CN109233244B - Thermosetting resin composition, prepreg, laminate, and printed wiring board - Google Patents
Thermosetting resin composition, prepreg, laminate, and printed wiring board Download PDFInfo
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- CN109233244B CN109233244B CN201810965929.6A CN201810965929A CN109233244B CN 109233244 B CN109233244 B CN 109233244B CN 201810965929 A CN201810965929 A CN 201810965929A CN 109233244 B CN109233244 B CN 109233244B
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- 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
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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
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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
- 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
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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
- 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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
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- 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
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- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
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- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
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- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- 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
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Abstract
The present disclosure provides a thermosetting resin composition, a prepreg, a laminate and a printed circuit board. The thermosetting resin composition comprises: a thermosetting resin; and a curing agent; and hollow glass spheres with inorganic coating layers; wherein the inorganic coating layer is selected from at least one of a silica coating layer and an alumina coating layer; and the inorganic coating layer accounts for 0.1 to 20 percent of the total weight of the hollow glass ball with the inorganic coating layer. According to the present disclosure, it is possible to provide a thermosetting resin composition and a dielectric layer for a laminate prepared therefrom, in which the interfacial bonding of hollow glass spheres and resin can be improved so that the entire laminate has an excellent dielectric constant.
Description
Technical Field
The disclosure relates to the technical field of laminates, in particular to a dielectric layer for a laminate, the laminate and application of the dielectric layer.
Background
The development of modern high frequency communications places increasing demands on the electrical properties of materials, especially low dielectric constant laminates for high frequencies, such as copper clad laminates comprising composite materials made from thermosetting resin compositions. In general, the effective dielectric constant of a composite material may approximate the weighted sum of the dielectric constants of the components and their volume fractions occupied in the composite material. Since most of the volume of the hollow glass sphere is air (the dielectric constant of the hollow glass sphere is 1.2 to 2.0), the hollow glass sphere has a low dielectric constant. The hollow glass spheres are widely researched in composite materials, but the hollow glass spheres are not particularly applied to a large number of composite materials, and one important reason is that the interface bonding between the hollow glass spheres and thermosetting resin is poor, so that the water resistance of the composite materials is influenced, the water absorption of the composite materials is increased, and the dielectric constant of the composite materials is influenced.
US5670250 relates to the use of a composition of hollow inorganic fillers in copper clad laminates, which define the content of hollow glass spheres, and the use of hollow glass spheres in combination with fused silica micropowder. CN100494280 relates to the modification of hollow microspheres by a silane coupling agent, thereby achieving the effect of low dielectric. JP2011068526 relates to modifying the surface of porous oxide particles with a surface treatment agent to achieve the effects of low dielectric, reducing the amount of hydroxyl groups on the surface of the filler and adsorbing water.
Disclosure of Invention
However, the inventors of the present application found in experiments that the introduction of hollow glass spheres brings about deterioration in water resistance of the laminate due to poor interfacial bonding between the hollow glass spheres and the resin.
Accordingly, it is desirable to provide a thermosetting resin composition and a dielectric layer for a laminate prepared therefrom, in which the interfacial bonding of the hollow glass spheres and the resin can be improved so that the entire laminate has an excellent dielectric constant.
The inventors of the present invention have intensively studied and found that the addition of hollow glass spheres having an inorganic coating layer to a thermosetting resin composition can improve the interfacial bonding between the hollow glass spheres and the resin, so that the entire laminate has an excellent dielectric constant, thereby completing the present invention.
In one aspect, the present disclosure provides a thermosetting resin composition comprising the following components:
(1) a thermosetting resin;
(2) a curing agent; and
(3) hollow glass spheres with inorganic coating layers;
wherein the inorganic coating layer is selected from at least one of a silica coating layer and an alumina coating layer; and the inorganic coating layer accounts for 0.1 to 20 percent of the total weight of the hollow glass ball with the inorganic coating layer.
According to one embodiment of the present disclosure, the inorganic coating layer is a silica coating layer.
According to another embodiment of the present disclosure, the inorganic coating layer accounts for 0.1 to 10% of the total weight of the hollow glass sphere having the inorganic coating layer.
According to another embodiment of the present disclosure, the hollow glass spheres having the inorganic coating layer have an average particle diameter of not more than 30 μm.
According to another embodiment of the present disclosure, the content of the hollow glass sphere having an inorganic coating layer is 1 to 30% with respect to the total weight of the thermosetting resin and the curing agent.
According to another embodiment of the present disclosure, the content of the hollow glass sphere having an inorganic coating layer is 5 to 25% with respect to the total weight of the thermosetting resin and the curing agent.
According to another embodiment of the present disclosure, the content of the hollow glass sphere having an inorganic coating layer is 5 to 20% with respect to the total weight of the thermosetting resin and the curing agent.
According to another embodiment of the present disclosure, the thermosetting resin is selected from at least one of epoxy resin, cyanate ester resin, polyphenylene ether resin, polybutadiene resin, styrene-butadiene resin, PTFE resin, phenol resin, acrylate resin, polyimide resin, liquid crystal resin, bismaleimide-triazine resin, bismaleimide resin, benzoxazine resin, phenoxy resin, nitrile rubber, and hydroxyl-terminated nitrile rubber.
According to another embodiment of the present disclosure, the hollow glass sphere having an inorganic coating layer is a hollow glass sphere having an inorganic coating layer treated with a surface treatment agent.
According to another embodiment of the present disclosure, the surface treatment agent is selected from at least one of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant.
According to another embodiment of the present disclosure, the surface treatment agent is selected from at least one of a silane coupling agent, a titanate, an aluminate, a zirconate, and a phenolic resin.
According to another embodiment of the present disclosure, the surfactant is selected from silicone oils.
According to another embodiment of the present disclosure, the nonionic surfactant is selected from polyethylene glycol.
In another aspect, the present disclosure provides a prepreg comprising a reinforcing material and a thermosetting resin composition according to any one of the above attached thereto after drying by impregnation.
In yet another aspect, the present disclosure provides a metal-clad laminate comprising: a sheet of prepreg as described above and a metal foil applied to one or both sides of the prepreg; or at least two superimposed prepregs, at least one of which is the prepreg described above, and a metal foil covering one or both sides of the superimposed prepregs.
In yet another aspect, the present disclosure provides a printed circuit board containing at least one prepreg according to the above.
According to the present disclosure, it is possible to provide a thermosetting resin composition and a dielectric layer for a laminate prepared therefrom, in which the interfacial bonding of hollow glass spheres and resin can be improved so that the entire laminate has an excellent dielectric constant.
Detailed Description
The technical solutions in the examples of the present disclosure will be clearly and completely described below in connection with the specific embodiments of the present disclosure, and it is obvious that the described embodiments and/or examples are only a part of the embodiments and/or examples of the present disclosure, and not all embodiments and/or examples. All other embodiments and/or all other examples that can be obtained by one of ordinary skill in the art without making any inventive step based on the embodiments and/or examples in the present disclosure are within the scope of the present disclosure.
In the present disclosure, all numerical features are meant to be within the error of measurement, for example within ± 10%, or within ± 5%, or within ± 1% of the defined numerical value.
The term "comprising", "including" or "containing" as used in this disclosure means that it may have, in addition to the recited components, other components which impart different properties to the prepreg. In addition, references to "comprising," including, "or" containing "in this disclosure may also include references to" consisting essentially of … …, "and may instead be" is "or" consists of … ….
In the present disclosure, amounts, ratios, etc., are by weight if not specifically indicated.
In the present disclosure, the hollow glass spheres are also sometimes referred to as hollow glass sphere powder.
As described above, the present disclosure may provide a thermosetting resin composition comprising the following components:
(1) a thermosetting resin;
(2) a curing agent; and
(3) hollow glass spheres with inorganic coating layers;
wherein the inorganic coating layer is selected from at least one of a silica coating layer and an alumina coating layer; and the inorganic coating layer accounts for about 0.1 to about 20% of the total weight of the hollow glass sphere having the inorganic coating layer.
The inorganic coating is preferably a silica coating. The inorganic coating layer may comprise about 0.1 to about 10% of the total weight of the hollow glass sphere having the inorganic coating layer. Hollow glass spheres with inorganic coating layers are used as fillers in thermosetting resin compositions. A prepreg may be prepared from the thermosetting resin composition.
The hollow glass spheres with inorganic coating have an average particle size of no greater than about 30 μm. If the average particle size of the hollow glass spheres with the inorganic coating layers exceeds about 30 μm, the filler particle size exceeds the thickness of the prepreg in the thin prepreg, causing the filler to be exposed and affecting the reliability of the laminated board.
Of hollow glass spheres prior to coating with an inorganic coatingThe dielectric constant may be in the range of 1.2 to 2.0. The hollow glass spheres may have a density of 0.1 to 0.8g/cm3Within the range of (1).
The preparation method of the hollow glass spheres with the silica coating layer (namely, the hollow glass spheres coated with the silica) can comprise slowly dripping Na into a suspension of hollow glass sphere powder in glycol2SiO3Or K2SiO3Aqueous solution, and with H2SO4The aqueous solution is adjusted to a basic pH, for example, pH9-11, and the reaction is carried out for a while, followed by filtration, washing and drying, to obtain hollow glass spheres having a silica coating layer (i.e., silica-coated hollow glass spheres).
The preparation method of the hollow glass spheres with the silica coating layer (namely the hollow glass spheres coated with the silica) can comprise the step of slowly dripping Al (NO) into a suspension of hollow glass sphere powder in glycol3)3Aqueous solution and with HNO3The aqueous solution is adjusted to a basic pH, for example, pH 5 to 6, and the reaction is carried out while maintaining for a while, followed by filtration, washing, and drying, to obtain hollow glass spheres having a silica coating layer (i.e., silica-coated hollow glass spheres).
The content of the hollow glass spheres having an inorganic coating layer may be about 1 to about 30%, preferably about 5 to about 25%, and more preferably about 5 to about 20%, relative to the total weight of the thermosetting resin and the curing agent.
The thermosetting resin may be at least one selected from the group consisting of epoxy resin, cyanate ester resin, polyphenylene ether resin, polybutadiene resin, styrene-butadiene resin, PTFE resin, phenol resin, acrylate resin, polyimide resin, liquid crystal resin, bismaleimide-triazine resin, bismaleimide resin, benzoxazine resin, phenoxy resin, nitrile rubber and hydroxyl-terminated nitrile rubber.
The hollow glass sphere having an inorganic coating layer may be a hollow glass sphere having an inorganic coating layer treated with a surface treatment agent.
The surface treatment agent may be at least one selected from the group consisting of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant.
The surface treatment agent may be selected from at least one of silane coupling agents, titanates, aluminates, zirconates, and phenolic resins, and preferably the surface active agent is selected from silicone oils or polyethylene glycols.
Specific examples of the combination of thermosetting resins may be a combination of an epoxy resin and a polyamide resin, a combination of a polyimide resin and a hydrocarbon resin, a combination of a cyanate resin, a polyamide resin and a polyether resin, a combination of a cyanate resin, a polyamide resin, a polyimide resin and an epoxy resin, and the like.
The thermosetting resin composition according to the present disclosure may further contain a curing accelerator, an initiator, and a solvent.
The curing agent may include a crosslinking curing agent.
For epoxy resins and combinations thereof with other resins, the curing agent may be one or a mixture of two or more of phenolic resin, anhydride compound, active ester compound, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, and maleimide. In addition, the optional curing accelerator is one or a mixture of two or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-methyl-4-phenylimidazole.
For phenolic resin and its combination with other resins, the curing agent can be organic acid anhydride, organic amine, Lewis acid, organic amide, imidazole compound, organic phosphine compound and their mixture mixed in any proportion.
For olefin resins, reactive polyphenylene ether resins containing two or more unsaturated double bonds, polyamide resins and combinations thereof with other resins, the curing agent is selected from styrene-butadiene copolymers or organic peroxide crosslinking curing agents. The organic peroxide crosslinking curing agent is preferably one or more of dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, diacetyl peroxide, tert-butyl peroxypivalate and diphenyl oxide peroxydicarbonate. The curing accelerator is an allyl organic compound, preferably one or more of triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate.
For silicone resins, the cure accelerator is selected from the group of organo-platinum compounds.
The thermosetting resin composition may further include a silane coupling agent or/and a wetting dispersant. These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment. Specific examples thereof include an aminosilane-based material such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, an alkoxysilane-based material such as γ -glycidoxypropyltrimethoxysilane, a vinylsilane-based material such as γ -methacryloxypropyltrimethoxysilane, an anionic silane-based material such as N- β - (N-vinylphenylamidoethyl) - γ -aminopropyltrimethoxysilane hydrochloride, and a phenylsilane-based material, and 1 or at least 2 of these materials may be used in appropriate combination. The wetting dispersant is not particularly limited as long as it is used in the solid resin composition. Examples thereof include wetting dispersants such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010 and W903 manufactured by BYK Chemie Japan.
The thermosetting resin composition may further contain various additives, and specific examples thereof include flame retardants such as ethyl-bis (tetrabromophthalimide), antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants and the like. These various additives may be used alone or in combination of two or more.
The solvent of the thermosetting resin composition of the present disclosure is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol and butyl carbitol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. The solvent may be used singly or in combination of two or more, and preferably an aromatic hydrocarbon solvent such as toluene, xylene or mesitylene is used in combination with a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. The amount of the solvent to be used can be selected by those skilled in the art according to their own experience, and the resin dope obtained may have a viscosity suitable for use.
The content of the thermosetting resin in the thermosetting resin composition may be about 20 to about 85% by weight, preferably about 25 to about 80% by weight, and further preferably about 30 to about 70% by weight.
The curing agent may be about 1 to 60 parts by weight, preferably about 2 to 55 parts by weight, and more preferably about 3 to 45 parts by weight, relative to 100 parts by weight of the thermosetting resin.
The curing accelerator may be 0 to 10 parts by weight, preferably 0.01 to about 10 parts by weight, and further preferably 0.02 to about 8 parts by weight, relative to 100 parts by weight of the thermosetting resin.
As a method for producing the resin composition of the present disclosure, it can be produced by a known method such as compounding, stirring, mixing filler, thermosetting resin, curing agent and curing accelerator, and various additives.
The present disclosure may also provide a prepreg comprising a reinforcing material and a thermosetting resin composition as described in any one of the above attached thereto by impregnation drying.
Examples of the reinforcing material may include glass cloth. In the following description, the glass cloth reinforcing material and the glass cloth may be used interchangeably.
Specifically, the thermosetting resin composition is prepared into glue solution by mechanical stirring, emulsification or ball milling dispersion, then the glass fiber cloth is soaked by the glue solution, and the prepreg is obtained by drying. The prepreg and a metal foil such as a copper foil are hot-pressed in a vacuum press to prepare a laminate.
The present disclosure may also provide a laminate and a printed circuit board.
The laminate may contain at least one prepreg as described in any one of the above. The laminate is for example a metal foil clad laminate. The metal-foil-clad laminate includes: a sheet of prepreg as described above and a metal foil applied to one or both sides of the prepreg; or at least two superimposed prepregs, at least one of which is the prepreg described above, or preferably each of which is the prepreg described above, and a metal foil covering one or both sides of the superimposed prepregs.
The printed circuit board may contain at least one prepreg as described in any one of the above.
Specifically, the method for preparing a laminate from the thermosetting resin composition may include the steps of:
(1) preparing glue: adding a solvent into a batching container, and respectively adding thermosetting resin, a curing agent and an optional curing accelerator under stirring; after stirring, adding a silicon dioxide filler with a boron nitride coating layer on the surface, and continuously stirring to obtain a glue solution;
(2) dipping: dipping the reinforced material in the glue solution;
(3) impregnation: making the reinforcing material soaked with the glue solution pass through a vertical or horizontal soaking machine, and preparing a prepreg by controlling the speed, linear speed, air temperature, furnace temperature and other conditions of an extruding wheel;
the vertical immersion machine is specifically shown as an example: and (3) extruding wheel speed: -1.3 to-2.5 ± 0.1M/min; main line speed: 4 to 18 m/min; wind temperature: 120 to 170 ℃; furnace temperature: 130 to 220 ℃; and
(4) pressing: combining the cut prepreg with a metal foil such as copper foil, placing the combined prepreg and metal foil into a vacuum hot press, and finally preparing a metal-clad laminate such as a copper-clad laminate according to certain temperature, time and pressure, wherein the specific examples are as follows:
temperature program:
130℃/30min+155℃/30min+190℃/90min+220℃/60min；
pressure program:
25kgf·cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/90min；
vacuum program:
30mmHg/130min+800mmHg/130min。
by the above procedure, a prepreg is laminated between metal foils such as copper foils, and a laminate (i.e., a copper clad laminate) is obtained after hot pressing.
According to the present disclosure, it is possible to provide a thermosetting resin composition and a dielectric layer for a laminate prepared therefrom, in which the interfacial bonding of hollow glass spheres and resin can be improved so that the entire laminate has an excellent dielectric constant.
Examples
The technical solution of the present disclosure is further explained by the following embodiments. In the following examples and comparative examples, percentages, ratios, etc., are by weight, if not specifically indicated.
The symbols and components used in the examples and comparative examples are as follows:
thermosetting resin a (polyphenylene ether resin): SABIC (usa), product name MX 9000.
Thermosetting resin B (brominated epoxy resin): dow chemical, epoxy equivalent 435, bromine content 19%, product name DER 530.
O-cresol novolac resin: kolon (Korea) product name KPH-2004, hydroxyl equivalent 105
Hollow glass ball powder: 3M (USA), product name S60(30 microns), IM16K (20 microns), IM16K (10 microns)
Reinforcing material (glass fiber cloth): japanese Hubeil 7628
Copper foil: suzhou Futian, loz
Median particle size: the particle size distribution is measured by a laser diffraction scattering method, which is a particle size distribution corresponding to a point having a volume of 50% when a cumulative power distribution curve based on the particle size is obtained with the total volume of the particles as 100%.
Preparation of example 1
Preparation of hollow glass spheres coated with silica (i.e., hollow glass spheres having a silica coating layer)
100g of hollow glass sphere powder is added into 400ml of ethylene glycol, and ultrasonic dispersion is carried out for 30min to obtain suspension. The suspension was added to a three-necked flask, heated to 80 ℃ with a water bath and maintained at 80 ℃. Then, 0.1mol/L Na was slowly added dropwise thereto2SiO3Aqueous solution, and with 1% by weight of H2SO4The pH of the aqueous solution was adjusted to 10.5, after which the reaction was maintained at this temperature for 3 h. Filtering, washing and drying to obtain the hollow glass ball coated with the silicon dioxide.
By adjusting 0.1mol/L of Na2SiO3The amount of the aqueous solution added dropwise was controlled to control the coating amount.
Preparation of alumina-coated hollow glass spheres (i.e., hollow glass spheres having an alumina coating layer)
The method for coating the hollow glass ball with the alumina comprises the following steps:
100g of hollow glass sphere powder is added into 400ml of ethylene glycol, and ultrasonic dispersion is carried out for 30min to obtain suspension. The suspension was added to a three-necked flask, heated in a water bath, heated to 80 ℃ with the water bath and maintained at a temperature of 80 ℃. Thereafter, 3 wt% of Al (NO) was slowly dropped thereto3)3Aqueous solution, and with 0.5 wt.% of HNO3The pH of the aqueous solution was adjusted to 5.5, after which the reaction was maintained at this temperature for 3 h. Filtering, washing and drying to obtain the hollow glass ball coated with the alumina.
By adjusting 3 wt.% Al (NO)3)3The amount of the aqueous solution added dropwise was controlled to control the coating amount.
Example 1
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 10g of hollow glass spheres having a median particle size of 8 μm and a coating treatment (coating layer is silica, and coating layer accounts for 1% by weight of the hollow glass spheres having an inorganic coating layer), followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Then, a copper-clad laminate was produced according to the following production steps (1) to (3).
(1) Dipping: dipping the reinforced material in the glue solution;
(2) impregnation: and (3) passing the reinforcing material soaked with the glue solution through a vertical soaking machine, and controlling the speed, linear speed, air temperature, furnace temperature and other conditions of an extruding wheel to prepare the prepreg. The conditions of the vertical immersion machine are as follows: and (3) extruding wheel speed: -1.8 ± 0.1M/min; main line speed: 10 m/min; wind temperature: 150 ℃; furnace temperature: 180 ℃ is carried out.
(3) Pressing: 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 laminated board according to certain temperature, time and pressure, wherein the specific conditions are as follows:
temperature program:
130℃/30min+155℃/30min+190℃/90min+220℃/60min；
pressure program:
25kgf·cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/90min；
vacuum program:
30mmHg/130min+800mmHg/130min。
by the above procedure, 8 sheets of prepreg having a thickness of 0.2mm were laminated between copper foils having a thickness of 35 μm, and hot-pressed to obtain a laminate having a thickness of 1.6 mm.
Example 2
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, and then 25g of hollow glass spheres having a median particle size of 20 μm and subjected to coating treatment (the coating layer was silica, and the coating layer accounted for 10% by weight of the hollow glass spheres having an inorganic coating layer) were added, followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
Example 3
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 30g of hollow glass spheres having a median particle size of 30 μm and a coating treatment (coating layer is silica, and coating layer accounts for 20% by weight of the hollow glass spheres having an inorganic coating layer), followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
Example 4
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 5g of hollow glass spheres having a median particle size of 20 μm and a coating treatment (coating layer of alumina, coating layer accounting for 10% by weight of the hollow glass spheres having an inorganic coating layer) and mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
Example 5
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 20g of hollow glass spheres having a median particle size of 10 μm and subjected to coating treatment (the coating layer was alumina, and the coating layer accounted for 20% by weight of the hollow glass spheres having an inorganic coating layer), followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
Example 6
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 30g of hollow glass spheres having a median particle size of 30 μm and subjected to coating treatment (the coating layer was alumina, and the coating layer accounted for 20% by weight of the hollow glass spheres having an inorganic coating layer), followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
Example 7
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolac resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 30g of hollow glass spheres having a median particle size of 30 μm and subjected to coating treatment (the coating layer was alumina, and the coating layer accounted for 5% by weight of the hollow glass spheres having an inorganic coating layer), followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a glue solution). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
Example 8
The alumina coated hollow glass spheres added were treated with a vinylsilane coupling agent (silane content 1% by weight of hollow filler) as in example 7.
Comparative example 1
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolak resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 10g of hollow glass spheres having a median particle size of 10 μm, followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a cement). Then preparing the copper clad laminate by the same steps as
Example 1.
Comparative example 2
55g of polyphenylene ether resin (thermosetting resin A) and 55g of brominated epoxy resin (thermosetting resin B) were dissolved in ethylene glycol monomethyl ether, and 7g of o-cresol novolak resin and 0.05g of 2-MI (2-methylimidazole) were added, followed by addition of 30g of silica having a median particle diameter of 10 μm, followed by mixing at room temperature to obtain a thermosetting resin composition (i.e., a cement). Thereafter, a copper clad laminate was prepared in the same manner as in example 1.
The copper-clad laminates prepared in examples 1 to 8 and comparative examples 1 to 2 were subjected to the following performance tests. The test results are shown in table 1.
1. Water absorption: the percentage ratio of the weight gain of the plate to the weight of the plate was measured after cooking in a pressure cooker at 103kPa for 2 hours.
2. Dielectric properties: the SPDR (split post dielectric resonator) method, IEC-61189-2-721-.
TABLE 1
Table 1 test results show that the hollow glass spheres having an inorganic coating layer such as an inorganic oxide coating layer have excellent dielectric properties, and the hollow glass spheres have good binding force with resin, thereby having low water absorption.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the disclosure without departing from the spirit and scope of the disclosure. Thus, if such modifications and variations of the present disclosure fall within the scope of the present disclosure according to the claims and their equivalents, the present disclosure is also intended to encompass such modifications and variations.
Claims (15)
1. A thermosetting resin composition comprising the following components:
(1) a thermosetting resin;
(2) a curing agent; and
(3) hollow glass spheres with inorganic coating layers;
wherein the inorganic coating layer is selected from at least one of a silica coating layer and an alumina coating layer; and the inorganic coating layer accounts for 0.1 to 20 percent of the total weight of the hollow glass ball with the inorganic coating layer.
2. The thermosetting resin composition of claim 1, wherein the inorganic coating layer is a silica coating layer.
3. The thermosetting resin composition of claim 1, wherein the inorganic coating layer accounts for 0.1 to 10% of the total weight of the hollow glass sphere having an inorganic coating layer.
4. The thermosetting resin composition claimed in claim 1, wherein the hollow glass spheres having an inorganic coating layer have an average particle diameter of not more than 30 μm.
5. The thermosetting resin composition of claim 1, wherein the content of the hollow glass spheres having an inorganic coating layer is 1 to 30% with respect to the total weight of the thermosetting resin and the curing agent.
6. The thermosetting resin composition of claim 1, wherein the content of the hollow glass spheres having an inorganic coating layer is 5 to 25% by weight relative to the total weight of the thermosetting resin and the curing agent.
7. The thermosetting resin composition of claim 1, wherein the content of the hollow glass spheres having an inorganic coating layer is 5 to 20% with respect to the total weight of the thermosetting resin and the curing agent.
8. The thermosetting resin composition of claim 1, wherein the thermosetting resin is selected from at least one of epoxy resin, cyanate ester resin, polybutadiene resin, styrene-butadiene resin, phenol resin, acrylate resin, polyimide resin, bismaleimide-triazine resin, bismaleimide resin, benzoxazine resin, and phenoxy resin.
9. The thermosetting resin composition claimed in claim 1, wherein the hollow glass sphere having an inorganic coating layer is a hollow glass sphere having an inorganic coating layer treated with a surface treatment agent.
10. The thermosetting resin composition as claimed in claim 9, wherein said surface treatment agent is selected from at least one of a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a nonionic surfactant.
11. The thermosetting resin composition of claim 9, wherein the surface treatment agent is selected from at least one of a silane coupling agent and a titanate.
12. The thermosetting resin composition of claim 10, wherein said surfactant is selected from the group consisting of silicone oils.
13. A prepreg comprising a reinforcing material and a thermosetting resin composition according to claim 1 attached thereto after drying by impregnation.
14. A metal-clad laminate comprising: a sheet of prepreg according to claim 13 and a metal foil applied to one or both sides of the prepreg; or at least two superimposed prepregs, at least one of which is a prepreg according to claim 13, and a metal foil applied to one or both sides of the superimposed prepregs.
15. A printed circuit board containing at least one prepreg according to claim 13.
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| CN109825081B (en) * | 2019-01-30 | 2021-06-04 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg containing thermosetting resin composition, metal foil-clad laminate and printed circuit board |
| CN109852031B (en) * | 2019-02-02 | 2021-07-30 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg, laminate, and printed wiring board |
| CN109836631A (en) | 2019-02-02 | 2019-06-04 | 广东生益科技股份有限公司 | Vinyl thermoset resin composition, prepreg, laminate and printed circuit board |
| CN111057271B (en) * | 2019-11-26 | 2021-09-28 | 广东盈骅新材料科技有限公司 | Titanium suboxide composite material and application thereof |
| CN112500686B (en) * | 2020-12-11 | 2022-12-30 | 广东生益科技股份有限公司 | Resin composition and application thereof |
| CN114716802B (en) * | 2022-03-30 | 2024-10-18 | 郑州圣莱特空心微珠新材料有限公司 | Low-dielectric mobile phone middle frame base material and preparation method thereof |
| CN114621606A (en) * | 2022-03-31 | 2022-06-14 | 郑州圣莱特空心微珠新材料有限公司 | Hollow glass bead surface modifier, preparation method thereof and preparation method of hollow glass beads |
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