WO2024045159A1 - Epoxy resin adhesive film material applied to semiconductor system-level packaging - Google Patents

Epoxy resin adhesive film material applied to semiconductor system-level packaging Download PDF

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Publication number
WO2024045159A1
WO2024045159A1 PCT/CN2022/116732 CN2022116732W WO2024045159A1 WO 2024045159 A1 WO2024045159 A1 WO 2024045159A1 CN 2022116732 W CN2022116732 W CN 2022116732W WO 2024045159 A1 WO2024045159 A1 WO 2024045159A1
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Prior art keywords
resin
epoxy resin
modified
styrene
vinyl
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PCT/CN2022/116732
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French (fr)
Chinese (zh)
Inventor
罗遂斌
于淑会
于均益
徐鹏鹏
孙蓉
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深圳先进技术研究院
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Priority to PCT/CN2022/116732 priority Critical patent/WO2024045159A1/en
Publication of WO2024045159A1 publication Critical patent/WO2024045159A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins

Definitions

  • the present invention belongs to the technical field of new electronic packaging materials. More specifically, the present invention relates to an epoxy resin film material used in semiconductor system-level packaging.
  • Insulating dielectric materials are an important material in electronic packaging technology. Its high-frequency characteristics have a lot of impact on the signal transmission of electronic packaging devices.
  • Epoxy resin has many applications in printed circuit boards due to its good heat resistance, chemical resistance, easy processing, and low price.
  • Conventional substrates such as FR-4 use epoxy resin as the polymer Prepared from a material matrix.
  • epoxy resin composite materials have a large dielectric loss of 0.04 to 0.06 under high frequency (1GHz to 20GHz) conditions due to the presence of more hydroxyl groups, which is not conducive to high frequency applications.
  • adding non-polar compounds such as hyperbranched polymers to increase the free volume of the resin system can reduce the high-frequency dielectric loss of epoxy resin composites, but at the same time lower the glass transition temperature of the composite.
  • the present invention provides an epoxy resin composite material with low dielectric loss at high frequency and a glass transition temperature higher than 200°C. After thermal curing, the composite material has a high frequency in the frequency range of 1GHz to 20GHz. The dielectric loss is less than 0.003, which is suitable for high-frequency semiconductor packaging field.
  • the present invention provides a low dielectric loss epoxy resin composite material that can be used in the field of high-frequency semiconductor packaging.
  • the present invention adopts the following technical solutions.
  • One aspect of the present invention provides an insulating dielectric slurry, which contains an ethylene modified resin, a cross-linking agent, an epoxy resin, a filler and a solvent;
  • the ethylene-modified resin is a styrene-based or vinyl-modified resin, and the ethylene-modified resin contains more than two styrenes and or vinyl groups; the ethylene-modified resin is a non-epoxy resin;
  • the epoxy resin is an epoxy resin or a combination of multiple epoxy resins, and the epoxy resin includes at least one epoxy resin containing an ethylene structure;
  • the cross-linking agent is a combination of a first cross-linking agent, a second cross-linking agent and a third cross-linking agent, wherein the first cross-linking agent is one or more of a phenolic resin, a cyanate ester resin and an active ester resin.
  • a combination of more than one type the second cross-linking agent is one or a combination of more than one of triallyl isocyanate, trimethylolpropane trimethacrylate, and trimethallyl isocyanate;
  • the third cross-linking agent is one or a combination of more than one of dicumyl peroxide, di-tert-butyl cumene peroxy, and dibenzoyl peroxide.
  • the vinyl-modified resin is selected from the group consisting of styrene-modified phenolic resin, styrene-modified alkyd resin, styrene acrylic resin, styrene-modified terpene resin, and ethylene-modified phenolic resin.
  • the styrene-modified phenolic resin or vinyl-modified phenolic resin is obtained by coupling the hydroxyl group of the phenolic resin with a compound containing a styrene group or a vinyl group to obtain a phenolic resin with styrene or vinyl groups.
  • the styrene-modified alkyd resin or ethylene-modified alkyd resin is obtained by coupling the hydroxyl group of the alkyd resin with a compound containing a styrene group or a vinyl group to obtain styrene or vinyl group.
  • Alkyd resin is obtained by coupling the hydroxyl group of the alkyd resin with a compound containing a styrene group or a vinyl group to obtain styrene or vinyl group.
  • the styrene-modified acrylic resin or ethylene-modified acrylic resin is obtained by coupling the acrylic group of the acrylic resin with a compound containing a styrene group or a vinyl group to obtain a phenolic resin with styrene or vinyl groups. resin.
  • the styrene-modified terpene resin or ethylene-modified terpene resin is obtained by coupling the hydroxyl group of the terpene resin with a compound containing a styrene group or a vinyl group to obtain a styrene- or ethylene-modified terpene resin. Based terpene resin.
  • the ethylene modification refers to the modification of vinyl groups or styrene groups on both ends and/or side chains of the resin.
  • the styrene group or vinyl group is at the terminal position of the resin molecular structure, or on the branch of the molecular segment, or at both the terminal position and the branch; preferably, it is at the styrene group or Vinyl groups are used in terminal and branched chains or as a mixture of resins with two molecular structures.
  • the ethylene modified resin is a phenolic resin with styrene group and or vinyl group modification.
  • the ethylene modified resin is represented by the following structural formula (1), (2) or (3):
  • R is selected from dicyclopentadiene, alkyl, aromatic ring, substituted aromatic ring, heteroaromatic ring, and n is 1-100.
  • the aromatic ring is selected from naphthalene ring, anthracene, and biphenyl;
  • the heteroaromatic ring is selected from pyridine ring, pyrrole ring, pyrazole ring, pyrimidine ring, pyrazine ring, pyridazine ring, thiophene ring, and furan ring;
  • the R group is preferably biphenyl, dicyclopentadiene, naphthalene ring, or anthracene.
  • n is selected from 2-200, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190.
  • the usage amount of the ethylene modified resin is 20% to 50% of the total resin mass, and the total resin mass is the total mass of the ethylene modified resin, cross-linking agent, and epoxy resin. For example 20%, 25%, 30%, 35%, 40%, 45% or 50%.
  • the added amount of ethylene modified resin is less than 20%, the effect of reducing the high-frequency dielectric loss of the composite material is not obvious.
  • the added amount of ethylene modified resin is higher than 50%, the effect of reducing the high-frequency dielectric loss of the composite material is not obvious. The binding force will be significantly reduced.
  • the total resin mass is the total mass of ethylene modified resin, cross-linking agent and epoxy resin.
  • the molecular structure of the ethylene modified resin contains at least two vinyl groups and the molecular weight is ⁇ 245.
  • the molecular weight of the ethylene modified resin is 2,000 to 10,000.
  • the molecular structure of the ethylene modified resin is obtained by coupling vinyl molecules with hydroxyl groups in the non-epoxy resin resin; more preferably, more than 50% of the hydroxyl groups in the non-epoxy resin resin are obtained by coupling vinyl molecules
  • the molecules are modified either by 60%, 70%, 80%, 90%, 95% or 100%.
  • the molecular structure of the cured product is dominated by linear structures and the glass transition temperature is low.
  • the molecular weight of the ethylene modified resin is lower than 245 , the introduction of ethylene modified resin has a difficult effect on reducing the polarity of composite materials. Therefore, the molecular structure of ethylene modified resin must have more than two vinyl groups and a molecular weight higher than 245.
  • the molecular weight of the ethylene modified resin is 2,000 to 10,000, which is beneficial to film formation.
  • the phenolic resin as the cross-linking agent is selected from linear phenol formaldehyde resin and its hydroxyl equivalent is 100-115g/eq; linear bisphenol A formaldehyde resin and its hydroxyl equivalent is 115-125g/eq; XYLOK phenolic resin and its hydroxyl equivalent 170 ⁇ 185g/eq; biphenyl phenolic resin with a hydroxyl equivalent weight of 190 ⁇ 250g/eq; nitrogen-containing phenolic resin with a hydroxyl equivalent weight of 110 ⁇ 140g/eq; phosphorus-containing phenolic resin with a hydroxyl equivalent weight of 250 ⁇ 350g/eq.
  • linear phenol formaldehyde resin and its hydroxyl equivalent is 100-115g/eq
  • linear bisphenol A formaldehyde resin and its hydroxyl equivalent is 115-125g/eq
  • XYLOK phenolic resin and its hydroxyl equivalent 170 ⁇ 185g/eq biphenyl phenolic resin with a
  • the cyanate ester resin as the cross-linking agent is selected from the group consisting of bisphenol A-type cyanate ester, bisphenol F-type cyanate ester, bisphenol E-type cyanate ester, bisphenol M-type cyanate ester, and dicyclopentadiene.
  • One or more types of cyanate ester, phenolic cyanate ester, and tetramethylbisphenol F cyanate ester are used in combination.
  • the active ester resin as the cross-linking agent is selected from the group consisting of linear phenol formaldehyde active ester resin, bisphenol A formaldehyde active ester resin, bis-XYLOK active ester resin, biphenyl active ester resin, dicyclopentadiene active ester resin, phosphorus-containing One or more of active ester resin, double bond-containing active ester resin, etc. are mixed and used; double bond-containing active ester resin is preferred.
  • the mass ratio between the first cross-linking agent, the second cross-linking agent and the third cross-linking agent is 50-100:20-60:1, preferably 55-65:25-50:1.
  • the epoxy resin used in the dielectric film of the present invention refers to an organic resin containing one or more epoxy functional groups in its molecular structure.
  • the epoxy resin containing a vinyl structure in the epoxy resin is selected from the group consisting of allyl bisphenol A epoxy resin and allyl novolac epoxy resin.
  • the epoxy resin also includes at least one other epoxy resin, and the other epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin.
  • Oxygen resin, phenolic epoxy resin, o-cresol-type epoxy resin, o-cresol-type epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber modified ring At least one or a combination of at least one of oxygen resin, polyurethane modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin.
  • bisphenol A type epoxy resin such as Nanya NPEL-128, NPEL-127, NPEL-144, NPES-609, NPES-901, NPES-902, NPES-903, NPES-904, NPES-907 , NPES-909, such as Guodu Chemical YD-001, YD-012, YD-013k, YD-014, YD-134, YD-134D, YD-134L, YD-136, YD-128, YD-127, Hens Produced by Mai GY 2600, GY 6010, GY 6020, MY 790-1 ⁇ LY 1556, GY 507, etc., bisphenol F epoxy resin such as NPEF-170 produced by Nanya, EPALLOY 8220, EPALLOY 8220E, EPALLOY 8230 produced by CVC, and EPALLOY 8230 produced by Huntsman GY 281, GY 282, GY 285,
  • resorcinol epoxy resins such as ERISYS RDGE produced by CVC
  • rubber modified epoxy resins HyPox RA 95, HyPox RA 840, HyPox RA 1340 produced by CVC
  • polyurethane modified epoxy resin biphenyl epoxy resin such as YX4000, YX4000K, YX4000H, YX4000HK, YL6121H, produced by Mitsui Chemicals of Japan.
  • YL6121HN dicyclopentadiene epoxy resin, such as one or more of CYDB-500, CYDB-700, CYDB-900, CYDB-400, CYDB-450A80, etc. produced by Yueyang Baling Petrochemical.
  • epoxy resin accounts for 10-30% of the total resin mass.
  • the filler is spherical, has a maximum particle size less than 3 ⁇ m, a minimum particle size greater than 10 nm, and is insoluble in organic solvents.
  • the filler is selected from one of fused silica, hydrothermal silica, precipitated silica, alumina, boron nitride, titanium dioxide, zinc oxide, zirconia, magnesium oxide, calcium carbonate, etc. or examples of mixtures.
  • the added amount of the filler particles accounts for more than 65% of the total mass of the medium layer without solvent, such as 70%-95%, such as 75%, 80%, 85%, and 90%.
  • the medium layer of the present invention also includes auxiliary agents, and the added amounts are less than 1% of the total mass; the auxiliary agents are selected from coupling agents, dispersants, defoaming agents, pigments, and flame retardants.
  • Another aspect of the present invention provides an insulating dielectric layer, which is a layered composite material made of the above-mentioned insulating dielectric slurry.
  • the dielectric loss of the insulating dielectric layer under high frequency conditions is 0.003 or less, and the high frequency is 1-20 GHz. Preferably it is 0.001-0.0025.
  • the glass transition temperature of the insulating dielectric layer under high-frequency conditions is 210°C or higher, preferably 210°C-230°C.
  • the epoxy resin composite material is composed of three parts: a carrier film, a dielectric layer, and a cover film, wherein the dielectric layer is located between the carrier film and the cover film to form a sandwich structure. , the dielectric layer is the above-mentioned insulating dielectric layer.
  • Another aspect of the present invention provides a method for preparing the above-mentioned epoxy resin composite material.
  • the above-mentioned insulating dielectric slurry is mixed evenly with a mixer, and after being dispersed by a sand mill, a coater is used to coat the dispersed insulating dielectric slurry on the carrier film.
  • the surface is dried with a solvent and then combined with the covering film to form the epoxy resin composite material of the present invention.
  • the carrier film material is a polymer film material or a paper-based film material
  • the polymer film material is polyester film (PET), polyether ether ketone film (PEEK), polyetherimide film (PEI), poly Imide film (PI), polycarbonate film (PC);
  • the paper base film material is selected from release paper and laminated paper.
  • the thickness of the carrier film material is 10 ⁇ m to 300 ⁇ m, preferably 20 ⁇ m to 100 ⁇ m, and more preferably 30 ⁇ m to 60 ⁇ m.
  • the insulating dielectric slurry can form a uniform and smooth film on the surface of the supporting film material.
  • the covering film material is selected from polymer film materials; preferably polyester film (PET), polypropylene film (OPP), and polyethylene film (PE).
  • PET polyester film
  • OPP polypropylene film
  • PE polyethylene film
  • the thickness of the protective film material is 10 ⁇ m to 300 ⁇ m, preferably 20 ⁇ m to 100 ⁇ m, and more preferably 30 ⁇ m to 60 ⁇ m.
  • the thickness of the insulating polymer composite between the carrier film and the cover film is 1 ⁇ m to 300 ⁇ m, preferably 10 ⁇ m to 20 ⁇ m, and more preferably 15 ⁇ m to 100 ⁇ m.
  • Another aspect of the present invention provides the use of the above-mentioned insulating dielectric layer or epoxy resin composite material as a packaging dielectric layer in the field of semiconductor electronic packaging.
  • the semiconductor electronic packaging field is selected from the fields of FC-BGA high-density packaging substrate, chip rewiring dielectric layer, chip plastic packaging, chip bonding, and chip bump underfilling.
  • the present invention prepares dielectric layer slurry by adding ethylene modified resin and epoxy resin with vinyl.
  • the dielectric layer prepared thereby has the advantages of lower dielectric loss and higher glass transition temperature at high frequency. Can be used in advanced manufacturing fields as chip packaging.
  • This embodiment provides a compound of dielectric layers in semiconductor electronic packaging fields that can be applied in advanced packaging fields such as FC-BGA high-density packaging substrates, chip rewiring dielectric layers, chip plastic packaging, chip bonding, chip bump bottom filling, etc. Materials and methods of preparation.
  • the prepared dielectric layer was further tested to detect its dielectric loss and glass transition temperature (Tg*) at 10GHz.
  • Real-time Examples 2-3 and Comparative Examples 1-3 adopted the method of Example 1, and the only difference was that the raw material preparation shown in Table 1 was used for substitution.
  • the dielectric film composed of vinyl resin, cross-linking agent, epoxy resin, filler, etc. can achieve high frequency, low dielectric loss and high glass transition temperature.
  • the present invention further adds coupling agents, dispersants, defoaming agents, pigments, flame retardants and other additives to the compositions of Examples 1-3, and detects and confirms the impact of adding additives on dielectric loss and glass transition temperature.
  • Experimental results show that when the total additive content is less than 1% of the dielectric layer content, it has almost no impact on the dielectric loss and glass transition temperature.

Abstract

Disclosed in the present invention is an epoxy resin adhesive film material applied to semiconductor system-level packaging. The insulating adhesive film material consists of a lower carrier film, an intermediate dielectric film, and an upper covering film, wherein the dielectric film is located between the carrier film and the covering film to form a sandwich structure. The dielectric film is made from ethylene resin, a cross-linking agent, epoxy resin, a filler and the like, the high-frequency dielectric loss of a cured product is lower than 0.003, and the glass transition temperature is higher than 200°C.

Description

应用于半导体系统级封装用的环氧树脂胶膜材料Epoxy resin film materials for semiconductor system-level packaging 技术领域Technical field
本发明属于新型电子封装材料技术领域，更具体地，本发明涉及一种应用于半导体系统级封装用的环氧树脂胶膜材料。The present invention belongs to the technical field of new electronic packaging materials. More specifically, the present invention relates to an epoxy resin film material used in semiconductor system-level packaging.
背景技术Background technique
随着电子信息技术的发展，特别是近年来以可穿戴电子、智能手机、超薄电脑、无人驾驶、物联网技术和5G通讯技术为主的快速发展，对电子系统的小型化、轻薄化、多功能、高性能等方面提出了越来越高的要求。绝缘电介质材料是电子封装技术的一种重要材料。其高频特性对电子封装器件信号的传输具有很多的影响。环氧树脂基于其良好的耐热性、耐化学腐蚀性、易加工、价格低廉等优势在印刷线路板中具有非常多的应用，常规的基材如FR-4都是采用环氧树脂作为聚合物基体制备的。一般地，环氧树脂复合材料经热固化后因存在较多的羟基导致在高频(1GHz～20GHz)条件下产生较大的介电损耗，为0.04～0.06，不利于高频应用。通常，添加非极性化合物如超支化聚合物等增加树脂体系的自由体积可降低环氧树脂复合材料的高频介电损耗，但同时降低复合材料的玻璃化转变温度。With the development of electronic information technology, especially the rapid development in recent years of wearable electronics, smartphones, ultra-thin computers, driverless driving, Internet of Things technology and 5G communication technology, the need for miniaturization and thinning of electronic systems has , multi-function, high performance and other aspects have put forward increasingly higher requirements. Insulating dielectric materials are an important material in electronic packaging technology. Its high-frequency characteristics have a lot of impact on the signal transmission of electronic packaging devices. Epoxy resin has many applications in printed circuit boards due to its good heat resistance, chemical resistance, easy processing, and low price. Conventional substrates such as FR-4 use epoxy resin as the polymer Prepared from a material matrix. Generally, after thermal curing, epoxy resin composite materials have a large dielectric loss of 0.04 to 0.06 under high frequency (1GHz to 20GHz) conditions due to the presence of more hydroxyl groups, which is not conducive to high frequency applications. Generally, adding non-polar compounds such as hyperbranched polymers to increase the free volume of the resin system can reduce the high-frequency dielectric loss of epoxy resin composites, but at the same time lower the glass transition temperature of the composite.
发明内容Contents of the invention
基于此，本发明提供一种在高频下具有低介电损耗且玻璃化转变温度高于200℃的环氧树脂复合材料，该复合材料经热固化后在高频1GHz～20GHz频率范围内的介电损耗小于0.003，适用于高频半导体封装领域。Based on this, the present invention provides an epoxy resin composite material with low dielectric loss at high frequency and a glass transition temperature higher than 200°C. After thermal curing, the composite material has a high frequency in the frequency range of 1GHz to 20GHz. The dielectric loss is less than 0.003, which is suitable for high-frequency semiconductor packaging field.
为了克服现有技术的缺陷，本发明提供一种可用于高频半导体封装领域的低介电损耗环氧树脂复合材料。In order to overcome the shortcomings of the prior art, the present invention provides a low dielectric loss epoxy resin composite material that can be used in the field of high-frequency semiconductor packaging.
为了实现上述发明目的，本发明采取了以下技术方案。In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions.
本发明一个方面提供了绝缘电介质浆料，所述绝缘电介质浆料中包含乙烯改性树脂、交联剂、环氧树脂、填料和溶剂；One aspect of the present invention provides an insulating dielectric slurry, which contains an ethylene modified resin, a cross-linking agent, an epoxy resin, a filler and a solvent;
所述乙烯改性树脂为苯乙烯基或乙烯基改性的树脂，且所述乙烯改性树脂中包含两个以上苯乙烯和或乙烯基；乙烯改性树脂为非环氧树脂；The ethylene-modified resin is a styrene-based or vinyl-modified resin, and the ethylene-modified resin contains more than two styrenes and or vinyl groups; the ethylene-modified resin is a non-epoxy resin;
所述环氧树脂为一种环氧树脂或多种环氧树脂的组合，所述环氧树脂中至少包含一种含乙烯结构的环氧树脂；The epoxy resin is an epoxy resin or a combination of multiple epoxy resins, and the epoxy resin includes at least one epoxy resin containing an ethylene structure;
所述交联剂为第一交联剂、第二交联剂以及第三交联剂的组合，其中第一交联剂为酚醛树脂、氰酸酯树脂、活性酯树脂中的一种或一种以上的组合；第二交联剂为三烯丙基异三聚氰酸酯、三羟甲基丙烷三甲基丙烯酸酯、三甲代烯丙基异氰酸酯中的一种或一种以上的组合；第三交联剂为过氧化二异丙苯、双叔丁基过氧异丙基苯、过氧化二苯甲酰中的一种或一种以上的组合。The cross-linking agent is a combination of a first cross-linking agent, a second cross-linking agent and a third cross-linking agent, wherein the first cross-linking agent is one or more of a phenolic resin, a cyanate ester resin and an active ester resin. A combination of more than one type; the second cross-linking agent is one or a combination of more than one of triallyl isocyanate, trimethylolpropane trimethacrylate, and trimethallyl isocyanate; The third cross-linking agent is one or a combination of more than one of dicumyl peroxide, di-tert-butyl cumene peroxy, and dibenzoyl peroxide.
进一步地，所述乙烯改性树脂选自苯乙烯改性酚醛树脂、苯乙烯改性醇酸树脂、苯乙烯丙烯酸树脂、苯乙烯改性萜烯树脂、乙烯改性酚醛树脂。Further, the vinyl-modified resin is selected from the group consisting of styrene-modified phenolic resin, styrene-modified alkyd resin, styrene acrylic resin, styrene-modified terpene resin, and ethylene-modified phenolic resin.
进一步地，所述苯乙烯改性酚醛树脂或乙烯改性酚醛树脂通过将酚醛树脂的羟基与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的酚醛树脂。Further, the styrene-modified phenolic resin or vinyl-modified phenolic resin is obtained by coupling the hydroxyl group of the phenolic resin with a compound containing a styrene group or a vinyl group to obtain a phenolic resin with styrene or vinyl groups.
进一步地，所述苯乙烯改性醇酸树脂或乙烯改性醇酸树脂通过将醇酸树脂的羟基与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的醇酸树脂。Further, the styrene-modified alkyd resin or ethylene-modified alkyd resin is obtained by coupling the hydroxyl group of the alkyd resin with a compound containing a styrene group or a vinyl group to obtain styrene or vinyl group. Alkyd resin.
进一步地，所述苯乙烯改性丙烯酸树脂或乙烯改性丙烯酸树脂通过将丙烯酸树脂的丙烯酸基团与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的酚醛树脂。Further, the styrene-modified acrylic resin or ethylene-modified acrylic resin is obtained by coupling the acrylic group of the acrylic resin with a compound containing a styrene group or a vinyl group to obtain a phenolic resin with styrene or vinyl groups. resin.
进一步地，所述苯乙烯改性萜烯树脂或乙烯改性萜烯树脂通过将萜烯树脂的羟基基团与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的萜烯树脂。Further, the styrene-modified terpene resin or ethylene-modified terpene resin is obtained by coupling the hydroxyl group of the terpene resin with a compound containing a styrene group or a vinyl group to obtain a styrene- or ethylene-modified terpene resin. Based terpene resin.
在本发明中，所述的乙烯改性指树脂的两端和或侧链上修饰乙烯基团或苯乙烯基团。In the present invention, the ethylene modification refers to the modification of vinyl groups or styrene groups on both ends and/or side chains of the resin.
进一步地，所述乙烯改性树脂中苯乙烯基或乙烯基在树脂分子结构的端位，或在分子链段的支链上，或同时在端位和支链；优选地在苯乙烯基或乙烯基在端位和支链上或具有两种分子结构树脂的混合使用。Further, in the ethylene modified resin, the styrene group or vinyl group is at the terminal position of the resin molecular structure, or on the branch of the molecular segment, or at both the terminal position and the branch; preferably, it is at the styrene group or Vinyl groups are used in terminal and branched chains or as a mixture of resins with two molecular structures.
进一步地，所述乙烯改性树脂为具有苯乙烯基和或乙烯基改性的酚醛树脂，优选地，所 述乙烯改性树脂如下结构式(1)、(2)或(3)所示：Further, the ethylene modified resin is a phenolic resin with styrene group and or vinyl group modification. Preferably, the ethylene modified resin is represented by the following structural formula (1), (2) or (3):
Figure PCTCN2022116732-appb-000001
Figure PCTCN2022116732-appb-000001
其中，R选自双环戊二烯、烷基、芳环、取代的芳环、杂芳环，n为1-100。Among them, R is selected from dicyclopentadiene, alkyl, aromatic ring, substituted aromatic ring, heteroaromatic ring, and n is 1-100.
进一步地，所述芳环选自萘环、蒽、联苯；杂芳环选自吡啶环、吡咯环、吡唑环、嘧啶环、吡嗪环、哒嗪环、噻吩环、呋喃环；Further, the aromatic ring is selected from naphthalene ring, anthracene, and biphenyl; the heteroaromatic ring is selected from pyridine ring, pyrrole ring, pyrazole ring, pyrimidine ring, pyrazine ring, pyridazine ring, thiophene ring, and furan ring;
进一步地，在结构式(1)、(2)或(3)中，R基优选为联苯、双环戊二烯、萘环、蒽。Furthermore, in the structural formula (1), (2) or (3), the R group is preferably biphenyl, dicyclopentadiene, naphthalene ring, or anthracene.
进一步地，在结构式(1)、(2)或(3)中，n选自2-200，例如5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100、110、120、130、140、150、160、170、180、190。Further, in structural formula (1), (2) or (3), n is selected from 2-200, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190.
进一步地，所述乙烯改性树脂的使用量为总树脂质量的20％～50％，所述总树脂质量为乙 烯改性树脂、交联剂、环氧树脂的总质量。例如20％、25％、30％、35％、40％、45％或50％。当乙烯改性树脂添加量低于20％时，对复合材料高频介电损耗的降低效用体现不明显，当乙烯改性树脂添加量高于50％时，复合材料与金属基材之间的结合力将明显降低。Further, the usage amount of the ethylene modified resin is 20% to 50% of the total resin mass, and the total resin mass is the total mass of the ethylene modified resin, cross-linking agent, and epoxy resin. For example 20%, 25%, 30%, 35%, 40%, 45% or 50%. When the added amount of ethylene modified resin is less than 20%, the effect of reducing the high-frequency dielectric loss of the composite material is not obvious. When the added amount of ethylene modified resin is higher than 50%, the effect of reducing the high-frequency dielectric loss of the composite material is not obvious. The binding force will be significantly reduced.
在本发明中，所述总树脂质量为乙烯改性树脂、交联剂和环氧树脂的总质量。In the present invention, the total resin mass is the total mass of ethylene modified resin, cross-linking agent and epoxy resin.
进一步地，乙烯改性树脂分子结构中至少含有两个以上乙烯基团且分子量≥245。优选地乙烯改性树脂的分子量2000～10000。Furthermore, the molecular structure of the ethylene modified resin contains at least two vinyl groups and the molecular weight is ≥245. Preferably, the molecular weight of the ethylene modified resin is 2,000 to 10,000.
进一步地，乙烯改性树脂分子结构中通过包含乙烯基分子与非环氧树脂的树脂中的羟基偶联获得；更优选地，非环氧树脂的树脂中的50％以上的羟基通过包含乙烯基分子进行改性，或者60％以上、70％以上、80％以上、90％以上、95％以上或100％。Further, the molecular structure of the ethylene modified resin is obtained by coupling vinyl molecules with hydroxyl groups in the non-epoxy resin resin; more preferably, more than 50% of the hydroxyl groups in the non-epoxy resin resin are obtained by coupling vinyl molecules The molecules are modified either by 60%, 70%, 80%, 90%, 95% or 100%.
从热学和电学性能角度出发，当分子结构中乙烯基团数量为1时，固化物分子结构中以线性结构为主，玻璃化转变温度较低，而当乙烯改性树脂的分子量低于245时，乙烯改性树脂的引入对复合材料极性的降低效果难以体现。因此，乙烯改性树脂分子结构必须具有两个以上乙烯基团且分子量高于245。优选地乙烯改性树脂的分子量2000～10000，利于成膜。From the perspective of thermal and electrical properties, when the number of vinyl groups in the molecular structure is 1, the molecular structure of the cured product is dominated by linear structures and the glass transition temperature is low. When the molecular weight of the ethylene modified resin is lower than 245 , the introduction of ethylene modified resin has a difficult effect on reducing the polarity of composite materials. Therefore, the molecular structure of ethylene modified resin must have more than two vinyl groups and a molecular weight higher than 245. Preferably, the molecular weight of the ethylene modified resin is 2,000 to 10,000, which is beneficial to film formation.
进一步地，作为交联剂的酚醛树脂选自线性苯酚甲醛树脂且其羟基当量为100～115g/eq；线性双酚A甲醛树脂且其羟基当量115～125g/eq；XYLOK酚醛树脂且其羟基当量170～185g/eq；联苯酚醛树脂且其羟基当量190～250g/eq；含氮酚醛树脂且其羟基当量110～140g/eq；含磷酚醛树脂且其羟基当量250～350g/eq中的一种或多种混合使用。Further, the phenolic resin as the cross-linking agent is selected from linear phenol formaldehyde resin and its hydroxyl equivalent is 100-115g/eq; linear bisphenol A formaldehyde resin and its hydroxyl equivalent is 115-125g/eq; XYLOK phenolic resin and its hydroxyl equivalent 170～185g/eq; biphenyl phenolic resin with a hydroxyl equivalent weight of 190～250g/eq; nitrogen-containing phenolic resin with a hydroxyl equivalent weight of 110～140g/eq; phosphorus-containing phenolic resin with a hydroxyl equivalent weight of 250～350g/eq. One kind or a mixture of several kinds is used.
进一步地，作为交联剂的氰酸酯树脂选自双酚A型氰酸酯、双酚F型氰酸酯、双酚E型氰酸酯、双酚M型氰酸酯、双环戊二烯型氰酸酯、酚醛型氰酸酯、四甲基双酚F型氰酸酯中的一种或多种混合使用。Further, the cyanate ester resin as the cross-linking agent is selected from the group consisting of bisphenol A-type cyanate ester, bisphenol F-type cyanate ester, bisphenol E-type cyanate ester, bisphenol M-type cyanate ester, and dicyclopentadiene. One or more types of cyanate ester, phenolic cyanate ester, and tetramethylbisphenol F cyanate ester are used in combination.
进一步地，作为交联剂的活性酯树脂选自线性苯酚甲醛活性酯树脂、双酚A甲醛活性酯树脂、双XYLOK活性酯树脂、联苯活性酯树脂、双环戊二烯活性酯树脂、含磷活性酯树脂、含双键活性酯树脂等中的一种或多种混合使用；优选含双键活性酯树脂。Further, the active ester resin as the cross-linking agent is selected from the group consisting of linear phenol formaldehyde active ester resin, bisphenol A formaldehyde active ester resin, bis-XYLOK active ester resin, biphenyl active ester resin, dicyclopentadiene active ester resin, phosphorus-containing One or more of active ester resin, double bond-containing active ester resin, etc. are mixed and used; double bond-containing active ester resin is preferred.
进一步地，第一交联剂、第二交联剂以及第三交联剂之间的质量比为50-100：20-60：1，优选为55-65:25-50:1。Further, the mass ratio between the first cross-linking agent, the second cross-linking agent and the third cross-linking agent is 50-100:20-60:1, preferably 55-65:25-50:1.
本发明介质膜中所使用的环氧树脂指分子结构中含有一个及以上环氧官能团有机树脂。The epoxy resin used in the dielectric film of the present invention refers to an organic resin containing one or more epoxy functional groups in its molecular structure.
进一步地，所述环氧树脂中含乙烯结构的环氧树脂选自烯丙基双酚A环氧树脂、烯丙基酚醛环氧树脂。Further, the epoxy resin containing a vinyl structure in the epoxy resin is selected from the group consisting of allyl bisphenol A epoxy resin and allyl novolac epoxy resin.
进一步地，所述环氧树脂中除含乙烯结构的环氧树脂外还包含至少一种其他环氧树脂，所述其他环氧树脂选自为双酚A型环氧树脂、双酚F型环氧树脂、酚醛型环氧树脂、邻甲酚醛型环氧树脂、邻甲酚醛型环氧树脂、多官能团环氧树脂、脂环族环氧树脂、间苯二酚环氧树脂、橡胶改性环氧树脂、聚氨酯改性环氧树脂、联苯环氧树脂、双环戊二烯环氧树脂中的至少一种或多种的组合。Further, in addition to the epoxy resin containing a vinyl structure, the epoxy resin also includes at least one other epoxy resin, and the other epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin. Oxygen resin, phenolic epoxy resin, o-cresol-type epoxy resin, o-cresol-type epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber modified ring At least one or a combination of at least one of oxygen resin, polyurethane modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin.
在本发明中，双酚A型环氧树脂，如南亚NPEL-128、NPEL-127、NPEL-144、NPES-609、NPES-901、NPES-902、NPES-903、NPES-904、NPES-907、NPES-909,如国都化工YD-001、YD-012、YD-013k、YD-014、YD-134、YD-134D、YD-134L、YD-136、YD-128、YD-127，亨斯迈生产的
Figure PCTCN2022116732-appb-000002
GY 2600、
Figure PCTCN2022116732-appb-000003
GY 6010、
Figure PCTCN2022116732-appb-000004
GY 6020、
Figure PCTCN2022116732-appb-000005
MY 790-1、
Figure PCTCN2022116732-appb-000006
LY 1556、
Figure PCTCN2022116732-appb-000007
GY 507等，双酚F型环氧树脂如南亚生产的NPEF-170、CVC生产的EPALLOY 8220、EPALLOY 8220E、EPALLOY 8230，亨斯迈生产的
Figure PCTCN2022116732-appb-000008
GY 281、
Figure PCTCN2022116732-appb-000009
GY 282、
Figure PCTCN2022116732-appb-000010
GY 285、
Figure PCTCN2022116732-appb-000011
PY 306、
Figure PCTCN2022116732-appb-000012
PY 302-2、
Figure PCTCN2022116732-appb-000013
PY 313等，酚醛型环氧树脂如南亚生产的NPPN-638S、NPPN-631，CVC生产的EPALLOY 8240、EPALLOY 8240、EPALLOY 8250、EPALLOY 8330等，邻甲酚醛型环氧树脂如南亚生产的NPCN-701、NPCN-702、NPCN-703、NPCN-704、NPCN-704L、NPCN-704K80等，多官能团环氧树脂如南亚生产的NPPN-431A70、CVC生产的ERISYS GA-240等，脂环族环氧树脂如CVC生产的EPALLOY 5000、EPALLOY 5200、JE-8421等，间苯二酚环氧树脂如CVC生产的ERISYS RDGE，橡胶改性环氧树脂CVC生产的HyPox RA 95、HyPox RA 840、HyPox  RA 1340、HyPox RF 928、HyPox RM 20、HyPox RM 22、HyPox RK 84L、HyPox RK 820等，聚氨酯改性环氧树脂，联苯环氧树脂如日本三井化学生产的YX4000、YX4000K、YX4000H、YX4000HK、YL6121H、YL6121HN，双环戊二烯环氧树脂，如岳阳巴陵石化生产的CYDB-500、CYDB-700、CYDB-900、CYDB-400、CYDB-450A80等中的一种或多种。 In the present invention, bisphenol A type epoxy resin, such as Nanya NPEL-128, NPEL-127, NPEL-144, NPES-609, NPES-901, NPES-902, NPES-903, NPES-904, NPES-907 , NPES-909, such as Guodu Chemical YD-001, YD-012, YD-013k, YD-014, YD-134, YD-134D, YD-134L, YD-136, YD-128, YD-127, Hens Produced by Mai
Figure PCTCN2022116732-appb-000002
GY 2600,
Figure PCTCN2022116732-appb-000003
GY 6010,
Figure PCTCN2022116732-appb-000004
GY 6020,
Figure PCTCN2022116732-appb-000005
MY 790-1、
Figure PCTCN2022116732-appb-000006
LY 1556,
Figure PCTCN2022116732-appb-000007
GY 507, etc., bisphenol F epoxy resin such as NPEF-170 produced by Nanya, EPALLOY 8220, EPALLOY 8220E, EPALLOY 8230 produced by CVC, and EPALLOY 8230 produced by Huntsman
Figure PCTCN2022116732-appb-000008
GY 281,
Figure PCTCN2022116732-appb-000009
GY 282,
Figure PCTCN2022116732-appb-000010
GY 285,
Figure PCTCN2022116732-appb-000011
PY 306,
Figure PCTCN2022116732-appb-000012
PY 302-2、
Figure PCTCN2022116732-appb-000013
PY 313, etc., phenolic epoxy resins such as NPPN-638S and NPPN-631 produced by Nan Ya, EPALLOY 8240, EPALLOY 8240, EPALLOY 8250, EPALLOY 8330 produced by CVC, etc., o-cresol-type epoxy resins such as NPCN- produced by Nan Ya 701, NPCN-702, NPCN-703, NPCN-704, NPCN-704L, NPCN-704K80, etc., multifunctional epoxy resins such as NPPN-431A70 produced by Nanya, ERISYS GA-240 produced by CVC, etc., alicyclic epoxy Resins such as EPALLOY 5000, EPALLOY 5200, JE-8421, etc. produced by CVC, resorcinol epoxy resins such as ERISYS RDGE produced by CVC, rubber modified epoxy resins HyPox RA 95, HyPox RA 840, HyPox RA 1340 produced by CVC , HyPox RF 928, HyPox RM 20, HyPox RM 22, HyPox RK 84L, HyPox RK 820, etc., polyurethane modified epoxy resin, biphenyl epoxy resin such as YX4000, YX4000K, YX4000H, YX4000HK, YL6121H, produced by Mitsui Chemicals of Japan. YL6121HN, dicyclopentadiene epoxy resin, such as one or more of CYDB-500, CYDB-700, CYDB-900, CYDB-400, CYDB-450A80, etc. produced by Yueyang Baling Petrochemical.
进一步地，环氧树脂占总树脂质量的10-30％。Further, epoxy resin accounts for 10-30% of the total resin mass.
在本发明中，所述填料为球形，最大粒径小于3μm，最小粒径大于10nm，不溶于有机溶剂。In the present invention, the filler is spherical, has a maximum particle size less than 3 μm, a minimum particle size greater than 10 nm, and is insoluble in organic solvents.
进一步地，所述填料选自熔融二氧化硅、水热二氧化硅、沉淀法二氧化硅、氧化铝、氮化硼、二氧化钛、氧化锌、氧化锆、氧化镁、碳酸钙等中的一种或多种混合物的例子。Further, the filler is selected from one of fused silica, hydrothermal silica, precipitated silica, alumina, boron nitride, titanium dioxide, zinc oxide, zirconia, magnesium oxide, calcium carbonate, etc. or examples of mixtures.
进一步地，所述填料粒子的添加量占介质层不含溶剂的总质量的65％以上，例如70％-95％，例如75％、80％、85％、90％。Further, the added amount of the filler particles accounts for more than 65% of the total mass of the medium layer without solvent, such as 70%-95%, such as 75%, 80%, 85%, and 90%.
本发明所述的介质层中还包括助剂，添加量均低于总质量的1％；所述助剂选自偶联剂、分散剂、消泡剂、色素、阻燃剂。The medium layer of the present invention also includes auxiliary agents, and the added amounts are less than 1% of the total mass; the auxiliary agents are selected from coupling agents, dispersants, defoaming agents, pigments, and flame retardants.
本发明另一个方面提供了一种绝缘电介质层，所述绝缘电介质层为由上述绝缘电介质浆料制成的层状复合材料。Another aspect of the present invention provides an insulating dielectric layer, which is a layered composite material made of the above-mentioned insulating dielectric slurry.
进一步地，绝缘电介质层的在高频条件下的介电损耗为0.003以下，所述高频为1-20GHz。优选为0.001-0.0025。Further, the dielectric loss of the insulating dielectric layer under high frequency conditions is 0.003 or less, and the high frequency is 1-20 GHz. Preferably it is 0.001-0.0025.
进一步地，绝缘电介质层的在高频条件下的玻璃转化温度为210℃以上，优选为210℃-230℃。Furthermore, the glass transition temperature of the insulating dielectric layer under high-frequency conditions is 210°C or higher, preferably 210°C-230°C.
本发明又一个方面提供了一种环氧树脂复合材料，所述环氧树脂复合材料由载体膜、介质层、覆盖膜三部分组成，其中所述介质层位于载体膜和覆盖膜中间形成三明治结构，所述介质层为上述绝缘电介质层。Another aspect of the present invention provides an epoxy resin composite material. The epoxy resin composite material is composed of three parts: a carrier film, a dielectric layer, and a cover film, wherein the dielectric layer is located between the carrier film and the cover film to form a sandwich structure. , the dielectric layer is the above-mentioned insulating dielectric layer.
本发明又一个方面提供了上述环氧树脂复合材料的制备方法，将上述绝缘电介质浆料用 搅拌机混合均匀，经过砂磨机分散后使用涂布机将分散的绝缘电介质浆料涂覆于载体膜表面，经溶剂烘干后与覆盖膜复合，形成本发明所述环氧树脂复合材料。Another aspect of the present invention provides a method for preparing the above-mentioned epoxy resin composite material. The above-mentioned insulating dielectric slurry is mixed evenly with a mixer, and after being dispersed by a sand mill, a coater is used to coat the dispersed insulating dielectric slurry on the carrier film. The surface is dried with a solvent and then combined with the covering film to form the epoxy resin composite material of the present invention.
进一步地，载体膜材料聚合物薄膜材料或纸基膜材料，所述聚合物薄膜材料为聚酯薄膜(PET)、聚醚醚酮薄膜(PEEK)、聚醚酰亚胺薄膜(PEI)、聚酰亚胺薄膜(PI)、聚碳酸酯薄膜(PC)；所述纸基膜材料选自离型纸、淋膜纸。Further, the carrier film material is a polymer film material or a paper-based film material, and the polymer film material is polyester film (PET), polyether ether ketone film (PEEK), polyetherimide film (PEI), poly Imide film (PI), polycarbonate film (PC); the paper base film material is selected from release paper and laminated paper.
进一步地，载体膜材料厚度为10μm～300μm，优选为20μm～100μm，更优选为30μm～60μm。Further, the thickness of the carrier film material is 10 μm to 300 μm, preferably 20 μm to 100 μm, and more preferably 30 μm to 60 μm.
所述绝缘电介质浆料能够在支撑薄膜材料表面形成均匀、光滑的薄膜。The insulating dielectric slurry can form a uniform and smooth film on the surface of the supporting film material.
进一步地，覆盖膜材料选自聚合物薄膜材料；优选为聚酯薄膜(PET)、聚丙烯薄膜(OPP)、聚乙烯薄膜(PE)。Further, the covering film material is selected from polymer film materials; preferably polyester film (PET), polypropylene film (OPP), and polyethylene film (PE).
进一步地，保护薄膜材料的厚度为10μm～300μm，优选为20μm～100μm，更优选为30μm～60μm。介于载体膜和覆盖膜之间的绝缘聚合物复合物的厚度为1μm～300μm，优选为10μm～20μm，更优选为15μm～100μm。Further, the thickness of the protective film material is 10 μm to 300 μm, preferably 20 μm to 100 μm, and more preferably 30 μm to 60 μm. The thickness of the insulating polymer composite between the carrier film and the cover film is 1 μm to 300 μm, preferably 10 μm to 20 μm, and more preferably 15 μm to 100 μm.
本发明再一个方面提供了上述绝缘电介质层或环氧树脂复合材料在半导体电子封装领域作为封装介质层中的用途。Another aspect of the present invention provides the use of the above-mentioned insulating dielectric layer or epoxy resin composite material as a packaging dielectric layer in the field of semiconductor electronic packaging.
进一步地，所述半导体电子封装领域选自FC-BGA高密度封装基板、芯片再布线介质层、芯片塑封、芯片粘结、芯片凸点底部填充领域。Further, the semiconductor electronic packaging field is selected from the fields of FC-BGA high-density packaging substrate, chip rewiring dielectric layer, chip plastic packaging, chip bonding, and chip bump underfilling.
有益效果beneficial effects
本发明通过添加乙烯改性树脂以及具有乙烯基的环氧树脂制备介质层浆料，由此制备的介质层具有在高频下介电损耗更低，而玻璃转化温度更高的优势。能够应用于先进制造领域，作为芯片封装。The present invention prepares dielectric layer slurry by adding ethylene modified resin and epoxy resin with vinyl. The dielectric layer prepared thereby has the advantages of lower dielectric loss and higher glass transition temperature at high frequency. Can be used in advanced manufacturing fields as chip packaging.
具体实施方式Detailed ways
为了使本发明的上述目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明，但不能理解为对本发明的可实施范围的限定。In order to make the above objects, features and advantages of the present invention more obvious and understandable, specific embodiments of the present invention are described in detail below, but this should not be understood as limiting the implementable scope of the present invention.
为了使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明，但不能理解为对本发明的可实施范围的限定。In order to make the above objects, features and advantages of the present invention more obvious and understandable, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings, but this should not be understood as limiting the implementable scope of the present invention.
本实施例提供了一种可应用于先进封装领域诸如FC-BGA高密度封装基板、芯片再布线介质层、芯片塑封、芯片粘结、芯片凸点底部填充等半导体电子封装领域中介质层的复合材料及其制备方法。This embodiment provides a compound of dielectric layers in semiconductor electronic packaging fields that can be applied in advanced packaging fields such as FC-BGA high-density packaging substrates, chip rewiring dielectric layers, chip plastic packaging, chip bonding, chip bump bottom filling, etc. Materials and methods of preparation.
合成例1含乙烯结构的酚醛树脂合成物A的制备：Synthesis Example 1 Preparation of phenolic resin composition A containing vinyl structure:
将200g双环戊二烯酚醛树脂SH7117(山东圣泉，羟基当量200g/eq，由双环戊二烯苯酚与甲醛聚合的产物)和90g丙烯酰氯
Figure PCTCN2022116732-appb-000014
溶解于300g甲苯当中，加入反应器并通氮气，升温至50℃，滴加250g浓度为20％的氢氧化钠水溶液，滴加完毕后继续反应2小时。此后，静置分层，去除水层，然后加水搅拌，重复3次以上，待合成物pH值为7时，加热减压蒸馏去除溶剂，得到含乙烯结构的酚醛树脂合成物A。 Mix 200g of dicyclopentadiene phenolic resin SH7117 (Shandong Shengquan, hydroxyl equivalent 200g/eq, polymerized product of dicyclopentadiene phenol and formaldehyde) and 90g of acryloyl chloride
Figure PCTCN2022116732-appb-000014
Dissolve it in 300g of toluene, add it to the reactor and vent it with nitrogen, raise the temperature to 50°C, add dropwise 250g of 20% sodium hydroxide aqueous solution, and continue the reaction for 2 hours after the dropwise addition. Thereafter, the mixture is left to separate and separate, the water layer is removed, and then water is added and stirred, and the process is repeated more than three times. When the pH value of the composition reaches 7, the solvent is removed by heating and vacuum distillation to obtain a phenolic resin composition A containing a vinyl structure.
合成例2含乙烯结构的环氧树脂合成物B的制备：Synthesis Example 2 Preparation of epoxy resin composition B containing ethylene structure:
将30.8g 2,2'-二烯丙基双酚A
Figure PCTCN2022116732-appb-000015
和100g环氧氯丙烷
Figure PCTCN2022116732-appb-000016
溶解至200g二甲苯中，加热至120℃反应2小时，然后降温至60℃。滴加200g浓度为20％的氢氧化钠水溶液，滴加完毕后继续反应2小时。此后，静置分层，去除水层，然后加水搅拌，重复3次以上，待合成物pH值为7时，加热减压蒸馏去除溶剂，得到含乙烯结构的环氧树脂合成物B。 30.8g of 2,2'-diallylbisphenol A
Figure PCTCN2022116732-appb-000015
and 100g epichlorohydrin
Figure PCTCN2022116732-appb-000016
Dissolve in 200g xylene, heat to 120°C for 2 hours, then cool to 60°C. Add 200g of sodium hydroxide aqueous solution with a concentration of 20% dropwise, and continue the reaction for 2 hours after the dropwise addition is completed. Thereafter, the mixture was allowed to stand for stratification, the water layer was removed, and then water was added and stirred, and the process was repeated more than three times. When the pH value of the composition reached 7, the solvent was removed by heating and distillation under reduced pressure to obtain an epoxy resin composition B containing an ethylene structure.
实施例1：Example 1:
根据表1中的原料制备绝缘电介质浆料，用搅拌机混合均匀，经过砂磨机分散后使用涂布机将分散的绝缘电介质浆料涂覆于载体膜表面，经溶剂烘干后获得介质层。Prepare the insulating dielectric slurry according to the raw materials in Table 1, mix it evenly with a mixer, disperse it with a sand mill, and use a coater to coat the dispersed insulating dielectric slurry on the surface of the carrier film. After drying with the solvent, a dielectric layer is obtained.
制备获得的介质层进一步进行测试，检测其在10GHz下的介电损耗，以及玻璃化转变温度(Tg*)。The prepared dielectric layer was further tested to detect its dielectric loss and glass transition temperature (Tg*) at 10GHz.
实时例2-3和对比例1-3采用实施例1的方法，区别仅在于采用表1所示的原料制备进行替换。Real-time Examples 2-3 and Comparative Examples 1-3 adopted the method of Example 1, and the only difference was that the raw material preparation shown in Table 1 was used for substitution.
表1Table 1
Figure PCTCN2022116732-appb-000017
Figure PCTCN2022116732-appb-000017
由上述结果可知，介质膜由乙烯树脂、交联剂、环氧树脂、填料等组成可获得高频低介电损耗和高玻璃化转变温度。It can be seen from the above results that the dielectric film composed of vinyl resin, cross-linking agent, epoxy resin, filler, etc. can achieve high frequency, low dielectric loss and high glass transition temperature.
本发明进一步在实施例1-3的组合物中添加偶联剂、分散剂、消泡剂、色素、阻燃剂等助剂，并检测确认增加助剂对于介电损耗和玻璃转化温度的影响，实验结果显示当助剂总含量低于介质层含量1％时，对介电损耗和玻璃转化温度几乎没有影响。The present invention further adds coupling agents, dispersants, defoaming agents, pigments, flame retardants and other additives to the compositions of Examples 1-3, and detects and confirms the impact of adding additives on dielectric loss and glass transition temperature. , Experimental results show that when the total additive content is less than 1% of the dielectric layer content, it has almost no impact on the dielectric loss and glass transition temperature.

Claims (10)

  1. 一种绝缘电介质浆料，其特征在于，所述绝缘电介质浆料中包含乙烯改性树脂、交联剂、环氧树脂、填料和溶剂；An insulating dielectric slurry, characterized in that the insulating dielectric slurry contains vinyl modified resin, cross-linking agent, epoxy resin, filler and solvent;
    所述乙烯改性树脂为苯乙烯基或乙烯基改性的树脂，且所述乙烯改性树脂中包含两个以上苯乙烯和或乙烯基；乙烯改性树脂为非环氧树脂；The ethylene-modified resin is a styrene-based or vinyl-modified resin, and the ethylene-modified resin contains more than two styrenes and or vinyl groups; the ethylene-modified resin is a non-epoxy resin;
    所述环氧树脂为一种环氧树脂或多种环氧树脂的组合，所述环氧树脂中至少包含一种含乙烯结构的环氧树脂；The epoxy resin is an epoxy resin or a combination of multiple epoxy resins, and the epoxy resin includes at least one epoxy resin containing an ethylene structure;
    所述交联剂为第一交联剂、第二交联剂以及第三交联剂的组合，其中第一交联剂为酚醛树脂、氰酸酯树脂、活性酯树脂中的一种或一种以上的组合；第二交联剂为三烯丙基异三聚氰酸酯、三羟甲基丙烷三甲基丙烯酸酯、三甲代烯丙基异氰酸酯中的一种或一种以上的组合；第三交联剂为过氧化二异丙苯、双叔丁基过氧异丙基苯、过氧化二苯甲酰中的一种或一种以上的组合。The cross-linking agent is a combination of a first cross-linking agent, a second cross-linking agent and a third cross-linking agent, wherein the first cross-linking agent is one or more of a phenolic resin, a cyanate ester resin and an active ester resin. A combination of more than one type; the second cross-linking agent is one or a combination of more than one of triallyl isocyanate, trimethylolpropane trimethacrylate, and trimethallyl isocyanate; The third cross-linking agent is one or a combination of more than one of dicumyl peroxide, di-tert-butyl cumene peroxy, and dibenzoyl peroxide.
  2. 权利要求1所述的绝缘电介质浆料，其特征在于，所述乙烯改性树脂选自苯乙烯改性酚醛树脂、苯乙烯改性醇酸树脂、苯乙烯丙烯酸树脂、苯乙烯改性萜烯树脂、乙烯改性酚醛树脂；The insulating dielectric slurry of claim 1, wherein the vinyl-modified resin is selected from the group consisting of styrene-modified phenolic resin, styrene-modified alkyd resin, styrene acrylic resin, and styrene-modified terpene resin. , Ethylene modified phenolic resin;
    优选地，所述苯乙烯改性酚醛树脂或乙烯改性酚醛树脂通过将酚醛树脂的羟基与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的酚醛树脂；Preferably, the styrene-modified phenolic resin or ethylene-modified phenolic resin is obtained by coupling the hydroxyl group of the phenolic resin with a compound containing a styrene group or a vinyl group to obtain a phenolic resin with styrene or vinyl groups;
    优选地，所述苯乙烯改性醇酸树脂或乙烯改性醇酸树脂通过将醇酸树脂的羟基与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的醇酸树脂；Preferably, the styrene-modified alkyd resin or ethylene-modified alkyd resin is obtained by coupling the hydroxyl group of the alkyd resin with a compound containing a styrene group or a vinyl group. Alkyd resin;
    优选地，所述苯乙烯改性丙烯酸树脂或乙烯改性丙烯酸树脂通过将丙烯酸树脂的丙烯酸基团与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的酚醛树脂；Preferably, the styrene-modified acrylic resin or ethylene-modified acrylic resin is obtained by coupling the acrylic group of the acrylic resin with a compound containing a styrene group or vinyl group to obtain a phenolic resin with styrene or vinyl groups. Resin;
    优选地，所述苯乙烯改性萜烯树脂或乙烯改性萜烯树脂通过将萜烯树脂的羟基基团与含有苯乙烯基团或乙烯基团的化合物进行偶联获得带有苯乙烯或乙烯基的萜烯树脂。Preferably, the styrene-modified terpene resin or ethylene-modified terpene resin is obtained by coupling the hydroxyl group of the terpene resin with a compound containing a styrene group or vinyl group. Based terpene resin.
  3. 权利要求1所述的绝缘电介质浆料，其特征在于，所述的乙烯改性指树脂的两端和或侧链上修饰乙烯基团或苯乙烯基团；The insulating dielectric slurry of claim 1, wherein the vinyl modification refers to the modification of vinyl groups or styrene groups on both ends and or side chains of the resin;
    优选地，所述乙烯改性树脂中苯乙烯基或乙烯基在树脂分子结构的端位，或在分子链段的支链上，或同时在端位和支链；Preferably, the styrene group or vinyl group in the ethylene modified resin is at the terminal position of the resin molecular structure, or on the branch chain of the molecular chain segment, or at the terminal position and branch chain at the same time;
    优选地，在苯乙烯基或乙烯基在端位和支链上或具有两种分子结构树脂的混合使用。Preferably, a mixture of resins having styrene groups or vinyl groups at terminal and branched chains or having two molecular structures is used.
  4. 权利要求1所述的绝缘电介质浆料，其特征在于，所述乙烯改性树脂为具有苯乙烯基和或乙烯基改性的酚醛树脂；The insulating dielectric slurry of claim 1, wherein the vinyl-modified resin is a phenolic resin having a styrene base and/or vinyl modification;
    优选地，所述乙烯改性树脂如下结构式(1)、(2)或(3)所示：Preferably, the ethylene modified resin is represented by the following structural formula (1), (2) or (3):
    Figure PCTCN2022116732-appb-100001
    Figure PCTCN2022116732-appb-100001
    Figure PCTCN2022116732-appb-100002
    Figure PCTCN2022116732-appb-100002
    其中，R选自双环戊二烯、烷基、芳环、取代的芳环、杂芳环，n为1-100；Wherein, R is selected from dicyclopentadiene, alkyl, aromatic ring, substituted aromatic ring, heteroaromatic ring, n is 1-100;
    更优选地，所述芳环选自萘环、蒽、联苯；杂芳环选自吡啶环、吡咯环、吡唑环、嘧啶环、吡嗪环、哒嗪环、噻吩环、呋喃环；More preferably, the aromatic ring is selected from naphthalene ring, anthracene, and biphenyl; the heteroaromatic ring is selected from pyridine ring, pyrrole ring, pyrazole ring, pyrimidine ring, pyrazine ring, pyridazine ring, thiophene ring, and furan ring;
    更优选地，在结构式(1)、(2)或(3)中，R基为联苯、双环戊二烯、萘环、蒽；More preferably, in the structural formula (1), (2) or (3), the R group is biphenyl, dicyclopentadiene, naphthalene ring, or anthracene;
    更优选地，在结构式(1)、(2)或(3)中，n选自2-200。More preferably, in structural formula (1), (2) or (3), n is selected from 2-200.
  5. 权利要求1所述的绝缘电介质浆料，其特征在于，所述乙烯改性树脂的使用量为总树脂质量的20％～50％，所述总树脂质量为乙烯改性树脂、交联剂、环氧树脂的总质量；The insulating dielectric slurry according to claim 1, wherein the usage amount of the ethylene modified resin is 20% to 50% of the total resin mass, and the total resin mass is ethylene modified resin, cross-linking agent, Total mass of epoxy resin;
    所述总树脂质量为乙烯改性树脂、交联剂和环氧树脂的总质量；The total resin mass is the total mass of ethylene modified resin, cross-linking agent and epoxy resin;
    优选地，乙烯改性树脂分子结构中至少含有两个以上乙烯基团且分子量≥245，更优选地乙烯改性树脂的分子量2000～10000；Preferably, the molecular structure of the ethylene modified resin contains at least two or more vinyl groups and the molecular weight is ≥245, and more preferably the molecular weight of the ethylene modified resin is 2,000 to 10,000;
    优选地，乙烯改性树脂分子结构中通过包含乙烯基分子与非环氧树脂的树脂中的羟基偶联获得；更优选地，非环氧树脂的树脂中的50％以上的羟基通过包含乙烯基分子进行改性，或者60％以上、70％以上、80％以上、90％以上、95％以上或100％；Preferably, the molecular structure of the ethylene-modified resin is obtained by coupling vinyl molecules with hydroxyl groups in resins other than epoxy resins; more preferably, more than 50% of the hydroxyl groups in resins other than epoxy resins are obtained by coupling vinyl molecules The molecules are modified, or more than 60%, more than 70%, more than 80%, more than 90%, more than 95% or 100%;
    优选地，作为交联剂的酚醛树脂选自线性苯酚甲醛树脂且其羟基当量为100～115g/eq；线性双酚A甲醛树脂且其羟基当量115～125g/eq；XYLOK酚醛树脂且其羟基当量170～185g/eq；联苯酚醛树脂且其羟基当量190～250g/eq；含氮酚醛树脂且其羟基当量110～140g/eq；含磷酚醛树脂且其羟基当量250～350g/eq中的一种或多种混合使用；Preferably, the phenolic resin as the cross-linking agent is selected from linear phenol formaldehyde resin and its hydroxyl equivalent is 100-115g/eq; linear bisphenol A formaldehyde resin and its hydroxyl equivalent is 115-125g/eq; XYLOK phenolic resin and its hydroxyl equivalent 170～185g/eq; biphenyl phenolic resin with a hydroxyl equivalent weight of 190～250g/eq; nitrogen-containing phenolic resin with a hydroxyl equivalent weight of 110～140g/eq; phosphorus-containing phenolic resin with a hydroxyl equivalent weight of 250～350g/eq. Used alone or in combination;
    优选地，作为交联剂的氰酸酯树脂选自双酚A型氰酸酯、双酚F型氰酸酯、双酚E型氰 酸酯、双酚M型氰酸酯、双环戊二烯型氰酸酯、酚醛型氰酸酯、四甲基双酚F型氰酸酯中的一种或多种混合使用；Preferably, the cyanate ester resin as the cross-linking agent is selected from the group consisting of bisphenol A-type cyanate ester, bisphenol F-type cyanate ester, bisphenol E-type cyanate ester, bisphenol M-type cyanate ester, and dicyclopentadiene. One or more types of cyanate ester, phenolic cyanate ester, and tetramethylbisphenol F cyanate ester are used in combination;
    优选地，作为交联剂的活性酯树脂选自线性苯酚甲醛活性酯树脂、双酚A甲醛活性酯树脂、双XYLOK活性酯树脂、联苯活性酯树脂、双环戊二烯活性酯树脂、含磷活性酯树脂、含双键活性酯树脂等中的一种或多种混合使用；优选含双键活性酯树脂；Preferably, the active ester resin as the cross-linking agent is selected from linear phenol formaldehyde active ester resin, bisphenol A formaldehyde active ester resin, bis-XYLOK active ester resin, biphenyl active ester resin, dicyclopentadiene active ester resin, phosphorus-containing active ester resin One or more of active ester resin, double bond-containing active ester resin, etc. are mixed for use; double bond-containing active ester resin is preferred;
    优选地，第一交联剂、第二交联剂以及第三交联剂之间的质量比为50-100：20-60：1，优选为55-65:25-50:1；Preferably, the mass ratio between the first cross-linking agent, the second cross-linking agent and the third cross-linking agent is 50-100:20-60:1, preferably 55-65:25-50:1;
    优选地，所述环氧树脂中含乙烯结构的环氧树脂选自烯丙基双酚A环氧树脂、烯丙基酚醛环氧树脂；Preferably, the epoxy resin containing a vinyl structure in the epoxy resin is selected from allyl bisphenol A epoxy resin and allyl phenolic epoxy resin;
    优选地，所述环氧树脂中除含乙烯结构的环氧树脂外还包含至少一种其他环氧树脂，所述其他环氧树脂选自为双酚A型环氧树脂、双酚F型环氧树脂、酚醛型环氧树脂、邻甲酚醛型环氧树脂、邻甲酚醛型环氧树脂、多官能团环氧树脂、脂环族环氧树脂、间苯二酚环氧树脂、橡胶改性环氧树脂、聚氨酯改性环氧树脂、联苯环氧树脂、双环戊二烯环氧树脂中的至少一种或多种的组合；Preferably, in addition to the epoxy resin containing a vinyl structure, the epoxy resin also contains at least one other epoxy resin, and the other epoxy resin is selected from the group consisting of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol F-type epoxy resin. Oxygen resin, phenolic epoxy resin, o-cresol-type epoxy resin, o-cresol-type epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber modified ring At least one or a combination of at least one of oxygen resin, polyurethane modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin;
    优选地，环氧树脂占总树脂质量的10-30％；Preferably, epoxy resin accounts for 10-30% of the total resin mass;
    优选地，所述填料选自熔融二氧化硅、水热二氧化硅、沉淀法二氧化硅、氧化铝、氮化硼、二氧化钛、氧化锌、氧化锆、氧化镁、碳酸钙中的一种或多种混合物；Preferably, the filler is selected from one of fused silica, hydrothermal silica, precipitated silica, alumina, boron nitride, titanium dioxide, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, or various mixtures;
    优选地，所述填料粒子的添加量占介质层不含溶剂的总质量的65％以上。Preferably, the added amount of the filler particles accounts for more than 65% of the total mass of the medium layer without solvent.
  6. 权利要求1所述的绝缘电介质浆料，其特征在于，绝缘电介质浆料还包括助剂，添加量均低于总质量的1％；所述助剂选自偶联剂、分散剂、消泡剂、色素、阻燃剂。The insulating dielectric slurry according to claim 1, characterized in that the insulating dielectric slurry also includes auxiliary agents, and the added amounts are less than 1% of the total mass; the auxiliary agents are selected from the group consisting of coupling agents, dispersants, and defoaming agents. agents, pigments, and flame retardants.
  7. 一种绝缘电介质层，其特征在于，所述绝缘电介质层为由权利要求1-6任一项所述的 绝缘电介质浆料制成的层状复合材料；An insulating dielectric layer, characterized in that the insulating dielectric layer is a layered composite material made of the insulating dielectric slurry according to any one of claims 1-6;
    优选地，绝缘电介质层的在高频条件下的介电损耗为0.003以下，所述高频为1-20GHz；Preferably, the dielectric loss of the insulating dielectric layer under high frequency conditions is 0.003 or less, and the high frequency is 1-20 GHz;
    优选地，绝缘电介质层在高频条件下的玻璃转化温度为210℃以上，更优选为210℃-230℃。Preferably, the glass transition temperature of the insulating dielectric layer under high frequency conditions is 210°C or above, more preferably 210°C to 230°C.
  8. 一种环氧树脂复合材料，其特征在于，所述环氧树脂复合材料由载体膜、介质层、覆盖膜三部分组成，其中所述介质层位于载体膜和覆盖膜中间形成三明治结构，所述介质层为权利要求7所述的绝缘电介质层；An epoxy resin composite material, characterized in that the epoxy resin composite material is composed of three parts: a carrier film, a dielectric layer, and a covering film, wherein the dielectric layer is located between the carrier film and the covering film to form a sandwich structure, and the The dielectric layer is the insulating dielectric layer according to claim 7;
    优选地，载体膜材料聚合物薄膜材料或纸基膜材料，所述聚合物薄膜材料为聚酯薄膜(PET)、聚醚醚酮薄膜(PEEK)、聚醚酰亚胺薄膜(PEI)、聚酰亚胺薄膜(PI)、聚碳酸酯薄膜(PC)；所述纸基膜材料选自离型纸、淋膜纸；Preferably, the carrier film material is a polymer film material or a paper-based film material, and the polymer film material is polyester film (PET), polyether ether ketone film (PEEK), polyetherimide film (PEI), poly Imide film (PI), polycarbonate film (PC); the paper base film material is selected from release paper and coated paper;
    优选地，载体膜材料厚度为10μm～300μm；Preferably, the thickness of the carrier film material is 10 μm to 300 μm;
    优选地，覆盖膜材料选自聚合物薄膜材料；优选为聚酯薄膜(PET)、聚丙烯薄膜(OPP)、聚乙烯薄膜(PE)；Preferably, the covering film material is selected from polymer film materials; preferably polyester film (PET), polypropylene film (OPP), polyethylene film (PE);
    优选地，保护薄膜材料的厚度为10μm～300μm；Preferably, the thickness of the protective film material is 10 μm to 300 μm;
    优选地，介于载体膜和覆盖膜之间的绝缘聚合物复合物的厚度为1μm～300μm。Preferably, the thickness of the insulating polymer composite between the carrier film and the cover film is 1 μm to 300 μm.
  9. 权利要求8所述的环氧树脂复合材料的制备方法，其特征在于，将权利要求1-6任一项所述的绝缘电介质浆料用搅拌机混合均匀，经过砂磨机分散后使用涂布机将分散的绝缘电介质浆料涂覆于载体膜表面，经溶剂烘干后与覆盖膜复合，形成权利要求8所述环氧树脂复合材料。The preparation method of epoxy resin composite material according to claim 8, characterized in that the insulating dielectric slurry according to any one of claims 1 to 6 is mixed evenly with a stirrer, and then dispersed by a sand mill and then a coater is used. The dispersed insulating dielectric slurry is coated on the surface of the carrier film, dried with a solvent and then combined with the covering film to form the epoxy resin composite material of claim 8.
  10. 权利要求7所述的绝缘电介质层或权利要求8所述的环氧树脂复合材料在半导体电 子封装领域作为封装介质层中的用途；The use of the insulating dielectric layer of claim 7 or the epoxy resin composite material of claim 8 as a packaging dielectric layer in the field of semiconductor electronic packaging;
    优选地，所述半导体电子封装领域选自FC-BGA高密度封装基板、芯片再布线介质层、芯片塑封、芯片粘结、芯片凸点底部填充领域。Preferably, the semiconductor electronic packaging field is selected from the field of FC-BGA high-density packaging substrate, chip rewiring dielectric layer, chip plastic packaging, chip bonding, and chip bump underfilling.
PCT/CN2022/116732 2022-09-02 2022-09-02 Epoxy resin adhesive film material applied to semiconductor system-level packaging WO2024045159A1 (en)

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