CN114957922A - Prepreg coating material, prepreg and copper-clad plate - Google Patents

Prepreg coating material, prepreg and copper-clad plate Download PDF

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Publication number
CN114957922A
CN114957922A CN202210855156.2A CN202210855156A CN114957922A CN 114957922 A CN114957922 A CN 114957922A CN 202210855156 A CN202210855156 A CN 202210855156A CN 114957922 A CN114957922 A CN 114957922A
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resin
prepreg
epoxy resin
coating material
cyanate ester
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朱向忠
梁先文
易安
封力行
赖志强
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Nano Guangdong Materials Technology Co ltd
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Nano Guangdong Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a prepreg coating material, a prepreg and a copper-clad plate, wherein the prepreg coating material comprises a resin composition, and the resin composition consists of epoxy resin, a curing agent, cyanate ester resin, bismaleimide resin and liquid resin containing unsaturated double bonds in preset contents, so that the prepreg coating material has the effects of high heat resistance, high toughness, high bonding strength, high oxidation resistance, low heat shrinkage and low dielectric property. The prepreg adopts the prepreg coating material provided by the invention as a prepreg coating, and has good heat resistance and cohesiveness. The copper-clad plate adopts the prepreg provided by the invention, and has the effects of low glue overflow amount, high peel strength, high tin immersion heat resistance, high bending strength, high tensile strength and low heat shrinkage rate.

Description

Prepreg coating material, prepreg and copper-clad plate
Technical Field
The invention relates to the technical field of prepregs, in particular to a prepreg coating material, a prepreg and a copper-clad plate.
Background
The prepreg is also called as bonding sheet, and generally refers to a solid film prepared by impregnating a glass fiber cloth with a resin glue solution and then baking. Under certain temperature and pressure, the resin glue solution in the glue film is in a semi-cured state, and can be melted and bonded again and cured completely at high temperature, so that different types of semi-cured sheet substrates can be utilized for superposition, and a copper-clad plate or a multilayer printed circuit laminated plate meeting the requirements is formed after high-temperature hot pressing by adopting a laminating machine. The prepreg is one of main raw materials of a copper-clad plate, mainly comprises a reinforcing material and a prepreg coating, wherein the reinforcing material is divided into several types such as glass fiber cloth, a paper base, a composite material and the like, the prepreg coating material is generally resin glue, but the existing prepreg coating material has low heat resistance and poor caking property.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a prepreg coating material, a prepreg and a copper-clad plate, which are used for solving the problems of low heat resistance and poor caking property of the prepreg coating material in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the prepreg coating material comprises a resin composition, wherein the resin composition comprises the following components in parts by mass: 50 to 70 percent of epoxy resin; 1-20% of curing agent; 10 to 30 percent of cyanate ester resin; 1 to 10 percent of bismaleimide resin; 1-10% of liquid resin containing unsaturated double bonds; wherein the cyanate ester resin is a compound containing a cyanate ester group in the structure; the unsaturated bond in the liquid resin containing the unsaturated double bond is a carbon-carbon double bond and/or a carbon-oxygen double bond.
Preferably, the structural formula of the liquid resin containing unsaturated double bonds is shown as a formula I,
Figure BDA0003754115280000011
wherein R is selected from epoxypropyl or a structure containing a benzene ring and a substituent group, and the substituent group is selected from at least one of hydroxyl, carboxyl and epoxypropyl.
Still preferably, the liquid resin containing an unsaturated double bond is at least one selected from the group consisting of an acrylic resin, an allyl resin, a styrene resin and a substituted styrene resin.
Preferably, the epoxy resin is selected from at least one of a phosphorous epoxy resin, a nitrogen-containing epoxy resin, a polyfunctional epoxy resin, a bisphenol a epoxy resin, a bisphenol F epoxy resin, a tetraphenylethane epoxy resin, a triphenylmethane epoxy resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin, a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, an aralkyl novolac epoxy resin, a polyphenylene ether-modified epoxy resin, an alicyclic type epoxy resin, a glycidylamine type epoxy resin, and a glycidylester type epoxy resin; and/or the presence of a gas in the gas,
the curing agent is selected from at least one of aliphatic amine, aromatic amine, alicyclic amine, heterocyclic amine, aromatic anhydride, alicyclic anhydride, aliphatic anhydride, polyamide resin, novolac resin, polyphenol resin, arylamine formaldehyde resin, polysulfide compound, polyester resin, latent curing agent, flame retardant curing agent and active ester curing agent; and/or the presence of a gas in the gas,
the cyanate ester resin is selected from at least one of bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, dicyclopentadiene cyanate ester resin, o-methyl novolac epoxy resin, phenol cyanate ester resin and polyphenyl ether modified cyanate ester resin; and/or the presence of a gas in the gas,
the bismaleimide is a prepolymer produced by prepolymerization of an allyl compound and maleimide resin, and the number average molecular weight of the prepolymer is 2000-5000.
More preferably, the allyl compound is selected from at least one of allyl ether compounds, allyl phenol oxide resins, allyl phenol aldehyde resins, diallyl bisphenol a and diallyl bisphenol S; and/or the presence of a gas in the gas,
the maleimide resin is at least one selected from the group consisting of 4, 4 '-diphenylmethane bismaleimide resin, 4' -diphenyl ether bismaleimide resin, 4 '-diphenylisopropyl bismaleimide resin and 4, 4' -diphenylsulfone bismaleimide resin.
Preferably, the prepreg coating material further comprises a solvent, and the solid content of the prepreg coating material is 33% -65%.
Still preferably, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene, toluene, p-xylene, tetrahydrofuran, N-methylpyrrolidone, and dimethylsulfoxide.
The invention also provides a prepreg, which comprises the prepreg coating, a reinforcing material and the prepreg coating which are sequentially stacked, wherein the prepreg coating is made of the prepreg coating material.
Preferably, the thickness of the prepreg coating is 10 to 150 μm.
The invention also provides a copper-clad plate which comprises the prepreg.
The prepreg coating material provided by the embodiment of the invention comprises a resin composition, wherein the resin composition comprises epoxy resin, a curing agent, cyanate ester resin, bismaleimide resin and liquid resin containing unsaturated double bonds in specified content, so that the prepreg coating material has the effects of high heat resistance, high toughness, high bonding strength, high oxidation resistance, low heat shrinkage and low dielectric property.
The prepreg provided by the embodiment of the invention adopts the prepreg coating material provided by the embodiment of the invention as a prepreg coating, and has good heat resistance and cohesiveness.
The copper-clad plate provided by the embodiment of the invention adopts the prepreg provided by the embodiment of the invention, and has the effects of low glue overflow amount, high peeling strength, high tin immersion heat resistance, high bending strength, high tensile strength and low heat shrinkage.
Drawings
Fig. 1 is a schematic structural diagram of a copper-clad plate provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the solution according to the present invention are shown in the drawings, and other details not so related to the present invention are omitted.
The invention provides a prepreg coating material, a prepreg and a copper-clad plate according to the problems of low heat resistance and poor caking property of the prepreg coating material in the prior art, wherein the prepreg coating material has the effects of high heat resistance, high bending strength, high tensile strength, high bonding strength and low heat shrinkage rate.
The invention firstly provides a prepreg coating material which comprises a resin composition, wherein the resin composition comprises the following components in percentage by mass: 50 to 70 percent of epoxy resin; 1-20% of curing agent; 10 to 30 percent of cyanate ester resin; 1 to 10 percent of bismaleimide resin; 1-10% of liquid resin containing unsaturated double bonds; wherein the cyanate ester resin is a compound containing a cyanate ester group in the structure; the unsaturated bond in the liquid resin containing the unsaturated double bond is a carbon-carbon double bond and/or a carbon-oxygen double bond.
In the resin composition, the mass fraction of the epoxy resin is higher, and the epoxy resin generally contains aromatic ether bonds, is easy to degrade and exercise after being irradiated by sunlight, and has poor weather resistance, so that the resin composition of the prepreg coating material provided by the embodiment of the invention contains 1-10% by mass of liquid resin containing unsaturated double bonds, further improves the weather resistance, and simultaneously improves the bonding capability, thereby facilitating the prepreg coating material to have no glue overflow during glue filling. The mass fraction of the unsaturated double bond-containing liquid resin may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.
Specifically, the structural formula of the liquid resin containing unsaturated double bonds is shown as a formula I,
Figure BDA0003754115280000041
wherein R is selected from epoxypropyl or a structure containing a benzene ring and a substituent group, and the substituent group is selected from at least one of hydroxyl, carboxyl and epoxypropyl.
In the structure containing a benzene ring and a substituent, the substituent may be a structure in which a hydrogen atom on the benzene ring is directly substituted by the substituent, or a structure in which another structure is bonded to the benzene ring and the substituent is further bonded to the other structure.
More specifically, the liquid resin containing an unsaturated double bond is selected from at least one of an acrylic resin, an allyl resin, a styrene resin and a substituted styrene resin.
It is worth mentioning that the epoxy resin has small relative molecular mass, good fluidity at normal temperature, and is convenient for molding and curing. In addition, the epoxy resin has active epoxy groups and more polar groups, the epoxy groups can enable the resin composition to have high adhesive force to other substances, and the polar groups can enable the molecular structure in the cured prepreg coating material to be more compact, so that the mechanical property is further improved. Therefore, in the resin composition of the prepreg coating material provided in the embodiment of the present invention, the mass fraction of the epoxy resin should be in a range of 50% to 70% to ensure the adhesion of the prepreg coating material. The mass fraction of the epoxy resin may be, for example, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, or 70%.
Specifically, the epoxy resin is selected from at least one of a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, a polyfunctional epoxy resin, a bisphenol a epoxy resin, a bisphenol F epoxy resin, a tetraphenylethane epoxy resin, a triphenylmethane epoxy resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin, a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, an aralkyl novolac epoxy resin, a polyphenylene ether-modified epoxy resin, an alicyclic type epoxy resin, a glycidylamine type epoxy resin, and a glycidylester type epoxy resin;
in addition, although the epoxy resin does not substantially generate low-molecular volatiles during curing, the epoxy resin has poor curing performance, is slowly cured in an environment of less than 10 ℃, and is inconvenient to use in winter. Therefore, the resin composition of the embodiment of the invention comprises 1-20% of the curing agent by mass so as to improve the curing performance of the semi-cured layer coating. The mass fraction of the curing agent may be, for example, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, or 20%.
Specifically, the curing agent is at least one selected from the group consisting of aliphatic amines, aromatic amines, alicyclic amines, heterocyclic amines, aromatic acid anhydrides, alicyclic acid anhydrides, aliphatic acid anhydrides, polyamide resins, phenol-novolac resins, and polyphenol resins, aromatic amine-formaldehyde resins, polysulfide compounds, polyester resins, latent curing agents, flame-retardant curing agents, and active ester curing agents;
it should be noted that, because cyanate ester groups of the cyanate ester resin can undergo a cyclization and auto-polymerization reaction to generate a highly heat-resistant triazine ring cross-linked structure, and a cured product thereof has excellent temperature resistance, mechanical properties and dielectric properties, the resin composition provided in the embodiment of the present invention further contains 10% to 30% by mass of the cyanate ester resin, and under the combination of the cyanate ester resin, the epoxy resin and the curing agent, the curing property and the heat resistance are further improved on the premise of ensuring the adhesive property of the prepreg coating material.
The cyanate ester resin is selected from at least one of bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, dicyclopentadiene cyanate ester resin, o-methyl novolac epoxy resin, phenol cyanate ester resin and polyphenyl ether modified cyanate ester resin;
actually, the prepreg coating material provided by the embodiment of the invention contains 1% -10% of bismaleimide, the bismaleimide is a prepolymer produced by prepolymerization of an allyl compound and a maleimide resin, and the number average molecular weight of the prepolymer is 2000-5000.
More specifically, the allyl compound is selected from at least one of allyl ether compounds, allyl phenol oxide resins, allyl phenol aldehyde resins, diallyl bisphenol a and diallyl bisphenol S;
more specifically, the maleimide resin is at least one selected from the group consisting of 4, 4 '-diphenylmethane bismaleimide resin, 4' -diphenylether bismaleimide resin, 4 '-diphenylisopropyl bismaleimide resin and 4, 4' -diphenylsulfone bismaleimide resin.
In addition, the prepreg coating material provided by the embodiment of the invention further comprises a solvent, and the solid content in the prepreg coating material is 33% -65%.
It should be noted that when the solid content in the prepreg coating material is 33% to 65%, the prepreg coating material can be better kept in a semi-cured state, and is convenient to be melted again for use, and the solid content in the prepreg coating material may be 33%, 35%, 40%, 45%, 50%, 55%, 60%, or 65%, for example.
Specifically, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, acetone, methyl ethyl ketone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene, toluene, p-xylene, tetrahydrofuran, N-methylpyrrolidone, and dimethyl sulfoxide.
The prepreg coating material provided by the embodiment of the invention comprises a resin composition, wherein the resin composition comprises epoxy resin, a curing agent, cyanate ester resin, bismaleimide resin and liquid resin containing unsaturated double bonds in specified content, so that the prepreg coating material has the effects of high heat resistance, high toughness, high bonding strength, high oxidation resistance, low heat shrinkage and low dielectric property.
The invention also provides a prepreg, which comprises a prepreg coating, a reinforcing material and a prepreg coating which are sequentially stacked, wherein the prepreg coating is made of the prepreg coating material.
Specifically, the reinforcing material is selected from at least one of glass fiber cloth, paper base and composite material.
Specifically, the thickness of the prepreg coating is 10-150 μm.
In a specific embodiment, the structure of the prepreg is as shown in fig. 1, and the prepreg 2 includes a prepreg coating 21, a fiberglass cloth 22, and a prepreg coating 21 that are sequentially stacked.
The prepreg provided by the embodiment of the invention adopts the prepreg coating material provided by the embodiment of the invention as a prepreg coating, and has good heat resistance and cohesiveness.
The invention also provides a copper-clad plate which comprises the prepreg.
In a specific embodiment, the structure of the copper-clad plate is shown in fig. 1, and the copper-clad plate comprises polyimide 1, the prepreg 2 and the copper foil 3 which are sequentially stacked.
Specifically, the polyimide 1 is a flexible board polyimide substrate.
In a specific embodiment, the invention also provides a preparation method of the copper-clad plate, and the prepreg coating material, the prepreg and the copper-clad plate provided by the embodiment of the invention can be sequentially prepared in the preparation process of the copper-clad plate. The preparation method of the copper-clad plate comprises the following steps:
s1 preparation of prepreg coating material
Comprises the following components: 50-70% of epoxy resin; 1-20% of curing agent; 10 to 30 mass percent of cyanate ester resin; 1-10% of bismaleimide resin; 1-10% by mass of liquid resin containing unsaturated double bonds; mixing to obtain the resin composition.
And adding the resin composition and the solvent into a glue mixing kettle, and stirring for 0.5-2 h to obtain the prepreg coating material with the solid content of 33-65%.
S2 preparation of prepreg
And soaking the glass fiber cloth in the prepreg coating material and then baking to obtain a prepreg with the thickness of 10-150 mu m of the prepreg coating.
S3, preparing copper-clad plate
And placing the prepreg between the soft board polyimide substrate and the copper foil, and heating, pressurizing and curing in a hot press to form the copper-clad plate.
The copper-clad plate provided by the embodiment of the invention adopts the prepreg provided by the embodiment of the invention, and has the effects of low glue overflow amount, high peeling strength, high tin immersion heat resistance, high bending strength, high tensile strength and low heat shrinkage.
For further illustration of the present invention, the prepreg coating material, the prepreg and the copper clad laminate provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
S1 preparation of prepreg coating material
Comprises the following components: the epoxy resin model 3700 with the mass percent of 50 percent; dicyandiamide with the mass percentage of 18 percent; 13% of cyanate ester resin MID44 v; 9 percent of bismaleimide resin opvc 1; 10 percent of liquid resin 1151 containing unsaturated double bonds; mixing to obtain the resin composition.
And adding the resin composition and butanone into a glue mixing kettle, and stirring for 2 hours to obtain the prepreg coating material with the solid content of 60%.
S2 preparation of prepreg
And soaking the glass fiber cloth in the prepreg coating material and then baking to obtain a prepreg.
S3, preparation of copper-clad plate
And placing the prepreg between the soft board polyimide substrate and the copper foil, and heating, pressurizing and curing in a hot press to form the copper-clad plate.
Copper-clad plate performance test
Testing the following parameters of the copper-clad plate: the adhesive overflow amount, peel strength, tin immersion heat resistance, bending strength, tensile strength and heat shrinkage rate, and the performance data are shown in table 1.
Example 2
This example is different from example 1 in that, in step S1, the resin composition contains the following components in mass fraction: 62% epoxy model 3700; 20% dicyandiamide; 10% of cyanate ester resin MID44 v; 3 percent of bismaleimide resin opvc 1; 5% of liquid resin 3609 containing unsaturated double bonds; the solids content in the resulting prepreg coating material was 50%. The other preparation processes in this embodiment are completely the same as those in embodiment 1, and thus are not described again.
The copper-clad plate I and the copper-clad plate II are prepared according to the preparation method of the embodiment 1, the copper-clad plate III and the copper-clad plate IV are prepared according to the preparation method of the embodiment 2, the prepreg thickness measurement and the performance test of the glue overflow amount, the peeling strength, the tin immersion heat resistance, the bending strength, the tensile strength and the heat shrinkage rate are carried out on the prepared copper-clad plate I, the copper-clad plate II, the copper-clad plate III and the copper-clad plate IV, wherein,
the amount of the overflow was measured by the method specified in IPC-TM-6502.3.17.2 to evaluate the size of the overflow under the hot pressing condition.
The peel strength was measured according to the "post thermal stress" experimental conditions of IPC-TM-6502.4.8 method for testing the peel strength of the metal cap layer.
The heat resistance of the immersion tin was measured by immersing a 50 x 50mm copper-containing sample in solder at 288 ℃ and recording the time for delamination and blistering of the sample.
The test methods of the bending strength and the compressive strength are all tested by adopting a universal tester.
The testing method of the thermal shrinkage rate is to adopt a quadratic element measuring instrument for testing.
The performance data are shown in Table 1, where the flash amount is in mm, the peel strength is in kg/cm, the immersion tin heat resistance is in MPa, the bending strength is in MPa, and the tensile strength is in MPa.
TABLE 1
Figure BDA0003754115280000091
As can be seen from the data in Table 1, the copper-clad plate provided by the embodiment of the invention has the effects of low glue overflow amount, high peel strength, high tin immersion heat resistance, high bending strength, high tensile strength and low heat shrinkage.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.

Claims (10)

1. The prepreg coating material is characterized by comprising a resin composition, wherein the resin composition comprises the following components in percentage by mass: 50 to 70 percent of epoxy resin; 1-20% of curing agent; 10 to 30 percent of cyanate ester resin; 1 to 10 percent of bismaleimide resin; 1-10% of liquid resin containing unsaturated double bonds; wherein the cyanate ester resin is a compound containing cyanate ester group in the structure; the unsaturated bond in the liquid resin containing the unsaturated double bond is a carbon-carbon double bond and/or a carbon-oxygen double bond.
2. The prepreg coating material according to claim 1, wherein the liquid resin containing unsaturated double bonds has a structural formula shown in formula I,
Figure FDA0003754115270000011
wherein R is selected from cyclopropyl or a structure containing a benzene ring and a substituent group, and the substituent group is selected from at least one of hydroxyl, carboxyl and epoxypropyl.
3. The prepreg coating material according to claim 2, wherein the liquid resin containing an unsaturated double bond is at least one selected from an acrylic resin, an allyl resin, a styrene resin and a substituted styrene resin.
4. The prepreg coating material according to any one of claims 1 to 3, wherein the epoxy resin is at least one selected from a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, a polyfunctional epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a tetraphenylethane epoxy resin, a triphenylmethane epoxy resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin, a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, an aralkyl novolac epoxy resin, a polyphenylene ether-modified epoxy resin, an alicyclic type epoxy resin, a glycidylamine type epoxy resin, and a glycidyl ester type epoxy resin; and/or the presence of a gas in the gas,
the curing agent is selected from at least one of aliphatic amine, aromatic amine, alicyclic amine, heterocyclic amine, aromatic acid anhydride, alicyclic acid anhydride, aliphatic acid anhydride, polyamide resin, phenol novolac resin, polyphenol resin, arylamine formaldehyde resin, polysulfide compound, polyester resin, latent curing agent, flame retardant curing agent and active ester curing agent; and/or the presence of a gas in the gas,
the cyanate ester resin is selected from at least one of bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, dicyclopentadiene cyanate ester resin, o-methyl novolac epoxy resin, phenol cyanate ester resin and polyphenyl ether modified cyanate ester resin; and/or the presence of a gas in the gas,
the bismaleimide is a prepolymer produced by prepolymerization of an allyl compound and maleimide resin, and the number average molecular weight of the prepolymer is 2000-5000.
5. The prepreg coating material according to claim 4, wherein the allyl compound is at least one selected from the group consisting of allyl ether compounds, allyl phenoxy resins, allyl phenolic resins, diallyl bisphenol A and diallyl bisphenol S; and/or the presence of a gas in the gas,
the maleimide resin is at least one selected from the group consisting of 4, 4 '-diphenylmethane bismaleimide resin, 4' -diphenyl ether bismaleimide resin, 4 '-diphenylisopropyl bismaleimide resin and 4, 4' -diphenylsulfone bismaleimide resin.
6. The prepreg coating material according to claim 1, further comprising a solvent, wherein the solid content of the prepreg coating material is 33% to 65%.
7. The prepreg coating material according to claim 6, wherein the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, acetone, methyl ethyl ketone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene, toluene, p-xylene, tetrahydrofuran, N-methylpyrrolidone, and dimethylsulfoxide.
8. A prepreg, which is characterized by comprising a prepreg coating, a reinforcing material and the prepreg coating which are sequentially stacked, wherein the material of the prepreg coating is the prepreg coating material according to any one of claims 1 to 8.
9. Prepreg according to claim 8, characterized in that the thickness of the prepreg coating is between 10 and 150 μm.
10. A copper-clad plate characterized by comprising the prepreg according to claim 8 or 9.
CN202210855156.2A 2022-07-19 2022-07-19 Prepreg coating material, prepreg and copper-clad plate Pending CN114957922A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885900A (en) * 2010-07-02 2010-11-17 广东生益科技股份有限公司 Resin composition, bonding sheet and copper-clad plate made using same, manufacturing method thereof
CN103131130A (en) * 2011-11-22 2013-06-05 台光电子材料股份有限公司 Epoxy resin composition and low dielectric constant insulating material employing same
CN103937156A (en) * 2014-03-05 2014-07-23 浙江华正新材料股份有限公司 Thermosetting resin composition and method for manufacturing prepreg and laminated board by using thermosetting resin composition
CN105385107A (en) * 2015-12-07 2016-03-09 浙江华正新材料股份有限公司 High dielectric thermosetting resin composition and laminated board for substrate
CN110028758A (en) * 2018-01-12 2019-07-19 联茂(无锡)电子科技有限公司 Halogen-free epoxy resin composition, laminated plates and printed circuit board

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885900A (en) * 2010-07-02 2010-11-17 广东生益科技股份有限公司 Resin composition, bonding sheet and copper-clad plate made using same, manufacturing method thereof
CN103131130A (en) * 2011-11-22 2013-06-05 台光电子材料股份有限公司 Epoxy resin composition and low dielectric constant insulating material employing same
CN103937156A (en) * 2014-03-05 2014-07-23 浙江华正新材料股份有限公司 Thermosetting resin composition and method for manufacturing prepreg and laminated board by using thermosetting resin composition
CN105385107A (en) * 2015-12-07 2016-03-09 浙江华正新材料股份有限公司 High dielectric thermosetting resin composition and laminated board for substrate
CN110028758A (en) * 2018-01-12 2019-07-19 联茂(无锡)电子科技有限公司 Halogen-free epoxy resin composition, laminated plates and printed circuit board

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