CN115109387B - Resin composition and application thereof - Google Patents
Resin composition and application thereof Download PDFInfo
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- CN115109387B CN115109387B CN202210811103.0A CN202210811103A CN115109387B CN 115109387 B CN115109387 B CN 115109387B CN 202210811103 A CN202210811103 A CN 202210811103A CN 115109387 B CN115109387 B CN 115109387B
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a resin composition and application thereof, wherein the resin composition comprises the following components: isocyanate modified epoxy resin, phenol dicyclopentadiene epoxy resin, sulfur-containing phenoxy resin, p-tert-butylphenol aldehyde resin and polyvinyl acetal. The resin composition disclosed by the invention has flexibility, heat resistance and pressure resistance, still keeps excellent insulation stability and reliability at high and low temperatures, is suitable for the use of an aluminum-based copper-clad laminate, and can meet the requirements of the field of 3D-LED illumination.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a resin composition and application thereof.
Background
The LED is increasingly applied to landscape lighting, building lighting, indoor lighting and stage lighting with the advantages of environmental protection, low energy consumption, long service life and the like. Conventional LED substrates are planar, and LED lighting tends to evolve in the 3D direction as the lighting industry evolves.
Compared with the conventional LED illumination, the 3D-LED illumination requires that the substrate aluminum substrate has excellent toughness and flexibility under the conditions of ensuring excellent heat dissipation, heat resistance, insulation and peeling strength, and the insulation layer is not broken or separated in the special-shaped processing and bending processes of the 3D-LED.
CN106633675a discloses a high thermal conductivity resin composition, which comprises the following components in parts by weight: 35-70 parts of bismaleimide modified epoxy resin, 5-20 parts of phenolic resin, 10-30 parts of flexible modified epoxy resin, 360-480 parts of heat conducting filler, 8-14 parts of curing agent, 2-5 parts of coupling agent, 0.05-0.85 part of curing accelerator and 2-6 parts of additive. The high heat-conducting resin composition disclosed by the invention has high heat resistance of bismaleimide and good manufacturability of epoxy resin, and simultaneously, the phenolic oxygen resin and the flexible epoxy resin are added, so that the novel resin composition has excellent adhesiveness, flexibility, heat conductivity, heat resistance, insulativity and flame retardance.
CN110283427a discloses a halogen-free epoxy resin prepreg, which comprises the following components in parts by weight: 10-25 parts of macromolecular epoxy resin and high T g 6-18 parts of epoxy resin, 5-15 parts of phosphorus-containing epoxy resin, 3-8 parts of UV-resistant organic matters, 10-25 parts of phenolic resin, 10-25 parts of flexible resin, 1-5 parts of curing agent, 0.03-0.1 part of catalyst, 2-10 parts of additive flame retardant, 0-40 parts of filler and 20-50 parts of solvent. The halogen-free epoxy resin prepreg disclosed by the method has the characteristics of halogen-free flame retardance FV0 grade, has extremely low fluidity, and has high bonding, infiltration filling and high T g And high heat resistance, the soft and hard combined board, the rigid-flex printed circuit board or the multi-layer PCB manufactured by the halogen-free epoxy resin prepreg disclosed by the invention have good dimensional stability, and the problems of layered explosion board, copper wire falling, copper wire shifting short circuit after deformation and the like caused by white spots and dry flowers can not occur due to good filling and bonding performance, so that the product qualification rate and reliability are improved.
CN108192291a discloses an epoxy resin composition for high heat resistance aluminum substrate, and a preparation method and application thereof. The epoxy resin composition for the high heat-resistant aluminum substrate comprises the following raw material components in parts by weight: 55-65 parts of phenolic epoxy resin, 20-24 parts of phenolic resin and 17-21 parts of diluent. The LED aluminum substrate circuit board prepared from the epoxy resin composition for the high-heat-resistance aluminum substrate has higher heat resistance, can meet the requirement of welding processing on heat resistance, and ensures the welding reliability.
With the development of the application field of aluminum substrates, the requirements on the service life and reliability of electronic products are higher and higher, so that the 3D-LED products are required to have excellent pressure-resistant stability when the flexibility is met, and the service life of the products is ensured. Meanwhile, in order to widen the application field of the product, the aluminum substrate is required to have excellent insulation reliability under cold and high temperature conditions. However, the resin composition in the prior art has many disadvantages in heat resistance, pressure resistance, reliability, flexibility and the like, and cannot meet the use requirements of the aluminum substrate.
In view of the above, it is important to develop a resin composition having excellent heat resistance and pressure-resistant stability while satisfying flexibility, and capable of having excellent insulation reliability under cold and high temperature conditions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a resin composition and application thereof, wherein the resin composition has flexibility, heat resistance and pressure resistance, still keeps excellent insulation stability and reliability at high and low temperatures, is suitable for the use of an aluminum-based copper-clad laminate, and can meet the requirements of the field of 3D-LED illumination.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a resin composition comprising the following components: isocyanate modified epoxy resin, phenol dicyclopentadiene epoxy resin, sulfur-containing phenoxy resin, p-tert-butylphenol aldehyde resin and polyvinyl acetal.
According to the invention, the flexibility of the resin composition is improved by the polyvinyl butyral, and the sulfur-containing phenoxy resin and the phenol dicyclopentadiene epoxy resin improve the bonding force of the toughened resin (bonding force refers to interlayer peeling strength, namely bonding force between laminated boards formed by the resin composition) on the basis that the flexibility of the resin composition is not obviously lost, so that the problems of insufficient heat resistance and lower glass transition temperature of the resin composition are solved. The combination of polyvinyl butyral, sulfur-containing phenoxy resin and phenol dicyclopentadiene epoxy resin ensures that the resin composition has higher binding force, better flexibility and heat resistance and higher glass transition temperature. In addition, the isocyanate modified epoxy resin and the para-tert-butyl phenol aldehyde resin are compounded for use, so that the heat resistance and the binding force of the resin composition are further improved, the glass transition temperature of the resin composition is higher when the resin composition is used for an aluminum-based copper-clad laminate, the pressure resistance of the laminate is ensured, and the resin composition has excellent insulation reliability under cold and high temperature conditions.
Preferably, the resin composition comprises the following components in parts by weight:
according to the invention, the resin composition is compounded and used by polyvinyl butyral, sulfur-containing phenoxy resin and phenol dicyclopentadiene epoxy resin in a specific proportion, so that the resin composition has high binding force on the basis of good flexibility, and the resin composition has high heat resistance and high glass transition temperature. The isocyanate modified epoxy resin and the para-tertiary butyl phenol aldehyde resin are compounded and used in a specific proportion, so that the glass transition temperature of the system is further improved, and the resin composition is ensured to have excellent heat resistance and pressure resistance.
The resin composition can solve the problems that an aluminum substrate insulating layer is large in brittleness and easy to break in the 3D processing process, and can meet the requirements of the 3D-LED and special-shaped processing illumination fields. The resin composition has high flexibility, can achieve better glass transition temperature, heat resistance and pressure resistance stability, and can achieve the use conditions in cold and high temperature areas.
In the present invention, the isocyanate-modified epoxy resin is 30 to 40 parts by weight, for example, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, etc.
The weight parts of the phenol dicyclopentadiene epoxy resin are 10 to 20 parts, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and the like.
The sulfur-containing phenoxy resin is 5-20 parts by weight, for example 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, etc.
The weight parts of the p-tert-butylphenol aldehyde resin are 15 to 25 parts, for example, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, etc.
The polyvinyl acetal is 8 to 20 parts by weight, for example 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, etc.
Preferably, the isocyanate modified epoxy resin has an epoxy equivalent weight of 550-650g/eq (e.g., 560g/eq, 580g/eq, 600g/eq, 620g/eq, 640g/eq, etc.) and a viscosity of 3800-4200 mPas (e.g., 3850 mPas, 3900 mPas, 3950 mPas, 4000 mPas, 4050 mPas, 4100 mPas, 4150 mPas, etc.).
In the present invention, the viscosity is measured at 25℃by a rotational viscometer according to the HG/T3660-1999 standard.
Preferably, the isocyanate modified epoxy resin comprises MDI modified epoxy resin.
Preferably, the phenol dicyclopentadiene epoxy resin has an epoxy equivalent weight of 470-580g/eq (e.g., 480g/eq, 500g/eq, 520g/eq, 540g/eq, 560g/eq, etc.).
Preferably, the sulfur-containing phenoxy resin has a weight average molecular weight of 70000 to 90000g/mol, for example 75000g/mol, 80000g/mol, 85000g/mol, etc.
Preferably, the sulfur content of the sulfur-containing phenoxy resin is 10mol% to 40mol%, for example, 15mol%, 20mol%, 25mol%, 30mol%, 35mol%, etc.
In the invention, the unit of the mole percent of sulfur in the sulfur-containing phenoxy resin is mol percent, and the testing method comprises the following steps: the molar fraction of sulfur, multiplied by the molar mass of sulfur, divided by the molar fraction of each species in the mixture, multiplied by the sum of the respective molar masses.
Preferably, the viscosity of the p-tert-butylphenol aldehyde resin is 8400-15000 mPas, for example 8500 mPas, 9000 mPas, 10000 mPas, 11000 mPas, 12000 mPas, 13000 mPas, 14000 mPas, etc.
In the present invention, the p-tert-butylphenol aldehyde resin has the following structure:
wherein n is selected from positive integers of 40-80, such as 45, 50, 55, 60, 65, 70, 75, etc.
Preferably, the polyvinyl acetal has a number average molecular weight of 90000-200000g/mol, e.g. 100000g/mol, 120000g/mol, 140000g/mol, 160000g/mol, 180000g/mol, etc.
Preferably, the molar percentage of hydroxyl groups in the polyvinyl acetal is 15mol% to 35mol%, e.g. 20mol%, 25mol%, 30mol%, etc.
In the invention, the unit of the mole percent of hydroxyl in the polyvinyl acetal is 'mole percent', and the testing method is the same as that of sulfur mole percent.
Preferably, the resin composition further comprises a curing agent, a curing accelerator, and a filler.
Preferably, the curing agent comprises any one or a combination of at least two of dicyandiamide, diaminodiphenyl sulfone or diaminodiphenyl methane, wherein typical but non-limiting combinations include: a combination of dicyandiamide and diaminodiphenyl sulfone, a combination of diaminodiphenyl sulfone and diaminodiphenyl methane, a combination of dicyandiamide, diaminodiphenyl sulfone and diaminodiphenyl methane, and the like.
Preferably, the cure accelerator comprises any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole or 1-cyanoethyl-2-methylimidazole, wherein typical but non-limiting combinations include: a combination of 2-methylimidazole and 2-ethyl-4-methylimidazole, a combination of 2-phenylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl-2-methylimidazole, a combination of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl-2-methylimidazole, and the like.
Preferably, the filler comprises a thermally conductive filler.
In the present invention, the filler is preferably a heat conductive filler because it can give the resin composition good heat dissipation.
Preferably, the filler comprises a combination of spherical alumina and silica.
Preferably, the weight ratio of the spherical alumina to the silica is 1: (0.05-0.2), wherein 0.05-0.2 can be 0.06, 0.08, 0.1, 0.12, 0.14, 0.16, 0.18, etc.
Preferably, the spherical alumina has a particle size of 1.0 to 4.5 μm, for example 1.5 μm,2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc.
Preferably, the silica has a particle size of 5.0 to 9.0 μm, for example 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, etc.
Preferably, the curing agent is 1.5 to 4.0 parts by weight, for example 2 parts, 3 parts, 3.5 parts, 4 parts, etc.
Preferably, the curing accelerator is 0.2 to 1.0 parts by weight, for example 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, etc.
Preferably, the filler is present in an amount of 430-560 parts by weight, such as 440 parts, 460 parts, 480 parts, 500 parts, 520 parts, 540 parts, etc.
In a second aspect, the present invention provides a prepreg comprising a reinforcing material and the resin composition according to the first aspect attached thereto after drying by impregnation.
Preferably, the reinforcing material comprises any one or a combination of at least two of fiberglass cloth, non-woven cloth, or organic fiber cloth, wherein typical but non-limiting combinations include: a combination of glass fiber cloth and nonwoven cloth, a combination of nonwoven cloth and organic fiber cloth, a combination of glass fiber cloth, nonwoven cloth and organic fiber cloth, and the like.
In a third aspect, the present invention provides an aluminium-based copper-clad laminate comprising at least one (e.g. 2, 5, 10, 15, 20, etc.) prepreg according to the second aspect, and copper foil and aluminium sheet respectively clad on both sides of the laminated prepreg.
In a fourth aspect, the present invention provides a printed circuit board comprising at least one (e.g. 2, 5, 10, 15, 20, etc.) aluminium-based copper-clad laminate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The thermal conductivity of the aluminum-based copper-clad laminate prepared by the resin composition is more than 2.39W/m.K, the maximum thermal conductivity is 2.63W/m.K, the peeling strength of a bending surface is more than or equal to 1.90N/mm, the frying plate at 288 ℃ is more than or equal to 100min, the appearance of the baking plate at 260 ℃ is normal for 2 hours, and T is equal to that of the aluminum-based copper-clad laminate g The breakdown voltage of the 360-degree bending surface is equal to or higher than 172 ℃, the breakdown voltage after the wet heat treatment is equal to or higher than 8.4kV, the CTI is equal to or higher than 600V, and the heat-dissipating performance, the heat resistance, the peeling strength and the insulation reliability are excellent.
(2) After the aluminum-based copper-clad laminate prepared by the resin composition is subjected to circulation for 3000 times at-40 ℃/30min and 125 ℃/30min, the breakdown voltage of a bending surface is above 7.1kV, and excellent insulation stability and reliability are still maintained.
(3) The aluminum-based copper-clad laminate prepared by the resin composition disclosed by the invention can not separate layers from an aluminum plate after being bent for 360 degrees, has no adhesive drop, has excellent processing flexibility in the field of 3D-LEDs, and can meet the lighting requirements of LEDs in different shapes.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw material information of each embodiment and comparative example of the invention is as follows:
(A) Isocyanate modified epoxy resin:
(A1) An isocyanate modified epoxy resin having an epoxy equivalent of 562g/eq and a viscosity (25 ℃) of 3880 mPas, purchased from North oasis;
(A2) An isocyanate modified epoxy resin with an epoxy equivalent of 634g/eq and a viscosity (25 ℃) of 4060 mPas, purchased from North oasis;
(B) Phenol dicyclopentadiene epoxy resin:
(B1) Phenol dicyclopentadiene epoxy resin with an epoxy equivalent of 483g/eq, purchased from holy spring;
(B2) Phenol dicyclopentadiene epoxy resin with an epoxy equivalent of 571g/eq is purchased from holy spring;
(C) P-tert-butylphenol aldehyde resin:
the structural formula is as follows:
(C1) P-tert-butylphenol aldehyde resin having n of 43 and a viscosity (25 ℃) of 950 mPas, obtained from Shengquan;
(C2) P-tert-butylphenol aldehyde resin having n of 59 and a viscosity (25 ℃) of 11300 mPas, obtained from Shengquan;
(C3) P-tert-butylphenol aldehyde resin having n of 80 and a viscosity (25 ℃) of 14960mPa.s, available from Shengquan;
(D) Polyvinyl acetal:
(D1) A polyvinyl acetal having a hydroxyl group content of 15.0mol% and a number average molecular weight of 97800 g/mol;
(D2) A polyvinyl acetal having a hydroxyl group content of 18.3mol% and a number average molecular weight of 176400 g/mol;
(D3) A polyvinyl acetal having a hydroxyl group content of 29.1mol% and a number average molecular weight of 114300 g/mol;
(D4) A polyvinyl acetal having a hydroxyl group content of 33.9mol% and a number average molecular weight of 189200 g/mol;
(E) Sulfur-containing phenoxy resin:
(E1) Sulfur content 13.1mol%, number average molecular weight 75100g/mol of sulfur-containing phenoxy resin;
(E2) Sulfur content 16.2mol%, number average molecular weight 89300g/mol sulfur-containing phenoxy resin;
(E3) Sulfur content 37.0mol%, number average molecular weight 74300g/mol sulfur-containing phenoxy resin;
(E4) Sulfur content 32.5mol%, number average molecular weight 86750g/mol sulfur-containing phenoxy resin;
(F) Curing agent:
(F1) Dicyandiamide
(F2) Diamino diphenyl sulfone
(F3) Diaminodiphenyl methane
(G) Curing accelerator: 2-methylimidazole, purchased from japan four-country chemical synthesis;
(H) And (3) a heat conducting filler:
(H1) The weight ratio of spherical alumina with the particle size of 2.0 μm to silicon dioxide with the particle size of 5.6 μm is 1:0.06 of a thermally conductive filler;
(H2) The weight ratio of spherical alumina with the particle size of 4.5 μm to silicon dioxide with the particle size of 6.7 μm is 1:0.20 of a thermally conductive filler;
(H3) The weight ratio of spherical alumina with the particle size of 3.9 μm to silicon dioxide with the particle size of 8.7 μm is 1:0.14 of a thermally conductive filler;
bisphenol a epoxy resin: purchasing from the star of Nantong;
phenol-oxygen resin: purchasing from Shandong Shengquan;
nitrile rubber: purchased from Taiwan Nandi;
bisphenol a phenolic resin: purchasing from Shandong Shengquan;
polyvinyl formal: purchased from colali.
Examples 1 to 6 and comparative examples 1 to 9
The formulation compositions of the resin compositions of examples 1 to 6 and comparative examples 1 to 9 are shown in tables 1 to 2.
TABLE 1
TABLE 2
Note that: the dimensionless components in the table are all in parts by weight.
The resin compositions of examples 1 to 6 and comparative examples 1 to 9 were prepared as aluminum-based copper-clad laminates prepared by the following method:
the first step: weighing isocyanate modified epoxy resin, phenol dicyclopentadiene epoxy resin, p-tert-butyl phenol aldehyde resin and polyvinyl acetal, adding into a solvent, and uniformly stirring by using a common stirrer;
and a second step of: slowly adding the heat-conducting filler according to the proportion while stirring, dispersing for 45min by using a high-speed shearing machine at 2000rpm, then injecting the dispersed filler slurry into a ball mill, and ball-milling and dispersing for 25min at 1500 rpm;
and a third step of: sequentially adding sulfur-containing phenoxy resin, a curing agent, a curing accelerator and the rest additives, and stirring and curing for 8 hours to prepare a resin composition;
fourth step: the prepared resin composition is coated on the surface of copper foil, and the resin composition system is in a B-stage after being baked for 4min at 170 ℃. The adhesive copper foil at B-stage is adhered with aluminum plate at 190 deg.C in vacuum press at 35kg/cm 2 And (5) pressing for 150min to obtain the aluminum-based copper-clad plate.
Performance testing
The aluminum-based copper-clad laminates prepared from the resin compositions of examples 1 to 6 and comparative examples 1 to 9 were subjected to the following test:
(1) Thermal conductivity: the test was performed according to ASTM 5470-06.
(2) Bending surface peel strength: after 10s of treatment at 288℃under thermal stress, the test was carried out using the IPC TM 650.2.4.9 method in the bent state.
(3) Thermal stress: the panels were fried at 288℃and the time the laminate could withstand was observed.
(4) And (3) baking: baking at 260 deg.C for 2 hr, and observing the state of the laminated board.
(5) Glass transition temperature: the DSC test was performed at a rate of 10℃per minute under a nitrogen atmosphere.
(6) Breakdown voltage of 360 DEG bending surface: 360 ° bend planes were tested at a and D-48/50.
(7) Breakdown voltage of cold and hot impact: the breakdown voltage was tested by cycling 3000 times at-40 ℃/30min and 125 ℃/30 min.
(8) Relative tracking index (CTI): the test was performed in the a state.
(9) Bendability (insulating layer and aluminum plate): 360 ° bending along a 1/2 inch radius mold, the laminate was observed for delamination and gumming.
The test results are summarized in tables 3-4.
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from an analysis of the data in tables 3 and 4, the resin composition according to the present invention (examples) has the following characteristics relative to the resin compositions of the prior art (comparative examples 1 to 9):
(1) The thermal conductivity of the aluminum-based copper-clad laminate prepared by the resin composition is more than 2.39W/m.K, the maximum thermal conductivity is 2.63W/m.K, the peeling strength of a bending surface is more than or equal to 1.90N/mm, the frying plate at 288 ℃ is more than or equal to 100min, the appearance of the baking plate at 260 ℃ is normal for 2 hours, and T is equal to that of the aluminum-based copper-clad laminate g The breakdown voltage A of the 360-degree bending surface is more than or equal to 172 ℃, the breakdown voltage after wet heat treatment is more than or equal to 8.4kV, the CTI is more than or equal to 600V, and the heat-dissipating performance, the heat resistance, the peeling strength and the insulation reliability are excellent.
(2) After the aluminum-based copper-clad laminate prepared by the resin composition is subjected to circulation for 3000 times at-40 ℃/30min and 125 ℃/30min, the breakdown voltage of a bending surface is above 7.1kV, and excellent insulation stability and reliability are still maintained.
(3) The aluminum-based copper-clad laminate prepared by the resin composition disclosed by the invention can not separate layers from an aluminum plate after being bent for 360 degrees, has no adhesive drop, has excellent processing flexibility in the field of 3D-LEDs, and can meet the lighting requirements of LEDs in different shapes.
Comparative examples 1 to 4 were analyzed to find that the properties of comparative examples 1 to 4 were inferior to those of each example, and it was confirmed that the properties of the resin composition of the present invention were better.
As can be seen from the analysis of comparative examples 5 to 9 and example 2, the performance of comparative examples 5 to 9 is not as good as that of example 2, and it is proved that the resin composition of the present invention has better performance, lacks any one, and has poor performance through isocyanate modified epoxy resin, phenol dicyclopentadiene epoxy resin, sulfur-containing phenoxy resin, p-tert-butylphenol aldehyde resin and polyvinyl acetal.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (16)
1. The resin composition is characterized by comprising the following components in parts by weight:
the epoxy equivalent of the isocyanate modified epoxy resin is 550-650g/eq, and the viscosity of the isocyanate modified epoxy resin is 3800-4200 mPa.s at 25 ℃;
the epoxy equivalent of the phenol dicyclopentadiene epoxy resin is 470-580g/eq;
the molar percentage of sulfur in the sulfur-containing phenoxy resin is 10mol percent to 40mol percent;
the number average molecular weight of the polyvinyl acetal is 90000-200000g/mol;
the weight average molecular weight of the sulfur-containing phenoxy resin is 70000-90000g/mol;
the viscosity of the para-tertiary butyl phenol aldehyde resin at 25 ℃ is 8400-15000 mPa.s
The molar percentage of hydroxyl groups in the polyvinyl acetal is 15mol percent to 35mol percent.
2. The resin composition of claim 1, further comprising a curing agent, a curing accelerator, and a filler.
3. The resin composition of claim 2, wherein the curing agent comprises any one or a combination of at least two of dicyandiamide, diaminodiphenyl sulfone, or diaminodiphenyl methane.
4. The resin composition according to claim 2, wherein the curing accelerator comprises any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole or 1-cyanoethyl-2-methylimidazole.
5. The resin composition of claim 2, wherein the filler comprises a thermally conductive filler.
6. The resin composition of claim 2, wherein the filler comprises a combination of spherical alumina and silica.
7. The resin composition of claim 6, wherein the weight ratio of spherical alumina to silica is 1: (0.05-0.2).
8. The resin composition according to claim 6, wherein the spherical alumina has a particle diameter of 1.0 to 4.5. Mu.m.
9. The resin composition according to claim 6, wherein the silica has a particle diameter of 5.0 to 9.0. Mu.m.
10. The resin composition according to claim 2, wherein the weight part of the curing agent is 1.5 to 4.0 parts.
11. The resin composition according to claim 2, wherein the weight part of the curing accelerator is 0.2 to 1.0 part.
12. The resin composition according to claim 2, wherein the filler is 430 to 560 parts by weight.
13. A prepreg comprising a reinforcing material and the resin composition according to any one of claims 1 to 12 attached thereto after drying by impregnation.
14. The prepreg of claim 13, wherein the reinforcing material comprises any one or a combination of at least two of fiberglass cloth or non-woven cloth.
15. An aluminum-based copper-clad laminate, characterized in that the aluminum-based copper-clad laminate comprises at least one prepreg according to claim 13, and copper foil and aluminum plate respectively coated on both sides of the laminated prepreg.
16. A printed circuit board comprising at least one aluminum-based copper-clad laminate according to claim 15.
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