二叔丁基对甲基苯酚、5-亚硝基-8-羟基喹啉、1-亚硝基-2-萘酚、2-亚硝基-1-萘酚和2-亚硝基-5-(N-乙基-磺基丙基氨基)苯酚中的一种或多种；以所述树脂为100重量份计，所述阻聚剂为0.01-10重量份。
  17. 如权利要求14所述的感光树脂组合物，其特征在于，所述溶剂包括N-甲基吡咯烷酮、N,N’-二甲基乙酰胺、N,N’-二甲基甲酰胺、二甲基亚砜、四甲基脲、γ-丁内酯、乳酸乙酯、环戊酮、环己酮、甲基乙基酮、四氢呋喃、乙酸乙酯和乙酸丁酯中的一种或多种；以所述树脂为100重量份计，所述溶剂为100-1000重量份。
  18. 如权利要求1-17任一项所述的感光树脂组合物，其特征在于，所述感光树脂组合物还包括无机填料。
  19. 如权利要求18所述的树脂组合物，其特征在于，所述无机填料包括二氧化硅、氧化铝、滑石粉、硫酸钡、玻璃粉、云母粉中的一种或多种；以所述树脂为100重量份计，所述无机填料为50-400重量份。
  20. 一种膜材，其特征在于，所述膜材包括感光树脂膜，所述感光树脂膜采用权利要求1-19任一项所述的感光树脂组合物制备得到。
  21. 权利要求1-19任一项所述的感光树脂组合物或权利要求20所述的膜材在制备电子封装结构中的应用。
  22. 如权利要求21所述应用，其特征在于，所述感光树脂组合物在制备电子封装结构中的应用包括用于制备封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层或再布线层。
  23. 如权利要求21所述应用，其特征在于，所述膜材在制备电子封装结构中的应用包括用于制备封装基板、保护层、钝化层、层间绝缘层、介电层、缓冲层、平坦化层、α射线屏蔽层或再布线层中，或用于构建弹性波滤波器和微机电系统中的封装腔体。
  24. 一种电子封装结构，其特征在于，所述电子封装结构包括权利要求1-19任一项所述的感光树脂组合物的固化物。
  25. 一种电子设备，其特征在于，所述电子设备包括权利要求24所述的电子封装结构。
  26. 一种含苯并环丁烯结构的环氧化合物，其特征在于，所述含苯并环丁烯结构的环氧化合物具有式(I)所示的结构：
    式(I)中，R1至R6中至少一个基团为式(1d)所示的含环氧基团的取代基，其余基团独立地选自氢原子、取代或未取代的C1至C20的脂肪族烃基、取代或未取代的C1至C20的脂肪族烃氧基、取代或 未取代的C6至C20的芳基、取代或未取代的C7至C20的芳基烷基、式(1a)所示的含环氧基团的取代基、式(1b)所示的含环氧基团的取代基、式(1c)所示的含环氧基团的取代基，
    式(1a)至式(1c)中，a为0至10的整数；式(1a)至式(1d)中，X为单键、取代或未取代的C1至C20的亚烷基、或取代或未取代的C1至C20的亚烷氧基。
  27. 如权利要求26所述的含苯并环丁烯结构的环氧化合物，其特征在于，所述R1至R6中，所述取代的C1至C20的脂肪族烃基、取代的C1至C20的脂肪族烃氧基、取代的C6至C20的芳基和取代的C7至C20的芳基烷基中的取代基团包括卤素原子、羟基、羟基烷基、羧基、羧基烷基、烷基、酯基和酰基中的一种或多种。
  28. 如权利要求26或27所述的含苯并环丁烯结构的环氧化合物，其特征在于，所述X中，取代的C1至C20的亚烷基、取代的C1至C20的亚烷氧基中的取代基团包括卤素原子、芳基、酯基、酰基中的一种或多种。
  29. 如权利要求26-28任一项所述的含苯并环丁烯结构的环氧化合物在制备涂料、复合材料、浇铸料、胶粘剂、固化剂、感光树脂组合物、感光树脂膜材、塑封料、模压材料和注射成型材料中的应用。
PCT/CN2023/101334 2022-06-23 2023-06-20 感光树脂组合物、膜材、含苯并环丁烯结构的环氧化合物及其应用 WO2023246762A1 (zh)

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