[go: up one dir, main page]

WO2024108837A1 - 低介电损耗的积层膜、其制备方法及电路基板结构 - Google Patents

低介电损耗的积层膜、其制备方法及电路基板结构 Download PDF

Info

Publication number
WO2024108837A1
WO2024108837A1 PCT/CN2023/084227 CN2023084227W WO2024108837A1 WO 2024108837 A1 WO2024108837 A1 WO 2024108837A1 CN 2023084227 W CN2023084227 W CN 2023084227W WO 2024108837 A1 WO2024108837 A1 WO 2024108837A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
weight
laminated film
low dielectric
dielectric loss
Prior art date
Application number
PCT/CN2023/084227
Other languages
English (en)
French (fr)
Inventor
伍得
王�义
廖述杭
苏峻兴
Original Assignee
武汉市三选科技有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 武汉市三选科技有限公司 filed Critical 武汉市三选科技有限公司
Priority to US18/523,968 priority Critical patent/US12098230B2/en
Publication of WO2024108837A1 publication Critical patent/WO2024108837A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676—Single layer compositions

Definitions

  • the present application relates to the technical field of integrated circuit packaging, and in particular to a laminated film with low dielectric loss, a preparation method thereof, and a circuit substrate structure.
  • Low-loss materials can be used not only as substrates or PCB boards, but also in advanced packaging, such as Antenna in Package (AiP). As the frequency moves toward millimeter waves, the size of antenna elements will continue to decrease, down to the point where the antenna array can be placed in the package shell.
  • This integration method helps shorten the RF path and minimize transmission losses, but at the same time requires the use of low-loss materials as substrates. Therefore, the development of low-dielectric-loss laminated film materials is in line with current market demand.
  • the purpose of the present application is to provide a laminated film with low dielectric loss, a preparation method thereof and a circuit substrate structure, wherein the laminated film has both low dielectric loss and high tensile strength.
  • the present application provides a laminated film with low dielectric loss, wherein the raw materials include 5-10 parts by weight of indene oligomer monofunctional benzoxazine, 40-65 parts by weight of aromatic polymerized polymaleimide, 30-50 parts by weight of allyl benzoxazine, 0.1-3 parts by weight of initiator, 250-400 parts by weight of inorganic filler, and 0.1-5 parts by weight of silane coupling agent;
  • the chemical structural formula of the indene oligomer monofunctional benzoxazine is , where R is , n and m are both integers, 1 ⁇ n ⁇ 10, 1 ⁇ m ⁇ 6.
  • the raw materials of the laminated film preferably include 8-10 parts by mass of indene oligomer monofunctional benzoxazine, 40-50 parts by mass of aromatic polymerized polymaleimide, 42-50 parts by mass of allyl benzoxazine, 0.1-3 parts by mass of initiator, 300-400 parts by mass of inorganic filler, and 0.1-5 parts by mass of silane coupling agent.
  • the indene oligomer monofunctional benzoxazine is prepared by the following method:
  • the initiator is selected from di-tert-butylcumene peroxide.
  • the inorganic filler is selected from silica.
  • the silane coupling agent is 3-glycidoxypropyltrimethoxysilane.
  • Another aspect of the present application provides a method for preparing a laminated film with low dielectric loss, as follows:
  • the mixed slurry is coated on the base film by a coating machine, and after drying, a laminated film is obtained on the base film.
  • the mixed slurry is coated on the base film by a coating machine, and after drying, a laminated film is obtained on the base film.
  • an embodiment of the present application provides a circuit substrate structure, which includes a central substrate layer and a laminated film; the laminated film is obtained by the following method: the laminated film prepared by the above preparation method is covered on the upper and/or lower surface of the central substrate layer, and then subjected to hot pressing and heat curing in sequence.
  • the circuit substrate covered with a low dielectric loss laminate film also has low loss characteristics. Using this circuit substrate to make integrated circuits and apply it to the 5G field can minimize transmission losses.
  • the laminated film of the present application has both low dielectric loss and high tensile strength.
  • the low dielectric loss enables it to be applied to the 5G field.
  • the laminated film of the present application can be used to package integrated circuit substrates, which is beneficial to minimize transmission loss.
  • the embodiment of the present application provides a laminated film with low dielectric loss, the raw materials of which include 5-10 parts by mass of indene oligomer monofunctional benzoxazine, 40-65 parts by mass of aromatic polymer polymaleimide, 30-50 parts by mass of allyl benzoxazine, 0.1-3 parts by mass of initiator, 250-400 parts by mass of inorganic filler, and 0.1-5 parts by mass of silane coupling agent.
  • R is , n and m are both integers, 1 ⁇ n ⁇ 10, 1 ⁇ m ⁇ 6.
  • the indene oligomer monofunctional benzoxazine is prepared by the following method:
  • n and m are both integers, 1 ⁇ n ⁇ 10, 1 ⁇ m ⁇ 6.
  • the initiator can decompose active free radicals under the action of heat to initiate the formation of cross-linked macromolecular polymers.
  • the initiator is a conventional initiator, such as an organic peroxide, preferably di-tert-butyl peroxide isopropylbenzene.
  • the initiator is used in a conventional amount, generally 0.1-3 parts by mass, and preferably 0.2 parts by mass in the embodiment of the present application.
  • the inorganic filler is selected from conventional inorganic fillers, such as silicon dioxide, titanium dioxide, calcium silicate, boron nitride, etc., preferably silicon dioxide.
  • the amount of the inorganic filler is conventional, preferably 250-400 parts by mass in the examples of the present application, and further preferably 250-300 parts by mass, 300-400 parts by mass.
  • the silane coupling agent is between the inorganic and organic interfaces, and is used to form a bonding layer of organic matrix-silane coupling agent-inorganic matrix at the interface, which plays a role in connecting materials with different properties.
  • the silane coupling agent selects a conventional silane coupling agent, preferably 3-glycidyloxypropyltrimethoxysilane, such as KMB-403 silane coupling agent on the market.
  • the amount of silane coupling agent is conventionally used, generally 0.1-5 parts by mass, and preferably 1 part by mass in the embodiment of the present application.
  • indene oligomer monofunctional benzoxazine, aromatic polymerized polymaleimide, and allyl benzoxazine are all resin monomers, which react to obtain polymers under the action of an initiator.
  • aromatic polymerized polymaleimide After curing, aromatic polymerized polymaleimide can show strong toughness, and has excellent properties such as high temperature resistance, moisture and heat resistance, high modulus, and high strength, and can achieve high flame retardancy and low dielectric loss.
  • the embodiment of the present application uses aromatic polymerized polymaleimide as the main resin monomer, and introduces indene oligomer monofunctional benzoxazine to blend and modify aromatic polymerized polymaleimide, to reduce the viscosity of aromatic polymerized polymaleimide prepolymer, and to improve the overall performance without affecting the dielectric properties.
  • allyl benzoxazine is introduced into the aromatic polymerized polymaleimide system, which can reduce the curing shrinkage of the system and make the system have a low dielectric constant and a low loss factor.
  • the amount of aromatic polymerized polymaleimide is 40-65 parts by mass, and more preferably 50-65 parts by mass and 40-50 parts by mass;
  • the amount of indene oligomer monofunctional benzoxazine is 5-10 parts by mass, and more preferably 5-8 parts by mass and 8-10 parts by mass;
  • the amount of allyl benzoxazine is 30-50 parts by mass, and more preferably 30-42 parts by mass and 42-50 parts by mass.
  • the laminated film of the present application is prepared by a coating process, and the method is as follows:
  • the base film generally uses a PET film.
  • the prepolymer When preparing the laminated film, the prepolymer is generally stirred at 110° C. to 150° C. for 25 to 40 minutes to obtain a clear prepolymer system.
  • the inorganic solvent may be, but is not limited to, propylene glycol methyl ether acetate.
  • the laminated film obtained in the embodiment of the present application can be used to prepare a low-loss circuit substrate.
  • the prepared circuit substrate structure includes: a central substrate layer and a laminated film after heat curing, and the laminated film after heat curing covers the upper and/or lower surface of the central substrate layer.
  • the preparation process of the circuit substrate is: the laminated film is bonded to the upper and/or lower surface of the central substrate layer, and pressurized and evacuated for 60 seconds at a temperature of 90°C and a pressure of 0.1MPa to make the laminated film fit better with the central substrate layer, and then heated and cured at a temperature of 150°C.
  • the laminated film can fill the surface gap of the central substrate layer and is tightly combined with the central substrate layer.
  • the obtained low-loss circuit substrate can be used to make circuits.
  • Aniline monomer and paraformaldehyde purchased from the market, tested in Shanghai;
  • Indene oligomer phenol Nippon Steel Corporation, model IP-100, its structural formula is as follows, wherein n and m are both integers, 1 ⁇ n ⁇ 10, 1 ⁇ m ⁇ 6:
  • Bisphenol F type benzoxazine Model BZ-130;
  • Aromatic polymerized polymaleimide commercially available MIR-3000 product, with the following structural formula, where n is an integer, 1 ⁇ n ⁇ 2:
  • Allylbenzoxazine Commercially available BZ-1706 product, its structural formula is as follows:
  • Di-tert-butyl peroxide isopropylbenzene BIPB used as initiator, commercially available, CAS No. 2212-81-9, its structural formula is as follows:
  • Silicon dioxide Spherical silicon powder with a particle size of 0.1 ⁇ 5 ⁇ m.
  • Silane coupling agent KMB-403 silane coupling agent.
  • Test method for fluidity Take a 5mm ⁇ 5mm square laminated film, clamp it between two copper sheets, bake it at 120°C for 5 minutes, and observe the flow distance of the laminated film on the copper sheet. If the flow distance exceeds 2mm, it means good fluidity, which is marked as ⁇ ; if it does not exceed 2mm, it means poor fluidity, which is marked as ⁇ .
  • Test method for dielectric constant Dk and loss factor Df Refer to IPC TM-650 2.5.5.13-2007 standard "Relative dielectric constant and loss tangent using split cylinder resonator", take a square laminated film sample of size 50mm ⁇ 70mm ⁇ 0.1mm, and use a network analyzer to test the dielectric constant Dk and loss factor Df of the sample at a frequency of 10GHz.
  • Test method for tensile strength Refer to GB/T 1040.1-2018 standard "Determination of tensile properties of plastics", take a laminated film specimen of size 200mm ⁇ 5mm ⁇ 1mm, use a universal tensile testing machine to stretch the specimen at a speed of 50mm/min, until the maximum tensile stress when the specimen breaks, that is, the tensile strength.
  • the performance parameter data of the embodiment and the comparative example are shown in Table 2. It can be seen from Table 2 that when indene oligomer benzoxazine and allyl benzoxazine are used to blend and modify aromatic polymerized polymaleimide, the dielectric loss can be reduced and the tensile strength can be improved. Indene oligomer benzoxazine can improve the shortcomings of diaromatic polymerized polymaleimide resin, such as poor solubility, high curing molding temperature and high brittleness of the cured product; and then allyl benzoxazine is introduced into the aromatic polymerized polymaleimide system through double bond addition reaction, which can reduce curing shrinkage and reduce dielectric loss.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

本发明公开了一种低介电损耗的积层膜、其制备方法及电路基板结构，该积层膜的原料包括包括5-10质量份茚低聚物单官能团苯并噁嗪，40-65质量份芳香基聚合多马来酰亚胺，30-50质量份烯丙基苯并噁嗪，0.1-3质量份引发剂，250-400质量份无机填料，0.1-5质量份硅烷偶联剂。本发明积层膜兼具低介电损耗和高拉伸强度，低介电损耗使其可应用于5G领域，例如可将本申请积层膜用于封装集成电路基板，有利于最大限度降低传输损耗。

Description

低介电损耗的积层膜、其制备方法及电路基板结构 技术领域
本申请涉及集成电路封装技术领域，具体涉及一种低介电损耗的积层膜、其制备方法及电路基板结构。
 背景技术
高频信号会导致严重的传输损耗，传输损耗是5G应用中天线设计和射频（RF）集成电路（IC）的痛点。随着未来5G毫米波的兴起，低损耗材料在5G应用领域发挥起重要的作用。低损耗材料不仅可用作基板或PCB板，还可用于先进封装，例如封装天线（Antenna in Package，AiP）。随着频率向毫米波方向发展，天线元件的尺寸将不断减小，减小至可将天线阵列置于封装壳内。这种集成方式有助于缩短射频路径，最大限度降低传输损耗，但同时需要采用低损耗材料作为基板。 所以研发低介电损耗积层膜材料是顺应目前市场需求的。
 发明内容
本申请的目的是提供一种低介电损耗的积层膜、其制备方法及电路基板结构，该积层膜同时具备低介电损耗和高拉伸强度。
为达到上述目的，本申请实施例一方面提供一种低介电损耗的积层膜，其原料包括包括5-10质量份茚低聚物单官能团苯并噁嗪，40-65质量份芳香基聚合多马来酰亚胺，30-50质量份烯丙基苯并噁嗪，0.1-3质量份引发剂，250-400质量份无机填料，0.1-5质量份硅烷偶联剂；
所述茚低聚物单官能团苯并噁嗪的化学结构式为 ，其中，R为 ，n和m均为整数，1≤n≤10，1≤m≤6。
在一些具体实施方式中，积层膜的原料优选包括8-10质量份茚低聚物单官能团苯并噁嗪，40-50质量份芳香基聚合多马来酰亚胺，42-50质量份烯丙基苯并噁嗪，0.1-3质量份引发剂，300-400质量份无机填料，0.1-5质量份硅烷偶联剂。
在一些具体实施方式中，茚低聚物单官能团苯并噁嗪采用如下方法制备：
按（1-1.2）：（1-1.4）：（2-2.4） 的摩尔比取苯胺单体、茚低聚物苯酚和多聚甲醛加入反应容器，同时加入有机反应溶剂；在80-150℃温度下保持搅拌4-15h进行曼尼奇反应，得茚低聚物单官能团苯并噁嗪。
在一些具体实施方式中，引发剂选择双叔丁基过氧化异丙基苯。
在一些具体实施方式中，无机填料选择二氧化硅。
在一些具体实施方式中，硅烷偶联剂选择3-缩水甘油醚氧基丙基三甲氧基硅烷。
本申请实施例另一方面提供一种低介电损耗的积层膜的制备方法，如下：
取5-10质量份茚低聚物单官能团苯并噁嗪和40-65质量份芳香基聚合多马来酰亚胺混合得预聚物，于110℃-150℃温度下搅拌预聚物；
待预聚物体系澄清，降至室温，加入30-50质量烯丙基苯并噁嗪、0.1-3质量份引发剂、250-400质量份无机填料、0.1-5质量份硅烷偶联剂和无机溶剂，经搅拌得混合浆料；
利用涂膜机将混合浆料涂覆于基膜上，经烘干，即在基膜上得到积层膜。
上述制备方法的优选方案为：
取8-10质量份茚低聚物单官能团苯并噁嗪和40-50质量份芳香基聚合多马来酰亚胺混合得预聚物，于110℃-150℃温度下搅拌预聚物；
待预聚物体系澄清，降至室温，加入42-50质量烯丙基苯并噁嗪、0.1-3质量份引发剂、300-400质量份无机填料、0.1-5质量份硅烷偶联剂和无机溶剂，经搅拌得混合浆料；
利用涂膜机将混合浆料涂覆于基膜上，经烘干，即在基膜上得到积层膜。
本申请实施例再一方面提供一种电路基板结构，其包括中心基板层和积层膜；所述积层膜通过如下方法获得：将上述制备方法所制备的积层膜覆盖于所述中心基板层的上和/或下表面，之后依次经热压、热固化。
覆盖了低介电损耗积层膜的电路基板，其同样具有低损耗特性，采用该电路基板制作集成电路，并应用于5G领域，可最大限度降低传输损耗。
本申请具有如下优点和有益效果：
本申请积层膜兼具低介电损耗和高拉伸强度，低介电损耗使其可应用于5G领域，例如可将本申请积层膜用于封装集成电路基板，有利于最大限度降低传输损耗。
 具体实施方式
为了使本申请的目的、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。
本申请实施例提供的一种低介电损耗的积层膜，其原料包括包括5-10质量份茚低聚物单官能团苯并噁嗪，40-65质量份芳香基聚合多马来酰亚胺，30-50质量份烯丙基苯并噁嗪，0.1-3质量份引发剂，250-400质量份无机填料，0.1-5质量份硅烷偶联剂。
本申请实施例中茚低聚物单官能团苯并噁嗪的化学结构式如下：
                 （Ⅰ）
其中，R为 ，n和m均为整数，1≤n≤10，1≤m≤6。
本申请实施例中茚低聚物单官能团苯并噁嗪采用如下方法制备：
按（1-1.2）：（1-1.4）：（2-2.4） 摩尔比取苯胺单体、茚低聚物苯酚和多聚甲醛加入反应容器，同时加入有机反应溶剂；在80-150℃温度下保持搅拌4-15h进行Mannich反应(曼尼奇反应)，得茚低聚物单官能团苯并噁嗪。
本申请实施例中茚低聚物苯酚的化学结构式如下：
                （Ⅱ）
其中，n和m均为整数，1≤n≤10，1≤m≤6。
本申请实施例中，引发剂在热作用下能分解活性自由基，用来引发生成交联的大分子聚合物。引发剂选择常规引发剂，例如有机过氧化物，优选双叔丁基过氧化异丙基苯。引发剂用量按常规用量，一般用量0.1-3质量份份，本申请实施例中优选0.2质量份。
本申请实施例中，无机填料选择常规无机填料，例如二氧化硅、二氧化钛、硅酸钙、氮化硼等，优选二氧化硅。无机填料用量按常规用量，本申请实施例中优选250-400质量份，进一步优选250-300质量份、300-400质量份。
本申请实施例中，硅烷偶联剂介于无机和有机界面间，用来在界面形成有机基体-硅烷偶联剂-无机基体的结合层，起到连接性质悬殊材料的作用。硅烷偶联剂选择常规硅烷偶联剂，优选3-缩水甘油醚氧基丙基三甲氧基硅烷，例如市面上的KMB-403硅烷偶联剂。硅烷偶联剂用量按常规用量，一般用量0.1-5质量份，本申请实施例中优选1质量份。
本申请实施例积层膜的原料中，茚低聚物单官能团苯并噁嗪、芳香基聚合多马来酰亚胺、烯丙基苯并噁嗪均为树脂单体，在引发剂的作用下反应得到聚合物。芳香基聚合多马来酰亚胺固化后，可表现出强韧性，且具耐高温、耐湿热、高模量、高强度等优异性能，可实现高阻燃性和低介电损耗，因此本申请实施例以芳香基聚合多马来酰亚胺为主要的树脂单体，并引入茚低聚物单官能团苯并噁嗪，用来对芳香基聚合多马来酰亚胺进行共混改性，用来降低芳香基聚合多马来酰亚胺预聚物粘度，还可在不影响介电性能的同时改善综合性能。另外，基于双键加成反应，将烯丙基苯并噁嗪引入芳香基聚合多马来酰亚胺体系，可降低体系的固化收缩，使体系具有低介电常数和低损耗因子。
本申请实施例中，芳香基聚合多马来酰亚胺用量40-65质量份，进一步优选50-65质量份、40-50质量份；茚低聚物单官能团苯并噁嗪用量5-10质量份，进一步优选5-8质量份、8-10质量份；烯丙基苯并噁嗪用量30-50质量份，进一步优选30-42质量份、42-50质量份。
本申请实施例积层膜采用涂膜工艺制备，方法如下：
按重量份取茚低聚物单官能团苯并噁嗪和芳香基聚合多马来酰亚胺混合得预聚物，于130℃条件下搅拌预聚物；待预聚物体系澄清，降至室温，按重量份加入烯丙基苯并噁嗪、引发剂、无机填料、硅烷偶联剂和无机溶剂，经搅拌得混合浆料；利用涂膜机将混合浆料涂覆于基膜上，于120℃下烘干6min，即在基膜上得到本申请积层膜。具体实施时，基膜一般采用PET膜。
在制备积层膜时，一般于110℃-150℃温度下搅拌预聚物25-40分钟，即可获得澄清的预聚物体系。无机溶剂可采用但不限于丙二醇甲醚醋酸酯。
本申请实施例所得积层膜可用于制备低损耗的电路基板，所制备的电路基板结构包括：中心基板层和经热固化后的积层膜，经热固化后的积层膜覆盖于中心基板层的上和/或下表面。该电路基板的制备工艺为：将积层膜贴合在中心基板层的上和/或下表面，于90℃温度、0.1MPa的压力下加压并抽真空60s，以使积层膜与中心基板层更为贴合，之后于150℃温度下加热固化，积层膜可填充中心基板层表面间隙，与中心基板层紧密结合。所获得的低损耗电路基板，可用来制作电路。
下面将提供若干实施例和对比例，实施例和对比例中所用原材料如下：
茚低聚物单官能团苯并噁嗪，自制；
苯胺单体和多聚甲醛：市购，沪试试剂；
茚低聚物苯酚：新日铁株式会社，型号IP-100，其结构式如下，其中，n和m均为整数，1≤n≤10，1≤m≤6：
                （Ⅱ）
双酚F型苯并噁嗪：型号BZ-130；
芳香基聚合多马来酰亚胺：市购MIR-3000 型号产品，其结构式如下，其中n为整数，1≤n≤2：
           （Ⅲ）
烯丙基苯并噁嗪：市购BZ-1706型号产品，其结构式如下：
  （Ⅳ）
双叔丁基过氧化异丙基苯BIPB：用作引发剂，市购，CAS号2212-81-9，其结构式如下：                 
                  （Ⅴ）
二氧化硅：球形硅微粉，粒径为0.1‑5μm。
硅烷偶联剂：KMB-403型硅烷偶联剂。
本申请实施例中茚低聚物单官能团苯并噁嗪的制备方法如下：
按1：1：2.1取苯胺单体、茚低聚物苯酚和多聚甲醛加入反应容器，同时加入二甲苯作为反应溶剂；于120℃温度下保持搅拌8h，进行Mannich反应(曼尼奇反应)，得茚低聚物单官能团苯并噁嗪。
本申请实施例和对比例中各组分的用量见表1。对表1中各实施例和对比例积层膜按如下方法进行性能测试。
流动性的测试方法：取大小5mm×5mm的方形积层膜，用两铜片夹住积层膜，置于120℃下烘烤5min，观察积层膜在铜片上的流动距离。流动距离超过2mm，表示流动性良好，记为◎；不超过2mm，表示流动性较差，记为×。
介电常数Dk和损耗因子Df的测试方法：参照IPC TM-650 2.5.5.13-2007标准《使用分体式气缸谐振器的相对介电常数和损失正切》，取大小50mm×70mm×0.1mm的方块形积层膜样品，采用网络分析仪测试10GHz频率下样品的介电常数Dk、损耗因子Df。
拉伸强度的测试方法：参照GB/T 1040.1-2018 标准《塑料拉伸性能的测定》，取大小200mm×5mm×1mm的积层膜样条，使用万能拉力机以50mm/min速度拉伸样条，至样条断裂时最大拉伸应力，即拉伸强度。
表1 实施例和对比例各组分用量
 
实施例和对比例的性能参数数据见表2。从表2可以看出，当同时采用茚低聚物苯并噁嗪和烯丙基苯并噁嗪共混改性芳香基聚合多马来酰亚胺，可降低介电损耗，提升拉伸强度。茚低聚物苯并噁嗪可改善双芳香基聚合多马来酰亚胺树脂存在的溶解性差,固化成型温度高以及固化物脆性高等缺点；再通过双键加成反应，将烯丙基苯并噁嗪引入到芳香基聚合多马来酰亚胺体系中，可降低固化收缩和降低介电损耗。
表2 实施例和对比例产品性能参数
 
上述实施例仅是为了清楚地说明所做的实施例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或者变动，这里无需也无法对所有的实施方式予以穷举，因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。

Claims (10)

  1. 一种低介电损耗的积层膜，其特征是：
    其原料包括包括5-10质量份茚低聚物单官能团苯并噁嗪，40-65质量份芳香基聚合多马来酰亚胺，30-50质量份烯丙基苯并噁嗪，0.1-3质量份引发剂，250-400质量份无机填料，0.1-5质量份硅烷偶联剂；
    所述茚低聚物单官能团苯并噁嗪的化学结构式为  ，其中，R为 ，n和m均为整数，1≤n≤10，1≤m≤6。
  2. 如权利要求1所述的一种低介电损耗的积层膜，其特征是：
    其原料包括包括8-10质量份茚低聚物单官能团苯并噁嗪，40-50质量份芳香基聚合多马来酰亚胺，42-50质量份烯丙基苯并噁嗪，0.1-3质量份引发剂，300-400质量份无机填料，0.1-5质量份硅烷偶联剂；
    所述茚低聚物单官能团苯并噁嗪的化学结构式为 ，其中，R为 ，n和m均为整数，1≤n≤10，1≤m≤6。
  3. 如权利要求1所述的一种低介电损耗的积层膜，其特征是：
    所述茚低聚物单官能团苯并噁嗪采用如下方法制备：
    按（1-1.2）：（1-1.4）：（2-2.4） 的摩尔比取苯胺单体、茚低聚物苯酚和多聚甲醛加入反应容器，同时加入有机反应溶剂；在80-150℃温度下保持搅拌4-15h进行曼尼奇反应，得茚低聚物单官能团苯并噁嗪。
  4. 如权利要求3所述的一种低介电损耗的积层膜，其特征是：
    所述茚低聚物苯酚的化学式为 ，其中，n和m均为整数，1≤n≤10，1≤m≤6。
  5. 如权利要求1所述的一种低介电损耗的积层膜，其特征是：
    所述引发剂为双叔丁基过氧化异丙基苯。
  6. 如权利要求1所述的一种低介电损耗的积层膜，其特征是：
    所述无机填料为二氧化硅。
  7. 如权利要求1所述的一种低介电损耗的积层膜，其特征是：
    所述硅烷偶联剂为3-缩水甘油醚氧基丙基三甲氧基硅烷。
  8. 一种低介电损耗的积层膜的制备方法，其特征是：
    取5-10质量份茚低聚物单官能团苯并噁嗪和40-65质量份芳香基聚合多马来酰亚胺混合得预聚物，于110℃-150℃温度下搅拌预聚物；
    待预聚物体系澄清，降至室温，加入30-50质量烯丙基苯并噁嗪、0.1-3质量份引发剂、250-400质量份无机填料、0.1-5质量份硅烷偶联剂和无机溶剂，经搅拌得混合浆料；
    利用涂膜机将混合浆料涂覆于基膜上，经烘干，即在基膜上得到积层膜；
    所述茚低聚物单官能团苯并噁嗪的化学结构式为 ，其中，R为 ，n和m均为整数，1≤n≤10，1≤m≤6。
  9. 如权利要求1所述的一种低介电损耗的积层膜的制备方法，其特征是：
    取8-10质量份茚低聚物单官能团苯并噁嗪和40-50质量份芳香基聚合多马来酰亚胺混合得预聚物，于110℃-150℃温度下搅拌预聚物；
    待预聚物体系澄清，降至室温，加入42-50质量烯丙基苯并噁嗪、0.1-3质量份引发剂、300-400质量份无机填料、0.1-5质量份硅烷偶联剂和无机溶剂，经搅拌得混合浆料；
    利用涂膜机将混合浆料涂覆于基膜上，于120℃温度下烘干6min，即在基膜上得到积层膜；
    所述茚低聚物单官能团苯并噁嗪的化学结构式为 ，其中，R为 ，n和m均为整数，1≤n≤10，1≤m≤6。
  10. 一种电路基板结构，其特征是：
    包括中心基板层和积层膜；所述积层膜通过如下方法获得：将权利要求8-9中任一项所述制备方法所制备的积层膜覆盖于所述中心基板层的上和/或下表面，之后依次经热压、热固化。
PCT/CN2023/084227 2022-11-22 2023-03-28 低介电损耗的积层膜、其制备方法及电路基板结构 WO2024108837A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/523,968 US12098230B2 (en) 2022-11-22 2023-11-30 Build-up film with low dielectric loss, preparation method therefor and circuit substrate structure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211469785.8 2022-11-22
CN202211469785.8A CN115521411B (zh) 2022-11-22 2022-11-22 低介电损耗的积层膜、其制备方法及电路基板结构

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/523,968 Continuation US12098230B2 (en) 2022-11-22 2023-11-30 Build-up film with low dielectric loss, preparation method therefor and circuit substrate structure

Publications (1)

Publication Number Publication Date
WO2024108837A1 true WO2024108837A1 (zh) 2024-05-30

Family

ID=84704718

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/084227 WO2024108837A1 (zh) 2022-11-22 2023-03-28 低介电损耗的积层膜、其制备方法及电路基板结构

Country Status (3)

Country Link
US (1) US12098230B2 (zh)
CN (1) CN115521411B (zh)
WO (1) WO2024108837A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115521411B (zh) 2022-11-22 2023-03-03 武汉市三选科技有限公司 低介电损耗的积层膜、其制备方法及电路基板结构

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012167141A (ja) * 2011-02-10 2012-09-06 Nippon Steel Chem Co Ltd エポキシ樹脂組成物及び硬化物
CN106700424A (zh) * 2016-12-30 2017-05-24 浙江华正新材料股份有限公司 一种低损耗树脂组合物、半固化片和层压板
JP2018168217A (ja) * 2017-03-29 2018-11-01 住友ベークライト株式会社 封止用樹脂組成物及びこれを用いた半導体装置
JP2020158705A (ja) * 2019-03-27 2020-10-01 味の素株式会社 樹脂組成物、樹脂組成物の硬化物、樹脂シート、プリント配線板及び半導体装置
US20210147680A1 (en) * 2018-04-26 2021-05-20 Mitsubishi Gas Chemical Company, Inc. Resin composition, laminate, semiconductor wafer with resin composition layer, substrate for mounting semiconductor with resin composition layer, and semiconductor device
CN113121999A (zh) * 2019-12-31 2021-07-16 广东生益科技股份有限公司 一种树脂组合物及使用它的预浸料、层压板和印制电路板
CN114989418A (zh) * 2022-08-04 2022-09-02 武汉市三选科技有限公司 聚苯醚树脂的改性方法、积层膜复合料、积层膜、基板
CN115521411A (zh) * 2022-11-22 2022-12-27 武汉市三选科技有限公司 低介电损耗的积层膜、其制备方法及电路基板结构

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106565746B (zh) * 2015-10-12 2021-06-15 3M创新有限公司 苯并噁嗪化合物、其聚合物及其制法和由其制得的粘合剂
KR102383690B1 (ko) * 2016-06-30 2022-04-06 코오롱인더스트리 주식회사 벤족사진계 혼합물, 및 이의 용도
CN112210210B (zh) * 2019-07-11 2023-04-25 台光电子材料(昆山)有限公司 一种树脂组合物及其制品
CN113736255B (zh) * 2020-05-27 2023-07-14 台光电子材料(昆山)有限公司 一种树脂组合物及其制品

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012167141A (ja) * 2011-02-10 2012-09-06 Nippon Steel Chem Co Ltd エポキシ樹脂組成物及び硬化物
CN106700424A (zh) * 2016-12-30 2017-05-24 浙江华正新材料股份有限公司 一种低损耗树脂组合物、半固化片和层压板
JP2018168217A (ja) * 2017-03-29 2018-11-01 住友ベークライト株式会社 封止用樹脂組成物及びこれを用いた半導体装置
US20210147680A1 (en) * 2018-04-26 2021-05-20 Mitsubishi Gas Chemical Company, Inc. Resin composition, laminate, semiconductor wafer with resin composition layer, substrate for mounting semiconductor with resin composition layer, and semiconductor device
JP2020158705A (ja) * 2019-03-27 2020-10-01 味の素株式会社 樹脂組成物、樹脂組成物の硬化物、樹脂シート、プリント配線板及び半導体装置
CN113121999A (zh) * 2019-12-31 2021-07-16 广东生益科技股份有限公司 一种树脂组合物及使用它的预浸料、层压板和印制电路板
CN114989418A (zh) * 2022-08-04 2022-09-02 武汉市三选科技有限公司 聚苯醚树脂的改性方法、积层膜复合料、积层膜、基板
CN115521411A (zh) * 2022-11-22 2022-12-27 武汉市三选科技有限公司 低介电损耗的积层膜、其制备方法及电路基板结构

Also Published As

Publication number Publication date
US12098230B2 (en) 2024-09-24
US20240182619A1 (en) 2024-06-06
CN115521411A (zh) 2022-12-27
CN115521411B (zh) 2023-03-03

Similar Documents

Publication Publication Date Title
JP7450488B2 (ja) ポリアミック酸樹脂、ポリイミド樹脂およびこれらを含む樹脂組成物
CN102115569B (zh) 介电材料组合物及电路基板
TWI876067B (zh) 異氰酸酯改質聚醯亞胺樹脂、樹脂組成物及其硬化物
KR101115598B1 (ko) 에폭시 수지 조성물
EP0559338B1 (en) Thermosetting resin compositions
JP2008218496A (ja) 封止用樹脂フィルム
CN111844951A (zh) 一种高频导热基板及其制备方法
TWI730757B (zh) 熱固性聚醯亞胺樹脂及其製造方法、組成物、預聚物、薄膜、黏著劑、及其用途
CN117801745B (zh) 低热膨胀系数的底部填充胶、其制备方法及芯片封装结构
CN113403010B (zh) 一种耐高温的环氧树脂胶粘剂及其制备方法
WO2024108837A1 (zh) 低介电损耗的积层膜、其制备方法及电路基板结构
CN113512138A (zh) 一种双苯并环丁烯基乙烯树脂的制备方法
JP5405959B2 (ja) エポキシ樹脂組成物、および、それによる接着フィルム
TW202421708A (zh) 樹脂組成物
KR20210015760A (ko) 열경화성 수지 조성물, 이를 포함하는 필름, 및 이들을 사용한 다층 배선판
TWI850000B (zh) 樹脂組成物
TW202248291A (zh) 熱固性檸康醯亞胺樹脂組合物
CN115806735A (zh) 树脂材料及金属基板
TWI825805B (zh) 橡膠樹脂材料及金屬基板
JP7710806B2 (ja) 熱硬化性ビスマレイミド樹脂組成物
JP2872701B2 (ja) 半導体封止用樹脂の製造方法
CN118834642A (zh) 低膨胀系数环氧膜及其制备方法、封装晶圆的制备方法
CN119875308A (zh) 固化性树脂组合物、固化物和物品
CN120209575A (zh) 一种无卤树脂组合物及其制备的高Tg低损耗覆铜板
TW202413489A (zh) 聚順丁烯二醯亞胺樹脂、樹脂組成物、固化物、片材、積層體、及印刷配線板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23892946

Country of ref document: EP

Kind code of ref document: A1