CN116751431B - Copper-clad plate based on benzocyclobutene and preparation method thereof - Google Patents

Copper-clad plate based on benzocyclobutene and preparation method thereof Download PDF

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CN116751431B
CN116751431B CN202310598092.7A CN202310598092A CN116751431B CN 116751431 B CN116751431 B CN 116751431B CN 202310598092 A CN202310598092 A CN 202310598092A CN 116751431 B CN116751431 B CN 116751431B
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benzocyclobutene
parts
clad plate
copper
stirring
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CN116751431A (en
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粟立军
高兴元
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Jiangmen Kingboard Electronic Development Co ltd
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Jiangmen Kingboard Electronic Development Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1018—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 using only vacuum
    • 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
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • 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
    • C08L63/04—Epoxynovolacs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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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    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract

The invention provides a benzocyclobutene-based copper-clad plate which is prepared from the following raw materials in parts by weight: 25-30 parts of modified benzocyclobutene resin, 20-25 parts of epoxy resin, 4-6 parts of curing agent, 0.5-1 part of curing accelerator, 30-35 parts of filler, 0.6-0.9 part of coupling agent and 45-50 parts of solvent. The invention also provides a preparation method of the copper-clad plate. The benzocyclobutene-based copper-clad plate provided by the invention has good dielectric property, heat resistance, toughness and adhesion property.

Description

Copper-clad plate based on benzocyclobutene and preparation method thereof
Technical Field
The invention relates to a copper-clad plate based on benzocyclobutene and a preparation method thereof.
Background
Thermosetting resins are widely used in the fields of aerospace, electronic and electrical appliances, automobiles, ships, buildings and the like because of excellent technological properties, good heat resistance and outstanding dimensional stability, and become important points and hot spots of research by people. Benzocyclobutene resin is one of typical representatives, and a unique nonpolar quaternary ring chemical structure endows the benzocyclobutene resin with moderate curing temperature, no small molecule emission in the curing process, low dielectric constant and loss factor, good mechanical properties and other comprehensive excellent properties.
The benzocyclobutene polymer has excellent performance (high temperature resistance, small dielectric constant and small dielectric loss) and is widely applied to the field of electronics and appliances. The miniaturization, high speed and densification of microelectronic components are in urgent need for new polymeric dielectric materials and for modified or compounded benzocyclobutene materials that are easy to process, good leveling behavior, low dielectric constant and good mechanical properties. The synthesis and application of the foreign benzocyclobutene have been studied very intensively, and the research and application of the foreign benzocyclobutene resin in China are still in the preliminary stage due to the high price.
Disclosure of Invention
The invention aims to solve the technical problem of providing a copper-clad plate based on benzocyclobutene, which has better dielectric property, heat resistance, toughness and adhesive property.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the copper-clad plate based on benzocyclobutene is prepared from the following raw materials in parts by weight: 25-30 parts of modified benzocyclobutene resin, 20-25 parts of epoxy resin, 4-6 parts of curing agent, 0.5-1 part of curing accelerator, 30-35 parts of filler, 0.6-0.9 part of coupling agent and 45-50 parts of solvent.
Further, the modified benzocyclobutene resin of the invention is prepared by the following steps:
A1. adding 4-bromobenzocyclobutene, ammonia water and cuprous chloride into a reaction bottle, heating to 155 ℃, stirring and reacting for 3-5 hours to obtain a reaction solution, cooling the reaction solution to room temperature, pouring into deionized water, extracting for 3 times by using dichloromethane, merging organic phases, washing for 3 times by using deionized water, and drying by using anhydrous magnesium sulfate for 24 hours to obtain 4-aminobenzocyclobutene;
A2. adding the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate obtained in the step A1 into deionized water, stirring until the mixture is uniform, adding 4-fluorobenzoyl chloride and methylene dichloride, stirring at 10 ℃ for reaction for 6-8 hours to obtain a reaction solution, evaporating the reaction solution to remove the methylene dichloride to obtain a solid, washing the solid with deionized water for 3 times, recrystallizing with ethanol, and drying at 85 ℃ until the weight is constant to obtain the modified benzocyclobutene resin.
Further, in the preparation step A1 of the modified benzocyclobutene resin, the mass concentration of ammonia water is 25%, and the ratio of 4-bromobenzocyclobutene, ammonia water, cuprous chloride, deionized water used in the reaction and dichloromethane used in each extraction is 1g:13mL:0.05g:10mL:14mL; in the preparation step A2 of the benzocyclobutene resin, the proportion of 4-aminobenzocyclobutene, sodium hydroxide, sodium dodecyl benzene sulfonate, deionized water used in the reaction, 4-fluorobenzoyl chloride and methylene dichloride is 1mol:2mol:4g:900mL:2mol:1600mL.
Further, the epoxy resin of the present invention is a novolac type epoxy resin.
Further, the curing agent is 4,4' -diaminodiphenyl sulfone.
Further, the curing accelerator of the present invention is 2-methylimidazole.
Further, the filler is aluminum nitride.
Further, the coupling agent is vinyltriethoxysilane.
Further, the solvent disclosed by the invention consists of N, N-dimethylformamide and propylene glycol methyl ether in a volume ratio of 2:1.
The invention aims to provide a preparation method of the benzocyclobutene-based copper-clad plate.
In order to solve the technical problems, the technical scheme is as follows:
a preparation method of a copper-clad plate based on benzocyclobutene comprises the following steps:
B1. weighing the raw materials according to the parts by weight, adding the modified benzocyclobutene resin and the solvent into a stirring kettle with the stirring speed of 200 r/min, stirring until the materials are uniformly mixed, adding the epoxy resin, stirring until the materials are uniformly mixed, adding the curing agent, the curing accelerator, the filler and the coupling agent, and stirring for 6-8 hours to obtain a resin composition glue solution;
B2. b, dipping the glass fiber cloth in the resin composition glue solution obtained in the step B1, and transferring the glass fiber cloth into an oven to be dried for 4-6 minutes at 165-175 ℃ to obtain a prepreg;
B3. taking 8 prepregs obtained in the step B2, stacking the prepregs in order, covering copper foils on the upper surface and the lower surface of the prepregs, and transferring the prepregs into a vacuum hot press for hot pressing to obtain a copper-clad plate based on benzocyclobutene; the hot pressing process comprises the following steps: heating from room temperature to 130 ℃ at a heating rate of 2.5 ℃/min, and setting the pressure to 100PSI; heating from 130 ℃ to 240 ℃ at a heating rate of 2 ℃/min, wherein the pressure is 350-450PSI, and the heat preservation time is 120-150 minutes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention firstly prepares 4-aminobenzocyclobutene by reacting 4-bromobenzocyclobutene with ammonia water under the catalysis of cuprous oxide, then prepares the modified benzocyclobutene resin by reacting 4-aminobenzocyclobutene with 4-fluorobenzoyl chloride, and compared with the common benzocyclobutene resin, the modified benzocyclobutene resin prepared by the invention has better heat resistance, toughness and adhesiveness, and the copper-clad plate prepared by the invention has better dielectric property, heat resistance, toughness and adhesiveness due to the excellent dielectric property of the benzocyclobutene resin.
(2) The filler used in the invention is aluminum nitride, which has better heat conductivity, so that the heat conductivity of the copper-clad plate can be improved.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments of the present invention and the descriptions thereof are provided for the purpose of illustrating the present invention, but are not to be construed as limiting the present invention.
Example 1
The benzocyclobutene-based copper-clad plate is prepared from the following raw materials in parts by weight: 28 parts of modified benzocyclobutene resin, 22 parts of linear phenolic epoxy resin, 5 parts of 4,4' -diaminodiphenyl sulfone, 0.8 part of 2-methylimidazole, 33 parts of aluminum nitride, 0.8 part of vinyltriethoxysilane and 49 parts of solvent consisting of N, N-dimethylformamide and propylene glycol methyl ether in a volume ratio of 2:1. Wherein the modified benzocyclobutene resin is prepared by the following steps:
A1. adding 4-bromobenzocyclobutene, ammonia water with the mass concentration of 25% and cuprous chloride into a reaction bottle, heating to 155 ℃, stirring and reacting for 4 hours to obtain a reaction liquid, cooling the reaction liquid to room temperature, pouring into deionized water, extracting 3 times with methylene chloride, merging organic phases, washing 3 times with deionized water, drying with anhydrous magnesium sulfate for 24 hours to obtain 4-aminobenzocyclobutene, 4-bromobenzocyclobutene, ammonia water, cuprous chloride, deionized water used in the reaction and methylene chloride used in each extraction, wherein the ratio of 1g to 13mL to 0.05g to 10mL to 14mL;
A2. adding the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate obtained in the step A1 into deionized water, stirring until the mixture is uniform, adding 4-fluorobenzoyl chloride, methylene dichloride, the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate, and the deionized water, the 4-fluorobenzoyl chloride and the methylene dichloride which are used in the reaction are mixed according to the ratio of 1mol to 2mol to 4g to 900mL to 2mol to 160 mL, stirring and reacting for 7 hours at 10 ℃ to obtain a reaction solution, evaporating the reaction solution to remove the methylene dichloride to obtain a solid, washing the solid with the deionized water for 3 times, recrystallizing with ethanol, and drying at 85 ℃ until the weight is constant to obtain the modified benzocyclobutene resin.
The preparation method of the embodiment comprises the following steps:
B1. weighing the raw materials according to parts by weight, adding the modified benzocyclobutene resin and the solvent into a stirring kettle with the stirring speed of 200 r/min, stirring until the materials are uniformly mixed, adding the linear phenolic epoxy resin, stirring until the materials are uniformly mixed, adding the 4,4' -diaminodiphenyl sulfone, the 2-methylimidazole, the aluminum nitride and the vinyl triethoxysilane, and stirring for 7 hours to obtain a resin composition glue solution;
B2. b, dipping the glass fiber cloth in the resin composition glue solution obtained in the step B1, and transferring the glass fiber cloth into an oven to be dried at 170 ℃ for 5 minutes to obtain a prepreg;
B3. taking 8 prepregs obtained in the step B2, stacking the prepregs in order, covering copper foils on the upper surface and the lower surface of the prepregs, and transferring the prepregs into a vacuum hot press for hot pressing to obtain a copper-clad plate based on benzocyclobutene; the hot pressing process comprises the following steps: heating from room temperature to 130 ℃ at a heating rate of 2.5 ℃/min, and setting the pressure to 100PSI; the temperature was increased from 130℃to 240℃at a rate of 2℃per minute, the pressure was 400PSI, and the incubation time was 135 minutes.
Example 2
The benzocyclobutene-based copper-clad plate is prepared from the following raw materials in parts by weight: 25 parts of modified benzocyclobutene resin, 25 parts of linear phenolic epoxy resin, 4 parts of 4,4' -diaminodiphenyl sulfone, 0.7 part of 2-methylimidazole, 35 parts of aluminum nitride and 0.9 part of vinyltriethoxysilane, wherein the volume ratio is 2:1, 50 parts of a solvent consisting of N, N-dimethylformamide and propylene glycol methyl ether. Wherein the modified benzocyclobutene resin is prepared by the following steps:
A1. adding 4-bromobenzocyclobutene, ammonia water with the mass concentration of 25% and cuprous chloride into a reaction bottle, heating to 155 ℃, stirring and reacting for 3 hours to obtain a reaction liquid, cooling the reaction liquid to room temperature, pouring into deionized water, extracting 3 times with methylene chloride, merging organic phases, washing 3 times with deionized water, drying with anhydrous magnesium sulfate for 24 hours to obtain 4-aminobenzocyclobutene, 4-bromobenzocyclobutene, ammonia water, cuprous chloride, deionized water used in the reaction and methylene chloride used in each extraction, wherein the ratio of 1g to 13mL to 0.05g to 10mL to 14mL;
A2. adding the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate obtained in the step A1 into deionized water, stirring until the mixture is uniform, adding 4-fluorobenzoyl chloride, methylene dichloride, the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate, and the deionized water, the 4-fluorobenzoyl chloride and the methylene dichloride which are used in the reaction are mixed for reaction for 6 hours at the temperature of 10 ℃ in the ratio of 1 mol:2:4 g:900mL:2mol:160 mL, steaming the reaction liquid to remove the methylene dichloride to obtain a solid, washing the solid with the deionized water for 3 times, recrystallizing with ethanol, and drying at the temperature of 85 ℃ until the weight is constant to obtain the modified benzocyclobutene resin.
The preparation method of the embodiment comprises the following steps:
B1. weighing the raw materials according to parts by weight, adding the modified benzocyclobutene resin and the solvent into a stirring kettle with the stirring speed of 200 r/min, stirring until the materials are uniformly mixed, adding the linear phenolic epoxy resin, stirring until the materials are uniformly mixed, adding the 4,4' -diaminodiphenyl sulfone, the 2-methylimidazole, the aluminum nitride and the vinyl triethoxysilane, and stirring for 8 hours to obtain a resin composition glue solution;
B2. b, dipping the glass fiber cloth in the resin composition glue solution obtained in the step B1, and transferring the glass fiber cloth into an oven to be dried for 4 minutes at 175 ℃ to obtain a prepreg;
B3. taking 8 prepregs obtained in the step B2, stacking the prepregs in order, covering copper foils on the upper surface and the lower surface of the prepregs, and transferring the prepregs into a vacuum hot press for hot pressing to obtain a copper-clad plate based on benzocyclobutene; the hot pressing process comprises the following steps: heating from room temperature to 130 ℃ at a heating rate of 2.5 ℃/min, and setting the pressure to 100PSI; the temperature was increased from 130℃to 240℃at a rate of 2℃per minute, the pressure was 450PSI, and the incubation time was 120 minutes.
Example 3
The benzocyclobutene-based copper-clad plate is prepared from the following raw materials in parts by weight: 27 parts of modified benzocyclobutene resin, 24 parts of linear phenolic epoxy resin, 6 parts of 4,4' -diaminodiphenyl sulfone, 0.5 part of 2-methylimidazole, 30 parts of aluminum nitride, 0.6 part of vinyltriethoxysilane and 45 parts of solvent consisting of N, N-dimethylformamide and propylene glycol methyl ether in a volume ratio of 2:1. Wherein the modified benzocyclobutene resin is prepared by the following steps:
A1. adding 4-bromobenzocyclobutene, ammonia water with the mass concentration of 25% and cuprous chloride into a reaction bottle, heating to 155 ℃, stirring and reacting for 3.5 hours to obtain a reaction liquid, cooling the reaction liquid to room temperature, pouring into deionized water, extracting 3 times with methylene chloride, merging organic phases, washing 3 times with deionized water, drying with anhydrous magnesium sulfate for 24 hours to obtain 4-aminobenzocyclobutene, 4-bromobenzocyclobutene, ammonia water, cuprous chloride, deionized water used in the reaction and methylene chloride used in each extraction, wherein the ratio of 1g to 13mL to 0.05g to 10mL to 14mL;
A2. adding the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate obtained in the step A1 into deionized water, stirring until the mixture is uniform, adding 4-fluorobenzoyl chloride, methylene dichloride, the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate, and the deionized water, the 4-fluorobenzoyl chloride and the methylene dichloride which are used in the reaction are mixed for reaction for 6.5 hours at the temperature of 10 ℃ in the ratio of 1 mol:2:4 g:900mL:2mol:160 mL, steaming the reaction liquid to remove the methylene dichloride to obtain a solid, washing the solid with the deionized water for 3 times, recrystallizing with ethanol, and drying at the temperature of 85 ℃ to constant weight to obtain the modified benzocyclobutene resin.
The preparation method of the embodiment comprises the following steps:
B1. weighing the raw materials according to the parts by weight, adding the modified benzocyclobutene resin and the solvent into a stirring kettle with the stirring speed of 200 r/min, stirring until the materials are uniformly mixed, adding the linear phenolic epoxy resin, stirring until the materials are uniformly mixed, adding the 4,4' -diaminodiphenyl sulfone, the 2-methylimidazole, the aluminum nitride and the vinyl triethoxysilane, and stirring for 7.5 hours to obtain resin composition glue solution;
B2. b, dipping the glass fiber cloth in the resin composition glue solution obtained in the step B1, and transferring the glass fiber cloth into an oven to be dried at 170 ℃ for 5 minutes to obtain a prepreg;
B3. taking 8 prepregs obtained in the step B2, stacking the prepregs in order, covering copper foils on the upper surface and the lower surface of the prepregs, and transferring the prepregs into a vacuum hot press for hot pressing to obtain a copper-clad plate based on benzocyclobutene; the hot pressing process comprises the following steps: heating from room temperature to 130 ℃ at a heating rate of 2.5 ℃/min, and setting the pressure to 100PSI; the temperature was increased from 130℃to 240℃at a rate of 2℃per minute, the pressure was 400PSI, and the incubation time was 130 minutes.
Example 4
The benzocyclobutene-based copper-clad plate is prepared from the following raw materials in parts by weight: 30 parts of modified benzocyclobutene resin, 20 parts of linear phenolic epoxy resin, 4.5 parts of 4,4' -diaminodiphenyl sulfone, 1 part of 2-methylimidazole, 32 parts of aluminum nitride and 0.7 part of vinyltriethoxysilane, wherein the volume ratio is 2:1, 48 parts of a solvent consisting of N, N-dimethylformamide and propylene glycol methyl ether. Wherein the modified benzocyclobutene resin is prepared by the following steps:
A1. adding 4-bromobenzocyclobutene, ammonia water with the mass concentration of 25% and cuprous chloride into a reaction bottle, heating to 155 ℃, stirring and reacting for 5 hours to obtain a reaction liquid, cooling the reaction liquid to room temperature, pouring into deionized water, extracting 3 times with methylene chloride, merging organic phases, washing 3 times with deionized water, drying with anhydrous magnesium sulfate for 24 hours to obtain 4-aminobenzocyclobutene, 4-bromobenzocyclobutene, ammonia water, cuprous chloride, deionized water used in the reaction and methylene chloride used in each extraction, wherein the ratio of 1g to 13mL to 0.05g to 10mL to 14mL;
A2. adding the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate obtained in the step A1 into deionized water, stirring until the mixture is uniform, adding 4-fluorobenzoyl chloride, methylene dichloride, the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate, and the deionized water, the 4-fluorobenzoyl chloride and the methylene dichloride which are used in the reaction are mixed according to the ratio of 1mol to 2mol to 4g to 900mL to 2mol to 160 mL, stirring and reacting for 8 hours at 10 ℃ to obtain a reaction solution, evaporating the reaction solution to remove the methylene dichloride to obtain a solid, washing the solid with the deionized water for 3 times, recrystallizing with ethanol, and drying at 85 ℃ until the weight is constant to obtain the modified benzocyclobutene resin.
The preparation method of the embodiment comprises the following steps:
B1. weighing the raw materials according to parts by weight, adding the modified benzocyclobutene resin and the solvent into a stirring kettle with the stirring speed of 200 r/min, stirring until the materials are uniformly mixed, adding the linear phenolic epoxy resin, stirring until the materials are uniformly mixed, adding the 4,4' -diaminodiphenyl sulfone, the 2-methylimidazole, the aluminum nitride and the vinyl triethoxysilane, and stirring for 6 hours to obtain a resin composition glue solution;
B2. b, dipping the glass fiber cloth in the resin composition glue solution obtained in the step B1, and transferring the glass fiber cloth into an oven to be dried for 6 minutes at 165 ℃ to obtain a prepreg;
B3. taking 8 prepregs obtained in the step B2, stacking the prepregs in order, covering copper foils on the upper surface and the lower surface of the prepregs, and transferring the prepregs into a vacuum hot press for hot pressing to obtain a copper-clad plate based on benzocyclobutene; the hot pressing process comprises the following steps: heating from room temperature to 130 ℃ at a heating rate of 2.5 ℃/min, and setting the pressure to 100PSI; the temperature was increased from 130℃to 240℃at a rate of 2℃per minute, the pressure was 350PSI, and the incubation time was 150 minutes.
Comparative example 1
The difference from example 1 is that: the modified benzocyclobutene resin in the raw materials is replaced by unmodified benzocyclobutene resin, so that the preparation step of the modified benzocyclobutene resin is omitted.
Comparative example 2
Unlike example 1, the following is: the starting materials do not include vinyltriethoxysilane.
Experimental example one: dielectric property test
Test reference standard/method: and (5) a bridge method.
Test instrument: and a capacitance meter.
Test object, target: dielectric constants at 1GHz of the copper clad laminates prepared in examples 1 to 4.
The smaller the dielectric constant, the better the dielectric properties, and the test results are shown in table 1:
dielectric constant
Example 1 3.15
Example 2 3.19
Example 3 3.14
Example 4 3.11
TABLE 1
As can be seen from Table 1, the dielectric constants of the embodiments 1-4 of the invention are smaller, which indicates that the copper-clad plate prepared by the invention has better dielectric properties.
Experimental example two: heat resistance test
Test reference standard/method: immersing the copper-clad plate in soldering tin at 288 ℃, starting timing from the time of immersing the copper-clad plate, and recording the time T' when layering bubbles appear.
Test object, target: t' of the copper-clad plates prepared in examples 1 to 4 and comparative example 1.
The longer T' indicates better heat resistance. The test results are shown in table 2:
T’(s)
example 1 389
Example 2 383
Example 3 390
Example 4 395
Comparative example 1 378
TABLE 2
As can be seen from Table 2, the T's of the examples 1-4 of the present invention are all longer, which indicates that the present invention has better heat resistance. The difference between the partial raw materials and the preparation steps used in comparative example 1 and those in example 1 is that the T' in comparative example 1 is shortened compared with example 1, which shows that the modified benzocyclobutene resin used in the invention has better effect of improving the heat resistance of the copper-clad plate compared with the unmodified benzocyclobutene resin.
Experimental example three: toughness testing
Test reference standard/method: IPC-TM-650 standard.
Test instrument: a universal material testing machine.
Test object, target: flexural strength of the copper-clad sheets prepared in examples 1 to 4 and comparative example 1.
Higher flexural strength indicates better toughness. The test results are shown in table 3:
flexural Strength (N.mm) -2 )
Example 1 434
Example 2 429
Example 3 435
Example 4 438
Comparative example 1 425
TABLE 3 Table 3
As can be seen from Table 3, the flexural strength of examples 1-4 of the present invention is higher, indicating that the present invention has better toughness. The difference between the raw materials and the preparation steps used in comparative example 1 and those in example 1 is that the flexural strength of comparative example 1 is reduced compared with example 1, which means that the modified benzocyclobutene resin used in the invention has a better effect of improving the toughness of the copper-clad plate compared with the unmodified benzocyclobutene resin.
Experimental example four: adhesive property test
Test reference standard/method: IPC-TM-650 standard.
Test instrument: peel strength tester.
Test object, target: peel strength of copper clad laminates prepared in examples 1 to 4, comparative example 1 and comparative example 2.
Higher peel strength indicates better adhesion. The test results are shown in table 4:
peel strength (N.mm) -1 )
Example 1 0.87
Example 2 0.83
Example 3 0.86
Example 4 0.91
Comparative example 1 0.80
Comparative example 2 0.78
TABLE 4 Table 4
As can be seen from Table 4, the peel strength of examples 1-4 of the present invention is higher, indicating that the present invention has better adhesion properties. The difference between the partial raw materials and the preparation steps used in the comparative examples 1 and 2 and the example 1 is that the peel strength of the comparative example 1 is reduced compared with the example 1, which shows that the modified benzocyclobutene resin used in the invention has better effect of improving the adhesive property of the copper-clad plate compared with the unmodified benzocyclobutene resin; the peel strength of comparative example 2 was also reduced compared to example 1, indicating that the vinyltriethoxysilane used in the present invention also improves the adhesion properties of the copper clad laminate.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (6)

1. The utility model provides a copper-clad plate based on benzocyclobutene which characterized in that: the material is prepared from the following raw materials in parts by weight: 25-30 parts of modified benzocyclobutene resin, 20-25 parts of epoxy resin, 4-6 parts of curing agent, 0.5-1 part of curing accelerator, 30-35 parts of filler, 0.6-0.9 part of coupling agent and 45-50 parts of solvent; the coupling agent is vinyl triethoxysilane, and the filler is aluminum nitride;
the modified benzocyclobutene resin is prepared by the following steps:
A1. adding 4-bromobenzocyclobutene, ammonia water and cuprous chloride into a reaction bottle, heating to 155 ℃, stirring and reacting for 3-5 hours to obtain a reaction solution, cooling the reaction solution to room temperature, pouring into deionized water, extracting for 3 times by using dichloromethane, merging organic phases, washing for 3 times by using deionized water, and drying by using anhydrous magnesium sulfate for 24 hours to obtain 4-aminobenzocyclobutene; the mass concentration of the ammonia water is 25%, and the ratio of the 4-bromobenzocyclobutene, the ammonia water, the cuprous chloride, the deionized water used in the reaction to the dichloromethane used in each extraction is 1g:13mL:0.05g:10mL:14mL;
A2. adding the 4-aminobenzocyclobutene, sodium hydroxide and sodium dodecyl benzene sulfonate obtained in the step A1 into deionized water, stirring until the mixture is uniform, adding 4-fluorobenzoyl chloride and methylene dichloride, stirring at 10 ℃ for reaction for 6-8 hours to obtain a reaction solution, evaporating the reaction solution to remove the methylene dichloride to obtain a solid, washing the solid with deionized water for 3 times, recrystallizing with ethanol, and drying at 85 ℃ until the weight is constant to obtain the modified benzocyclobutene resin; the ratio of 4-aminobenzocyclobutene, sodium hydroxide, sodium dodecyl benzene sulfonate, deionized water used in the reaction, 4-fluorobenzoyl chloride and dichloromethane is 1mol:2mol:4g:900mL:2mol:160 mL.
2. The benzocyclobutene-based copper-clad plate of claim 1, wherein: the epoxy resin is a novolac epoxy resin.
3. The benzocyclobutene-based copper-clad plate of claim 1, wherein: the curing agent is 4,4' -diamino diphenyl sulfone.
4. The benzocyclobutene-based copper-clad plate of claim 1, wherein: the curing accelerator is 2-methylimidazole.
5. The benzocyclobutene-based copper-clad plate of claim 1, wherein: the solvent consists of N, N-dimethylformamide and propylene glycol methyl ether in a volume ratio of 2:1.
6. The method for preparing the benzocyclobutene-based copper-clad plate according to any one of claims 1 to 5, which is characterized by comprising the following steps: the method comprises the following steps:
B1. weighing the raw materials according to the parts by weight, adding the modified benzocyclobutene resin and the solvent into a stirring kettle with the stirring speed of 200 r/min, stirring until the materials are uniformly mixed, adding the epoxy resin, stirring until the materials are uniformly mixed, adding the curing agent, the curing accelerator, the filler and the coupling agent, and stirring for 6-8 hours to obtain a resin composition glue solution;
B2. b, dipping the glass fiber cloth in the resin composition glue solution obtained in the step B1, and transferring the glass fiber cloth into an oven to be dried for 4-6 minutes at 165-175 ℃ to obtain a prepreg;
B3. taking 8 prepregs obtained in the step B2, stacking the prepregs in order, covering copper foils on the upper surface and the lower surface of the prepregs, and transferring the prepregs into a vacuum hot press for hot pressing to obtain a copper-clad plate based on benzocyclobutene; the hot pressing process comprises the following steps: heating from room temperature to 130 ℃ at a heating rate of 2.5 ℃/min, and setting the pressure to 100PSI; heating from 130 ℃ to 240 ℃ at a heating rate of 2 ℃/min, wherein the pressure is 350-450PSI, and the heat preservation time is 120-150 minutes.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1369046A (en) * 1963-08-01 1964-08-07 Ciba Geigy New benzocyclobutenes and their preparation process
US4675370A (en) * 1986-04-29 1987-06-23 University Of Dayton Resin systems derived from benzocyclobutene-alkyne imide monomers
US5869693A (en) * 1995-12-21 1999-02-09 Carleton University Benzocyclobutenones and polymers derived therefrom
CN105585808A (en) * 2016-01-26 2016-05-18 广东汕头超声电子股份有限公司覆铜板厂 Low-dielectric-loss high-heat-conductivity resin composition and preparation method thereof, and prepreg and laminated board prepared from resin composition
CN105968713A (en) * 2015-11-23 2016-09-28 重庆市锦艺硅材料开发有限公司苏州分公司 Preparation method of filling material used for copper-clad plate, resin composition used for copper-clad plate and copper-clad plate thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1369046A (en) * 1963-08-01 1964-08-07 Ciba Geigy New benzocyclobutenes and their preparation process
US4675370A (en) * 1986-04-29 1987-06-23 University Of Dayton Resin systems derived from benzocyclobutene-alkyne imide monomers
US5869693A (en) * 1995-12-21 1999-02-09 Carleton University Benzocyclobutenones and polymers derived therefrom
CN105968713A (en) * 2015-11-23 2016-09-28 重庆市锦艺硅材料开发有限公司苏州分公司 Preparation method of filling material used for copper-clad plate, resin composition used for copper-clad plate and copper-clad plate thereof
CN105585808A (en) * 2016-01-26 2016-05-18 广东汕头超声电子股份有限公司覆铜板厂 Low-dielectric-loss high-heat-conductivity resin composition and preparation method thereof, and prepreg and laminated board prepared from resin composition

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