WO2024050892A1 - 树脂组合物及胶粘剂 - Google Patents

树脂组合物及胶粘剂 Download PDF

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Publication number
WO2024050892A1
WO2024050892A1 PCT/CN2022/121745 CN2022121745W WO2024050892A1 WO 2024050892 A1 WO2024050892 A1 WO 2024050892A1 CN 2022121745 W CN2022121745 W CN 2022121745W WO 2024050892 A1 WO2024050892 A1 WO 2024050892A1
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Prior art keywords
resin
resin composition
epoxy resin
diamine
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/CN2022/121745
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English (en)
French (fr)
Inventor
王宏远
张翼蓝
潘瑞
王和志
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AAC Technologies Holdings Nanjing Co Ltd
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AAC Technologies Holdings Nanjing Co Ltd
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Priority to US18/091,307 priority Critical patent/US20240092963A1/en
Publication of WO2024050892A1 publication Critical patent/WO2024050892A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the invention belongs to the technical field of electronic glue, and in particular relates to a resin composition and an adhesive.
  • the adhesive material is the resin composition, but the adhesive material composed of the existing resin composition can no longer meet the bonding, sealing and potting properties required by the new flexible copper-clad laminate.
  • the object of the present invention is to provide a resin composition to solve the problem that the adhesive material composed of the existing resin composition cannot meet the needs of the new flexible copper-clad laminate.
  • the present invention provides a resin composition, which consists of the following components:
  • Benzoxazine which is a synthetic product of a primary amine-terminated flexible polyimide oligomer, an aldehyde compound and a monofunctional phenolic compound;
  • the mixed resin is one or more of epoxy resin, maleimide resin and cyanate ester resin containing two or more functional groups; the mass fraction of the mixed resin is the 0.1%-70% of benzoxazines.
  • R 1 , R 2 , R 3 and R 4 are independently selected from -H and alkyl, alkoxy, cycloalkyl and aromatic groups, and at least one of them is -H;
  • X 1 is the main chain Or the side chain contains an alkyl group or/and an alkoxy group with a long chain structure; or more.
  • X 1 is an alkyl group or an alkoxy group with a carbon number of 5-30.
  • the molecular weight of the primary amine-terminated flexible polyimide oligomer is Mn1000-50000.
  • the primary amine-terminated flexible polyimide oligomer is the reaction product of tetracarboxylic dianhydride and flexible diamine, and the dianhydride in the tetracarboxylic dianhydride and the flexible diamine are The molar ratio of diamine is 1:1.01-1:1.1.
  • the tetracarboxylic dianhydride is 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 4,4'-diphenyl ether dianhydride, 3,3',4,4' -One or more of benzophenone tetracarboxylic dianhydride, hexafluoro dianhydride and bisphenol A-type diether dianhydride.
  • the flexible diamine is a mixture of a diamine with a flexible long-chain structure and an aromatic diamine in the main chain or side chain, and the main chain or side chain contains a diamine with a flexible long-chain structure and the aromatic diamine.
  • the molar ratio of diamines is 1:9-10:0.
  • X 3 is an alkyl group or/and alkoxy group containing a long chain structure in the main chain or side chain;
  • the aromatic diamines are m-phenylenediamine, 4,4-diaminodiphenyl ether, p-phenylenediamine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Any one of aminophenoxy)benzene and 1,4-bis(4-aminophenoxy)benzene.
  • X 3 is an alkyl group or an alkoxy group with a carbon number between 5-30.
  • the preparation method of the primary amine-terminated flexible polyimide oligomer includes the following steps:
  • aldehyde compounds include formaldehyde and/or paraformaldehyde.
  • the monofunctional phenolic compound is any one of phenol, methylphenol and ethylphenol.
  • the epoxy resin is a phenolic epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, an alicyclic epoxy resin, or a silane modified epoxy resin. Any one of epoxy resin, vinyl dioxide epoxy resin, epoxidized polybutadiene epoxy resin, trifunctional epoxy resin and tetraglycidyl epoxy resin.
  • the maleimide in the maleimide resin is m-phenylene bismaleimide, 4,4-diphenylmethane bismaleimide, 4,4- Any one of diphenyl ether bismaleimide and N,N-m-phenylene bismaleimide.
  • the cyanate ester in the cyanate ester resin is bisphenol A cyanate, bisphenol E cyanate, bisphenol F cyanate, bisphenol M cyanate, tetramethyl bisphenol A Any one of cyanate ester and dicyclopentadienyl cyanate ester.
  • the present invention provides an adhesive, which includes the resin composition as described above, a curing accelerator and an organic solvent.
  • the curing accelerator is imidazole, 1-methylimidazole, 1,2-dimethylimidazole, formic acid, acetic acid, propionic acid, aniline, benzylamine, azobisisobutyronitrile, azobisisobutyronitrile.
  • the organic solvent is toluene, xylene, dioxane, tetrahydrofuran, methanol, ethanol, acetone, butanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethyl One or more of acetamide and N-methylpyrrolidone.
  • the adhesive is applied to film-like adhesive materials, adhesive layers, adhesive sheets, resin-coated copper foil, copper-clad laminates and resin multi-layer substrates.
  • the resin composition in the present invention is composed of benzoxazine and mixed resin, so that the adhesive material composed of benzoxazine and mixed resin can meet the new flexibility requirements. demand for copper clad laminates.
  • This embodiment provides a resin composition consisting of a benzoxazine and a mixed resin; wherein the benzoxazine is a primary amine-terminated flexible polyimide oligomer, an aldehyde compound, and a monofunctional phenolic compound.
  • a synthetic product, the mixed resin is one or more of epoxy resin, maleimide resin and cyanate ester resin containing two or more functional groups.
  • the mass fraction of the mixed resin is 0.1%-70% of the benzoxazine. More preferably, the mass part of the mixed resin is 0.5%-50%.
  • R 1 , R 2 , R 3 and R 4 are independently selected from -H and alkyl, alkoxy, cycloalkyl and aromatic groups, and at least one of them is -H;
  • X 1 is the main chain Or the side chain contains an alkyl group or/and an alkoxy group with a long chain structure; or more.
  • X 1 in the molecular formula of the resin composition is an alkyl group or an alkoxy group with a carbon number of 5-30.
  • the molecular weight of the primary amine-terminated flexible polyimide oligomer is Mn1000-50000g/mol.
  • the primary amine-terminated flexible polyimide oligomer is the reaction product of tetracarboxylic dianhydride and flexible diamine.
  • the moles of dianhydride in tetracarboxylic dianhydride and diamine in flexible diamine are The ratio is 1:1.01-1:1.1.
  • the tetracarboxylic dianhydride is 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 4,4'-diphenyl ether dianhydride, 3,3',4,4'-benzophenone
  • tetracarboxylic dianhydrides on the market such as tetracarboxylic dianhydride, hexafluoro dianhydride and bisphenol A type diether dianhydride.
  • the flexible diamine is a mixture of diamines with flexible long-chain structures in the main chain or side chains and other aromatic diamines.
  • the molar ratio of diamines with flexible long-chain structures in the main chain or side chains with aromatic diamines is 1: 9-10:0.
  • the molar ratio of the diamine containing a flexible long chain structure in the main chain or side chain to the aromatic diamine is 2:8-10:0.
  • X 3 contains an alkyl group or/and alkoxy group with a long chain structure in the main chain or side chain.
  • X 3 is an alkyl group or an alkoxy group with a carbon number of 5-30.
  • aromatic diamines are m-phenylenediamine, 4,4-diaminodiphenyl ether, p-phenylenediamine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Any one of aminophenoxy)benzene and 1,4-bis(4-aminophenoxy)benzene.
  • the preparation method of primary amine-terminated flexible polyimide oligomers includes the following steps:
  • the first preset temperature and the first preset time are set according to the selected compound and are not specifically limited here.
  • the first preset temperature can be -20-30°C
  • the first preset time can be 0.5-24h.
  • the second preset temperature and the second preset time are also set according to the selected compound and are not specifically limited here.
  • the preparation method of benzoxazine is as follows: dissolving the primary amine-terminated flexible polyimide oligomer, aldehyde compounds and monofunctional phenolic compounds in a solvent, and making them in the third preset Under temperature conditions, the reaction is continued for a third preset time, thereby obtaining benzoxazine.
  • the third preset temperature and the third preset time are set according to the selected compound and are not specifically limited here.
  • the third preset temperature can be 60-180°C
  • the third preset time can be 0.5-10h.
  • the aldehyde compound includes formaldehyde and/or paraformaldehyde;
  • the monofunctional phenolic compound is any one of phenol, methylphenol and ethylphenol.
  • the epoxy resin is a phenolic epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, an alicyclic epoxy resin, a silane-modified epoxy resin, Any one of epoxy resin, vinyl dioxide epoxy resin, epoxidized polybutadiene epoxy resin, trifunctional epoxy resin and tetraglycidyl epoxy resin.
  • the maleimide in the maleimide resin is m-phenylene bismaleimide, 4,4-diphenylmethane bismaleimide, 4,4 - Any one of diphenyl ether bismaleimide and N,N-m-phenylene bismaleimide.
  • the cyanate ester in the cyanate ester resin is bisphenol A cyanate, bisphenol E cyanate, bisphenol F cyanate, bisphenol M cyanate, and tetramethyl bisphenol Any one of A cyanate ester and dicyclopentadiene cyanate ester.
  • the resin composition in this embodiment is composed of benzoxazine and mixed resin, so that the adhesive material composed of benzoxazine and mixed resin can meet the needs of new flexible demand for copper-clad laminates.
  • the adhesive includes the resin composition in Embodiment 1, a curing accelerator and an organic solvent.
  • the curing accelerator is imidazole, 1-methylimidazole, 1,2-dimethylimidazole, formic acid, acetic acid, propionic acid, aniline, benzylamine, azobisisobutyronitrile, azobisisoheptan One or more of nitrile, benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxide, etc.
  • the organic solvent is toluene, xylene, dioxane, tetrahydrofuran, methanol, ethanol, acetone, butanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethyl One or more of acetamide and N-methylpyrrolidone.
  • the adhesive is mainly used in film-like adhesive materials, adhesive layers, adhesive sheets, resin-coated copper foil, copper-clad laminates (flexible copper-clad laminates), and resin multi-layer substrates.
  • the adhesive in this embodiment includes the resin composition in Embodiment 1, when applied to the new flexible copper-clad laminate, it can meet the performance requirements of the new flexible copper-clad laminate for adhesive materials.
  • This embodiment provides a preparation method of benzoxazine.
  • the specific steps are: under nitrogen protection, add 21g of polyetheramine D400 and 110.03g into a one-neck flask equipped with magnetic stirring and water separator. N-methylpyrrolidone (NMP) was evenly mixed; after uniform mixing, 26.16g of bisphenol A-type diether dianhydride (Zhongtai Chemical Technology Co., Ltd.-BPADA) was slowly added, and then reacted at room temperature for 1 hour, and then The temperature was raised to 140°C and reacted for 10 hours to obtain a primary amine-terminated flexible polyimide oligomer solution; after the solution cooled, 0.24g of phenol, 0.15g of paraformaldehyde and 0.90g of toluene were added to the single-necked flask, and then , replace the water separator with a condenser tube, raise the temperature to 90°C and reflux for 6 hours until the reaction is completed, thereby obtaining a yellow
  • This embodiment provides a resin composition.
  • the specific steps are: mixing 10 g of the benzoxazine prepared in Example 3 with 0.15 g of epoxy resin (Shell Company-EPON1031) to obtain a resin composition.
  • NMP is the solvent (solid content 30%wt) to prepare the composition.
  • This embodiment provides a resin composition.
  • the specific steps are: mixing 10g of the benzoxazine prepared in Example 3 with 0.15g of bismaleimide (Honghu Shuangma New Material Technology Co., Ltd.-BMI- 01) Mix to obtain a resin composition.
  • NMP is the solvent (solid content 30%wt) to prepare the composition.
  • This embodiment provides a resin composition.
  • the specific steps are: mix 10g of the benzoxazine prepared in Example 3 with 0.15g of cyanate ester (Yangzhou Tianqi New Materials Co., Ltd.-C01PO) to obtain a resin composition. things. Among them, NMP is the solvent (solid content 30%wt) to prepare the composition.
  • This embodiment provides a resin composition.
  • the specific steps are: mixing 10g of the benzoxazine prepared in Example 3 with 0.3g of trifunctional epoxy resin (Shanghai Huayi Resin Co., Ltd.-AFG-90), Thereby, a resin composition is obtained.
  • NMP is the solvent (solid content 30%wt) to prepare the composition.
  • This comparative example provides a method for preparing a flexible polyimide solution.
  • the specific steps are: under nitrogen protection, add 8g of polyetheramine D400 and 43.08 to a single-necked flask equipped with a magnetic stirrer and a water separator. g of N-methylpyrrolidone was dissolved; after the dissolution was completed, 10.46g of bisphenol A-type diether dianhydride (BPADA) was slowly added, and then reacted at room temperature for 1 hour, then raised the temperature to 140°C for 10 hours to obtain a flexible poly imide solution.
  • BPADA bisphenol A-type diether dianhydride
  • This comparative example provides the benzoxazine prepared in Example 3.
  • This embodiment provides a method for preparing an adhesive sheet.
  • the specific steps are as follows: apply the compositions prepared in Examples 4 to 7 and Comparative Examples 1 to 2 on polyimide at a thickness of 12.5 ⁇ m after drying. on the amine film, and then dried at 220°C for 3 minutes to obtain an adhesive sheet.
  • This embodiment provides a method for preparing a copper foil laminate.
  • the specific steps are as follows: the adhesive sheet prepared based on Examples 4 to 7 and Comparative Examples 1 to 2 is overlapped onto the rough surface of the copper foil, and then Process at 160-300°C and 2-10MPa pressure for 5-30 minutes to obtain a copper-clad laminate.
  • Example 4-1 the copper-clad laminates prepared based on Examples 4 to 7 are respectively regarded as Example 4-1, Example 5-1, Example 6-1, and Example 7-1, while those prepared based on Comparative Examples 1 to 2
  • the obtained copper foil laminates were used as Comparative Example 1-1 and Comparative Example 2-1.
  • Example 4-1 to Example 7-1 and Comparative Examples 1-1 to 2-1 are shown in Table 2 below:
  • the adhesive properties in the table are obtained through the test of peel strength, and the test of peel strength is as follows: according to the IPC-TM-650-2.4.8 test specification, cut the sample into 3.18mm splines, then start the testing machine, and Apply tensile force in the vertical direction at a speed of 50mm/min until a minimum length of 25.4mm is peeled off. The test is conducted at least 4 times, and then the average value is calculated to obtain the bonding performance results.
  • the testing machine used is the electronic universal testing machine of Shenzhen Sansi Zongheng Co., Ltd. or other types of testing machines.
  • the soldering resistance in the table has passed the soldering resistance test.
  • the above copper-clad single panel (copper-clad laminate or Sample) is cut into 50mm ⁇ 50mm splines.
  • Dk is the dielectric constant
  • Df is the dielectric loss tangent.
  • the corresponding example is coated on PTFE (fluorocarbon solid) with a cured film thickness of 50 ⁇ m, and then cured under dry conditions at 220°C for 20 minutes. After peeling off, a sample for dielectric measurement with a film thickness of about 50 ⁇ m was obtained.
  • dielectric constant testing device After obtaining the sample for dielectric measurement, use a commercially available (marketed) dielectric constant testing device to test the dielectric constant and dielectric loss tangent at 10 GHz in accordance with the IPC-TM-650-2.5.5.10 test specification, where , Dielectric constant test equipment such as cavity resonator type and test equipment manufactured by AET, etc.
  • This embodiment provides a method for preparing a resin multilayer substrate.
  • the specific steps are: the adhesive sheets prepared based on Examples 4 to 7 and Comparative Examples 1 to 2 are overlapped together, and then heated at 160-300°C. Press together for 1-30 minutes under a pressure of 2-10MPa to obtain a resin multi-layer substrate.
  • Example 4 to 7 the copper-clad laminates prepared based on Examples 4 to 7 are respectively regarded as Example 4-2, Example 5-2, Example 6-2, and Example 7-2, while those prepared based on Comparative Examples 1 to 2
  • the obtained copper foil laminates were used as Comparative Example 1-2 and Comparative Example 2-2.
  • Example 4-2 The bonding performance test results of Example 4-2 to Example 7-2 and Comparative Examples 1-2 to 2-2 are shown in Table 3 below:
  • the adhesive properties in the table are obtained through the test of peel strength, and the test of peel strength is as follows: according to the IPC-TM-650-2.4.8 test specification, cut the sample into 3.18mm splines, then start the testing machine, and Apply tensile force in the vertical direction at a speed of 50mm/min until a minimum length of 25.4mm is peeled off. The test is conducted at least 4 times, and then the average value is calculated to obtain the bonding performance results.
  • the testing machine used is the electronic universal testing machine of Shenzhen Sansi Zongheng Co., Ltd. or other types of testing machines.

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Abstract

一种树脂组合物及胶粘剂，其中，所述树脂组合物由如下组分组成：苯并噁嗪，所述苯并噁嗪为伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物以及单官能酚类化合物的合成产物；混合树脂，所述混合树脂为含有两个或两个以上官能团的环氧树脂、马来酰亚胺树脂以及氰酸酯树脂中的一种或多种；所述混合树脂的质量分数为所述苯并噁嗪的0.1％-70％。树脂组合物可以通过苯并噁嗪和混合树脂的特性，使其组成的胶粘材料能满足新型挠性覆铜板的需求。

Description

树脂组合物及胶粘剂 【技术领域】
本发明属于电子胶技术领域，尤其涉及一种树脂组合物及胶粘剂。
【背景技术】
随着信息科技的发展，电子传输速度已向着高频及高速化发展，电子产品则向着多功能化、多密度化及多层次化发展，挠性印刷电路板越来越多的应用在电子设备中，其性能受到了越来越高的挑战。
如何降低在高频传输下的损耗，在较高的温度下仍然保持稳定性，是近年来不断挑战的课题，为此，作为挠性覆铜板的重要组成部分的胶粘材料，其性能也需要不断提升。
其中，胶粘材料中最重要组成部分的便是树脂组合物，但现有树脂组合物组成的胶粘材料已无法满足新型挠性覆铜板所需的粘接、密封及灌封等性能。
【发明内容】
本发明的目的在于如何提供一种树脂组合物，以解决现有树脂组合物组成的胶粘材料已无法满足新型挠性覆铜板的需求的问题。
第一方面，本发明提供了一种树脂组合物，所述树脂组合物由如下组分组成：
苯并噁嗪，所述苯并噁嗪为伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物以及单官能酚类化合物的合成产物；以及，
混合树脂，所述混合树脂为含有两个或两个以上官能团的环氧树脂、马来酰亚胺树脂以及氰酸酯树脂中的一种或多种；所述混合树脂的质量分数为所述苯并噁嗪的0.1％-70％。
更进一步地，所述苯并噁嗪的分子式如下：
Figure PCTCN2022121745-appb-000001
其中：R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基、芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种。
更进一步地，所述苯并噁嗪的分子式中X 1为碳原子数为5-30之间的烷基和烷氧基。
更进一步地，所述伯胺封端的柔性聚酰亚胺齐聚物的分子量为Mn1000-50000。
更进一步地，所述伯胺封端的柔性聚酰亚胺齐聚物为四羧酸二酐和柔性二胺的反应产物，所述四羧酸二酐中的二酐和所述柔性二胺中的二胺的摩尔比为1：1.01-1：1.1。
更进一步地，所述四羧酸二酐为3，3'，4，4'-联苯四羧酸二酐、4，4'-联苯醚二酐、3，3'，4，4'-二苯酮四酸二酐、六氟二酐以及双酚A型二醚二酐中的一种或多种。
更进一步地，所述柔性二胺为主链或侧链含有柔性长链结构的二胺和芳香族二胺的混合物，所述主链或侧链含有柔性长链结构的二胺和所述芳香族二胺的摩尔比为1：9-10：0。
更进一步地，所述主链或侧链含有柔性长链结构的二胺的分子式如下：
H 2N-X 3——NH 2；
其中：X 3为主链或侧链含有长链结构的烷基或/和烷氧基；
所述芳香族二胺为间苯二胺、4，4-二氨基二苯醚、对苯二胺、1，3- 双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯以及1，4-双(4-氨基苯氧基)苯中的任意一种。
更进一步地，所述主链或侧链含有柔性长链结构的二胺的分子式中X 3为碳原子数为5-30之间的烷基和烷氧基。
更进一步地，所述伯胺封端的柔性聚酰亚胺齐聚物的制备方法包括如下步骤：
S1、在氮气保护的条件下，将所述柔性二胺溶解在溶剂中以形成第一混合溶剂；
S2、往所述第一混合溶剂中逐步加入所述四羧酸二酐，并使其在第一预设温度的条件下，持续反应第一预设时间以形成第二混合溶剂；
S3、往所述第二混合溶剂中加入催化剂或带水剂，并使其在第二预设温度的条件下，持续反应第二预设时间，之后析出或干燥后得到所述伯胺封端的柔性聚酰亚胺齐聚物。
更进一步地，所述醛类化合物包括甲醛和/或多聚甲醛。
更进一步地，所述单官能酚类化合物为苯酚、甲基苯酚以及乙基苯酚中的任意一种。
更进一步地，所述环氧树脂为酚醛型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、脂环族环氧树脂、硅烷改性环氧树脂、二氧化乙烯基环氧树脂、环氧化聚丁二烯环氧树脂、三官能环氧树脂以及四缩水甘油基环氧树脂中的任意一种。
更进一步地，所述马来酰亚胺树脂中的马来酰亚胺为间亚苯基双马来酰亚胺、4，4-二苯基甲烷双马来酰亚胺、4，4-二苯基醚双马来酰亚胺以及N，N-间苯撑双马来酰亚胺中的任意一种。
更进一步地，所述氰酸酯树脂中的氰酸酯为双酚A氰酸酯、双酚E氰酸酯、双酚F氰酸酯、双酚M氰酸酯、四甲基双酚A氰酸酯以及双环戊二烯氰酸酯中的任意一种。
第二方面，本发明提供了一种胶粘剂，所述胶粘剂包括如上所述的树脂组合物、固化促进剂以及有机溶剂。
更进一步地，所述固化促进剂为咪唑、1-甲基咪唑、1，2-二甲基咪唑、甲酸、乙酸、丙酸、苯胺、苄胺、偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化甲乙酮以及过氧化叔丁酯中的一种或多种。
更进一步地，所述有机溶剂为甲苯、二甲苯、二氧六环、四氢呋喃、甲醇、乙醇、丙酮、丁酮、环己酮、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺以及N-甲基吡咯烷酮中的一种或多种。
更进一步地，所述胶粘剂应用于膜状胶粘材料、胶粘层、胶粘片、带树脂的铜箔、覆铜箔层压板以及树脂多层基板。
与现有技术相比，本发明中的树脂组合物通过苯并噁嗪以及混合树脂混合组成，从而可以通过苯并噁嗪和混合树脂的特性，使其组成的胶粘材料能满足新型挠性覆铜板的需求。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例一
本实施例提供了一种树脂组合物，由苯并噁嗪以及混合树脂组成；其中，苯并噁嗪为伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物以及单官能酚类化合物的合成产物，混合树脂为含有两个或两个以上官能团的环氧树脂、马来酰亚胺树脂以及氰酸酯树脂中的一种或多种。
具体地，混合树脂的质量分数为苯并噁嗪的0.1％-70％。更优的，混合树脂的质量份为0.5％-50％。
本实施例中，苯并噁嗪的分子式如下：
Figure PCTCN2022121745-appb-000002
其中：R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基、芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种。
更优的，树脂组合物的分子式中X 1为碳原子数为5-30之间的烷基和烷氧基。
本实施例中，伯胺封端的柔性聚酰亚胺齐聚物的分子量为Mn1000-50000g/mol。
本实施例中，伯胺封端的柔性聚酰亚胺齐聚物为四羧酸二酐和柔性二胺的反应产物，四羧酸二酐中的二酐和柔性二胺中的二胺的摩尔比为1：1.01-1：1.1。
其中，四羧酸二酐为3，3'，4，4'-联苯四羧酸二酐、4，4'-联苯醚二酐、3，3'，4，4'-二苯酮四酸二酐、六氟二酐以及双酚A型二醚二酐等市面上销售的四羧酸二酐中的一种或多种。
柔性二胺为主链或侧链含有柔性长链结构的二胺和其它芳香族二胺的混合物，主链或侧链含有柔性长链结构的二胺和芳香族二胺的摩尔比为1：9-10：0。
更优的，主链或侧链含有柔性长链结构的二胺和芳香族二胺的摩尔比2:8-10:0。
主链或侧链含有柔性长链结构的二胺的分子式如下：
H 2N-X 3——NH 2；
其中：X 3为主链或侧链含有长链结构的烷基或/和烷氧基。
更优的，主链或侧链含有柔性长链结构的二胺的分子式中X 3为碳原子数为5-30之间的烷基和烷氧基。
其它的芳香族二胺为间苯二胺、4，4-二氨基二苯醚、对苯二胺、1，3-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯以及1，4-双(4-氨基苯氧基)苯中的任意一种。
本实施例中，伯胺封端的柔性聚酰亚胺齐聚物的制备方法包括如下步骤：
S1、在氮气(N 2)保护的条件下，将柔性二胺溶解在溶剂中以形成第一混合溶剂。
S2、往第一混合溶剂中逐步加入四羧酸二酐，并使其在第一预设温度的条件下，持续反应第一预设时间以形成第二混合溶剂。
其中，第一预设温度和第一预设时间根据选取的化合物进行设定，在此不作具体限定。当然，根据实际需求，第一预设温度可以为-20-30℃，第一预设时间可以为0.5-24h。
S3、往第二混合溶剂中加入催化剂或带水剂，并使其在第二预设温度的条件下，持续反应第二预设时间，之后析出或干燥后得到伯胺封端的柔性聚酰亚胺齐聚物。
其中，第二预设温度和第二预设时间也根据选取的化合物进行设定，在此不作具体限定。
本实施例中，苯并噁嗪的制备方法为：将伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物以及单官能酚类化合物溶解在溶剂中，并使其在第三预设温度的条件下，持续反应第三预设时间，从而得到苯并噁嗪。
其中，第三预设温度和第三预设时间根据选取的化合物进行设定，在此不作具体限定。当然，根据实际需求，第三预设温度可以为60-180℃，第三预设时间可以为0.5-10h。
本实施例中，醛类化合物包括甲醛和/或多聚甲醛；单官能酚类化合物为苯酚、甲基苯酚以及乙基苯酚中的任意一种。
本实施例中，所述环氧树脂为酚醛型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、脂环族环氧树脂、硅烷改性环氧树脂、二氧化乙烯基环氧树脂、环氧化聚丁二烯环氧树脂、三官能环氧树脂以及四缩水甘油基环氧树脂中的任意一种。
本实施例中，所述马来酰亚胺树脂中的马来酰亚胺为间亚苯基双马来酰亚胺、4，4-二苯基甲烷双马来酰亚胺、4，4-二苯基醚双马来酰亚胺以及N，N-间苯撑双马来酰亚胺中的任意一种。
本实施例中，所述氰酸酯树脂中的氰酸酯为双酚A氰酸酯、双酚E氰酸酯、双酚F氰酸酯、双酚M氰酸酯、四甲基双酚A氰酸酯以及双环戊二烯氰酸酯中的任意一种。
与现有技术相比，本实施例中的树脂组合物通过苯并噁嗪以及混合树脂混合组成，从而可以通过苯并噁嗪和混合树脂的特性，使其组成的胶粘材料能满足新型挠性覆铜板的需求。
实施例二
本实施例提供了一种胶粘剂，胶粘剂包括实施例一中的树脂组合物、固化促进剂以及有机溶剂。
本实施例中，固化促进剂为咪唑、1-甲基咪唑、1，2-二甲基咪唑、甲酸、乙酸、丙酸、苯胺、苄胺、偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化甲乙酮以及过氧化叔丁酯等中的一种或多种。
本实施例中，有机溶剂为甲苯、二甲苯、二氧六环、四氢呋喃、甲醇、乙醇、丙酮、丁酮、环己酮、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺以及N-甲基吡咯烷酮等中的一种或多种。
本实施例中，胶粘剂主要应用于膜状胶粘材料、胶粘层、胶粘片、带树脂的铜箔、覆铜箔层压板(挠性覆铜板)以及树脂多层基板等。
由于本实施例中的胶粘剂包括实施例一中的树脂组合物，因此，其应用于新型挠性覆铜板时，可以满足新型挠性覆铜板对于胶粘材料的性能需求。
实施例三
本实施例提供了一种苯并噁嗪的制备方法，具体步骤为：在氮气的保护的条件下，往装有磁力搅拌和分水器的单口烧瓶中加入21g的聚醚胺D400和110.03g的N-甲基吡咯烷酮(NMP)进行均匀混合；均匀混合完毕后缓慢加入26.16g的双酚A型二醚二酐(众泰化工科技有限公司-BPADA)，然后，先在常温下反应1h，再升温至140℃反应10h，从而得到伯胺封端的柔性聚酰亚胺齐聚物溶液；待溶液冷却后在单口烧瓶中加入0.24g的苯酚、0.15g的多聚甲醛以及0.90g的甲苯，然后，将分水器更换为冷凝管，并使其升温至90℃回流6h直至反应结束，从而得到固含量为30％的黄色透明液体，便为苯并噁嗪。
实施例四
本实施例提供了一种树脂组合物，具体步骤为：将10g实施例三制备得到的苯并噁嗪与0.15g的环氧树脂(壳牌公司-EPON1031)混合，从而得到树脂组合物。其中，NMP为溶剂(固含量30％wt)制备组合物。
实施例五
本实施例提供了一种树脂组合物，具体步骤为：将10g实施例三制备得到的苯并噁嗪与0.15g的双马来酰亚胺(洪湖市双马新材料科技有限公司-BMI-01)混合，从而得到树脂组合物。其中，NMP为溶剂(固含量30％wt)制备组合物。
实施例六
本实施例提供了一种树脂组合物，具体步骤为：将10g实施例三制备得到的苯并噁嗪与0.15g的氰酸酯(扬州天启新材料有限公司-C01PO)混合，从而得到树脂组合物。其中，NMP为溶剂(固含量30％wt)制备组合物。
实施例七
本实施例提供了一种树脂组合物，具体步骤为：将10g实施例三制备得到的苯并噁嗪与0.3g的三官能团环氧树脂(上海华谊树脂有限公司-AFG-90)混合，从而得到树脂组合物。其中，NMP为溶剂(固含量30％wt)制备组合物。
对比例一
本对比例提供了一种柔性聚酰亚胺溶液的制备方法，具体步骤为：在氮气保护的条件下，往装有磁力搅拌和分水器的单口烧瓶中加入8g的聚醚胺D400和43.08g的N-甲基吡咯烷酮进行溶解；溶解完毕后缓慢加入10.46g双酚A型二醚二酐(BPADA)，然后，先在常温下反应1h，再升温至140℃反应10h，从而得到柔性聚酰亚胺溶液。
对比例二
本对比例提供的是实施例三制备得到的苯并噁嗪。
其中，实施例四至实施例七与对比例一至二的成分对比情况如下表一：
表一、实施例四至实施例七与对比例一的成分对比表
Figure PCTCN2022121745-appb-000003
实施例八
本实施例提供了一种胶粘片的制备方法，具体步骤为：将实施例四至实施例七以及对比例一至二制备得到的组合物，分别以干燥后12.5μm的方式涂布在聚酰亚胺膜上，然后进行220℃的干燥3min后得到胶粘片。
实施例九
本实施例提供了一种覆铜箔层压板的制备方法，具体步骤为：将基于实施例四至实施例七以及对比例一至二制备得到胶粘片，分别重叠到铜箔的粗糙面，然后在160-300℃、2-10MPa压力的条件下处理5-30min，从而 得到覆铜箔层压板。
其中，基于实施例四至实施例七制备得到的覆铜箔层压板分别作为实施例四-1、实施例五-1、实施例六-1、实施例七-1，而基于对比例一至二制备得到的覆铜箔层压板则作为对比例一-1、对比例二-1。
实施例四-1至实施例七-1以及对比例一-1至二-1的各性能测试结果如下表二所示：
表二、实施例四-1至实施例七-1以及对比例一-1至二-1的各性能测试结果表
Figure PCTCN2022121745-appb-000004
表中的粘接性能通过剥离强度的测试获取，而剥离强度的测试具体为：按照IPC-TM-650-2.4.8测试规范，将样品裁成3.18mm的样条，然后启动实验机，以50mm/min的速度在垂直方向上施加拉力，直至最少剥离25.4mm的长度，测试进行至少4次，之后计算平均值得到粘接性能结果。其中，所用的试验机为深圳三思纵横股份有限公司的电子式万能试验机或其它类型的试验机。
表中的耐锡焊性能通过耐锡焊性能测试，而耐锡焊性能测试进行前，先按照IPC-TM-650-2.4.13测试规范将上述覆铜箔单面板(覆铜箔层压板或样品)裁成50mm×50mm的样条。
Dk为介电常数，Df为介电损耗角正切，测试前先将对应例子以固化后膜厚50μm的方式涂布到PTFE(氟碳固体)上，再在220℃干燥的条件 下固化20min后剥离，从而得到膜厚约50um的介电测定用样品。
得到介电测定用样品后，按照IPC-TM-650-2.5.5.10测试规范，使用市售(市场上销售)的介电常数测试装置测试10GHz下的介电常数和介电损耗角正切，其中，介电常数测试装置如空腔共振器型以及AET制造的测试设备等。
通过对比可知，实施例四-1至实施例七-1以及对比例二-1的粘接性能和耐锡焊性能均优于对比例一-1，即说明基于实施例三中的苯并噁嗪所制备的覆铜箔层压板中粘接性能和耐锡焊性能均优于现有技术制备的覆铜箔层压板。
实施例十
本实施例提供了一种树脂多层基板的制备方法，具体步骤为：将基于实施例四至实施例七以及对比例一至二制备得到胶粘片，分别重叠在一起，然后在160-300℃、2-10MPa压力的条件下压合1-30min，从而得到树脂多层基板。
其中，基于实施例四至实施例七制备得到的覆铜箔层压板分别作为实施例四-2、实施例五-2、实施例六-2、实施例七-2，而基于对比例一至二制备得到的覆铜箔层压板则作为对比例一-2、对比例二-2。
实施例四-2至实施例七-2以及对比例一-2至二-2的粘接性能测试结果如下表三所示：
表三、实施例四-2至实施例七-2以及对比例一-2至二-2的粘接性能测试结果表
Figure PCTCN2022121745-appb-000005
表中的粘接性能通过剥离强度的测试获取，而剥离强度的测试具体为：按照IPC-TM-650-2.4.8测试规范，将样品裁成3.18mm的样条，然后启动 实验机，以50mm/min的速度在垂直方向上施加拉力，直至最少剥离25.4mm的长度，测试进行至少4次，之后计算平均值得到粘接性能结果。其中，所用的试验机为深圳三思纵横股份有限公司的电子式万能试验机或其它类型的试验机。
通过对比可知，实施例四-2至实施例七-2以及对比例二-2的粘接性能优于对比例一-2，即说明基于实施例三中的苯并噁嗪所制备的树脂多层基板中粘接性能优于现有技术制备的树脂多层基板。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (19)

  1. 一种树脂组合物，其特征在于，所述树脂组合物由如下组分组成：
    苯并噁嗪，所述苯并噁嗪为伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物以及单官能酚类化合物的合成产物；以及，
    混合树脂，所述混合树脂为含有两个或两个以上官能团的环氧树脂、马来酰亚胺树脂以及氰酸酯树脂中的一种或多种；所述混合树脂的质量分数为所述苯并噁嗪的0.1％-70％。
  2. 如权利要求1所述的树脂组合物，其特征在于，所述苯并噁嗪的分子式如下：
    Figure PCTCN2022121745-appb-100001
    其中：R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基、芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种。
  3. 如权利要求2所述的树脂组合物，其特征在于，所述苯并噁嗪的分子式中X 1为碳原子数为5-30之间的烷基和烷氧基。
  4. 如权利要求1所述的树脂组合物，其特征在于，所述伯胺封端的柔性聚酰亚胺齐聚物的分子量为Mn1000-50000。
  5. 如权利要求1所述的树脂组合物，其特征在于，所述伯胺封端的柔性聚酰亚胺齐聚物为四羧酸二酐和柔性二胺的反应产物，所述四羧酸二酐中的二酐和所述柔性二胺中的二胺的摩尔比为1∶1.01-1∶1.1。
  6. 如权利要求5所述的树脂组合物，其特征在于，所述四羧酸二酐为 3，3′，4，4′-联苯四羧酸二酐、4，4′-联苯醚二酐、3，3′，4，4′-二苯酮四酸二酐、六氟二酐以及双酚A型二醚二酐中的一种或多种。
  7. 如权利要求6所述的树脂组合物，其特征在于，所述柔性二胺为主链或侧链含有柔性长链结构的二胺和芳香族二胺的混合物，所述主链或侧链含有柔性长链结构的二胺和所述芳香族二胺的摩尔比为1∶9-10∶0。
  8. 如权利要求7所述的树脂组合物，其特征在于，所述主链或侧链含有柔性长链结构的二胺的分子式如下：
    H 2N-X 3-NH 2；
    其中：X 3为主链或侧链含有长链结构的烷基或/和烷氧基；
    所述芳香族二胺为间苯二胺、4，4-二氨基二苯醚、对苯二胺、1，3-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯以及1，4-双(4-氨基苯氧基)苯中的任意一种。
  9. 如权利要求8所述的树脂组合物，其特征在于，所述主链或侧链含有柔性长链结构的二胺的分子式中X 3为碳原子数为5-30的烷基和烷氧基。
  10. 如权利要求8所述的树脂组合物，其特征在于，所述伯胺封端的柔性聚酰亚胺齐聚物的制备方法包括如下步骤：
    S1、在氮气保护的条件下，将所述柔性二胺溶解在溶剂中以形成第一混合溶剂；
    S2、往所述第一混合溶剂中逐步加入所述四羧酸二酐，并使其在第一预设温度的条件下，持续反应第一预设时间以形成第二混合溶剂；
    S3、往所述第二混合溶剂中加入催化剂或带水剂，并使其在第二预设温度的条件下，持续反应第二预设时间，之后析出或干燥后得到所述伯胺封端的柔性聚酰亚胺齐聚物。
  11. 如权利要求1所述的树脂组合物，其特征在于，所述醛类化合物包括甲醛和/或多聚甲醛。
  12. 如权利要求1所述的树脂组合物，其特征在于，所述单官能酚类化合物为苯酚、甲基苯酚以及乙基苯酚中的任意一种。
  13. 如权利要求1所述的树脂组合物，其特征在于，所述环氧树脂为酚醛型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、脂环族环氧树脂、硅烷改性环氧树脂、二氧化乙烯基环氧树脂、环氧化聚丁二烯环氧树脂、三官能环氧树脂以及四缩水甘油基环氧树脂中的任意一种。
  14. 如权利要求1所述的树脂组合物，其特征在于，所述马来酰亚胺树脂中的马来酰亚胺为间亚苯基双马来酰亚胺、4，4-二苯基甲烷双马来酰亚胺、4，4-二苯基醚双马来酰亚胺以及N，N-间苯撑双马来酰亚胺中的任意一种。
  15. 如权利要求1所述的树脂组合物，其特征在于，所述氰酸酯树脂中的氰酸酯为双酚A氰酸酯、双酚E氰酸酯、双酚F氰酸酯、双酚M氰酸酯、四甲基双酚A氰酸酯以及双环戊二烯氰酸酯中的任意一种。
  16. 一种胶粘剂，其特征在于，所述胶粘剂包括权利要求1至15任意一项所述的树脂组合物、固化促进剂以及有机溶剂。
  17. 如权利要求16所述的胶粘剂，其特征在于，所述固化促进剂为咪唑、1-甲基咪唑、1，2-二甲基咪唑、甲酸、乙酸、丙酸、苯胺、苄胺、偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化甲乙酮以及过氧化叔丁酯中的一种或多种。
  18. 如权利要求16所述的胶粘剂，其特征在于，所述有机溶剂为甲苯、二甲苯、二氧六环、四氢呋喃、甲醇、乙醇、丙酮、丁酮、环己酮、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺以及N-甲基吡咯烷酮中的一种或多种。
  19. 如权利要求16所述的胶粘剂，其特征在于，所述胶粘剂应用于膜状胶粘材料、胶粘层、胶粘片、带树脂的铜箔、覆铜箔层压板以及树脂多层基板。
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