CN114836147A - Novel FC-BGA packaging substrate is with increasing layer glued membrane and use rubber coating copper foil of its preparation - Google Patents
Novel FC-BGA packaging substrate is with increasing layer glued membrane and use rubber coating copper foil of its preparation Download PDFInfo
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- 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
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
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- 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
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C09J7/28—Metal sheet
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
Abstract
The invention discloses a novel layer-adding adhesive film for an FC-BGA (fiber channel-ball grid array) packaging carrier plate and a glue-coated copper foil manufactured by using the same, wherein the layer-adding adhesive film comprises the following components in parts by weight: 25-40 parts of epoxy resin, 40-45 parts of inorganic filler, 35-45 parts of modified cyanate ester, 35-45 parts of bismaleimide resin, 25-30 parts of polyphenyl ether and 10-20 parts of modified benzoxazine. The bismaleimide resin and the polyphenyl ether with good dielectric property are selected, the modified cyanate ester and the modified benzoxazine are added to introduce an aliphatic structure and a large-volume functional group, and the polyphenyl ether and the modified cyanate ester react to generate a triazine ring so as to reduce the dielectric constant and dielectric loss of the glued copper foil; and the flame retardant efficiency and the high temperature resistance of the layer-adding adhesive film are improved by means of the synergistic action of nitrogen and phosphorus in the modified cyanate ester and the modified benzoxazine, so that the coated copper foil coated with the layer-adding adhesive film is suitable for ultra-large scale integrated circuits, chip packaging and PCB (printed circuit board).
Description
Technical Field
The invention relates to the technical field of resin-coated copper foils, in particular to a novel layer-adding adhesive film for an FC-BGA (fiber channel-ball grid array) packaging carrier plate and a coated copper foil manufactured by using the same.
Background
The advent of the 5G era has meant that electronic communications are moving to high frequencies, with faster signal transmission frequencies, which places higher demands on the electronic materials used, such as low dielectric constant, low dielectric loss, high temperature resistance, good processability, and dimensional stability. High frequency, high speed Printed Circuit Boards (PCBs) require ultra-low dielectric constants and dielectric losses for the insulating resin dielectric layers they use, which means higher signal transmission rates and lower signal distortion, which is critical for applications with 5G electronic materials. Meanwhile, high temperature is easily generated at local part at high frequency and high speed, so that the insulating resin dielectric layer has good high temperature resistance and flame retardant property, normal operation of the product can be maintained, and reliability of product application is improved.
The dielectric property of the resin material in the prior RCC product is poor, so that the signal transmission is weakened; in addition, some products have poor high temperature resistance and flame retardant property, and the reliability is easily reduced at high frequency and high speed.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a novel build-up adhesive film for FC-BGA package carrier and a coated copper foil manufactured by using the same, and aims to solve the problems of high dielectric constant and dielectric loss, and poor high temperature resistance and flame retardant property of the insulating adhesive film in the prior art.
The technical scheme of the invention is as follows:
a novel layer-adding adhesive film for an FC-BGA packaging carrier plate comprises the following components in parts by weight:
the novel FC-BGA encapsulating carrier plate is used for the layer-adding adhesive film, wherein the modified cyanate is selected from one or more of bisphenol A cyanate, bisphenol E cyanate, dicyclopentadiene cyanate, phenolic cyanate or phosphorus cyanate.
The novel layer-adding adhesive film for the FC-BGA packaging carrier plate is characterized in that the phosphorus-containing cyanate is selected from one or more of phosphorus-containing cyanate (I), phosphorus-containing cyanate (II), phosphorus-containing cyanate (III) and phosphorus-containing cyanate (IV).
The novel FC-BGA encapsulating carrier plate is used for a build-up adhesive film, wherein the bismaleimide resin is selected from one or more of phenol type bismaleimide resin, diphenylmethane bismaleimide resin, diaminobenzene bismaleimide resin, diaminodiphenylmethane bismaleimide resin or aliphatic bismaleimide resin.
The novel FC-BGA encapsulating carrier plate is a build-up adhesive film, wherein the polyphenyl ether is selected from one or more of epoxy modified polyphenyl ether, carbon-carbon unsaturated double bond modified polyphenyl ether, phenol modified polyphenyl ether, allyl modified polyphenyl ether or hydroxyl modified polyphenyl ether.
The novel FC-BGA encapsulating carrier plate is a layer-adding adhesive film, wherein the hydroxyl modified polyphenyl ether is hydroxyl modified polyphenyl ether (I) and/or hydroxyl modified polyphenyl ether (II).
The novel FC-BGA encapsulating carrier plate is used for a layer-adding adhesive film, wherein the modified benzoxazine is selected from one or more of bisphenol A type polybenzoxazine, naphthol type polybenzoxazine, unsaturated bond-containing polybenzoxazine, diamine type polybenzoxazine or DOPO-containing benzoxazine.
The novel layer-adding adhesive film for the FC-BGA packaging carrier plate is characterized in that the DOPO-containing benzoxazine is selected from one or more of DOPO-containing benzoxazine (I), DOPO-containing benzoxazine (II), DOPO-containing benzoxazine (III) and DOPO-containing benzoxazine (IV).
The layer-adding adhesive film for the novel FC-BGA packaging carrier plate further comprises 2-5 parts by mass of a curing accelerator, 1-2 parts by mass of other auxiliaries and 100-300 parts by mass of an organic solvent;
wherein the other auxiliary agent is selected from one or more of a leveling agent, a defoaming agent or a coupling agent.
The glue-coated copper foil comprises a copper foil, a layer-adding adhesive film coated on the rough surface of the copper foil, and a protective film attached to the layer-adding adhesive film and far away from one surface of the copper foil; the layer-adding adhesive film is the layer-adding adhesive film for the novel FC-BGA packaging carrier plate.
Has the advantages that: the invention provides a novel layer-adding adhesive film for an FC-BGA (fiber channel-ball grid array) packaging carrier plate and a glue-coated copper foil manufactured by using the same, wherein the layer-adding adhesive film comprises the following components in parts by weight: 25-40 parts of epoxy resin, 40-45 parts of inorganic filler, 35-45 parts of modified cyanate ester, 35-45 parts of bismaleimide resin, 25-30 parts of polyphenyl ether and 10-20 parts of modified benzoxazine. The bismaleimide resin with good dielectric property and the polyphenyl ether are selected, the modified cyanate ester and the modified benzoxazine are added to introduce an aliphatic structure and a large-volume functional group, and the polyphenyl ether and the modified cyanate ester react to generate the triazine ring, so that the dielectric constant and the dielectric loss of the adhesive coated copper foil are reduced; in addition, by means of the synergistic effect of nitrogen and phosphorus in the modified cyanate ester and the modified benzoxazine, the flame retardant efficiency and the high temperature resistance of the layer-adding adhesive film are effectively improved, so that the adhesive coated copper foil coated with the layer-adding adhesive film is suitable for ultra-large scale integrated circuits, chip packaging and PCB circuit boards.
Drawings
Fig. 1 is a schematic view of the structure of the rubberized copper foil of the invention.
Detailed Description
The invention provides a novel layer-adding adhesive film for an FC-BGA (fiber channel-ball grid array) packaging carrier plate and a glued copper foil manufactured by using the same, and the invention is further described in detail below in order to make the purpose, the technical scheme and the effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The dielectric constant and dielectric loss of the insulating resin dielectric layer material used in the existing high-frequency and high-speed Printed Circuit Board (PCB) are high, which easily causes the weakening of signal transmission; and poor high temperature resistance and flame retardance, and the reliability of the cable is reduced at high frequency and high speed.
Therefore, how to reduce the dielectric constant and dielectric loss of the insulating adhesive film, thereby realizing the improvement of the signal transmission speed and the circuit density and avoiding the distortion of the signal transmission of the PCB; meanwhile, the high temperature resistance and the flame retardant property of the insulating adhesive film are ensured, and the reliability of the product in practical application is improved, so that the technical problem to be solved urgently at present is solved.
Based on the above, the invention provides a novel layer-adding adhesive film for an FC-BGA (fiber channel-ball grid array) packaging carrier plate, which comprises the following components in parts by weight:
polyphenylene Oxide (PPO) has the advantages of good dielectric property, heat resistance, extremely low water absorption rate and the like, and meets the development requirements of miniaturization, multifunctionalization and light weight of 5G communication high-frequency electronic components.
According to the invention, the bismaleimide resin and the polyphenyl ether have good dielectric properties, meanwhile, the modified cyanate ester and the modified benzoxazine are added into the components, the aliphatic structure and the bulky functional group are introduced, and the polyphenyl ether and the modified cyanate ester react to generate the triazine ring, so that the aims of reducing the dielectric constant and dielectric loss of the gummed copper foil are fulfilled; in addition, by means of the synergistic effect of nitrogen and phosphorus in the modified cyanate ester and the modified benzoxazine, the flame retardant efficiency and the high temperature resistance of the layer-adding adhesive film are effectively improved, so that the copper foil coated with the layer-adding adhesive film realizes the effects of improving the signal transmission speed and the circuit density, and the signal transmission distortion of a PCB (printed circuit board) is avoided; meanwhile, the high-temperature resistance and the flame retardant property of the coated copper foil are ensured, and the reliability of the product in practical application is improved. And the copper foil coated with the layer-adding adhesive film can be applied to ultra-large scale integrated circuits, chip packaging and PCB (printed circuit board).
In some embodiments, the epoxy resin includes, but is not limited to: 128E (Macrochang), 828US (Mitsubishi chemical company), 1750 (Mitsubishi chemical company), ZX1059 (New day iron), 2021P (xylonite), SQCN704H (Shandong Shengquan company), HP7200 (Japanese DIC company), HP4700 (Japanese DIC company), and HP4710 (Japanese DIC company).
Preferably, the epoxy resin may be 25 parts, 30 parts, 35 parts, or 40 parts by weight.
In some embodiments, the inorganic filler is silica and/or modified silica; exemplary include, but are not limited to: SQ023 (Suzhou brocade company), SC2050-MB (Yadama company, Japan), SC-2500-SEJ (Yadama company, Japan). Preferably, the inorganic filler may be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, or 45 parts by weight.
In some embodiments, the modified cyanate ester is selected from one or more of bisphenol a type cyanate ester, bisphenol E type cyanate ester, dicyclopentadiene type cyanate ester, phenolic type cyanate ester, or phosphorous-containing cyanate ester.
In a preferred embodiment, the modified cyanate ester is a phosphorus-containing cyanate ester; when the cyanate containing phosphorus is combusted, the phosphorus group can generate a phosphaphenanthrene group in a gas phase, and can capture a free radical of gas phase cracking gas to form a stable structure and play a role in quenching the free radical; the nitrogen-containing structure can also obtain a hindered amine structure with a quenching effect, form non-combustible gas and play a role in gas phase dilution, and the nitrogen-containing structure can be mutually cooperated in gas phase to enhance the flame retardant effect; according to the invention, by introducing phosphorus element into cyanate (containing nitrogen) and by means of phosphorus-nitrogen synergistic flame retardant effect, the flame retardant efficiency and high temperature resistance of the layer-adding adhesive film (insulating adhesive film) are effectively improved.
Specifically, the phosphorus-containing cyanate is selected from one or more of phosphorus-containing cyanate (I), phosphorus-containing cyanate (II), phosphorus-containing cyanate (III) and phosphorus-containing cyanate (IV);
the structural formula of the phosphorus-containing cyanate (I) is shown as
The structural formula of the phosphorus-containing cyanate (II) is shown as
The structural formula of the phosphorus-containing cyanate (III) is shown as
The structural formula of the cyanate (IV) containing phosphorus is shown as
In some embodiments, the bismaleimide resin is selected from one or more of a phenol type bismaleimide resin, a diphenylmethane type bismaleimide resin, a diaminobenzene type bismaleimide resin, a diaminodiphenylmethane type bismaleimide resin, or an aliphatic bismaleimide resin.
In a preferred embodiment, the bismaleimide resin is an aliphatic bismaleimide resin; by introducing the aliphatic structure into the bismaleimide resin and by means of the characteristic that the aliphatic structure has low polar bonds, the molecular polarizability of the material can be reduced, and the dielectric constant and the dielectric loss are further reduced, so that the purpose of low dielectric property of the build-up adhesive film is achieved.
In some embodiments, the polyphenylene ether is selected from one or more of epoxy-modified polyphenylene ether, carbon-carbon unsaturated double bond-modified polyphenylene ether, phenol-modified polyphenylene ether, allyl-modified polyphenylene ether, or hydroxyl-modified polyphenylene ether.
In a preferred embodiment, the polyphenylene ether is a hydroxyl-modified polyphenylene ether. The compatibility of an epoxy resin/polyphenyl ether system is poor, and the hydroxyl modified polyphenyl ether can be connected with the epoxy resin by virtue of a covalent bond and keeps a cross-linked structure and high strength; meanwhile, the hydroxyl modified polyphenyl ether can react with-OCN group in the modified cyanate ester to form imine-carbonate, and further reacts with-OCN group to produce triazine ring, so that the dielectric constant and dielectric loss of the layer-adding adhesive film are reduced.
Specifically, the hydroxyl modified polyphenylene ether is hydroxyl modified polyphenylene ether (I) and/or hydroxyl modified polyphenylene ether (II);
the structural formula of the hydroxyl modified polyphenyl ether (I) is shown as
The structural formula of the hydroxyl modified polyphenyl ether (II) is shown as
In some embodiments, the modified benzoxazine is selected from one or more of bisphenol a type polybenzoxazine, naphthol type polybenzoxazine, unsaturated bond containing type polybenzoxazine, diamine type polybenzoxazine, or DOPO containing benzoxazine.
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) belongs to the category of hexabasic phosphaphosphinate of organic phosphacycle compounds, and is a novel flame retardant intermediate; the structure of the derivative contains P-H bonds, has high activity on olefin, epoxy bonds and carbonyl groups, and can react to generate a plurality of derivatives.
In a preferred embodiment, the modified benzoxazine is DOPO-containing benzoxazine. The benzoxazine containing DOPO has a biphenyl rigid structure, the heat resistance and the mechanical property are good, the biphenyl rigid structure belongs to a large-volume functional group, the chemical bond polarizability is low, the free volume of a polymer can be increased, and the dielectric property of a layer-adding adhesive film can be effectively improved; meanwhile, DOPO has a hypophosphite structure and high thermal stability, and the DOPO (containing phosphorus) is introduced into benzoxazine (containing nitrogen), so that the flame retardant property and the high temperature resistance of the layer-adding adhesive film can be improved through the synergistic action of phosphorus and nitrogen.
Specifically, the DOPO-containing benzoxazine is selected from one or more of DOPO-containing benzoxazine (I), DOPO-containing benzoxazine (II), DOPO-containing benzoxazine (III) and DOPO-containing benzoxazine (IV);
the structural formula of the benzoxazine (I) containing DOPO is shown as
The structural formula of the benzoxazine (II) containing DOPO is shown as
The structural formula of the benzoxazine (III) containing DOPO is shown as
The structural formula of the benzoxazine (IV) containing DOPO is shown as
In some embodiments, the novel layer-adding adhesive film for the FC-BGA package carrier plate further comprises 2-5 parts by mass of a curing accelerator, 1-2 parts by mass of other auxiliaries and 100-300 parts by mass of an organic solvent; wherein the other auxiliary agent is selected from one or more of a leveling agent, a defoaming agent or a coupling agent.
In a preferred embodiment, the cure accelerator is selected from one or more of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dimethylol imidazole or 2-phenyl-4-methyl-5-hydroxymethyl imidazole;
the leveling agent is selected from one or more of BYK-306, BYK-310, BYK-330, BYK-S706, BYK-333, BYK-390, BYK-392 or FC-4430;
the defoaming agent is one or more of DP-60 defoaming agent, DP-61 defoaming agent, DP-62 defoaming agent, DP-63 defoaming agent produced by Guangdong Tianfeng defoaming company, or BYK-530 and BYK-520 produced by Germany Bikko company;
the coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (N-cyclohexylamino) -propyltrimethoxysilane, N- (N-butyl) -3-aminopropyltriethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, bis (3-triethoxysilylpropyl) amine or bis (3-trimethoxysilylpropyl) amine;
the organic solvent is selected from one or more of toluene, xylene, acetone, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate and N, N-dimethylformamide.
According to the novel layer-adding adhesive film for the FC-BGA packaging carrier plate, in a raw material formula, a phosphorus-containing cyanate is selected, a phosphorus element is introduced into the cyanate (containing nitrogen), a phosphaphenanthrene group generated by a phosphorus group and a hindered amine structure formed by a nitrogen-containing structure are cooperated with each other in a gas phase, so that the flame retardant effect is enhanced, and the flame retardant efficiency and the high temperature resistance of the layer-adding adhesive film (an insulating adhesive layer) are effectively improved by means of the phosphorus-nitrogen cooperation flame retardant effect; secondly, aliphatic bismaleimide resin is selected, and the molecular polarizability of the material is reduced by virtue of the characteristic that an aliphatic structure has low polar bonds; meanwhile, the hydroxyl modified polyphenyl ether reacts with-OCN group in cyanate to form imine-carbonate, and further reacts with-OCN group to generate triazine ring; the aliphatic bismaleimide resin and the hydroxyl modified polyphenyl ether act together to reduce the dielectric constant and dielectric loss of the insulating adhesive film; the DOPO-containing benzoxazine is selected, and has a biphenyl rigid structure, so that the heat resistance and the mechanical property are good, the biphenyl rigid structure belongs to a large-volume functional group, the chemical bond polarizability is low, the free volume of a polymer can be increased, and the dielectric property of the insulating adhesive film can be effectively improved; meanwhile, DOPO has a hypophosphite structure and is high in thermal stability, and DOPO (containing phosphorus) is introduced into benzoxazine (containing nitrogen), so that the flame retardant property and the high temperature resistance of the insulating adhesive film can be improved through the synergistic effect of nitrogen and phosphorus, and the layer-adding adhesive film is suitable for a super-large-scale integrated circuit, chip packaging and a PCB (printed circuit board), so that the signal transmission speed and the circuit density are improved, the signal distortion of the PCB is avoided, and the reliability of the product in practical application is improved.
In addition, as shown in fig. 1, the invention also provides a glued copper foil, which comprises a copper foil 10, a layer-adding adhesive film 20 coated on the rough surface of the copper foil, and a protective film 30 attached to the layer-adding adhesive film 20 and far away from the copper foil 10; the layer-adding adhesive film 20 is the layer-adding adhesive film for the novel FC-BGA package carrier board.
Specifically, the adhesive coated copper foil comprises a copper foil 10, a layer-adding adhesive film 20 and a protective film 30 which are sequentially stacked.
In some embodiments, the copper foil is a carrier copper foil, a rolled copper foil, or an electrolytic copper foil; the thickness of the copper foil is 2-35 mu m.
In some embodiments, the thickness of the layer-adding adhesive film is 10 to 150 μm; the thickness of the protective film is 12-50 mu m.
In some embodiments, the protective film is a PP film or a PET film.
In some embodiments, to prepare the gummed copper foil, a preparation method thereof includes the steps of:
step S10: stirring and mixing epoxy resin, inorganic filler, modified cyanate ester, bismaleimide resin, polyphenyl ether, modified benzoxazine, a curing agent, other auxiliaries and an organic solvent to obtain a resin composition;
step S20: coating the resin composition on the rough surface of the copper foil, and drying to obtain the copper foil with a layer-adding adhesive film;
step S30: and (3) attaching a protective film to one surface of the layer-adding adhesive film, which is far away from the copper foil, so as to obtain the adhesive coated copper foil.
In some embodiments, the temperature for stirring and mixing in the step S10 is 15-30 ℃; the stirring time is 40-240 min, and the stirring speed is 90-300 rpm.
In a preferred embodiment, after the stirring and mixing in step S10, the resin composition is further filtered and purified; and filtering the resin composition by using filter screens of 300 meshes, 500 meshes and 1000 meshes in sequence, and then removing impurities by using a 12000GS magnetic rod, so that the resin composition is fine and smooth and does not contain impurities.
In some embodiments, the drying temperature in the step S20 is 70-120 ℃; the drying time is 3-15 min.
In some embodiments, the bonding temperature is 40 to 100 ℃ and the bonding pressure is 2 to 8MPa when the protective film is bonded in the step S30.
In addition, the invention also provides application of the gummed copper foil in ultra-large scale integrated circuits, chip packaging and PCB circuit boards.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings.
Some of the component sources in the following examples and comparative examples are as follows:
epoxy resin: HP7200 (Nippon DIC Co.), 828US (Mitsubishi chemical Co.);
inorganic filler: SC-2500-SEJ (Yadama, Japan), SQ023 (Suzhou brocade company);
cyanate ester: BADCy (Lonza, switzerland);
bismaleimide: 4, 4-diphenylmethane bismaleimide (CAS number: 13676-54-5), LTY21006 (Guangdong TYADMT Co.);
polyphenylene ether resin: SA90 (saut Sabic), SA120 (saut Sabic);
leveling agent: BYK-310, BYK-330 (Bick, Germany);
defoaming agent: DP-60, DP-61 (Guangdong Tianfeng Co.);
carrier copper foil: MT18SD-H, MT18EX (Mitsui metals, Japan);
rolling the copper foil: RCF-TNBG (Fuda metals, Suzhou);
electrolytic copper foil: JCF-FCF-R (Jongcoph Yetz foil);
and (3) PP film: ZYGQ36U (orthowave, eastern guan);
PET film: DFTR11W0-36SH6 (Sichuan Dong wood Co.).
Example 1
The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a carrier copper foil, a layer-adding adhesive film layer and a PET film which are sequentially overlapped;
the thickness of the carrier copper foil (MT18SD-H) is 2 μm, the thickness of the layer-adding adhesive film layer is 40 μm, and the thickness of the PET film is 38 μm;
the layer-adding adhesive film layer is made of a resin composition;
the resin composition comprises the following raw material components in parts by weight: 40 parts of dicyclopentadiene epoxy resin (HP7200), 40 parts of silicon dioxide (SC-2500-SEJs), 35 parts of bisphenol A cyanate ester monomer (BADCy), 35 parts of aliphatic bismaleimide resin (LTY21006), 25 parts of polyphenylene ether resin (SA90), 10 parts of benzoxazine (I) containing DOPO, 5 parts of 1-cyanoethyl-2-ethyl-4 methylimidazole, 1 part of BYK-310 leveling agent, 1 part of DP-60 defoaming agent and 300 parts of acetone.
The preparation method of the adhesive coated copper foil comprises the following steps:
(1) mixing and stirring all components of the resin composition for 240min at the temperature of 30 ℃ and the rotating speed of 100rpm to obtain a uniform mixed solution, sequentially passing the mixed solution through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.
(2) Coating the resin composition on the rough surface of the carrier copper foil, and drying at 100 ℃ for 8min to obtain the carrier copper foil with the layer-adding adhesive film layer;
(3) and (3) attaching the PET film to the surface of the layer-adding adhesive film layer far away from the carrier copper foil under the conditions of 70 ℃ and the pressure of 5MPa to obtain the adhesive coated copper foil.
Example 2
The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a carrier copper foil, a layer-adding adhesive film layer and a PET film which are sequentially overlapped;
the thickness of the carrier copper foil (MT18EX) is 5 micrometers, the thickness of the layer-adding adhesive film layer is 10 micrometers, and the thickness of the PET film is 12 micrometers;
the layer-adding adhesive film layer is made of a resin composition;
the resin composition comprises the following raw material components in parts by weight: 40 parts of dicyclopentadiene epoxy resin (HP7200), 40 parts of silicon dioxide (SC-2500-SEJs), 35 parts of phosphorus-containing cyanate (II), 35 parts of aliphatic bismaleimide resin (LTY21006), 25 parts of polyphenylene oxide resin (SA90), 10 parts of benzoxazine (I) containing DOPO, 5 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 part of BYK-310 flatting agent, 1 part of DP-60 defoaming agent and 300 parts of acetone.
The preparation method of the adhesive coated copper foil comprises the following steps:
(1) mixing and stirring all components of the resin composition for 240min at the temperature of 30 ℃ and the rotating speed of 100rpm to obtain a uniform mixed solution, sequentially passing the mixed solution through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.
(2) Coating the resin composition on the rough surface of the carrier copper foil, and drying at 70 ℃ for 15min to obtain the carrier copper foil with the layer-adding adhesive film layer;
(3) and (3) attaching the PET film to the surface of the layer-adding adhesive film layer far away from the carrier copper foil under the conditions of 40 ℃ and the pressure of 8MPa to obtain the adhesive coated copper foil.
Example 3
The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a rolled copper foil, a layer-adding adhesive film layer and a PBT film which are sequentially stacked;
the thickness of the rolled copper foil is 12 micrometers, the thickness of the layer-adding adhesive film layer is 150 micrometers, and the thickness of the PET film is 50 micrometers;
the layer-adding adhesive film layer is made of a resin composition;
the resin composition comprises the following raw material components in parts by weight: 40 parts of dicyclopentadiene epoxy resin (HP7200), 40 parts of silicon dioxide (SC-2500-SEJs), 35 parts of phosphorus-containing cyanate (II), 35 parts of aliphatic bismaleimide resin (LTY21006), 25 parts of hydroxyl modified polyphenylene ether resin (I), 10 parts of benzoxazine containing DOPO (I), 5 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 part of BYK-310 flatting agent, 1 part of DP-60 defoaming agent and 300 parts of acetone.
The preparation method of the adhesive coated copper foil comprises the following steps:
(1) mixing and stirring all components of the resin composition for 240min at the temperature of 30 ℃ and the rotating speed of 100rpm to obtain a uniform mixed solution, sequentially passing the mixed solution through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.
(2) Coating the resin composition on the rough surface of the rolled copper foil, and drying at 120 ℃ for 3min to obtain the rolled copper foil with the layer-adding adhesive film layer;
(3) and (3) attaching the PET film to the surface of the layer-adding adhesive film layer far away from the rolled copper foil under the conditions of 100 ℃ and the pressure of 2MPa to obtain the adhesive coated copper foil.
Example 4
The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises an electrolytic copper foil, a layer-adding adhesive film layer and a PP film which are sequentially overlapped;
the thickness of the electrolytic copper foil is 35 mu m, the thickness of the layer-adding adhesive film layer is 60 mu m, and the thickness of the PP film is 18 mu m;
the layer-adding adhesive film layer is made of a resin composition;
the resin composition comprises the following raw material components in parts by weight: 25 parts of bisphenol A type epoxy resin (828US), 45 parts of silicon dioxide (SQ023), 45 parts of phosphorus-containing cyanate ester (I), 45 parts of 4, 4-diphenylmethane bismaleimide (CAS:13676-54-5), 30 parts of polyphenylene oxide resin (SA120), 10 parts of benzoxazine (II) containing DOPO, 2 parts of 2-phenyl-4, 5-dimethylol imidazole, 1 part of BYK-330 flatting agent, 1 part of DP-61 defoaming agent and 100 parts of cyclohexanone.
The preparation method of the adhesive coated copper foil comprises the following steps:
(1) mixing and stirring all components of the resin composition for 240min at the temperature of 30 ℃ and the rotating speed of 100rpm to obtain a uniform mixed solution, sequentially passing the mixed solution through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.
(2) Coating the resin composition on the rough surface of the electrolytic copper foil, and drying at 90 ℃ for 10min to obtain the electrolytic copper foil with the layer-adding adhesive film layer;
(3) and adhering a PP film to one surface of the layer-adding adhesive film layer, which is far away from the electrolytic copper foil, under the conditions of 80 ℃ and 4MPa to obtain the adhesive coated copper foil.
Example 5
The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a carrier copper foil, a layer-adding adhesive film layer and a PET film which are sequentially overlapped;
the thickness of the carrier copper foil (MT18SD-H) is 2 μm, the thickness of the layer-adding adhesive film layer is 40 μm, and the thickness of the PET film is 38 μm;
the layer-adding adhesive film layer is made of a resin composition;
the resin composition comprises the following raw material components in parts by weight: 25 parts of bisphenol A type epoxy resin (828US), 45 parts of silicon dioxide (SQ023), 45 parts of phosphorus-containing cyanate ester (I), 45 parts of aliphatic bismaleimide resin (LTY21006), 30 parts of polyphenyl ether resin (SA120), 10 parts of benzoxazine (II) containing DOPO, 2-phenyl-4, 5-dimethylolimidazole, 1 part of BYK-330 leveling agent, 1 part of DP-61 defoaming agent and 100 parts of cyclohexanone.
The preparation method of the adhesive coated copper foil comprises the following steps:
(1) mixing and stirring all components of the resin composition for 240min at the temperature of 30 ℃ and the rotating speed of 100rpm to obtain a uniform mixed solution, sequentially passing the mixed solution B through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.
(2) Coating the resin composition on the rough surface of the carrier copper foil, and drying at 100 ℃ for 8min to obtain the carrier copper foil with the layer-adding adhesive film layer;
(3) and (3) attaching the PET film to the surface of the layer-adding adhesive film layer far away from the carrier copper foil under the conditions of 70 ℃ and the pressure of 5MPa to obtain the adhesive coated copper foil.
Example 6
The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a carrier copper foil, a layer-adding adhesive film layer and a PET film which are sequentially overlapped;
the thickness of the carrier copper foil (MT18SD-H) is 2 μm, the thickness of the layer-adding adhesive film layer is 40 μm, and the thickness of the PET film is 38 μm;
the layer-adding adhesive film layer is made of a resin composition;
the resin composition comprises the following raw material components in parts by weight: 25 parts of bisphenol A type epoxy resin (828US), 45 parts of silicon dioxide (SQ023), 45 parts of phosphorus-containing cyanate ester (I), 45 parts of aliphatic bismaleimide resin (LTY21006), 30 parts of hydroxyl modified polyphenylene ether resin (II), 10 parts of benzoxazine (II) containing DOPO, 2-phenyl-4, 5-dimethylolimidazole, 1 part of BYK-330 leveling agent, 1 part of DP-61 defoaming agent and 100 parts of cyclohexanone.
The preparation method of the adhesive coated copper foil comprises the following steps:
(1) mixing and stirring all components of the resin composition for 240min at the temperature of 30 ℃ and the rotating speed of 100rpm to obtain a uniform mixed solution, sequentially passing the mixed solution B through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.
(2) Coating the resin composition on the rough surface of the carrier copper foil, and drying at 100 ℃ for 8min to obtain the carrier copper foil with the layer-adding adhesive film layer;
(3) and (3) attaching the PET film to the surface of the layer-adding adhesive film layer far away from the carrier copper foil under the conditions of 70 ℃ and the pressure of 5MPa to obtain the adhesive coated copper foil.
Comparative example 1
This comparative example provides a rubberized copper foil and a method for manufacturing the same, which are different from example 1 in that the resin polymer is not added with the aliphatic bismaleimide resin (LTY21006) and the DOPO-containing benzoxazine (i), and other conditions are the same as example 1.
Comparative example 2
This comparative example provides a rubberized copper foil and a method for manufacturing the same, which are different from example 4 in that the resin polymer is not added with the phosphorus-containing cyanate (i) and the DOPO-containing benzoxazine (ii), and other conditions are the same as example 4.
The performance of the gummed copper foils or resin compositions provided in the above examples and comparative examples was tested by the following methods:
dielectric constant and dielectric loss tangent: testing according to the method specified by IPC-TM-6502.5.5.9;
insulating property: testing the Insulation of the layer-adding adhesive film layer according to 'GX 13 Insulation Reliability/b-HAST (130 ℃, 85% RH, 3.3V)', and after the testing time exceeds 200h, if the layer-adding adhesive film layer still has the Insulation, no testing is carried out, and the testing time is recorded as '200 h', and if the layer-adding adhesive film layer fails in the testing process and does not have the Insulation, the testing time is recorded;
flame retardancy: the combustibility was measured according to the method specified in UL 94;
high temperature resistance: the test was carried out according to the method specified in IPC-TM-6502.6.8.
The results of the test standards for the performance of the gummed copper foils provided in the above examples and comparative examples are shown in the following table:
in summary, the invention provides a novel layer-adding adhesive film for an FC-BGA package carrier and a glue-coated copper foil manufactured by using the same, wherein the layer-adding adhesive film comprises the following components in parts by weight: 25-40 parts of epoxy resin, 40-45 parts of inorganic filler, 35-45 parts of modified cyanate ester, 35-45 parts of bismaleimide resin, 25-30 parts of polyphenyl ether and 10-20 parts of modified benzoxazine. The bismaleimide resin with good dielectric property and the polyphenyl ether are selected, the modified cyanate ester and the modified benzoxazine are added to introduce an aliphatic structure and a large-volume functional group, and the polyphenyl ether and the modified cyanate ester react to generate the triazine ring, so that the dielectric constant and the dielectric loss of the adhesive coated copper foil are reduced; in addition, by means of the synergistic effect of nitrogen and phosphorus in the modified cyanate ester and the modified benzoxazine, the flame retardant efficiency and the high temperature resistance of the layer-adding adhesive film are effectively improved, so that the adhesive coated copper foil coated with the layer-adding adhesive film is suitable for ultra-large scale integrated circuits, chip packaging and PCB circuit boards.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A novel layer-adding adhesive film for an FC-BGA (fiber channel-ball grid array) packaging carrier plate is characterized by comprising the following components in parts by weight:
2. the laminated adhesive film for the novel FC-BGA package carrier board according to claim 1, wherein the modified cyanate ester is selected from one or more of bisphenol A cyanate ester, bisphenol E cyanate ester, dicyclopentadiene cyanate ester, phenolic cyanate ester, or phosphorous cyanate ester.
3. The novel layer-adding adhesive film for the FC-BGA package carrier plate as claimed in claim 2, wherein the phosphorus-containing cyanate is selected from one or more of phosphorus-containing cyanate (I), phosphorus-containing cyanate (II), phosphorus-containing cyanate (III), and phosphorus-containing cyanate (IV);
the structural formula of the phosphorus-containing cyanate (I) is shown as
The structural formula of the phosphorus-containing cyanate (II) is shown as
The structural formula of the phosphorus-containing cyanate (III) is shown as
The structural formula of the cyanate (IV) containing phosphorus is shown as
4. The novel FC-BGA package carrier plate build-up adhesive film of claim 1, wherein the bismaleimide resin is selected from one or more of phenol type bismaleimide resin, diphenylmethane bismaleimide resin, diaminobenzene bismaleimide resin, diaminodiphenylmethane bismaleimide resin and aliphatic bismaleimide resin.
5. The novel FC-BGA package carrier plate layer-adding adhesive film as claimed in claim 1, wherein the polyphenylene ether is selected from one or more of epoxy modified polyphenylene ether, carbon-carbon unsaturated double bond modified polyphenylene ether, phenol modified polyphenylene ether, allyl modified polyphenylene ether or hydroxyl modified polyphenylene ether.
6. The novel FC-BGA package carrier plate build-up adhesive film of claim 5, wherein the hydroxyl-modified polyphenylene ether is hydroxyl-modified polyphenylene ether (I) and/or hydroxyl-modified polyphenylene ether (II);
the structural formula of the hydroxyl modified polyphenyl ether (I) is shown as
The structural formula of the hydroxyl modified polyphenyl ether (II) is shown as
7. The novel layer-adding adhesive film for the FC-BGA package carrier plate according to claim 1, wherein the modified benzoxazine is selected from one or more of bisphenol A type polybenzoxazine, naphthol type polybenzoxazine, unsaturated bond-containing polybenzoxazine, diamine type polybenzoxazine or DOPO-containing benzoxazine.
8. The novel layer-adding adhesive film for the FC-BGA package carrier plate as claimed in claim 7, wherein the DOPO-containing benzoxazine is selected from one or more of DOPO-containing benzoxazine (I), DOPO-containing benzoxazine (II), DOPO-containing benzoxazine (III) and DOPO-containing benzoxazine (IV);
the structural formula of the benzoxazine (I) containing DOPO is shown as
The structural formula of the benzoxazine (II) containing DOPO is shown as
The structural formula of the benzoxazine (III) containing DOPO is shown as
The structural formula of the benzoxazine (IV) containing DOPO is shown as
9. The novel layer-adding adhesive film for the FC-BGA package carrier plate as claimed in claim 1, further comprising 2-5 parts by mass of a curing accelerator, 1-2 parts by mass of other additives, and 100-300 parts by mass of an organic solvent;
wherein the other auxiliary agent is selected from one or more of a leveling agent, a defoaming agent or a coupling agent.
10. The glue-coated copper foil is characterized by comprising a copper foil, a layer-adding adhesive film coated on the rough surface of the copper foil, and a protective film attached to the layer-adding adhesive film and far away from one surface of the copper foil;
the layer-adding adhesive film is the layer-adding adhesive film for the novel FC-BGA package carrier board as recited in any one of claims 1 to 9.
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