CN114161804A - Epoxy paper and glass fiber cloth composite base copper-clad plate and preparation method thereof - Google Patents
Epoxy paper and glass fiber cloth composite base copper-clad plate and preparation method thereof Download PDFInfo
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- CN114161804A CN114161804A CN202111315269.5A CN202111315269A CN114161804A CN 114161804 A CN114161804 A CN 114161804A CN 202111315269 A CN202111315269 A CN 202111315269A CN 114161804 A CN114161804 A CN 114161804A
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- epoxy
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- fiber cloth
- clad plate
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 121
- 239000004744 fabric Substances 0.000 title claims abstract description 93
- 239000003365 glass fiber Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 47
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000011889 copper foil Substances 0.000 claims abstract description 10
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 8
- 239000011152 fibreglass Substances 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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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
- B32B29/00—Layered products comprising a layer of paper or cardboard
-
- 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
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/02—Layered products comprising a layer of paper or cardboard 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
-
- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to the technical field of copper-clad plates, in particular to an epoxy paper and glass fiber cloth composite base copper-clad plate and a preparation method thereof; the laminated substrate comprises a laminated substrate, wherein a prepreg is compounded on one surface of the laminated substrate, and a copper foil layer is compounded on one surface of the prepreg, which is far away from the laminated substrate; the low molecular weight polyphenylene ether can be cured and crosslinked with epoxy resin to form a polymer grid which is mutually penetrated, and by preparing the semi-cured epoxy paper substrate and the semi-cured epoxy glass fiber cloth plate, the peripheries of epoxy paper and epoxy glass fiber cloth molecules are provided with a large number of high-end epoxy groups with high reaction activity, so that the epoxy paper and epoxy glass fiber cloth molecules are easier to react with a curing agent to form a larger crosslinking network, the crosslinking density is further improved, the insulativity, the dielectric property and the water absorption rate of the prepared epoxy paper glass fiber cloth composite base copper-clad plate are improved, and the quality of the prepared epoxy paper glass fiber cloth composite base copper-clad plate is effectively improved.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to an epoxy paper and glass fiber cloth composite base copper-clad plate and a preparation method thereof.
Background
With the continuous development of science and technology, the living standard of people is gradually improved, the demand of electronic products is gradually increased, meanwhile, the updating and updating of the electronic products are found to be faster and faster, in each industry, for the future development, the electronic industry cannot be separated, the application of the electronic products is more and more extensive, and the electronic information industry gradually enters the golden period of rapid development. The copper-clad plate is used as the foundation of printed circuit boards and electronic products and can keep faster development.
A production method of an epoxy glass fiber cloth copper-clad plate is disclosed in Chinese patent application No. CN201510609644.5, and the specification describes that the method comprises the following steps: uniformly mixing bisphenol A type epoxy resin, alicyclic epoxy resin, photoinitiator, dicyandiamide and imidazole according to a mass ratio to obtain a glue solution; uniformly coating the glue solution on the glass fiber cloth by a roller to obtain prepreg cloth; thirdly, performing ultraviolet light pre-curing treatment on the prepreg cloth by using an ultraviolet light curing machine to obtain a prepreg; and fourthly, laying the copper foil on the prepreg, and then putting the prepreg into a hot press for hot-pressing and curing treatment to obtain the epoxy glass fiber cloth copper-clad plate. The invention overcomes the technical defects that the epoxy resin is diluted by a solvent, then the glass fiber cloth is soaked, and then the prepreg is baked to generate solvent volatilization to cause environmental pollution in the traditional method, the solvent remained on the prepreg influences the performance of the copper-clad plate, and the like, the produced copper-clad plate has the characteristics of low dielectric constant, high peel strength, high breakdown voltage, good resistance to soldering, and the like, the copper-clad plate prepared by the patent documents has a certain effect of low dielectric constant, but the effect is not good, and simultaneously, the copper-clad plate lacks good insulation and water absorption, and influences the performance and the quality of the prepared copper-clad plate.
In summary, the development of an epoxy paper and glass fiber cloth composite base copper-clad plate and a preparation method thereof remains a key problem to be solved urgently in the technical field of copper-clad plates.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an epoxy paper glass fiber cloth composite base copper-clad plate and a preparation method thereof, wherein low molecular weight polyphenylene ether can be cured and crosslinked with epoxy resin to form a polymer grid which is mutually penetrated, modification of the epoxy resin is realized through N, N-dimethylacetamide, a semi-cured epoxy paper substrate and a semi-cured epoxy sheet epoxy glass fiber cloth plate are prepared, so that the peripheries of epoxy paper and epoxy glass fiber cloth molecules are provided with a large number of high-end epoxy groups with high reaction activity, the curing agent reaction is easier, a larger crosslinking network is formed, the crosslinking density is further improved, the insulativity, the dielectric property and the water absorption rate of the prepared epoxy paper glass fiber cloth composite base copper-clad plate are improved, and meanwhile, the modified epoxy resin glue solution has higher activity through adding the curing agent and the accelerator, the reaction is relatively mild during the subsequent compression molding, so that the quality of the prepared epoxy paper and glass fiber cloth composite base copper-clad plate is effectively improved.
In order to achieve the purpose, the invention provides the following technical scheme:
the epoxy paper and glass fiber cloth composite base copper-clad plate comprises a laminated substrate, wherein a prepreg is compounded on one surface of the laminated substrate, and a copper foil layer is compounded on one surface of the prepreg, which is far away from the laminated substrate.
By adopting the technical scheme: according to the invention, the composite copper-based plate is formed by laminating the substrate, the prepreg and the copper foil layer, and the prepared epoxy paper glass fiber cloth composite copper-based plate has good insulativity, dielectric property and water absorption rate.
The invention is further provided with: the laminated substrate is a semi-cured epoxy paper substrate.
By adopting the technical scheme: the invention adopts the semi-cured epoxy paper substrate as the laminated board and provides a substrate for preparing the epoxy paper glass fiber cloth composite base copper-clad plate.
The invention is further provided with: the prepreg is a prepreg epoxy fiberglass cloth board.
By adopting the technical scheme: the invention adopts the prepreg epoxy fiberglass cloth board as the prepreg, and provides an intermediate layer for preparing the epoxy paper fiberglass cloth composite base copper-clad plate.
The invention also provides a preparation method of the epoxy paper and glass fiber cloth composite base copper-clad plate, which is characterized by comprising the following steps:
s1, preparing a semi-cured epoxy paper substrate and a semi-cured epoxy fiberglass cloth board;
s2, placing the semi-cured epoxy paper substrate on a semi-cured epoxy fiberglass cloth board;
s3, placing a copper foil layer on the ground of the prepreg epoxy fiberglass cloth board, and performing compression molding through a flat vulcanizing machine to obtain the epoxy paper fiberglass cloth composite base copper clad laminate.
By adopting the technical scheme: by preparing the semi-cured epoxy paper substrate and the semi-cured epoxy glass fiber cloth plate, a large number of high-end epoxy groups with high reaction activity are arranged on the peripheries of epoxy paper and epoxy glass fiber cloth molecules, so that the epoxy paper and epoxy glass fiber cloth molecules are easier to react with a curing agent to form a large cross-linking network, the cross-linking density is further improved, and the quality and quality of the epoxy paper and glass fiber cloth composite base copper-clad plate are guaranteed.
The invention is further provided with: in step S1, preparing a prepreg epoxy paper substrate and a prepreg epoxy fiberglass cloth board includes the following steps:
s101, preparing a modified epoxy resin solution;
s102, adding a curing agent and an accelerant into the modified epoxy resin solution, and uniformly mixing to obtain a modified epoxy resin glue solution;
s103, uniformly coating the linear epoxy resin glue solution on epoxy paper and glass fiber cloth respectively;
and S104, performing pre-curing treatment on the epoxy paper and the glass fiber cloth in the step S103 by using a curing machine to obtain a semi-cured epoxy paper substrate and a semi-cured epoxy glass fiber cloth plate.
By adopting the technical scheme: according to the invention, through the modified epoxy resin solution, after the modified epoxy resin is used, the insulativity, the dielectric property and the water absorption rate of the epoxy paper glass fiber cloth composite base copper-clad plate can be improved, and meanwhile, through adding the curing agent and the accelerator, the modified epoxy resin glue solution has higher activity, so that the reaction is relatively mild during the subsequent compression molding, and the quality of the epoxy paper glass fiber cloth composite base copper-clad plate is ensured.
The invention is further provided with: in step S101, the method for preparing the modified epoxy resin glue solution includes:
mixing low molecular weight polyphenylene ether and xylene in a beaker; continuously stirring and heating the beaker for 5-10min at the temperature of 100-110 ℃, and then cooling to room temperature to prepare a solution A; placing epoxy resin and sodium dichloroisocyanurate powder in a beaker, and continuously stirring and heating for 10min at the temperature of 100-105 ℃; then adding N, N-dimethylacetamide, keeping the temperature and continuously stirring for 5 min; cooling to normal temperature to obtain solution B; placing the solution A and the solution B in the same beaker, and continuously stirring and heating for 10-12min under the temperature condition of 120-130 ℃; cooling to normal temperature to obtain the modified epoxy resin solution.
By adopting the technical scheme: the low molecular weight polyphenylene ether can be cured and crosslinked with epoxy resin to form a polymer grid which is mutually penetrated, and the modification of the epoxy resin is realized through N, N-dimethylacetamide, so that the prepared epoxy paper and glass fiber cloth composite base copper-clad plate has good insulativity, dielectric property and water absorption.
The invention is further provided with: in the step S102, the curing agent is any one of dicyandiamide and diaminodiphenyl sulfone.
By adopting the technical scheme: the curing agent is used as an epoxy resin latent curing agent, so that epoxy paper and epoxy glass fiber cloth can be combined with a modified epoxy resin glue solution more precisely.
The invention is further provided with: in the step S102, the accelerator is any one of 2-methylimidazole, 2-ethyl-4-methylimidazole and substituted urea.
By adopting the technical scheme: the accelerant of the invention can improve the vulcanization crosslinking speed, reduce the vulcanization dosage and improve the performance of the modified epoxy resin glue solution.
The invention is further provided with: in the step S3, when the epoxy paper-glass fiber cloth composite-based copper clad laminate is manufactured by press molding through a flat vulcanizing machine, the press molding is divided into four stages, wherein the temperature condition of the first stage is 0-130 ℃, the pressure is 5Mpa, the heating rate is 15 ℃/min, the time is 9min, the temperature condition of the second stage is 130 ℃, the pressure is 15Mpa, the temperature is kept constant, the time is 15min, the temperature condition of the third stage is 130-.
By adopting the technical scheme: the invention provides proper process conditions for compression molding, so that the modified epoxy resin glue solution has certain fluidity in the compression process, the glue solution can be prevented from flowing out, and meanwhile, the prepared epoxy paper-glass fiber cloth composite base copper-clad plate has residues on the surface.
Advantageous effects
Compared with the known public technology, the technical scheme provided by the invention has the following beneficial effects:
the low molecular weight polyphenylene ether can be cured and crosslinked with epoxy resin to form a polymer grid which is mutually penetrated, the epoxy resin is modified through N, N-dimethylacetamide, the periphery of epoxy paper and epoxy glass fiber cloth molecules is provided with a large number of high-end epoxy groups with high reaction activity by preparing a semi-cured epoxy paper substrate and a semi-cured epoxy glass fiber cloth plate, the epoxy paper and epoxy glass fiber cloth molecules are easier to react with a curing agent to form a larger crosslinking network, so that the crosslinking density is improved, the insulativity, the dielectric property and the water absorption rate of the prepared epoxy paper glass fiber cloth composite-based copper clad laminate are improved, and meanwhile, the modified epoxy resin glue solution can have higher activity by adding the curing agent and an accelerator, so that the reaction is relatively mild during subsequent compression molding, and the quality of the epoxy paper glass fiber cloth composite-based copper clad laminate are guaranteed.
Drawings
FIG. 1 is a perspective view of an epoxy paper and glass fiber cloth composite base copper-clad plate;
FIG. 2 is a flow chart of a preparation method of an epoxy paper and glass fiber cloth composite base copper-clad plate.
The notation in the figure is:
100. laminating the substrate; 200. a prepreg; 300. copper foil layer
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further described with reference to the following examples.
Example 1
Referring to fig. 1, an epoxy paper and fiberglass cloth composite-based copper clad laminate includes a laminate substrate 100, a prepreg 200 is laminated on one side of the laminate substrate 100, and a copper foil layer 300 is laminated on one side of the prepreg 200 away from the laminate substrate 100.
The laminate substrate 100 is a semi-cured epoxy paper substrate.
The prepreg 200 is a prepreg epoxy fiberglass cloth board.
Referring to fig. 2, the invention also provides a preparation method of the epoxy paper and glass fiber cloth composite base copper-clad plate, which is characterized by comprising the following steps:
step one, preparing a semi-cured epoxy paper substrate and a semi-cured epoxy fiberglass cloth board.
The preparation method of the semi-cured epoxy paper substrate and the semi-cured epoxy fiberglass cloth board comprises the following steps:
101) and preparing a modified epoxy resin solution.
102) And adding a curing agent and an accelerant into the modified epoxy resin solution, and uniformly mixing to obtain the modified epoxy resin glue solution.
103) And respectively and uniformly coating the epoxy resin glue solution on epoxy paper and glass fiber cloth.
104) And carrying out pre-curing treatment on the epoxy paper and the glass fiber cloth in the step 103) by using a curing machine to obtain a semi-cured epoxy paper substrate and a semi-cured epoxy glass fiber cloth plate.
The method for preparing the modified epoxy resin glue solution comprises the following steps:
mixing low molecular weight polyphenylene ether and xylene in a beaker; continuously stirring and heating the beaker for 5min at the temperature of 100 ℃, and then cooling to room temperature to prepare a solution A; placing epoxy resin and sodium dichloroisocyanurate powder in a bottle, and continuously stirring and heating for 10min at 100 ℃; then adding N, N-dimethylacetamide, keeping the temperature and continuously stirring for 5 min; cooling to normal temperature to obtain solution B; placing the solution A and the solution B in the same beaker, and continuously stirring and heating for 10min under the temperature condition of 120 ℃; cooling to normal temperature to obtain the modified epoxy resin solution.
The curing agent is dicyandiamide.
The accelerator is 2-methylimidazole.
And step two, placing the semi-cured epoxy paper substrate on a semi-cured epoxy fiberglass cloth board.
And step three, placing the copper foil layer 300 on the ground of the prepreg epoxy fiberglass cloth board, and performing compression molding through a flat vulcanizing machine to obtain the epoxy paper fiberglass cloth composite base copper-clad plate.
And (2) performing press forming through a flat vulcanizing machine to obtain the epoxy paper-glass fiber cloth composite base copper-clad plate, wherein the press forming is divided into four stages, the temperature condition of the first stage is 0 ℃, the pressure is 5Mpa, the heating rate is 15 ℃/min, the time is 9min, the temperature condition of the second stage is 130 ℃, the pressure is 15Mpa, the temperature is kept unchanged, the time is 15min, the temperature condition of the third stage is 130 ℃, the pressure is 20Mpa, the heating rate is 15 ℃/min, the time is 5min, the temperature condition of the fourth stage is 180 ℃, the pressure is 25Mpa, the temperature is kept unchanged, and the time is 60 min.
Example 2
The epoxy paper and glass fiber cloth composite base copper-clad plate and the preparation method thereof provided by the embodiment are substantially the same as the embodiment 1, and the main differences are as follows:
in the first step, in the method for preparing the modified epoxy resin glue solution, a beaker is continuously stirred and heated for 7min at the temperature of 105 ℃, and then is cooled to room temperature to prepare a solution A; continuously stirring and heating for 10min at the temperature of 103 ℃; then adding N, N-dimethylacetamide, keeping the temperature and continuously stirring for 5min, and cooling to normal temperature to prepare a solution B; continuously stirring and heating for 11min at the temperature of 125 ℃, and cooling to normal temperature to prepare a modified epoxy resin solution;
the curing agent is diamino diphenyl sulfone;
the accelerant is 2-ethyl-4-methylimidazole;
in the third step, the temperature condition of the first stage is 65 ℃, the pressure is 5Mpa, the heating rate is 15 ℃/min, the time is 10min, the temperature condition of the second stage is 130 ℃, the pressure is 15Mpa, the temperature is kept unchanged, the time is 15min, the temperature condition of the third stage is 150 ℃, the pressure is 20Mpa, the heating rate is 15 ℃/min, the time is 5min, the temperature condition of the fourth stage is 180 ℃, the pressure is 25Mpa, the temperature is kept unchanged, and the time is 60 min;
example 3
The epoxy paper and glass fiber cloth composite base copper-clad plate and the preparation method thereof provided by the embodiment are substantially the same as the embodiment 1, and the main differences are as follows:
in the first step, in the method for preparing the modified epoxy resin glue solution, a beaker is continuously stirred and heated for 10min at the temperature of 110 ℃, and then is cooled to room temperature to prepare a solution A; continuously stirring and heating for 10min at the temperature of 105 ℃; then adding N, N-dimethylacetamide, keeping the temperature and continuously stirring for 5min, and cooling to normal temperature to prepare a solution B; continuously stirring and heating for 12min under the temperature condition of 130 ℃, and cooling to normal temperature to prepare a modified epoxy resin solution;
the curing agent is diamino diphenyl sulfone;
the accelerator is substituted urea;
in the third step, the temperature condition of the first stage is 130 ℃, the pressure is 5Mpa, the heating rate is 15 ℃/min, the time is 9min, the temperature condition of the second stage is 130 ℃, the pressure is 15Mpa, the temperature is kept unchanged, the time is 15min, the temperature condition of the third stage is 180 ℃, the pressure is 20Mpa, the heating rate is 15 ℃/min, the time is 5min, the temperature condition of the fourth stage is 180 ℃, the pressure is 25Mpa, the temperature is kept unchanged, and the time is 60 min;
performance testing
The copper-clad plate prepared by the patent with the patent application number of CN201510609644.5 in the embodiment 1-3 and the background technology is taken as a comparative example, and the related performance of the prepared copper-clad plate is detected, wherein the detection method comprises the following steps:
1. respectively detecting the dielectric properties of the copper-clad plates according to the detection standard GB/T1410-2006, and recording the obtained test results in table 1;
table 1 dielectric property detecting meter of copper clad laminate
| Test items | Dielectric constant |
| Example 1 | 3.28 |
| Example 2 | 3.31 |
| Example 3 | 3.30 |
| Comparative example | 5.12 |
2. Respectively detecting the insulation (volume resistivity) performance of each copper-clad plate according to the detection standard GB/T1410-;
table 2 copper-clad plate insulation performance detecting meter
| Test items | Volume resistivity (M omega cm) |
| Example 1 | 6.19×1010 |
| Example 2 | 6.20×1010 |
| Example 3 | 6.17×1010 |
| Comparative example | 5.69×1010 |
3. Respectively detecting the water absorption performance of each copper-clad plate according to detection standards GB4722-92, and recording the obtained test results in a table 3;
table 3 water absorption rate detecting meter of copper clad laminate
| Test items | Water absorption (%) |
| Example 1 | 0.68 |
| Example 2 | 0.67 |
| Example 3 | 0.67 |
| Comparative example | 0.56 |
By analyzing the relevant data in the tables, the copper-clad plate prepared by the invention not only has good dielectric constant, but also has good insulativity and water absorption. Therefore, the preparation method of the epoxy paper and glass fiber cloth composite base copper-clad plate provided by the invention has wider market prospect and is more suitable for popularization.
The low molecular weight polyphenylene ether can be cured and crosslinked with epoxy resin to form a polymer grid which is mutually penetrated, the epoxy resin is modified through N, N-dimethylacetamide, the periphery of epoxy paper and epoxy glass fiber cloth molecules is provided with a large number of high-end epoxy groups with high reaction activity by preparing a semi-cured epoxy paper substrate and a semi-cured epoxy glass fiber cloth plate, the epoxy paper and epoxy glass fiber cloth molecules are easier to react with a curing agent to form a larger crosslinking network, so that the crosslinking density is improved, the insulativity, the dielectric property and the water absorption rate of the prepared epoxy paper glass fiber cloth composite-based copper clad laminate are improved, and meanwhile, the modified epoxy resin glue solution can have higher activity by adding the curing agent and an accelerator, so that the reaction is relatively mild during subsequent compression molding, and the quality of the epoxy paper glass fiber cloth composite-based copper clad laminate are guaranteed.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. The epoxy paper and glass fiber cloth composite base copper-clad plate is characterized by comprising a laminated substrate, wherein a prepreg is compounded on one surface of the laminated substrate, and a copper foil layer is compounded on one surface, far away from the laminated substrate, of the prepreg.
2. The epoxy paper and fiberglass cloth composite-based copper-clad plate of claim 1, wherein the laminated substrate is a semi-cured epoxy paper substrate.
3. The epoxy paper and fiberglass cloth composite-based copper-clad plate according to claim 1, wherein the prepreg is a prepreg epoxy fiberglass cloth plate.
4. A preparation method of an epoxy paper and glass fiber cloth composite base copper-clad plate is characterized in that the epoxy paper and glass fiber cloth composite base copper-clad plate according to any one of claims 1 to 3 is used, and comprises the following steps:
s1, preparing a semi-cured epoxy paper substrate and a semi-cured epoxy fiberglass cloth board;
s2, placing the semi-cured epoxy paper substrate on a semi-cured epoxy fiberglass cloth board;
s3, placing a copper foil layer on the ground of the prepreg epoxy fiberglass cloth board, and performing compression molding through a flat vulcanizing machine to obtain the epoxy paper fiberglass cloth composite base copper clad laminate.
5. The method for preparing the epoxy paper and fiberglass cloth composite-based copper-clad plate according to claim 4, wherein in the step S1, the steps of preparing the semi-cured epoxy paper substrate and the prepreg epoxy fiberglass cloth plate comprise the following steps:
s101, preparing a modified epoxy resin solution;
s102, adding a curing agent and an accelerant into the modified epoxy resin solution, and uniformly mixing to obtain a modified epoxy resin glue solution;
s103, uniformly coating the linear epoxy resin glue solution on epoxy paper and glass fiber cloth respectively;
and S104, performing pre-curing treatment on the epoxy paper and the glass fiber cloth in the step S103 by using a curing machine to obtain a semi-cured epoxy paper substrate and a semi-cured epoxy glass fiber cloth plate.
6. The method for preparing the epoxy paper-glass fiber cloth composite-based copper-clad plate according to claim 5, wherein in the step S101, the method for preparing the modified epoxy resin glue solution comprises the following steps:
mixing low molecular weight polyphenylene ether and xylene in a beaker; continuously stirring and heating the beaker for 5-10min at the temperature of 100-110 ℃, and then cooling to room temperature to prepare a solution A; placing epoxy resin and sodium dichloroisocyanurate powder in a beaker, and continuously stirring and heating for 10min at the temperature of 100-105 ℃; then adding N, N-dimethylacetamide, keeping the temperature and continuously stirring for 5 min; cooling to normal temperature to obtain solution B; placing the solution A and the solution B in the same beaker, and continuously stirring and heating for 10-12min under the temperature condition of 120-130 ℃; cooling to normal temperature to obtain the modified epoxy resin solution.
7. The method for preparing the epoxy paper/fiberglass cloth composite copper-clad plate according to claim 5, wherein in the step S102, the curing agent is any one of dicyandiamide and diaminodiphenyl sulfone.
8. The method for preparing the epoxy paper/fiberglass cloth composite copper-clad plate according to claim 5, wherein in the step S102, the accelerator is any one of 2-methylimidazole, 2-ethyl-4-methylimidazole and substituted urea.
9. The method for preparing the epoxy paper and glass fiber cloth composite-based copper-clad plate according to claim 4, wherein in the step S3, when the epoxy paper and glass fiber cloth composite-based copper-clad plate is prepared by press molding through a flat vulcanizing machine, the press molding is divided into four stages, wherein the temperature condition of the first stage is 0-130 ℃, the pressure is 5MPa, the heating rate is 15 ℃/min, the time is 9min, the temperature condition of the second stage is 130 ℃, the pressure is 15MPa, the temperature is kept constant, the time is 15min, the temperature condition of the third stage is 130-.
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| CN116100917A (en) * | 2022-10-20 | 2023-05-12 | 安徽鸿海新材料股份有限公司 | High-heat-conductivity copper-clad plate and preparation process thereof |
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