CN109551837A - Aluminum-based copper-clad plate and preparation method thereof with high-fire resistance and high-termal conductivity - Google Patents
Aluminum-based copper-clad plate and preparation method thereof with high-fire resistance and high-termal conductivity Download PDFInfo
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- 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
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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- 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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- 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
- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08L2205/00—Polymer mixtures characterised by other features
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- 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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Abstract
The invention discloses a kind of preparation methods of aluminum-based copper-clad plate with high-fire resistance and high-termal conductivity, it solidifies to obtain the liquid-type epoxy resin containing mesomorphic structure with curing agent again after using epoxychloropropane to carry out epoxidation to the biphenyl compound of hydroxyl, using C8‑16It is epoxy resin toughened that alkyl dicarboxylic amine obtains straight chain type to bisphenol A epoxide resin progress toughening modifying, and it is aided with the curing system of diamino diphenyl sulfone and dicyandiamide composition, cooperate aluminium oxide and boron nitride as high thermal conductivity filler and prepares the resin adhesive liquid to be formed, copper foil another side is covered on one side at it after being stacked glass fabric impregnation tablet after drying after resin adhesive liquid is coated on glass fabric and covers alumina plate, most obtains aluminum-based copper-clad plate after Hot-press cooling afterwards；With excellent thermal conductivity while the aluminum-based copper-clad plate guarantees heat resistance, long period and when immersed solder more multiple thermal stress when being mainly manifested in floating weldering, using DC power supply when higher proof voltage and higher thermal conductivity.
Description
Technical field
The present invention relates to a kind of aluminum-based copper-clad plates and preparation method thereof, more particularly to one kind to have high-fire resistance and high thermal conductivity
The aluminum-based copper-clad plate and preparation method thereof of property, belongs to copper-clad plate and its processing technique field.
Background technique
As printed wiring board (PCB) is towards high density, the continuous development in multiple stratification direction, component carries on PCB,
The space of installation is greatly decreased, and complete machine electronic product is higher and higher to the power requirement of power component.The small big function in space
Rate inevitably results from more heat aggregations, and the decline of component electric property is caused even to damage, and then has high dissipate
High praise of the metal aluminum substrate of hot, good mechanical processability and high planarization by market.Aluminum substrate is as heat dissipation type high base
Plate has good heat dissipation effect to the heat generated in LED operation, improves the service life of LED light, therefore has obtained wide
General application.
Aluminum substrate mainly has two important indicators: one is thermal conductivity, refers mainly to the thermal conductivity of insulating layer, and insulating layer heat passes
It leads that performance is better, is more conducive to the diffusion of produced heat when device operation, while more advantageously reducing the running temperature of device,
Reach and improves the power load of module, reduce volume, extend the service life, improve the purpose of power output.It is with LED packaging
, internal heat caused by LED operation not only affects the brightness of LED, can also change the color of light, eventually result in LED
Failure；Furthermore the LED heat-radiating substrate of capacity of heat transmission difference can also be such that the input current size of LED is restricted.Secondly being resistance to
Hot, what is referred mainly to is also the heat resistance of insulating layer, this is because LED can generate higher heat, substrate in use
Need heat resistance with higher.Therefore it needs to develop a kind of aluminium base that can guarantee insulating layer thermal conductivity and heat resistance simultaneously
Plate.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of aluminum-based copper-clad plate with high-fire resistance and high-termal conductivity
And preparation method thereof.
The technical scheme is that
The invention discloses a kind of preparation method of aluminum-based copper-clad plate with high-fire resistance and high-termal conductivity, the preparation sides
Method includes the following steps:
S1: preparation resin adhesive liquid: weigh by weight liquid-type epoxy resin including 250~300 parts containing mesomorphic structure,
5~20 parts of straight chain types are epoxy resin toughened, 5~20 parts of diamino diphenyl sulfones (DDS), 1~5 part of dicyandiamide (DICY), 400~
500 parts of ball-aluminium oxide (Al2O3) and 150~200 parts of boron nitride (BN) raw material components, will weigh gained raw material components be added
In blender after 30~40 DEG C of 4~6h of stirring, resin adhesive liquid is obtained；
S2: above-mentioned resin adhesive liquid is coated on glass fabric and is placed in 2~4min of drying at 200~250 DEG C, is obtained
Glass fabric impregnation tablet；
S3: several above-mentioned glass fabric impregnation tablets are taken to stack together, according to needed for the copper-clad plate finally prepared
Thickness and shape and structure obtain insulating medium layer after being cut, in one layer of copper foil of one side superimposition of the insulating medium layer, and
Semi-finished product aluminum-based copper-clad plate is obtained after one layer of alumina plate of another side superimposition of the insulating medium layer；
S4: by above-mentioned semi-finished product aluminum-based copper-clad plate be placed in -700~-730mmHg, hot pressing 80 at 170~200 DEG C~
After 100min, cooling obtains the aluminum-based copper-clad plate with high-fire resistance and high-termal conductivity.
In above-mentioned preparation method, the liquid-type epoxy resin containing mesomorphic structure is by 100~120 parts by weight hydroxyls
Biphenyl compound be dissolved in 40~50 parts by weight solvent, then using 100 parts by weight epoxy chloropropanes (ECh) to contain hydroxyl
After the biphenyl compound of base carries out epoxidation, 1~3 curing agent is added and carries out solidification preparation gained；The wherein biphenyl of hydroxyl
Class compound is 4,4 '-dihydroxybiphenyls (BP), and solvent is isopropanol, and curing agent is phenyl trimethicone ammonium chloride (BTMAC).
In above-mentioned preparation method, the epoxy resin toughened straight chain type is with C8-16Alkyl dicarboxylic amine be plasticized modifier,
Using diethyl toluene diamine bisphenol A epoxide resin is modified as curing agent and to be prepared, wherein bisphenol A epoxide resin is
100 parts by weight, the C8-16Alkyl dicarboxylic amine is 15-30 parts by weight, and the diethyl toluene diamine is 3-5 parts by weight.
In above-mentioned preparation method, the diameter of particle of the ball-aluminium oxide and boron nitride is respectively 500nm~10 μm.
In above-mentioned preparation method, the copper foil with a thickness of 3~150 μm, the alumina plate with a thickness of 0.6~
2.0mm。
The invention also discloses a kind of above-mentioned preparation methods to prepare the resulting aluminium base with high-fire resistance and high-termal conductivity
Copper-clad plate, it is characterised in that: including insulating medium layer, the one side hot pressing superimposition of the insulating medium layer has copper foil, and the insulation is situated between
The another side superimposition of matter layer has alumina plate；The insulating medium layer is made of 1~2 layer of glass fabric impregnation tablet stacking,
It dries and obtains after every layer of glass fabric impregnation tablet fibreglass cloth impregnating resin glue, wherein the copper foil
With a thickness of 3~150 μm, and the aluminum-based copper-clad plate with a thickness of 0.6~2.0mm.
The method have the benefit that: the application is carried out using biphenyl compound of the epoxychloropropane to hydroxyl
Solidify to obtain the liquid-type epoxy resin containing mesomorphic structure with curing agent again after epoxidation, using C8-16Alkyl dicarboxylic amine is to bis-phenol
It is epoxy resin toughened that A epoxy resin progress toughening modifying obtains straight chain type, and is aided with diamino diphenyl sulfone and dicyandiamide composition
Curing system, cooperate aluminium oxide and boron nitride as high thermal conductivity filler and prepare the resin adhesive liquid to be formed, resin adhesive liquid is applied
Copper foil another side is covered on one side at it after being stacked glass fabric impregnation tablet after drying after overlaying on glass fabric covers oxidation
Aluminium sheet most obtains aluminum-based copper-clad plate after Hot-press cooling afterwards；The aluminum-based copper-clad plate guarantees to lead while heat resistance with excellent
Heating rate, long period and when immersed solder more multiple thermal stress when being mainly manifested in floating weldering, using DC power supply when it is higher resistance to
Voltage and higher thermal conductivity.
Specific embodiment
In order to better understand the technical means of the present invention, it and can be implemented in accordance with the contents of the specification, below
In conjunction with specific embodiments, specific embodiments of the present invention will be described in further detail, and following embodiment is for illustrating this hair
It is bright, but be not intended to limit the scope of the invention.
Specific embodiment 1
S1: preparation resin adhesive liquid: weigh by weight liquid-type epoxy resin including 260 parts containing mesomorphic structure, 8 parts it is straight
Chain is epoxy resin toughened, the original of 8 parts of diamino diphenyl sulfones, 2 parts of dicyandiamides, 400 parts of ball-aluminium oxides and 150 parts of boron nitride
Expect component, gained raw material components will be weighed and be added in blender after 32 DEG C of stirring 4h, resin adhesive liquid is obtained；Wherein spherical oxidation
The partial size of aluminium is 800nm, and the partial size of boron nitride is 1.5 μm；
S2: above-mentioned resin adhesive liquid is coated in be placed at 210 DEG C on glass fabric and dries 2min, obtains glass fibre
Cloth impregnation tablet；
S3: 1 above-mentioned glass fabric impregnation tablet is taken, according to the copper-clad plate required thickness and shape and structure finally prepared
Insulating medium layer is obtained after being cut, in one layer of 35 μm of copper foil of one side superimposition of the insulating medium layer, and in the dielectric
Semi-finished product aluminum-based copper-clad plate is obtained after the alumina plate of one layer of 0.8mm thickness of another side superimposition of layer；
S4: above-mentioned semi-finished product aluminum-based copper-clad plate is placed in -700mmHg, at 170 DEG C after hot pressing 80min, cooling is had
The aluminum-based copper-clad plate of high-fire resistance and high-termal conductivity.
Wherein the liquid-type epoxy resin containing mesomorphic structure is to be dissolved in 100 4,4 '-dihydroxybiphenyls of parts by weight (BP)
In 45 parts by weight of isopropyl alcohol solvents, ring then is carried out to 4,4 '-dihydroxybiphenyls using 100 parts by weight epoxy chloropropanes (ECh)
After oxidation, 1 parts by weight curing agent phenyl trimethicone ammonium chloride (BTMAC) is added and is prepared.
Wherein straight chain type Toughening Modification of Epoxy is with C10Alkyl dicarboxylic amine is plasticized modifier, with diethyltoluene two
Amine is that curing agent is modified bisphenol A epoxide resin and is prepared, and wherein bisphenol A epoxide resin is 100 parts by weight, C10Alkane
Base diamine is 20 parts by weight, and diethyl toluene diamine is 3 parts by weight.
Specific embodiment 2
S1: liquid-type epoxy resin including 300 parts containing mesomorphic structure, 18 parts preparation resin adhesive liquid: are weighed by weight
Straight chain type is epoxy resin toughened, 18 parts of diamino diphenyl sulfones, 4 parts of dicyandiamides, 450 parts of ball-aluminium oxides and 200 parts of boron nitride
Raw material components, will weigh gained raw material components be added blender in after 40 DEG C of stirring 5.5h, obtain resin adhesive liquid；Wherein ball
The partial size of shape aluminium oxide is 8 μm, and the partial size of boron nitride is 10 μm；
S2: above-mentioned resin adhesive liquid is coated in be placed at 240 DEG C on glass fabric and dries 3.5min, obtains glass fibers
Tie up cloth impregnation tablet；
S3: 2 above-mentioned glass fabric impregnation tablets are taken, according to the copper-clad plate required thickness and shape and structure finally prepared
Insulating medium layer is obtained after being cut, in one layer of 35 μm of copper foil of one side superimposition of the insulating medium layer, and in the dielectric
Semi-finished product aluminum-based copper-clad plate is obtained after the alumina plate of one layer of 1.78mm thickness of another side superimposition of layer；
S4: above-mentioned semi-finished product aluminum-based copper-clad plate is placed in -730mmHg, at 200 DEG C after hot pressing 100min, cooling is had
There is the aluminum-based copper-clad plate of high-fire resistance and high-termal conductivity.
Wherein the liquid-type epoxy resin containing mesomorphic structure is to be dissolved in 100 4,4 '-dihydroxybiphenyls of parts by weight (BP)
In 45 parts by weight of isopropyl alcohol solvents, ring then is carried out to 4,4 '-dihydroxybiphenyls using 100 parts by weight epoxy chloropropanes (ECh)
After oxidation, 1 parts by weight curing agent phenyl trimethicone ammonium chloride (BTMAC) is added and is prepared.
Wherein straight chain type Toughening Modification of Epoxy is with C14Alkyl dicarboxylic amine is plasticized modifier, with diethyltoluene two
Amine is that curing agent is modified bisphenol A epoxide resin and is prepared, and wherein bisphenol A epoxide resin is 100 parts by weight, C14Alkane
Base diamine is 30 parts by weight, and diethyl toluene diamine is 5 parts by weight.
Comparative example 1
Using commercially available similar aluminum-based copper-clad plate as comparative example.
The performance of aluminum-based copper-clad plate on sale is measured to the above-mentioned specific embodiment being prepared and on the market, main to survey
Determine the thermal stress, thermal conductivity and proof voltage of aluminum-based copper-clad plate to investigate the heat resistance, thermal conductivity and proof voltage of the copper-clad plate,
The measurement of middle thermal stress is respectively to carry out the test condition of floating weldering at 288 DEG C, and to carry out immersed solder at 288 DEG C and each 10s is
Test condition；Thermal conductivity is tested according to ASTM D5470 the method；Proof voltage is measured using direct current DC.Test
As a result as shown in table 1 below:
1 specific embodiment of table and comparative example performance test table
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the aluminum-based copper-clad plate with high-fire resistance and high-termal conductivity, which is characterized in that including following steps
It is rapid:
S1: preparation resin adhesive liquid: weigh by weight liquid-type epoxy resin including 250~300 parts containing mesomorphic structure, 5~
20 parts of straight chain types are epoxy resin toughened, 5~20 parts of diamino diphenyl sulfones, 1~5 part of dicyandiamide, 400~500 parts of spherical oxidations
The raw material components of aluminium and 150~200 parts of boron nitride will weigh gained raw material components and be added in blender in 30~40 DEG C of stirrings 4
After~6h, resin adhesive liquid is obtained；
S2: above-mentioned resin adhesive liquid is coated on glass fabric and is placed in 2~4min of drying at 200~250 DEG C, obtains glass
Fiber cloth impregnation tablet；
S3: several above-mentioned glass fabric impregnation tablets are taken to stack together, according to the copper-clad plate required thickness finally prepared
Insulating medium layer is obtained after being cut with shape and structure, in one layer of copper foil of one side superimposition of the insulating medium layer, and it is exhausted at this
Semi-finished product aluminum-based copper-clad plate is obtained after one layer of alumina plate of another side superimposition of edge dielectric layer；
S4: being placed in -700~-730mmHg for above-mentioned semi-finished product aluminum-based copper-clad plate, at 170~200 DEG C after 80~100min of hot pressing,
Cooling obtains the aluminum-based copper-clad plate with high-fire resistance and high-termal conductivity.
2. preparation method according to claim 1, it is characterised in that: the liquid-type epoxy resin containing mesomorphic structure is
The biphenyl compound of 100~120 parts by weight hydroxyls is dissolved in 40~50 parts by weight solvent, 100 weight are then used
After part epoxychloropropane carries out epoxidation to the biphenyl compound of hydroxyl, 1~3 curing agent is added and carries out solidification preparation institute
?.
3. preparation method according to claim 2, it is characterised in that: the biphenyl compound of the hydroxyl is 4,4 '-
Dihydroxybiphenyl, solvent are isopropanol, and curing agent is phenyl trimethicone ammonium chloride.
4. preparation method according to claim 1, it is characterised in that: the epoxy resin toughened straight chain type is with C8-16Alkane
Base diamine is plasticized modifier, is modified and is prepared to bisphenol A epoxide resin using diethyl toluene diamine as curing agent
, wherein bisphenol A epoxide resin is 100 parts by weight, the C8-16Alkyl dicarboxylic amine is 15-30 parts by weight, the diethyl first
Phenylenediamine is 3-5 parts by weight.
5. preparation method according to claim 1, it is characterised in that: the diameter of particle of the ball-aluminium oxide and boron nitride
Respectively 500nm~10 μm.
6. preparation method according to claim 1, it is characterised in that: the copper foil with a thickness of 3~150 μm.
7. preparation method according to claim 1, it is characterised in that: the alumina plate with a thickness of 0.6~2.0mm.
Resulting there is high-fire resistance and height to lead 8. in a kind of claim 1 to 7 prepared by preparation method described in any claim
Hot aluminum-based copper-clad plate, it is characterised in that: including insulating medium layer, the one side hot pressing superimposition of the insulating medium layer has copper foil,
And the another side superimposition of the insulating medium layer has alumina plate；The insulating medium layer is by 1~2 layer of glass fabric impregnation tablet
Stacking forms, and dries and obtains after every layer of glass fabric impregnation tablet fibreglass cloth impregnating resin glue.
9. aluminum-based copper-clad plate according to claim 8, it is characterised in that: the copper foil with a thickness of 3~150 μm.
10. aluminum-based copper-clad plate according to claim 8, it is characterised in that: the aluminum-based copper-clad plate with a thickness of 0.6~
2.0mm。
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| CN201811631531.5A CN109551837A (en) | 2018-12-29 | 2018-12-29 | Aluminum-based copper-clad plate and preparation method thereof with high-fire resistance and high-termal conductivity |
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| CN201811631531.5A CN109551837A (en) | 2018-12-29 | 2018-12-29 | Aluminum-based copper-clad plate and preparation method thereof with high-fire resistance and high-termal conductivity |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111031662A (en) * | 2019-12-30 | 2020-04-17 | 江苏联鑫电子工业有限公司 | High-flexibility high-TG (glass transition temperature) lead-free copper-clad plate and preparation method thereof |
| CN115403743A (en) * | 2022-09-27 | 2022-11-29 | 重庆大学 | Curing method of high-thermal-conductivity spherical boron nitride composite epoxy resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838843A (en) * | 2012-09-20 | 2012-12-26 | 宏昌电子材料股份有限公司 | Toughening epoxy resin composition and application thereof |
-
2018
- 2018-12-29 CN CN201811631531.5A patent/CN109551837A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838843A (en) * | 2012-09-20 | 2012-12-26 | 宏昌电子材料股份有限公司 | Toughening epoxy resin composition and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111031662A (en) * | 2019-12-30 | 2020-04-17 | 江苏联鑫电子工业有限公司 | High-flexibility high-TG (glass transition temperature) lead-free copper-clad plate and preparation method thereof |
| CN115403743A (en) * | 2022-09-27 | 2022-11-29 | 重庆大学 | Curing method of high-thermal-conductivity spherical boron nitride composite epoxy resin |
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