CN110607052A - Prepreg, laminated board and printed circuit board - Google Patents

Prepreg, laminated board and printed circuit board Download PDF

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Publication number
CN110607052A
CN110607052A CN201910900584.0A CN201910900584A CN110607052A CN 110607052 A CN110607052 A CN 110607052A CN 201910900584 A CN201910900584 A CN 201910900584A CN 110607052 A CN110607052 A CN 110607052A
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scavenger
ion
prepreg
glass
zirconium
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CN201910900584.0A
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CN110607052B (en
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郝良鹏
柴颂刚
曾杰
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • 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
    • B32B15/08—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 synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Abstract

The invention provides a prepreg, a laminated board and a printed circuit board, wherein an ion scavenger layer is coated on the surface of a reinforcing material in the prepreg, and the ion scavenger carried on the surface can scavenge free impurity ions, so that copper ions are difficult to migrate along glass fiber yarns, and the ion migration resistance of the laminated board is obviously improved.

Description

Prepreg, laminated board and printed circuit board
Technical Field
The invention belongs to the technical field of laminates, and relates to a prepreg, a laminate and a printed circuit board.
Background
With the rapid development of the IC packaging technology, the electronic products are developed to high density, multi-functionalization and light, thin and small, so that the component packaging density and the integration level on the circuit board are higher and higher, the line pitch and the hole pitch of the PCB are gradually reduced, and the ion migration resistance is particularly important.
The ion migration caf (conductive antistatic finish) refers to the phenomenon that copper wires grow in a dendritic manner along the surface of glass fibers in a high-temperature and humid environment with long-time electrification of a PCB. The ion migration phenomenon can cause short circuit of a PCB circuit, and electrical ignition is easily caused, so that the harm is large. In the prior art, the ion migration resistance of the laminated board is improved mainly by methods of improving the purity of resin, reducing the content of conductive ions, improving the interface bonding of the resin and glass fiber yarns, changing low-roughness copper foil and the like, but the methods do not obviously improve the CAF resistance of the laminated board and are greatly influenced by a later PCB (printed Circuit Board) processing process.
CN1861682A discloses a halogen-free, phosphorus-free and silicon-free epoxy resin composition and a flexible copper-clad plate prepared by using the same, wherein the composition comprises the following components in parts by weight: 10-50 parts of flexible benzoxazine resin, 10-50 parts of special epoxy resin, 10-35 parts of carboxyl-terminated butadiene-acrylonitrile rubber, 10-25 parts of carboxyl-terminated butadiene-acrylonitrile rubber modified epoxy resin, 1-30 parts of nitrogen flame retardant, 1-20 parts of curing agent, 0.01-1.0 part of curing accelerator, 0.01-1.0 part of antioxidant, 0.01-2.0 parts of ion scavenger, 0-100 parts of inorganic filler and a proper amount of organic solvent, wherein the solid component is dissolved in the organic solvent and accounts for 30-40% of the total weight. The invention uses an ion scavenger in the resin composition, thereby preventing ion migration between copper wires and improving the reliability of the product.
CN108137791A discloses a curable resin composition, a dry film and a printed circuit board using the same, the curable resin composition comprising: a carboxyl group-containing resin, a thermosetting component, a flame retardant, and an ion scavenger which is a mixture of a hydrotalcite-based ion scavenger and an ion scavenger other than hydrotalcite, and which is found to improve insulation reliability such as ion migration resistance without lowering flame retardancy.
Although the above two inventions can obtain the effect of improving the ion migration resistance, they all use the ion scavenger in the resin composition, the ion scavenger is uniformly distributed in the whole resin matrix, at the interface between the resin and the reinforcing material, the distributed ion scavenger is only a very small part added in the ion scavenger in the formula, but the ion scavenger which can really enter into the surface of the glass fiber yarn in the reinforcing material together with the resin is less, the ion migration caf (conductive ionic fiber) mentioned in the technical field refers to the phenomenon that copper wire dendritic growth appears along the surface of the glass fiber under the high-temperature and humid environment of long-time electrification of the PCB board, so it can be known that the ion migration is a phenomenon occurring on the surface of the reinforcing material, which results in that only a very small part of the ion scavenger added in the formula plays the role of improving the ion migration resistance, and most of the ion scavenger does not play a role in practical use, the overall improvement of the ion migration resistance of the plate is not significant.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a prepreg, a laminated board and a printed circuit board.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a prepreg, including a reinforcing material and a thermosetting resin composition attached thereto by impregnation and drying, wherein the reinforcing material is a reinforcing material whose surface is coated with an ion scavenger.
In the prepreg, the surface of the reinforcing material is coated with the ion scavenger, so that free impurity ions can be trapped, copper ions are difficult to migrate along the glass fiber yarns, and the ion migration resistance of the laminated board is obviously improved. In the invention, the ion capture agent is completely positioned on the surface of the reinforcing material, and when copper ions grow in a copper wire dendritic mode along the surface of the glass fiber in a high-temperature and humid environment with long-time electrification of the PCB, the copper ions firstly encounter the ion capture agent and are captured by the ion capture agent, so that the CAF phenomenon is prevented. In the invention, all the ion trapping agents are positioned on the surface of the reinforcing material, the function of improving the ion migration resistance can be exerted, and under the same dosage, the effect of improving the CAF performance of the plate is obviously better than that of adding the ion trapping agents into the resin formula.
Preferably, the mass of the ion scavenger is 0.01-5 wt% of the mass of the reinforcement material, such as 0.01 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%. When the coating amount of the ion scavenger is less than 0.01%, the coating effect is not obvious, and when the coating amount of the ion scavenger is more than 5%, the bonding strength of the resin matrix and the reinforcing material is influenced, so that the defects of the plate are easily caused, and the CAF resistance is not improved well. Further preferably, the mass of the ion scavenger is 0.01 to 2 wt% of the mass of the reinforcing material.
The "ion scavenger" in the present invention refers to a component capable of trapping ions, and is not particularly limited as long as it has a function of trapping at least one of a cation and an anion. That is, the compound may be referred to as a compound having an ion-capturing function. By coating the compound with the ion capture function on the surface of the reinforcing material, the ion migration phenomenon, particularly the migration of copper ions, along the surface of the glass fiber can be effectively inhibited under the high-temperature and humid environment of long-time electrification, and the prepreg, the laminated board and the printed circuit board with high CAF resistance can be obtained.
In the present invention, examples of the ion scavenger for trapping ions include: a cation scavenger for trapping cations, an anion scavenger for trapping anions (an anion scavenger reduces the ion content and conductivity in water vapor by trapping anions in water vapor, thereby inhibiting migration of copper ions), and a zwitterion scavenger for trapping cations and anions.
Examples of the cation scavenger for trapping cations include one or a combination of at least two of zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, zirconium polyphosphate and a polymeric heavy metal ion scavenger. As the cation scavenger, IXE-100 (Zr-containing compound), IXE-150 (Zr-containing compound) and the like commercially available from Toyo corporation can be used.
Examples of the anion scavenger for trapping anions include one or a combination of at least two of bismuth oxide hydrate and hydrotalcite anion scavenger. As the anion scavenger, IXE-500 (Bi-containing compound), IXE-530 (Bi-containing compound), IXE-550 (Bi-containing compound), IXE-700 (Mg-or Al-containing compound), IXE-700F (Mg-or Al-containing compound), IXE-770D (Mg-or Al-containing compound), IXE-702 (Al-containing compound), and IXE-800 (Zr-containing compound) commercially available from Toyo corporation can be used.
The zwitterion capturing agent for capturing the cation and the anion is one or a combination of at least two of metal hydrous oxides, and examples thereof include alumina hydrate, zirconia hydrate and the like. As the zwitterion capturing agent, IXE-1320 (a compound containing Mg and Al), IXE-600 (a compound containing Bi), IXE-633 (a compound containing Bi), IXE-680 (a compound containing Bi), IXE-6107 (a compound containing Zr and Bi), IXE-6136 (a compound containing Zr and Bi), IXEPLAS-A1 (a compound containing Zr, Mg and Al), IXEPLAS-A2 (a compound containing Zr, Mg and Al), IXEPLAS-B1 (a compound containing Zr and Bi), and the like, which are commercially available from Toyo Kagaku Co., Ltd.
In order to obtain a better CAF resistance effect, a cation scavenger and an anion scavenger may be used in combination, or a zwitterion scavenger may be used.
The ion scavenger of the present invention may be one or at least two of a nano-scale ion scavenger, a submicron-scale ion scavenger, or a micron-scale ion scavenger. For enhancing the coating effect, the average particle size of the ion trap is preferably 1 to 500nm, for example 1nm, 3nm, 5nm, 8nm, 10nm, 15nm, 20nm, 30nm, 50nm, 80nm, 100nm, 120nm, 180nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500 nm.
Preferably, the reinforcing material having the ion scavenger coated on the surface thereof can be obtained by immersing the reinforcing material in a treatment liquid containing the ion scavenger and drying the treatment liquid.
In the invention, the reinforcing material is a glass fiber cloth, a non-woven fabric and other reinforcing materials.
Preferably, the thermosetting resin in the thermosetting resin composition is one or a combination of at least two of epoxy resin, phenolic resin, bismaleimide resin, benzoxazine resin, phosphorus-containing active ester compound, cyanate ester, polytetrafluoroethylene, polyphenylene oxide (PPO) or liquid crystal resin. The thermosetting resin is not limited to the above-mentioned resins, and any resin composition used in the art for copper clad laminates can be used for the thermosetting resin composition of the present application. Any thermosetting resin composition is impregnated by the reinforcing material coated with the ion capturing agent on the surface, so that the adhesion of the ion capturing agent on the reinforcing material is not influenced, the ion migration phenomenon, particularly the migration of copper ions, along the surface of the glass fiber can be effectively inhibited under the high-temperature and humid environment of long-time electrification, and the prepreg, the laminated board and the printed circuit board with high CAF resistance can be obtained, and the effect of ion migration resistance is not different due to different thermosetting resin compositions.
Preferably, the thermosetting resin composition further comprises a curing agent, and the curing agent is preferably at least one selected from phenolic curing agents, amine curing agents or anhydride curing agents.
Preferably, the thermosetting resin composition further comprises a curing accelerator, and the curing accelerator is preferably at least one of an imidazole-based curing accelerator or an amine-based curing accelerator.
Preferably, the thermosetting resin composition further includes a filler.
Preferably, the filler includes any one or a combination of at least two of silica, boehmite, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, zinc molybdate, titanium oxide, alumina, aluminum nitride, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, glass powder, or hollow micro powder. Preferably, the glass powder is any one of E glass, S glass, D glass or NE glass or the combination of at least two of the E glass, the S glass, the D glass and the NE glass.
In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.
According to the invention, the prepreg and the laminated board can prevent copper ions from growing into the laminated board along the surface of the glass fiber by using the ion scavenger with the surface coated with a layer capable of absorbing ions in the prepreg, so that the CAF resistance of the laminated board can be obviously improved, and the laminated board with high CAF resistance is provided.
In another aspect, the present invention provides a printed circuit board comprising at least one prepreg as described above.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the reinforcing material with the surface coated with the ion scavenger is used in the prepreg, so that the ion scavenger loaded on the surface can capture free impurity ions, copper ions are difficult to migrate along glass fiber yarns, and the ion migration resistance of the laminated board is obviously improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The materials used in the examples and comparative examples are as follows:
multifunctional brominated epoxy resins: OLIN, XQ82937
Phosphorus-containing phenolic resin: KOLON, KPH-L2005TMP
Tetrafunctional epoxy resin: mezzanine, EPON1031A70
Benzoxazine resin: dongdai material, D125
Multifunctional epoxy resin: KOLON, KES-7695M75
Bismaleimide resin: large and synthetic, BMI-1000
Cyanate ester: CE01MO/G, Tianqi, Yangzhou
Modified polyphenylene ether: SABIC, MX9000
Organosilicon: wu Da, WD-V4
Free radical initiator: shanghai Gaoqiao, dicumyl peroxide (DCP)
Curing agent: indian atlas, Diamino Diphenyl Sulfone (DDS)
Imidazole accelerator: formation of four countries in Japan, 2E4MI
Imidazole accelerator: 2PZ of the Japanese four kingdoms chemical
Accelerator (b): yangzhou industry, cobalt acetylacetonate
Silicon micropowder: jiangsonirui New materials Co., Ltd, DS1032A
A cation scavenger: synthesized in east Asia, IXE100, average particle size 1.0 μm
Anion scavenger: synthesized in east Asia, IXE500, average particle size 1.5 μm
Zwitterionic scavenger: synthesized in east Asia, IXEPLAS-A2, average particle size 200nm
Glass fiber cloth: pearl glass 7628 type glass fiber cloth
Since commercially available cation scavengers and anion scavengers have a large particle size, the ion scavenger is pulverized to a desired particle size in practical use by the following method:
adding a certain amount of large-particle-size ion trapping agent into deionized water, stirring and dispersing for 1h, circularly sanding for a certain time at the rotating speed of 2500r/min by adopting a sand mill and 0.4mm zirconia balls until the particle size of the ion trapping agent meets the requirement, and preparing a treatment solution of a reinforcing material by using the ground dispersion liquid.
Hot pressing procedure used in examples and comparative examples:
and (3) combining the cut prepreg and the copper foil, putting the combined prepreg and the copper foil into a vacuum hot press, and finally preparing the copper-clad plate according to the temperature, the time and the pressure, wherein the formula is as follows:
temperature program: 130 ℃/30min +155 ℃/30min +190 ℃/90min +220 ℃/60 min;
pressure program: 25kgf cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/90min；
Vacuum program: 30mmHg/130min +800mmHg/130 min.
Method for coating ion trapping agent on surface of glass fiber cloth
Adding a certain amount of ion trapping agent into deionized water, stirring and dispersing for 2h, homogenizing and dispersing twice by a high-pressure homogenizer under the pressure of 15000Psi to obtain a treatment solution containing the ion trapping agent, coating the glass fiber cloth of the bead glass 7628 type by a dipping and pulling method, drying at 80 ℃ for 30min, and drying at 120 ℃ for 30 min. The impregnation can be repeated to achieve the desired coating amount (see the examples below for specific coating amounts). Thus, the glass fiber cloth coated with the ion scavenger was obtained.
Example 1
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%, 2E4MI produced by the four nations chemical synthesis of Japan) and silicon micro powder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, infiltrating 7628 type glass fiber cloth coated with an ion trapping agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 0.01 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 2
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%, 2E4MI produced by the four nations chemical synthesis of Japan) and silicon micro powder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, then infiltrating 7628 type glass fiber cloth coated with an ion trapping agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 3
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%) and silicon micropowder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, then infiltrating 7628 type glass fiber cloth coated with an ion capture agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 5 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 4
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%) and silicon micropowder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, and infiltrating 7628 type glass fiber cloth (IXE100 is sanded and crushed, the average particle size is 500nm, the dosage accounts for 0.01 wt% of the glass fiber cloth) coated with an ion trapping agent IXE100 by adopting the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 5
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%) and silicon micropowder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, and infiltrating 7628 type glass fiber cloth (IXE500 is sanded and crushed, the average particle size is 500nm, the dosage accounts for 0.01 wt% of the glass fiber cloth) coated by an ion scavenger IXE500 with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 6
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%) and silicon micropowder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, infiltrating 7628 type glass fiber cloth (IXE100 and IXE500 are ground and crushed by sanding, the average particle size is 500nm, and the using amount accounts for 0.01 wt% of the weight of the glass fiber cloth) which is subjected to compound coating treatment by an ion capturing agent IXE100 and IXE500 according to a ratio of 1:1, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 7
Dissolving multifunctional epoxy resin KES-7695M75(12.62 wt%), benzoxazine resin D125(55.68 wt%), phenolic resin KPH-L2005TMP (1.68 wt%), diaminodiphenyl sulfone (DDS) (0.84%), imidazole accelerator 2PZ (0.09 wt%) and silicon micropowder DS1032A (30.09 wt%) in propylene glycol methyl ether and butanone (1:1 ratio) solvent, mechanically stirring and dispersing to prepare glue solution with solid content of 65 wt%, infiltrating 7628 type glass fiber cloth (IXEPLAS-A2 accounts for 2 wt% of glass fiber cloth weight) coated with ion scavenger IXEPLAS-A2 with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 8
Dissolving cyanate CE01MO/G (48.96 wt%), multifunctional epoxy resin KES-7695M75(10.5 wt%), bismaleimide resin BMI-1000(10.5 wt%), cobalt acetylacetonate (0.04 wt%) and silicon micro powder DS1032A (30 wt%) in a solvent of dimethyl formamide and butanone (1:1 ratio), mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, and then infiltrating 7628 type glass fiber cloth coated with an ion trapping agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 2 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Example 9
Dissolving modified polyphenyl ether MX9000(62.3 wt%), organic silicon WD-V4(7 wt%) containing unsaturated double bonds, dicumyl peroxide (0.7 wt%) and silicon powder DS1032A (30 wt%) in a toluene solvent, mechanically stirring and dispersing to prepare a glue solution with a solid content of 65 wt%, infiltrating 7628 type glass fiber cloth coated with an ion capture agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 2 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 1
Dissolving multifunctional brominated epoxy resin (47.61 wt%), phosphorus-containing phenolic resin (24.85 wt%), tetrafunctional epoxy resin (2.45 wt%), imidazole accelerator (0.10 wt%, 2E4MI produced by the fourth country of Japan) and silicon powder DS1032A (25 wt%) in propylene glycol monomethyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, and then infiltrating 7628 type glass fiber cloth which is not coated by an ion capture agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 0 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 2
Dissolving multifunctional brominated epoxy resin (47.61 wt%), phosphorus-containing phenolic resin (24.85 wt%), tetrafunctional epoxy resin (2.45 wt%), imidazole accelerator (0.10 wt%, 2E4MI produced by the fourth country of Japan) and silicon powder DS1032A (25 wt%) in propylene glycol monomethyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, and then infiltrating 7628 type glass fiber cloth (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 0.005 wt%) coated by an ion trapping agent IXEPLAS-A2 with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 3
Dissolving multifunctional brominated epoxy resin (47.61 wt%), phosphorus-containing phenolic resin (24.85 wt%), tetrafunctional epoxy resin (2.45 wt%), imidazole accelerator (0.10 wt%, 2E4MI produced by the fourth country of Japan) and silicon powder DS1032A (25 wt%) in propylene glycol monomethyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, then infiltrating 7628 type glass fiber cloth coated with an ion trapping agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 8 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 4
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%) and silicon micropowder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, and then infiltrating 7628 type glass fiber cloth coated with an ion scavenger IXE500 (the average particle size of IXE500 is 1.5um, and the weight ratio of the IXE500 to the glass fiber cloth is 0.01 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 5
Dissolving multifunctional brominated epoxy resin XQ82937(47.61 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.85 wt%), tetrafunctional epoxy resin EPON1031A70(2.45 wt%), imidazole accelerator 2E4MI (0.10 wt%) and silicon micropowder DS1032A (25 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, infiltrating 7628 type glass fiber cloth (IXE100 is sanded and crushed, the average particle size is 500nm, the dosage accounts for 8 wt% of the glass fiber cloth) coated by an ion scavenger IXE100, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 6
Dissolving multifunctional brominated epoxy resin XQ82937(46.65 wt%), phosphorus-containing phenolic resin KPH-L2005TMP (24.35 wt%), tetrafunctional epoxy resin EPON1031A70(2.4 wt%), imidazole accelerator 2E4MI (0.10 wt%), silicon micro powder DS1032A (24.5 wt%) and ion capture agent IXEPLAS-A2(2 wt%) in propylene glycol methyl ether solvent, mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, infiltrating uncoated 7628 type glass fiber cloth with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 7
Dissolving multifunctional epoxy resin KES-7695M75(12.62 wt%), benzoxazine resin D125(55.68 wt%), phenolic resin KPH-L2005TMP (1.68 wt%), diaminodiphenyl sulfone (DDS) (0.84%), imidazole promoter 2PZ (0.09 wt%) and silicon micropowder DS1032A (30.09 wt%) in propylene glycol methyl ether and butanone (1:1 ratio) solvent, mechanically stirring and dispersing to prepare glue solution with solid content of 65 wt%, infiltrating 7628 type glass fiber cloth (IXEPLAS-A2 accounts for 7 wt% of glass fiber cloth weight) coated with ion trapping agent IXEPLAS-A2 with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 8
Dissolving cyanate CE01MO/G (48.96 wt%), multifunctional epoxy resin KES-7695M75(10.5 wt%), bismaleimide resin BMI-1000(10.5 wt%), cobalt acetylacetonate (0.04 wt%) and silicon micro powder DS1032A (30 wt%) in a solvent of dimethyl formamide and butanone (1:1 ratio), mechanically stirring and dispersing to prepare a glue solution with the solid content of 65 wt%, then infiltrating 7628 type glass fiber cloth coated with an ion trapping agent IXEPLAS-A2 (the weight ratio of IXEPLAS-A2 to the glass fiber cloth is 0.005 wt%) with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
Comparative example 9
Dissolving modified polyphenyl ether MX9000(62.3 wt%), organic silicon WD-V4(7 wt%) containing unsaturated double bonds, dicumyl peroxide (0.7 wt%) and silicon micropowder DS1032A (30 wt%) in a toluene solvent, mechanically stirring and dispersing to prepare a glue solution with a solid content of 65 wt%, infiltrating uncoated 7628 type glass fiber cloth with the glue solution, and drying to obtain the prepreg. Laminates were prepared by hot pressing 8 sheets of this prepreg between two copper foils in a vacuum press. The laminates were prepared into test samples according to the requirements of the determination and evaluation methods, and the test results are shown in table 1.
The plate performance measurement and evaluation method comprises the following steps:
the method for evaluating the ion migration resistance comprises the following steps: the HAST test method is carried out according to the IPC-TM-6502.6.25 standard, the test condition is 120 ℃/85% RH and 100VDC, and the test time is 550 h. Three samples were tested for each example, each sample tested for two well spacings of 0.6pitch, 0.7 pitch.
TABLE 1
In Table 1, it can be seen from examples 1 to 9 and comparative examples 1 to 9 that the CAF resistance of the laminate material is significantly improved after the reinforcing material is modified by coating with an ion scavenger in an appropriate ratio. As can be seen from examples 1 to 3 and comparative examples 2 to 3, example 4 and comparative example 5, example 7 and comparative example 7, example 8 and comparative example 8, when the ion scavenger coating amount is in the range of 0.01 to 5 wt%, the CAF resistance of the laminate material is most remarkably improved; when the coating amount of the ion capture agent is less than 0.01 wt%, the CAF resistance improvement effect of the laminated board material is not obvious, and the laminated board material cannot pass a HAST test of 550 h; when the coating amount of the ion capturing agent is more than 5 wt%, the combination of the resin matrix and the reinforcing material is affected, and the plate defects are easily caused, so that the CAF resistance of the laminated plate material is not improved well and cannot pass the HAST test of 550 h. From examples 1-3, comparative example 1, example 9 and comparative example 9, it can be seen that the laminate obtained with the extender which is not coated with the ion scavenger has poor CAF resistance and fails the HAST test at 550 h.
From the example 5 and the comparative example 4, it can be seen that when the particle size of the ion scavenger is 1-500nm, the modification effect is better, and when the particle size of the ion scavenger is larger than 500nm, the particle size of the ion scavenger is larger, the number of particles is reduced, the coating modification effect is poor, and the improvement of the ion migration resistance of the plate is not obvious; as can be seen from the comparative example 6, when the ion scavenger is directly added into the glue, the ion migration resistance of the plate is not remarkably improved due to the small amount of the effective ion scavenger distributed on the surface of the reinforcing material; as can be seen from examples 4 to 6, the effect is better when the anion scavenger and the cation scavenger are used in combination.
The applicant states that the present invention is illustrated by the above embodiments of the prepreg, the laminate and the printed circuit board of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented by the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The prepreg is characterized by comprising a reinforcing material and a thermosetting resin composition attached to the reinforcing material after impregnation and drying, wherein the surface of the reinforcing material is coated with an ion capture agent.
2. A prepreg according to claim 1, wherein the mass of the ion scavenger is 0.01 to 5 wt%, preferably 0.01 to 2 wt% of the mass of the reinforcement.
3. The prepreg according to claim 1 or 2, wherein the ion scavenger is one or a combination of at least two of a cation scavenger, an anion scavenger, or a zwitterion scavenger;
preferably, the cation scavenger is one or a combination of at least two of zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, zirconium polyphosphate or a high molecular heavy metal ion scavenger;
preferably, the anion scavenger is one or the combination of at least two of bismuth oxide hydrate or hydrotalcite anion scavenger;
preferably, the zwitterion trapping agent is one or a combination of at least two of metal hydrous oxides;
preferably, the ion scavenger is a combination of a cation scavenger and an anion scavenger or a zwitterion scavenger.
4. The prepreg according to any one of claims 1 to 3, wherein the ion scavenger has an average particle diameter of 1 to 500 nm.
5. The prepreg according to any one of claims 1 to 4, wherein the reinforcing material having the ion scavenger coated on the surface thereof is obtained by impregnating the reinforcing material with a treatment liquid containing the ion scavenger and drying the impregnated reinforcing material.
6. The prepreg according to any one of claims 1 to 5, wherein the thermosetting resin in the thermosetting resin composition is one or a combination of at least two of an epoxy resin, a phenolic resin, a bismaleimide resin, a benzoxazine resin, a phosphorus-containing active ester compound, a cyanate ester, polytetrafluoroethylene, a polyphenylene ether, or a liquid crystal resin.
7. The prepreg according to any one of claims 1 to 6, wherein the thermosetting resin composition further comprises a curing agent, preferably at least one of a phenolic curing agent, an amine curing agent or an anhydride curing agent;
preferably, the thermosetting resin composition further comprises a curing accelerator, and the curing accelerator is preferably at least one of an imidazole-based curing accelerator or an amine-based curing accelerator.
8. The prepreg of any one of claims 1-7, further comprising a filler in the thermosetting resin composition;
preferably, the filler comprises any one or a combination of at least two of silica, boehmite, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, zinc molybdate, titanium oxide, alumina, aluminum nitride, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, glass powder, or hollow micro powder;
preferably, the glass powder is any one of E glass, S glass, D glass or NE glass or the combination of at least two of the E glass, the S glass, the D glass and the NE glass.
9. A laminate comprising at least one prepreg according to any one of claims 1 to 8.
10. A printed circuit board comprising at least one prepreg according to any one of claims 1 to 8.
CN201910900584.0A 2019-09-23 2019-09-23 Prepreg, laminated board and printed circuit board Active CN110607052B (en)

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