CN116640404A - High-dielectric, high-heat-conductivity and low-loss electronic resin and application thereof - Google Patents

High-dielectric, high-heat-conductivity and low-loss electronic resin and application thereof Download PDF

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CN116640404A
CN116640404A CN202310742157.0A CN202310742157A CN116640404A CN 116640404 A CN116640404 A CN 116640404A CN 202310742157 A CN202310742157 A CN 202310742157A CN 116640404 A CN116640404 A CN 116640404A
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styrene
dielectric
electronic
resin
butadiene
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刘永成
向中荣
高玉佳
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Wuxi Relong New Material Technology Co ltd
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Wuxi Relong New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The application relates to the technical field of high-frequency electronic communication materials, and particularly discloses high-dielectric, high-heat-conductivity and low-loss electronic resin and application thereof. The electronic resin comprises the following components: hydrocarbon resin composition, functional filler, wetting dispersant, flame retardant, antioxidant and crosslinking agent; wherein, the hydrocarbon resin composition at least contains a styrene-butadiene-butylene-styrene block copolymer, and the hydrocarbon resin composition also contains at least one of a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer and maleic anhydride grafted polyolefin; the functional filler is pretreated by wetting dispersant. The electronic resin can be used for preparing a high-frequency copper-clad plate, and the prepared high-frequency copper-clad plate has the dielectric constant as high as 6.15, the dielectric loss value as low as 0.0035 and the heat conductivity coefficient as high as 0.8W/(m.k) under the detection condition of 10GHz, and has more excellent dielectric property and service performance.

Description

High-dielectric, high-heat-conductivity and low-loss electronic resin and application thereof
Technical Field
The application relates to the technical field of high-frequency electronic communication materials, in particular to an electronic resin with high dielectric property, high heat conduction and low loss and application thereof.
Background
The 5G communication has the characteristics of high-speed transmission, low time delay, high connection density and the like, and the copper-clad plate widely used in 5G equipment is required to have the characteristics of excellent dielectric property, high thermal conductivity, good heat resistance, high reliability and the like. With the rapid development of 5G and 6G, there is a higher requirement on the design and processing of high-frequency copper-clad plates, and there is a trend of information processing speed increase and signal transmission high frequency.
At present, polytetrafluoroethylene, polyphenyl ether and hydrocarbon resin are generally selected as matrix resins for the electronic resin for the high-frequency copper-clad plate. Although the polytetrafluoroethylene resin has better electrical property and excellent dielectric property stability, the prepared copper-clad plate needs special treatment, such as pre-treatment of plating holes, in the PCB processing. In addition, due to the extremely low surface energy of polytetrafluoroethylene, the obtained bonding sheet is usually subjected to pretreatment by adopting plasma, so that the interface can be better combined when the bonding sheet and the copper foil are mixed and pressed.
The polyphenylene ether resin has advantages of low specific gravity, low water absorption, excellent heat resistance and chemical resistance, good electrical insulation, excellent dielectric properties, and the like, but still has the following drawbacks: first, the polyphenylene ether resin can produce dielectric loss value D f The dielectric loss value of the copper-clad plate ranges from 0.005 to 0.006, and as a high-frequency copper-clad plate, the dielectric loss value still has a further reduced space. Second, the polyphenylene ether resin is difficult to undergo a curing reaction, and its processability is to be improved.
Hydrocarbon resins also have good dielectric properties. Unlike polytetrafluoroethylene, the high-frequency copper-clad plate prepared by the method does not need to be pretreated. The dielectric loss value of the copper-clad plate prepared by the method is controlled below 0.005. However, the heat conductivity coefficient of hydrocarbon resin is lower, and based on the requirement of high heat conductivity of the copper-clad plate, a heat-conducting filler is generally added into the hydrocarbon resin for modification. The density of the heat conducting filler is large, the mass ratio of the heat conducting filler in the electronic resin is large, the heat conducting filler is difficult to fully disperse in hydrocarbon resin, the heat conducting performance of the final electronic resin is limited to be improved, and the dielectric constant of the electronic resin is also improved. In addition to the above drawbacks, the incorporation of the filler may cause a decrease in the bonding performance of the adhesive sheet made of the electronic resin with a metal substrate such as copper foil, and also may easily cause an increase in the coefficient of thermal expansion of the adhesive sheet, and a decrease in the thermal stability.
In summary, the dielectric constant of the current high-frequency copper-clad plate is generally below 5.75 (10 GHz), the heat conductivity coefficient is below 0.50w/mk, and the dielectric loss value is difficult to meet the requirement below 0.0040 (10 GHz). Therefore, how to obtain the high-frequency copper-clad plate with high dielectric property, low loss, high heat conduction and stable performance still has the technical difficulties in the industry.
Disclosure of Invention
Aiming at the related problems, the application provides the high-dielectric, high-heat-conductivity and low-loss electronic resin and the application thereof, and the prepared copper-clad plate has the characteristics of high dielectric, low-loss and high heat conductivity and meets the requirements of better processability and thermal stability.
In a first aspect, the present application provides an electronic resin with high dielectric properties, high thermal conductivity and low loss, which adopts the following technical scheme:
the high-dielectric, high-heat-conductivity and low-loss electronic resin comprises the following components in parts by weight:
25-45 parts of hydrocarbon resin composition, 30-70 parts of functional filler, 0.1-5 parts of wetting dispersant, 10-30 parts of flame retardant, 0.1-1 part of antioxidant and 0.5-5 parts of cross-linking agent;
wherein the hydrocarbon resin composition at least contains a styrene-butadiene-butylene-styrene block copolymer, and at least one of a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer and a maleic anhydride grafted polyolefin;
the functional filler is pretreated by wetting dispersant.
By adopting the technical scheme, the styrene-butadiene-butylene-styrene block copolymer is obtained by directional partial hydrogenation of the styrene-butadiene-styrene block copolymer, and the main chain of the styrene-butadiene-styrene block copolymer still maintains partial carbon-carbon double bonds and has certain reaction crosslinking activity; compounding with high-reactivity resin such as styrene-butadiene copolymer, styrene-divinylbenzene copolymer, maleic anhydride grafted polyolefin and the like, on one hand, a three-dimensional crosslinked network structure is easy to form under the action of a crosslinking agent, and the adhesive sheet formed by curing the electronic resin is endowed with excellent dielectric property, low thermal expansion coefficient and higher glass transition temperature; on the other hand, the larger the molecular weight of the styrene-butadiene-butylene-styrene block copolymer is, the more the physical entanglement points of long molecular chains are, the toughness of the bonding sheet can be improved, and the processing performance of the bonding sheet is improved.
The functional filler can be selected from high dielectric filler titanium dioxide, strontium titanate, calcium titanate, barium titanate and the like, or can be selected from silicon micropowder, or can be compounded by selecting various powder with different functions. The wetting dispersant may be selected from the group consisting of, but not limited to, modified aminosilanes, anilinosilanes, vinylsilane coupling agents, epoxysilane coupling agents, methoxysilanes, phenylsilane coupling agents, coordinating titanate coupling agents, and polyphosphate solutions.
The functional filler is subjected to wetting dispersant modification treatment, and has the following advantages: firstly, no matter the density of the functional filler is too large or too small, the functional filler can be stably dispersed in the hydrocarbon resin composition, which is favorable for improving the tensile strength and the compressive strength of a condensate formed by the later-stage electronic resin and improving the stability of the high-frequency copper-clad plate. Second, due to the sufficient dispersion of the functional filler, the more interfaces between the filler and the hydrocarbon resin, the more significant the interface polarization effect during polarization, thereby also improving the dielectric properties of the electronic resin. Thirdly, in the process of curing the electronic resin, the electronic resin is not easy to be layered due to the density problem of the filler, so that the overall bonding strength and the thermal stability of the high-frequency copper-clad plate are improved.
The flame retardant in the application is selected from one or more of brominated flame retardant, phosphorus flame retardant, nitrogen flame retardant, organic silicon flame retardant and zinc stannate flame retardant; according to the application, the organic flame retardant and the inorganic flame retardant are compounded, so that the flame retardant efficiency can be greatly improved, and the UL-94V0 level can be obtained under the condition of less addition.
The antioxidant of the application comprises main antioxidants such as p-phenylenediamine, hydroxylamine, diphenylamine, alkyl polyphenols, thiobisphenol, hindered phenols and the like, and also comprises auxiliary antioxidants such as thioether and phosphite esters; the main antioxidant and the auxiliary antioxidant are compounded, so that the synergistic effect is good, the thermal stability of the hydrocarbon resin composition in processing and later application is greatly improved, especially the main chain oxidation of the styrene-butadiene-butylene-styrene block copolymer is inhibited, the defect that the hydrocarbon resin composition is easy to yellow is overcome, and the reliability of the high-frequency copper-clad plate is improved.
The cross-linking agent in the application is selected from azo initiators such as azo-diisoheptonitrile, benzoyl peroxide, organic peroxy initiators such as 1, 1-bis (tertiary butyl peroxy) -3, 5-trimethylcyclohexane and inorganic initiators such as mixtures of hot air vulcanization peroxides; in the application, initiator auxiliary agents such as stilbene, triallyl isocyanate and the like can be added, and the crosslinking rate of the electronic resin is controlled in a proper range through compounding of the crosslinking agent and the initiator auxiliary agents.
In summary, according to the application, the styrene-butadiene-butylene-styrene block copolymer is selected to be compounded with other high-activity hydrocarbon resins, and the functional filler subjected to the modification treatment of the wetting dispersant is added into the hydrocarbon resin composition, so that the electronic resin can form the bonding sheet with excellent dielectric property, excellent heat resistance and excellent processability under the action of the crosslinking agent. The inventor detects the copper-clad plate made of the bonding sheet to find that: at a high frequency of 10GHz, the dielectric constant of the copper-clad plate is up to 6.15, the dielectric loss value is reduced to 0.0035 (10 GHz), the heat conductivity coefficient is up to 0.8W/(m.k), and compared with the copper-clad plate on the market at present, the copper-clad plate has more excellent dielectric property and service performance. Thereby successfully solving the technical problems of the application.
Further, the hydrocarbon resin composition comprises a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer, a styrene-butadiene-butylene-styrene block copolymer and a maleic anhydride grafted polyolefin. Among these, the choice of maleic anhydride grafted polyolefin includes, but is not limited to, maleic anhydride grafted polybutadiene, maleic anhydride grafted polystyrene-butadiene.
Further, the weight ratio of the styrene-butadiene copolymer, the styrene-divinylbenzene copolymer, the styrene-butadiene-butylene-styrene block copolymer and the maleic anhydride grafted polyolefin in the hydrocarbon resin composition is (5-15): 5-10): 3.
By adopting the technical scheme, the hydrocarbon resin has the following advantages under the combined action:
firstly, the maleic anhydride grafted polyolefin can promote the compatibility among other hydrocarbon resins, so that the toughness of the electronic resin is improved, and the processability of the bonding sheet is improved. Secondly, as the compatibility among the resins is increased, and the styrene-butadiene copolymer, the styrene-divinylbenzene copolymer and the styrene-butadiene-butylene-styrene block copolymer have better dielectric properties, the defect that the addition of polar maleic anhydride grafted polyolefin easily causes the increase of dielectric loss is overcome, the dielectric constant of the electronic resin is obviously increased, and meanwhile, the dielectric loss is not increased and reduced; the hydrocarbon resin is used together to play a role in synergism in improving dielectric properties of the electronic resin, so that the electronic resin is suitable for preparing a higher-frequency copper-clad plate. Thirdly, in the styrene-butadiene copolymer, there is a polybutadiene structure with high 1,2 polymerization; the divinylbenzene in the styrene-divinylbenzene copolymer has side double bonds capable of being crosslinked, the resin reactivity is increased, so that the polymer has higher crosslinking density, and the prepared high-frequency copper-clad plate has higher glass transition temperature and greatly improves the heat resistance. Fourth, the maleic anhydride grafted polyolefin can promote the binding force between hydrocarbon resin and filler and between hydrocarbon resin and metal base material, so that the overall stability of the high-frequency copper-clad plate is enhanced.
Further, the number average molecular weight of the styrene-butadiene-butylene-styrene block copolymer in the hydrocarbon resin composition is 50000-200000, the number average molecular weight of the styrene-butadiene copolymer is 1000-100000, the number average molecular weight of the styrene-divinylbenzene copolymer is 5000-20000, and the number average molecular weight of the maleic anhydride grafted polyolefin is 1000-10000.
Further, the number average molecular weight of the styrene-butadiene-butylene-styrene block copolymer in the hydrocarbon resin composition is 100000-200000, the number average molecular weight of the styrene-butadiene copolymer is 2000-100000, the number average molecular weight of the styrene-divinylbenzene copolymer is 5000-10000, and the number average molecular weight of the maleic anhydride grafted polyolefin is 1000-5000.
By adopting the technical scheme, the lower the molecular weight of each resin in the hydrocarbon resin composition is, the lower the viscosity of the resin composition is, the better the impregnating effect on glass fibers can be achieved in the later stage of impregnating the glass fiber cloth, but when the molecular weight of the hydrocarbon resin is too low, particularly when the molecular weight of the styrene-butadiene-butylene-styrene block copolymer is too low, the whole toughness of the bonding sheet is reduced by curing the electronic resin, so that the later stage processing of the bonding sheet is not facilitated; therefore, in this number average molecular weight range, the comprehensive usability of the electronic resin can be balanced.
Further, the functional filler comprises a high-dielectric filler with a dielectric constant of more than or equal to 100.
Furthermore, the high dielectric filler is rutile titanium dioxide.
By adopting the technical scheme, the rutile titanium dioxide with high dielectric constant is selected as a component of the functional filler, so that the electronic resin is promoted to have more excellent dielectric property; the hydrocarbon resin and the wetting dispersant can be fully coated on the surface of the rutile type titanium dioxide, so that the defect that the rutile type titanium dioxide is easy to absorb moisture is overcome, and the electronic resin also has better temperature stability and frequency stability of dielectric property.
Further, the high dielectric filler consists of titanium dioxide with an average particle size of 0.5-5 mu m.
By adopting the technical scheme, titanium dioxide with various particle sizes is compounded, so that the stacking density of the dielectric filler can be improved, and the moisture absorption rate of the dielectric filler can be further reduced. Meanwhile, the titanium dioxide with small particle size has large specific surface area, and the interface between the titanium dioxide and the hydrocarbon resin composition is increased, so that the interface polarization effect is more remarkable in the polarization process, and the dielectric property is greatly improved.
Further, the titanium dioxide is pretreated by using a polyphosphate solution.
Through the adoption of the technical scheme, the polyphosphate solution has excellent wetting and dispersing effects on the titanium pigment, and meanwhile, the combination between the titanium pigment and the hydrocarbon resin composition can be enhanced, so that the dispersing effect of the titanium pigment in the electronic resin is excellent and stable, and the dielectric property of the electronic resin is further improved.
Further, the functional filler also comprises silica micropowder.
Further, the fine silica powder is composed of angular fine silica powder having an average particle diameter of 2 μm to 12 μm and spherical fine silica powder having a particle diameter of 3 μm to 10 μm.
Furthermore, the silicon micropowder is pretreated by using an acrylic silane coupling agent and an epoxy coupling agent.
By adopting the technical scheme, the silicon micro powder has excellent electrical insulation performance, is used as a component of the functional filler, and can be added into the electronic resin to endow the copper-clad material with excellent insulation, heat conductivity and thermal stability, improve the bending strength and dimensional stability of the board, reduce the thermal expansion rate of the board and improve the dielectric constant of the copper-clad plate;
the acrylic acid silane coupling agent and the epoxy coupling agent have better effect of improving the dispersion of the silicon micro powder, and meanwhile, the acrylic acid silane coupling agent and the epoxy coupling agent can also increase the crosslinking density inside the electronic resin, thereby assisting in improving the dielectric property and the heat resistance of the electronic resin.
In a second aspect, the present application provides an application of an electronic resin with high dielectric, high thermal conductivity and low loss, which adopts the following technical scheme:
the application of the high-dielectric, high-heat-conductivity and low-loss electronic resin is characterized in that the bonding sheet and the high-frequency copper-clad plate are prepared according to the following steps:
preparation of an adhesive sheet:
adding the hydrocarbon resin composition into a solvent for dispersion to obtain a resin dispersion;
dispersing a wetting dispersant in a solvent, and then adding a functional filler and a flame retardant for dispersion to obtain a filler suspension;
blending the resin dispersion liquid and the filler suspension liquid, adding an antioxidant and a cross-linking agent for dispersion, and obtaining electronic resin;
dipping the glass fiber base cloth in electronic resin, and baking to obtain a bonding sheet;
preparing a high-frequency copper-clad plate:
selecting bonding sheets, coating copper foils on two sides, and carrying out vacuum hot pressing to obtain the high-frequency copper-clad plate.
Compared with the prior art, the application has the following beneficial technical effects:
1. according to the application, the styrene-butadiene-butylene-styrene block copolymer is selected to be compounded with other high-activity hydrocarbon resins, and the functional filler subjected to the modification treatment of the wetting dispersant is added into the hydrocarbon resin composition, so that the electronic resin can form a bonding sheet with excellent dielectric property, excellent heat resistance and excellent processability under the action of the crosslinking agent. The inventor detects the copper-clad plate made of the bonding sheet to find that: at a high frequency of 10GHz, the dielectric constant of the copper-clad plate is up to 6.15, the dielectric loss value is reduced to 0.0035 (10 GHz), the heat conductivity coefficient is up to 0.8W/(m.k), and compared with the copper-clad plate on the market at present, the copper-clad plate has more excellent dielectric property and service performance.
2. The rutile titanium dioxide with different particle sizes is selected for compounding, so that the packing density of the filler can be improved, and the moisture absorption rate of the filler can be further reduced. Meanwhile, the titanium dioxide with small particle size has large specific surface area, and the interface between the titanium dioxide and the hydrocarbon resin composition is increased, so that the interface polarization effect is more remarkable in the polarization process, and the dielectric property is greatly improved.
3. The application has the advantages of easily obtained raw materials, easy realization of the process, certain similarity with the conventional thermosetting vertical sizing process and lamination, and convenience for mass production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be further described with reference to examples, comparative examples and application examples.
The sources of raw materials used in the following examples, comparative examples and application examples are as follows, unless otherwise specified:
styrene-butadiene-butylene-styrene block copolymers are custom products:
SBBS1: a number average molecular weight of 50000; SBBS2: number average molecular weight 100000; SBBS3: the number average molecular weight is 200000;
styrene-butadiene copolymers are custom products:
SBS1: a number average molecular weight of 1000; SBS2: a number average molecular weight of 2000; SBS3: number average molecular weight 10000;
styrene-divinylbenzene copolymers are custom products:
ST-DVB1: a number average molecular weight of 5000; ST-DVB2: number average molecular weight 10000; ST-DVB3: number average molecular weight 20000;
maleic anhydride grafted polybutadiene is a custom product:
MLPB1: a number average molecular weight of 1000; MLPB2: a number average molecular weight of 5000; MLPB3: number average molecular weight 10000;
epoxy silane coupling agent: the brand KH560 is from Shandong Siemens;
acrylic silane coupling agent: brand Z-6030, derived from daokanning;
polyphosphonate solution: the trademark DIPERBYK-110, from Pick chemistry;
coordinated titanate coupling agent: brand TYZOR 726, derived from Nanjing Pinning;
brominated flame retardant: the brand 8010 is derived from Yabao;
hydroxylamine antioxidant: the brand Revonox 420 is derived from Shanghai uncut exhibition industry.
Examples
An electronic resin with high dielectric property, high heat conduction and low loss is prepared by the following steps:
preparing a styrene-butadiene copolymer (SBS 2), a styrene-divinylbenzene copolymer (ST-DVB 2), a styrene-butadiene-butylene-styrene block copolymer (SBBS 2), a maleic anhydride-grafted polybutadiene (MLPB 2) as a hydrocarbon resin composition;
slowly adding hydrocarbon resin composition into toluene serving as a solvent under the condition of stirring at the speed of 400r/min, mixing and stirring for 75min until the hydrocarbon resin composition is completely dispersed in toluene to form uniform resin dispersion;
toluene is taken as a solvent, the rotating speed is set to be 200r/min, an epoxy silane coupling agent KH560, an acrylic silane coupling agent Z-6030 and a polyphosphate wetting dispersant DISPRBYK-110 are added, stirring is carried out for 20min, silicon micropowder, titanium dioxide and a flame retardant 8010 are sequentially added, the rotating speed is set to be 1200r/min, and stirring is continued for 90 min, so that filler suspension is prepared;
wherein the silicon micropowder consists of angular silicon micropowder with average particle diameters of 2 μm, 5 μm and 12 μm and spherical silicon micropowder with average particle diameters of 3 μm, 6 μm and 10 μm; the titanium dioxide consists of 0.5 mu m, 2 mu m and 5 mu m rutile type titanium dioxide;
mixing the resin dispersion liquid and the filler suspension liquid together, setting the rotating speed to 600r/min, sequentially adding an antioxidant Revonox 420, a cross-linking agent divinylbenzene and dicumyl peroxide, and continuously stirring for 160min to obtain electronic resin;
examples 1-3 were prepared according to the above protocol, except that the amounts of the respective materials were varied, and the specific amounts of the materials were as shown in Table 1 below.
TABLE 1 raw material composition (in g) for examples 1-3
Examples 4 to 8
An electronic resin with high dielectric, high heat conduction and low loss is based on the embodiment 1, and the difference from the embodiment 1 is that: the hydrocarbon resins were varied in composition and the specific compositions are shown in table 2 below.
TABLE 2 selection of hydrocarbon resin compositions of examples 4-8 (in g)
Examples 9 to 12
An electronic resin with high dielectric, high heat conduction and low loss is based on the embodiment 1, and is different from the embodiment 1 in the composition of the functional filler, and the specific composition is as follows:
in example 9, the titanium dioxide in example 1 is replaced by 40g of rutile titanium dioxide with an average particle size of 5 μm;
in example 10, the titanium dioxide in example 1 was replaced by anatase titanium dioxide having an average particle size of 0.5 μm, 2 μm, 5 μm, etc., wherein the weight ratio of the anatase titanium dioxide having an average particle size of 0.5 μm, 2 μm, 5 μm was 3:3:2.
In example 11, the fine silica powder in example 1 was replaced with 6g of fine silica powder having an average particle diameter of 2. Mu.m, 6g of fine silica powder having a spherical shape of 10. Mu.m, and the like.
In example 12, the silica fine powder in example 1 was replaced by 12g of spherical silica fine powder having an average particle diameter of 3 μm, 6 μm, 10 μm, etc., wherein the weight ratio of the spherical silica fine powder having an average particle diameter of 3 μm, 6 μm, 10 μm was 1:1:1.
Example 13
An electronic resin with high dielectric, high heat conduction and low loss is based on the embodiment 1, and is different from the embodiment 1 in the composition of the functional filler, and the specific composition is as follows:
in this example, 12g of alumina powder having an average particle diameter of 3 μm, 6 μm, 10 μm and the like was used instead of the silica powder, wherein the weight ratio of the alumina powder having an average particle diameter of 3 μm, 6 μm, 10 μm was 1:1:1.
Example 14
An electronic resin with high dielectric, high heat conduction and low loss is based on the embodiment 1, and the difference from the embodiment 1 is that: the wetting and dispersing agents adopted in the pretreatment of the titanium dioxide are different, and the specific steps are as follows:
in this example, the replacement of the polyphosphate solution with the coordination type titanate coupling agent TYZOR 726 was performed in equal parts by weight.
Examples 15 to 17
An electronic resin with high dielectric, high heat conduction and low loss is based on the embodiment 1, and the difference from the embodiment 1 is that: the wetting and dispersing agents adopted in the pretreatment of the silica micropowder are different, and the specific steps are as follows:
in example 15, 3g of acrylic silane coupling agent Z-6030 was used instead of 2g of acrylic silane coupling agent Z-6030 and 1g of epoxy silane coupling agent KH560;
in example 16, 3g of epoxy silane coupling agent KH560 was used instead of 2g of acrylic silane coupling agent Z-6030 and 1g of epoxy silane coupling agent KH560;
in example 17, 3g of vinyl silane coupling agent KH-172 was used instead of 2g of acrylic silane coupling agent Z-6030 and 1g of epoxy silane coupling agent KH560.
Comparative example
Comparative examples 1 to 4
An electronic resin based on example 1 differs from example 1 in that: the hydrocarbon resin composition may vary in composition,
in comparative example 1, a mass equivalent to maleic anhydride grafted polybutadiene MLPB2 was used instead of styrene-butadiene-butylene-styrene block copolymer SBBS2;
in comparative example 2, styrene-butadiene copolymer SBS2 was used in place of styrene-butadiene-butylene-styrene block copolymer SBBS2 in equal mass;
in comparative example 3, a mass such as SEBS (number average molecular weight 10000) was used instead of the styrene-butadiene-butylene-styrene block copolymer SBBS2;
in comparative example 4, 2.5g of styrene-butadiene copolymer SBS2 and 2.5g of SEBS (number average molecular weight 10000) were used in place of styrene-butadiene-butylene-styrene block copolymer SBBS2 in equal mass.
Comparative example 5
An electronic resin based on example 1 differs from example 1 in that: the electronic resin is not doped with wetting dispersant, i.e. the functional filler is not treated by the wetting dispersant.
Application example
Application example 1
The high-frequency copper-clad plate is manufactured according to the following steps:
using 1080 electronic grade glass fiber cloth as a reinforcing material, coating electronic resin prepared in the embodiment 1 on two sides, and drying to prepare a single bonding sheet with the thickness of 0.101 mm;
16 bonding sheets are selected, 1OZ TWS copper foil is coated on two sides, and the high-frequency copper-clad plate with high dielectric property, high heat conduction and low loss is prepared by hot pressing for 240min at the temperature of 240 ℃ and the pressure of 900psi by using a vacuum press.
Application examples 2 to 17 and application comparative examples 1 to 5
The high-frequency copper-clad plate is based on application example 1, and differs from application example 1 in that: the sources of the electronic resins vary and the specific sources are shown in Table 3 below.
TABLE 3 sources of electronic resins in application examples and comparative examples
Application example Sources of electronic resins Application example Sources of electronic resins Application example Sources of electronic resins
Application example 2 Example 2 Application example 9 Example 9 Application example 16 Example 16
Application example 3 Example 3 Application example 10 Example 10 Application example 17 Example 17
Application example 4 Example 4 Application example 11 Example 11 Comparative example 1 was used Comparative example 1
Application example 5 Example 5 Application example 12 Example 12 Comparative example 2 was used Comparative example 2
Application example 6 Example 6 Application example 13 Example 13 Comparative example 3 was used Comparative example 3
Application example 7 Example 7 Application example 14 Example 14 Comparative example 4 was used Comparative example 4
Application example 8 Example 8 Application example 15 Example 15 Comparative example 5 was used Comparative example 5
Performance detection
The following tests were carried out for application examples 1 to 17 and application comparative examples 1 to 5:
1. dielectric constant D k : using SPDR (separation column dielectric resonator)) A characteristic parameter test method of dielectric materials is used for measuring the dielectric constant at 10 GHz;
2. temperature change rate of dielectric constant:
the calculation is carried out according to the following formula: alpha ε ＝(1/ε)×(d ε /d t )；
When the relation between epsilon and t can be regarded as a straight line in a certain test temperature range, alpha ε ＝(1/ε 1 ) X (Δε/Δt), where Δε=ε 2 -ε 1 ，Δt＝t 2 -t 1 ,ε 2 、ε 1 At a temperature t 2 、t 1 Capacitance at time;
3. dielectric loss value D f : measuring a dielectric loss value at 10GHz by adopting a characteristic parameter test method of an SPDR (separation column dielectric resonator) dielectric material;
4.Z shaft coefficient of thermal conductivity: the thermal conductivity coefficient in the Z-axis direction is tested by referring to the detection method described in ASTMD5470, and the unit is W/mK;
5. coefficient of thermal expansion: measuring the thermal expansion coefficient on the Z axis by referring to GB/T36800.2-2018 plastic thermal mechanical analysis method 3.2, wherein the test temperature range is 50-260 ℃ and the unit ppm/°c;
6. peel strength: units (lb/inch)/1 oz copper foil, as specified in GB/15821-1995;
7. water absorption rate: reference is made to the method specified in IPC-TM-650 in units of 2.6.2.1.
Detection result
TABLE 4 detection results of application examples 1-3 and application comparative examples 1-5
TABLE 5 detection results of application examples 4-10
TABLE 6 detection results of application examples 11-17
As can be seen from the combination of application example 1 and application comparative example 1 and from table 4, the use of maleic anhydride grafted polybutadiene instead of styrene-butadiene-butylene-styrene block copolymer (i.e., partially hydrogenated styrene-butadiene-styrene copolymer) in application comparative example 1 significantly reduced the dielectric properties although the peel strength of application comparative example 1 was higher than that of application example 1.
As can be seen from the combination of application examples 1 and application comparative examples 2 to 4 and from table 4, the use of styrene-butadiene-styrene copolymer and fully hydrogenated styrene-butadiene-styrene copolymer in application comparative examples 2 to 4, respectively, instead of partially hydrogenated styrene-butadiene-styrene copolymer, was inferior to application example 1 in dielectric properties, mechanical properties and thermal stability, which may be due to the fact that: the styrene-butadiene-styrene copolymer and the fully hydrogenated styrene-butadiene-styrene copolymer are insufficiently crosslinked during the crosslinking of the system, and the reactivity decreases, resulting in a decrease in the crosslinking density of the final electronic resin, and a decrease in dielectric properties, mechanical properties and thermal stability.
As can be seen from the combination of application example 1 and application comparative example 5 and the combination of table 4, the dielectric filler and the heat conductive filler in application comparative example 5 were not modified by the wetting dispersant, and the dispersion performance in the hydrocarbon resin composition was poor, resulting in a significant decrease in the overall performance of the copper clad laminate.
As can be seen by combining examples 4-8 and table 5, the dielectric properties of the rutile type titanium dioxide composite pair copper-clad plates with various particle sizes are obviously improved; and the dielectric property improvement effect of the rutile titanium dioxide doping on the copper-clad plate is better than that of anatase titanium dioxide.
It can be seen from the combination of examples 9-17 and tables 5-6 that the compounding of the silica micropowder with various particle diameters and different shapes can significantly improve the heat conduction performance and the heat stability of the copper-clad plate.
In addition to the above-described detection data, the present inventors also detected flame retardant properties of an adhesive sheet made of an electronic resin in a manner referring to UL 94 standards. Through detection, the flame retardant grade of the bonding sheet made of the electronic resin can reach V0 grade.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
Moreover, the foregoing examples are illustrative of only a few embodiments of the application, and are not intended to limit the scope of the application in any way. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims (10)

1. The high-dielectric, high-heat-conductivity and low-loss electronic resin is characterized by comprising the following components in parts by weight:
25-45 parts of hydrocarbon resin composition, 30-70 parts of functional filler, 0.1-5 parts of wetting dispersant, 10-30 parts of flame retardant, 0.1-1 part of antioxidant and 0.5-5 parts of cross-linking agent;
wherein the hydrocarbon resin composition at least contains a styrene-butadiene-butylene-styrene block copolymer, and at least one of a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer and a maleic anhydride grafted polyolefin;
the functional filler is pretreated by wetting dispersant.
2. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 1, wherein: the hydrocarbon resin composition comprises styrene-butadiene-butylene-styrene block copolymer, styrene-butadiene copolymer, styrene-divinylbenzene copolymer and maleic anhydride grafted polyolefin.
3. A high dielectric, high thermal conductivity, low loss electronic resin according to claim 2, wherein: the number average molecular weight of the styrene-butadiene-butylene-styrene block copolymer in the hydrocarbon resin composition is 50000-200000, the number average molecular weight of the styrene-butadiene copolymer is 1000-100000, the number average molecular weight of the styrene-divinylbenzene copolymer is 5000-20000, and the number average molecular weight of the maleic anhydride grafted polyolefin is 1000-10000.
4. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 1, wherein: the functional filler comprises a high-dielectric filler with a dielectric constant more than or equal to 100.
5. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 4, wherein: the high dielectric filler consists of titanium dioxide with the average particle size of 0.5-5 mu m.
6. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 5, wherein: the titanium dioxide is pretreated by using a polyphosphate solution.
7. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 1, wherein: the functional filler also comprises silica micropowder.
8. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 7, wherein: the silicon micro powder consists of angular silicon micro powder with the average grain diameter of 2-12 mu m and spherical silicon micro powder with the average grain diameter of 3-10 mu m.
9. The high dielectric, high thermal conductivity, low loss electronic resin according to claim 8, wherein: the silicon micropowder is pretreated by using an acrylic acid silane coupling agent and an epoxy coupling agent.
10. The use of an electronic resin with high dielectric, high thermal conductivity and low loss according to any one of claims 1-9, wherein the adhesive sheet and the high frequency copper-clad plate are manufactured according to the following steps:
preparation of an adhesive sheet:
adding the hydrocarbon resin composition into a solvent for dispersion to obtain a resin dispersion;
dispersing a wetting dispersant in a solvent, and then adding a functional filler and a flame retardant for dispersion to obtain a filler suspension;
blending the resin dispersion liquid and the filler suspension liquid, adding an antioxidant and a cross-linking agent for dispersion, and obtaining electronic resin;
dipping the glass fiber base cloth in electronic resin, and baking to obtain a bonding sheet;
preparing a high-frequency copper-clad plate:
selecting bonding sheets, coating copper foils on two sides, and carrying out vacuum hot pressing to obtain the high-frequency copper-clad plate.
CN202310742157.0A 2023-06-21 2023-06-21 High-dielectric, high-heat-conductivity and low-loss electronic resin and application thereof Pending CN116640404A (en)

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