CN108724851A - A kind of high-toughness copper clad laminate material and preparation method thereof - Google Patents
A kind of high-toughness copper clad laminate material and preparation method thereof Download PDFInfo
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- CN108724851A CN108724851A CN201810419762.3A CN201810419762A CN108724851A CN 108724851 A CN108724851 A CN 108724851A CN 201810419762 A CN201810419762 A CN 201810419762A CN 108724851 A CN108724851 A CN 108724851A
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B15/092—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 comprising epoxy resins
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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
- 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
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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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
- B32B38/00—Ancillary operations in connection with laminating processes
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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
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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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
- 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
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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
- 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
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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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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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
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention provides a kind of high-toughness copper clad laminate materials and preparation method thereof, include the following steps：S1. purifying galapectite particle is prepared；S2. rare earth modified galapectite particle is prepared；S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, linear phenolic resin, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grinds and cures 4 ~ 8 h, obtains resin adhesive liquid；S4. dipping process is carried out to surface treated glass fabric, prepreg is obtained after drying, then copper foil will be covered with after prepreg trimming superposition, finally according to 150-160 DEG C of 1 h of solidification, then is warming up to 210-230 DEG C of 2 h of solidification, obtains copper-clad plate.The copper-clad plate material of the present invention has good mechanical property, dielectric properties, and very low hygroscopicity.
Description
Technical field
The present invention relates to field of electronic materials, and in particular to a kind of high-toughness copper clad laminate material and preparation method thereof.
Background technology
Copper-clad laminate（CCL, abbreviation copper-clad plate）It is the basic material of electronics industry, mainly for the manufacture of printed circuit
Plate is widely used in the electronic products such as computer, communication apparatus, instrument and meter.It is by reinforcing material impregnating resin, single side or double
Face is coated with copper foil, through a kind of board-like material made of hot pressing.Epoxy copperplate can be divided into cloth substrate by reinforcing material, paper base plate and
Composite plate three classes.Since that there is excellent comprehensive performance and moderate price to have become output at present is big for epoxy copperplate,
The wide a kind of baseplate material of purposes.But in recent years, with the rapid development of electronic technology and mobile communication, electronic computer,
The information processings such as electron exchanger and communication apparatus and transmission speed are further improved.To ensure its ever-increasing capacity
Communication modes are developed from analog signal to digitized signal, and the mobile communication of mobile phone, automobile telephone etc. is to realize the increasing of the number of channel
Add, the digitlization etc. of high performance, multifunction, target so that original epoxy resin copper-clad plate cannot meet the requirements to
To epoxy resin modification, keep epoxy copperplate high performance and multifunction extremely urgent.
Invention content
Technical problems to be solved：The object of the present invention is to provide a kind of high-toughness copper clad laminate materials, have good power
Learn performance, dielectric properties, and very low hygroscopicity.
Technical solution：A kind of high-toughness copper clad laminate material, includes the following steps：
Acrylic acid modified novolac epoxy resin 30-50 parts, 55-65 parts of end hydroxy butadiene modified epoxy, toughener 15-
30 parts, 45-65 parts of linear phenolic resin, 4-8 parts of rare earth nitrades, 20-40 parts of filler, 2-5 parts of curing agent, organic solvent 70-
100 parts；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly.About 4-6 is reacted under 70-75 DEG C of water bath condition
H obtains modified epoxy, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, coupling agent KH-550 and two bays
The mass ratio of sour dibutyl tin is 150-160：180-200：15-20：1-1.5；
Rare earth nitrades are La (NO3)3·6H2O, Nd (NO3)3·6H2O or Tb (NO3)3·6H2Any one or a few in O
Mixture, filler is galapectite.
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. halloysite nanotubes are cleaned, is dried, crossed 300-400 mesh and sieve the galapectite particle purified；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 300-400 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 4 ~ 8 h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 150-160 DEG C of 1 h of solidification, then 210-230 DEG C of 2 h of solidification is warming up to, obtains
Copper-clad plate.
Further, the curing agent is in 2- phenylimidazoles, 2-ethyl-4-methylimidazole or diaminodiphenylmethane
Any one.
Further, the organic solvent is any one in alcohols or ketone.
Further, the alcohols is methanol, and ketone is any one in butanone or acetone.
Further, the preparation method of the galapectite particle purified in the step S1 is that galapectite particle is dissolved in nothing
In water-ethanol, ultrasonic wave is dispersed to form uniform suspension, is then filtered suspension, by 60 DEG C in an oven of powder
It is dried to that quality is unchanged, then sieves the galapectite particle purified with 300-400 mesh.
Advantageous effect：The copper-clad plate material of the present invention has the following advantages：
First, the rare earth element in rare earth compound has very strong activity and electronegativity, can open galapectite surface layer and piece
- OH the keys and Si-O keys of interlayer form chelation structure key, while can also be formed altogether on the main chain or side chain in resin matrix
Valence link etc. can make inorganic galapectite particle form hybrid inorganic-organic network structure with organic matrix, improve organic-inorganic two
The interface compatibility of boundary, the drawing of material can be greatly improved by being used for reinforced resin matrix through rare earth modified galapectite
Intensity and toughness are stretched, the densification of copper-clad plate also improves, and water resistance also accordingly improves；
Secondly Si-O-Si segments flexible are introduced in the epoxy, be that a kind of raising epoxy resin toughness and water resistance are important
Innovation means.
Specific implementation mode
Embodiment 1
A kind of high-toughness copper clad laminate material, includes the following steps：
It is 50 parts of acrylic acid modified novolac epoxy resin, 55 parts of end hydroxy butadiene modified epoxy, 30 parts of toughener, linear
45 parts of phenolic resin, rare earth nitrades La (NO3)3·6H2O is 8 parts, 40 parts of galapectite, 5 parts of curing agent 2- phenylimidazoles, organic
100 parts of solvent methanol；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly, and about 4 h are reacted under 70 DEG C of water bath conditions, are obtained
Modified epoxy, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, coupling agent KH-550 and tin dilaurate two
The mass ratio of butyl tin is 160：180：20：1；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 300 mesh
Son；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 300 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 4 h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 150 DEG C of 1 h of solidification, then 230 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Embodiment 2
A kind of high-toughness copper clad laminate material, includes the following steps：
It is 30 parts of acrylic acid modified novolac epoxy resin, 65 parts of end hydroxy butadiene modified epoxy, 15 parts of toughener, linear
65 parts of phenolic resin, rare earth nitrades Nd (NO3)3·6H2O be 4 parts, 20 parts of galapectite, curing agent 2-ethyl-4-methylimidazole 2
Part, 70 parts of organic solvent butanone；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly, and about 6 h are reacted under -75 DEG C of water bath conditions, are obtained
Modified epoxy, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, coupling agent KH-550 and tin dilaurate two
The mass ratio of butyl tin is 150：200：15：1.5；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 400 mesh
Son；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 400 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 8 h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 160 DEG C of 1 h of solidification, then 210 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Embodiment 3
A kind of high-toughness copper clad laminate material, includes the following steps：
It is 35 parts of acrylic acid modified novolac epoxy resin, 65 parts of end hydroxy butadiene modified epoxy, 25 parts of toughener, linear
50 parts of phenolic resin, rare earth nitrades Tb (NO3)3·6H2O be 6 parts, 25 parts of galapectite, 2 parts of curing agent diaminodiphenylmethane,
90 parts of organic solvent-acetone；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly, and about 5 h are reacted under 70 DEG C of water bath conditions, are obtained
Modified epoxy, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, coupling agent KH-550 and tin dilaurate two
The mass ratio of butyl tin is 150：190：15：1.5；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 400 mesh
Son；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 400 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 5h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 150 DEG C of 1 h of solidification, then 220 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Embodiment 4
A kind of high-toughness copper clad laminate material, includes the following steps：
It is 45 parts of acrylic acid modified novolac epoxy resin, 58 parts of end hydroxy butadiene modified epoxy, 20 parts of toughener, linear
60 parts of phenolic resin, rare earth nitrades Nd (NO3)3·6H2O be 8 parts, 35 parts of galapectite, curing agent 2-ethyl-4-methylimidazole 5
Part, 80 parts of organic solvent methanol；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly, and about 5h is reacted under 75 DEG C of water bath conditions, must change
Property epoxy resin, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, two fourth of coupling agent KH-550 and tin dilaurate
The mass ratio of base tin is 160：185：20：1；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 300 mesh
Son；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 300 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 7h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 155 DEG C of 1 h of solidification, then 225 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Embodiment 5
A kind of high-toughness copper clad laminate material, includes the following steps：
It is 40 parts of acrylic acid modified novolac epoxy resin, 60 parts of end hydroxy butadiene modified epoxy, 23 parts of toughener, linear
55 parts of phenolic resin, rare earth nitrades La (NO3)3·6H2O is 2 parts, rare earth nitrades Nd (NO3)3·6H2O5 parts, galapectite 30
Part, 4 parts of curing agent diaminodiphenylmethane, 85 parts of organic solvent-acetone；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly, and about 5h is reacted under 70-75 DEG C of water bath condition,
Obtain modified epoxy, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, coupling agent KH-550 and tin dilaurate
The mass ratio of dibutyl tin is 155：185：18：1；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 400 mesh
Son；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 400 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 6 h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 155 DEG C of 1 h of solidification, then 220 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Comparative example 1
A kind of high-toughness copper clad laminate material, includes the following steps：
It is 50 parts of acrylic acid modified novolac epoxy resin, 55 parts of end hydroxy butadiene modified epoxy, 30 parts of toughener, linear
45 parts of phenolic resin, 40 parts of galapectite, 5 parts of curing agent 2- phenylimidazoles, 100 parts of organic solvent methanol；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly, and about 4 h are reacted under 70 DEG C of water bath conditions, are obtained
Modified epoxy, hydrogenated bisphenol A epoxy resin, hydroxyl-terminated injecting two methyl siloxane, coupling agent KH-550 and tin dilaurate two
The mass ratio of butyl tin is 160：180：20：1；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 300 mesh
Son；
S2. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth nitrades, purifying galapectite particle, curing agent and organic solvent, dispersion grind simultaneously cure 4 h, obtain resin glue
Liquid；
S3. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 150 DEG C of 1 h of solidification, then 230 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Comparative example 2
A kind of high-toughness copper clad laminate material, includes the following steps：
30 parts of acrylic acid modified novolac epoxy resin, 65 parts of end hydroxy butadiene modified epoxy, linear phenolic resin 65
Part, rare earth nitrades Nd (NO3)3·6H2O be 4 parts, 20 parts of galapectite, 2 parts of curing agent 2-ethyl-4-methylimidazole, You Jirong
70 parts of agent butanone；
A kind of preparation method of above-mentioned high-toughness copper clad laminate material, includes the following steps：
S1. galapectite particle is dissolved in absolute ethyl alcohol, ultrasonic wave is dispersed to form uniform suspension, then will suspend
Liquid is filtered, and powder is dried to that quality is unchanged for 60 DEG C in an oven, then the galapectite grain purified is sieved with 400 mesh
Son；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 400 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, linear phenolic resin, solidification
Agent and organic solvent, dispersion grind and cure 8 h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 160 DEG C of 1 h of solidification, then 210 DEG C of 2 h of solidification is warming up to, obtains copper-clad plate.
Bending strength：It is tested according to GB/T 9341-2008, loading velocity is 10 mm/min, and sample size is
120mm×10mm；
Dielectric constant：The dielectric constant of copper-clad plate is measured according to GB/T 4722-2017, test frequency is 1 MHz, test temperature
It is 25 DEG C, relative humidity 50%；
Water absorption rate test：It is measured according to GB/T 4722-2017.
。
Claims (6)
1. a kind of high-toughness copper clad laminate material, which is characterized in that include the following steps：
Acrylic acid modified novolac epoxy resin 30-50 parts, 55-65 parts of end hydroxy butadiene modified epoxy, toughener 15-
30 parts, 45-65 parts of linear phenolic resin, 4-8 parts of rare earth nitrades, 20-40 parts of filler, 2-5 parts of curing agent, organic solvent 70-
100 parts；
Wherein toughener is modified epoxy, and preparation method is：By hydrogenated bisphenol A epoxy resin, terminal hydroxy group poly dimethyl
Siloxanes, coupling agent KH-550 and dibutyl tin laurate, stir evenly；
About 4-6 h are reacted under 70-75 DEG C of water bath condition, obtain modified epoxy, hydrogenated bisphenol A epoxy resin, and terminal hydroxy group gathers
The mass ratio of dimethyl siloxane, coupling agent KH-550 and dibutyl tin laurate is 150-160：180-200：15-20：
1-1.5；
Rare earth nitrades are La (NO3)3·6H2O, Nd (NO3)3·6H2O or Tb (NO3)3·6H2Any one or a few in O
Mixture, filler is galapectite.
2. a kind of preparation method of high-toughness copper clad laminate material as described in claim 1, which is characterized in that including following step
Suddenly：
S1. halloysite nanotubes are cleaned, is dried, crossed 300-400 mesh and sieve the galapectite particle purified；
S2. rare earth nitrades are made into the aqueous solution that mass concentration is 1.2wt%, by galapectite particle earth solution after purification
In, using ultrasonic disperse to uniform suspension is formed, it is filtered after standing 5h under room temperature, powder is dried in 60 DEG C of baking ovens
It does unchanged to quality, powder is pulverized, then sieved with 300-400 mesh to obtain rare earth modified galapectite particle；
S3. by acrylic acid modified novolac epoxy resin, end hydroxy butadiene modified epoxy, toughener, novolac tree
Fat, rare earth modified galapectite particle, curing agent and organic solvent, dispersion grind and cure 4 ~ 8 h, obtain resin adhesive liquid；
S4. dipping process is carried out to surface treated glass fabric, obtains prepreg after drying, then by semi-solid preparation
It is covered with copper foil after piece trimming superposition, finally according to 150-160 DEG C of 1 h of solidification, then 210-230 DEG C of 2 h of solidification is warming up to, obtains
Copper-clad plate.
3. high-toughness copper clad laminate material according to claim 1, it is characterised in that：The curing agent is 2- phenyl miaows
Any one in azoles, 2-ethyl-4-methylimidazole or diaminodiphenylmethane.
4. high-toughness copper clad laminate material according to claim 1, it is characterised in that：The organic solvent is alcohols or ketone
In any one.
5. high-toughness copper clad laminate material according to claim 4, it is characterised in that：The alcohols is methanol, and ketone is fourth
Any one in ketone or acetone.
6. the preparation method of high-toughness copper clad laminate material according to claim 2, it is characterised in that：It is pure in the step S1
The preparation method of the galapectite particle of change is that galapectite particle is dissolved in absolute ethyl alcohol, and ultrasonic wave is dispersed to be formed uniformly
Then suspension is filtered by suspension, by powder in an oven 60 DEG C to be dried to quality unchanged, then with 300-400 mesh
Sieve the galapectite particle purified.
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