CN113025263A - Thermosetting resin composition for copper-clad plate, glue solution and preparation method thereof - Google Patents
Thermosetting resin composition for copper-clad plate, glue solution and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09J179/085—Unsaturated polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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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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Abstract
The invention relates to the technical field of copper-clad plates, in particular to a thermosetting resin composition for a copper-clad plate, glue solution and a preparation method thereof. The thermosetting resin composition for the copper-clad plate comprises the following components in parts by weight: 5-30 parts of epoxy resin, 5-20 parts of cyanate ester resin, 5-20 parts of bismaleimide resin and 2-10 parts of polystyrene-maleic anhydride resin. The resin composition contains epoxy resin, cyanate resin, bismaleimide resin and polystyrene-maleic anhydride resin, the epoxy resin can perform crosslinking reaction with the cyanate resin, the bismaleimide resin and the polystyrene-maleic anhydride resin to form a high crosslinking degree molecular network structure, and a curing unit contains rigid structures such as a five-membered oxazoline heterocyclic ring, a six-membered triazine ring, a benzene ring and the like, so that the thermosetting resin composition is endowed with better heat resistance; and the absence of a large amount of polar groups in the cured product reduces the hygroscopicity and simultaneously shows good dielectric properties.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a thermosetting resin composition for a copper-clad plate, glue solution and a preparation method thereof.
Background
Nowadays, society is developing vigorously towards electronization, electronic products are already full of our world, and with the development of science and technology and the diversification of application places, various high-tech equipment such as mobile phones, cameras, printers and the like are developing towards light, thin, short and small directions, and the technical development of product heat dissipation, precise layout, packaging design and the like brought by the light, thin, short and small development also provides more severe requirements for the innovation of the upstream copper-clad plate industry, and simultaneously requires the low cost of materials.
Due to the rapid development of the current electronic industry, the development of electronic products in the light weight, thinness, high performance, high reliability and environmental protection direction is required, so higher requirements are also put forward on printed circuit boards and copper-clad plates. The specific requirements of the product are high heat resistance, low expansion coefficient, high humidity resistance, environmental protection, flame retardance, low dielectric constant and dielectric loss, high elastic modulus and the like. The copper clad laminate is a basic material in the electronic industry, is mainly used for processing and manufacturing Printed Circuit Boards (PCB), is widely used in electronic products such as televisions, radios, computers, mobile communication and the like, and is also called a copper clad laminate, wherein a reinforcing material is soaked with resin, and one side or two sides of the reinforcing material are covered with copper foil. A plate-shaped material formed by hot pressing is called a copper clad laminate and is a basic material of a PCB.
Among them, in the IC packaging technology, a substrate of a package is required to have high heat resistance, moisture resistance, and rigidity (Low CTE), while having a small loss, i.e., a Low dielectric loss, for signal transmission. However, the high expansion coefficient and high dielectric loss of the thermosetting material used in FR-4 of the prior art do not satisfy this requirement.
Therefore, it is a technical problem to be solved by those skilled in the art to develop a thermosetting resin for copper-clad plate, a glue solution and a preparation method thereof, which have low expansion coefficient, low dielectric loss and high heat resistance.
Disclosure of Invention
The invention aims to provide a thermosetting resin composition for a copper-clad plate, and aims to solve the problems of high expansion coefficient and high dielectric loss of the thermosetting resin composition in the prior art.
The invention provides a thermosetting resin composition for a copper-clad plate, which comprises the following components in parts by weight:
5-30 parts of epoxy resin, 5-20 parts of cyanate ester resin, 5-20 parts of bismaleimide resin and 2-10 parts of polystyrene-maleic anhydride resin.
The thermosetting resin composition mainly comprises epoxy resin, cyanate ester resin, bismaleimide resin and polystyrene-maleic anhydride resin, wherein the epoxy resin can perform a crosslinking reaction with the cyanate ester resin, the bismaleimide resin and the polystyrene-maleic anhydride resin to form a high-crosslinking molecular network structure, and a curing unit contains rigid structures such as a penta-oxazoline heterocycle, a hexa-triazine ring, a benzene ring and the like, so that the thermosetting resin composition is endowed with better heat resistance; and the absence of a large amount of polar groups in the cured product reduces the hygroscopicity and simultaneously shows good dielectric properties.
Further, the epoxy resin comprises any one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic aldehyde type epoxy resin, polyfunctional group epoxy resin or dicyclopentadiene phenol epoxy resin.
Further, the cyanate ester resin comprises one or two of bisphenol A cyanate ester resin or bisphenol A cyanate ester prepolymer resin.
Further preferably, the bisphenol a cyanate ester resin and the bisphenol a cyanate ester prepolymer resin are respectively selected from LonzaBA230 and yangzhou CE01 PS.
Further, the bismaleimide resin comprises any one or two of BMI-5100 or BMI-4000.
And the bismaleimide resin is preferably BMI-5100 and BMI-4000 of Japan Dazhou chemical industry.
Further, the polystyrene-maleic anhydride resin includes any one or more of XiranEF 30, XiranEF 40, XiranEF 60, or XiranEF 80.
The polystyrene-maleic anhydride resin is preferably Polyscope's XiranEF 30, XiranEF 40, XiranEF 60, or XiranEF 80.
The invention also discloses a glue solution for the copper-clad plate, which comprises the following components in parts by weight:
0.05 to 1.5 parts of catalyst, 3 to 10 parts of flame retardant, 15 to 45 parts of filler, 35 to 60 parts of solvent and 17 to 80 parts of thermosetting resin composition according to any one of claims 1 to 5
Further, the catalyst comprises any one or more of 1-benzyl benzene-2-ethyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 1-aminoethyl-2-methyl imidazole or 1-cyanoethyl imidazole.
Further, the flame retardant comprises any one or two of a phosphorus flame retardant or a nitrogen flame retardant;
wherein the phosphorus flame retardant comprises any one or more of diphenyl cresyl phosphate, trichloropropyl phosphate, hexaphenoxycyclotriphosphazene, 1, 3-phenylene phosphoric acid (2, 6-xylyl) tetraester or DOPO;
the nitrogen-based flame retardant comprises one or two of melamine or melamine phosphate.
The flame retardant used in the invention is a phosphorus flame retardant or a nitrogen flame retardant, wherein the phosphorus flame retardant can generate a cross-linked solid substance or a carbonized layer with a more stable structure when being heated, and the formation of the carbonized layer can organize the polymer to be further pyrolyzed on one hand and prevent the thermal decomposition products in the carbonized layer from entering a gas phase to participate in the combustion process on the other hand; after the nitrogen flame retardant is decomposed by heating, ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and other non-combustible gases are easily released, and most heat is taken away by the generation of the non-combustible gases and the decomposition and heat absorption of the flame retardant, so that the surface temperature of the polymer is greatly reduced. The non-combustible gas not only plays a role in diluting oxygen in air and generating the concentration of combustible gas by thermal decomposition of high polymers, but also can react with oxygen in air to generate nitrogen, water and deep oxides, and achieves good flame retardant effect while consuming oxygen on the surface of the material.
Further, the inorganic filler comprises one or more of magnesium hydroxide, aluminum hydroxide monohydrate, fused silica micropowder, talcum powder or barium sulfate;
the solvent comprises any one or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, butanone, acetone, methanol or xylene.
In order to obtain a glue solution with good homogeneity, the solvent of the invention is preferably any one or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, butanone, acetone, methanol or xylene.
The preparation method of the glue solution comprises the following steps:
s1, adding the thermosetting resin composition into a solvent, and stirring for 1-3h at the rotating speed of 1300-1700r/min to obtain a mixed solution of the thermosetting resin composition;
s2, adding the rest components into the mixed solution, stirring for 2-4h at the rotation speed of 800-1200r/min, and then stirring for 1-3h at the rotation speed of 400-600r/min to obtain the glue solution.
In the preparation process of the glue solution, firstly, the thermosetting resin composition is added into a solvent to be fully dissolved, and a crosslinking reaction is carried out under the action of a curing agent to form a high crosslinking degree molecular network structure, so that the glue solution is endowed with good heat resistance, then, a catalyst, a flame retardant and a filler are added, the mixture is stirred at a high speed and then at a low speed, and when the gelation time of the glue solution is qualified, the glue solution is prepared. The preparation process of the glue is simple, easy to operate and high in practicability.
Compared with the prior art, the thermosetting resin composition for the copper-clad plate has the following advantages:
the thermosetting resin composition mainly comprises epoxy resin, cyanate ester resin, bismaleimide resin and polystyrene-maleic anhydride resin, wherein the epoxy resin can perform a crosslinking reaction with the cyanate ester resin, the bismaleimide resin and the polystyrene-maleic anhydride resin to form a high-crosslinking molecular network structure, and a curing unit contains rigid structures such as a penta-oxazoline heterocycle, a hexa-triazine ring, a benzene ring and the like, so that the thermosetting resin composition is endowed with better heat resistance; and the absence of a large amount of polar groups in the cured product reduces the hygroscopicity and simultaneously shows good dielectric properties.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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 bisphenol A cyanate ester resin and the bisphenol A cyanate ester prepolymer resin in the embodiment of the invention are respectively selected from the Switzerland Lonza BA230 and Yangzhou Tianqi CE01 PS; the bismaleimide resin is preferably BMI-5100 and BMI-4000 of Japan Dazhou chemical industry; the polystyrene-maleic anhydride resin is preferably Polyscope's XiranEF 30, XiranEF 40, XiranEF 60, or XiranEF 80; the multifunctional epoxy resin is selected from TFE1250A80 of Taiwan chemical industry or NPPN442K80 of Taiwan south Asia. And 1 part in the following examples each means 1 g.
Example 1
S11, cleaning a glue mixing tank by using acetone, adding 40 parts of propylene glycol methyl ether, adding 3 parts of bisphenol F epoxy resin, 5 parts of TFE1250A80 multifunctional group epoxy resin in Taiwan Changchun chemical industry, 10 parts of dicyclopentadiene phenol epoxy resin, 20 parts of bisphenol A cyanate ester resin, BMI-510020 parts and XiranEF 3015 parts, and stirring at the rotating speed of 1300r/min for 3 hours to obtain a mixed solution of the thermosetting resin composition;
s12, adding 0.05 part of 1-benzyl benzene-2-ethylimidazole, 8 parts of diphenyl cresyl phosphate and 27 parts of magnesium hydroxide into the mixed solution, stirring at the rotating speed of 800r/min for 4 hours, then stirring at the rotating speed of 400r/min for 3 hours, and obtaining the glue solution after the gelation time of the glue solution is qualified.
Example 2
S21, cleaning a glue mixing tank by using acetone, adding 50 parts of propylene glycol methyl ether acetate, adding 3 parts of bisphenol A epoxy resin, 5 parts of TFE1250A80 multifunctional group epoxy resin in Taiwan Changchun chemical industry, 10 parts of dicyclopentadiene phenol epoxy resin, 15 parts of bisphenol A cyanate ester prepolymer resin, BMI-400020 parts and XiranEF 4010 parts, and stirring at the rotating speed of 1500r/min for 2 hours to obtain a mixed solution of a thermosetting resin composition;
s22, adding 0.1 part of 1-benzyl benzene-2-ethylimidazole, 10 parts of diphenyl cresyl phosphate and 30 parts of aluminum hydroxide into the mixed solution, stirring at the rotating speed of 1000r/min for 3 hours, then stirring at the rotating speed of 500r/min for 2 hours, and obtaining the glue solution after the gelation time of the glue solution is tested to be qualified.
Example 3
S31, cleaning a glue mixing tank by using acetone, adding 35 parts of propylene glycol methyl ether, adding 5 parts of TFE1250A80 multifunctional group epoxy resin, 5 parts of bisphenol A type cyanate ester resin, BMI-51005 parts and XiranEF 302 parts of Taiwan Changchun chemical industry, and stirring at the rotating speed of 1300r/min for 2 hours to obtain a mixed solution of the thermosetting resin composition;
s32, adding 0.05 part of 1-benzyl benzene-2-ethylimidazole, 3 parts of trichloropropyl phosphate and 15 parts of magnesium hydroxide into the mixed solution, stirring at the rotating speed of 800r/min for 3 hours, then stirring at the rotating speed of 500r/min for 2 hours, and obtaining the glue solution after the gelation time of the glue solution is tested to be qualified.
Example 4
S41, cleaning the glue mixing tank by using acetone, and adding 60 parts of a mixture of 1: 1, adding 5 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 10 parts of phenolic epoxy resin, 5 parts of NPPN442K80 multifunctional epoxy resin of south Taiwan Asia, 10 parts of bisphenol A cyanate ester resin, 10 parts of bisphenol A cyanate ester prepolymer resin, BMI-510010 parts, BMI-400010 parts, XiranEF 305 parts and XiranEF 805 parts, and stirring at the rotating speed of 1700r/min for 2 hours to obtain a mixed solution of the thermosetting resin composition;
and S42, adding 1.5 parts of 2-ethyl-4-methylimidazole, 10 parts of hexaphenoxycyclotriphosphazene and 45 parts of talcum powder into the mixed solution, stirring at a rotating speed of 1200r/min for 3 hours, then stirring at a rotating speed of 600r/min for 2 hours, and obtaining the glue solution after the gelation time of the glue solution is tested to be qualified.
Example 5
S51, cleaning a glue mixing tank by using acetone, adding 45 parts of cyclohexanone, then adding 10 parts of bisphenol A type epoxy resin, 5 parts of bisphenol F type epoxy resin, 5 parts of novolac type epoxy resin, 5 parts of dicyclopentadiene phenol epoxy resin, 5 parts of bisphenol A type cyanate ester prepolymer resin, BMI-51005 parts, BMI-40005 parts, XiranEF 405 parts and XiranEF 605 parts, and stirring for 3 hours at a rotating speed of 1600r/min to obtain a mixed solution of the thermosetting resin composition;
s52, adding 0.5 part of 2-methylimidazole, 5 parts of DOPO and 25 parts of aluminum hydroxide monohydrate into the mixed solution, stirring at the rotating speed of 1100r/min for 4 hours, then stirring at the rotating speed of 500r/min for 3 hours, and testing the gelation time of the glue to be qualified to obtain the glue solution.
Comparative example 1
S1, cleaning a glue mixing tank by using acetone, adding 40 parts of propylene glycol methyl ether, adding 20 parts of bisphenol A type cyanate ester resin, 20 parts of BMI-510020 parts of bisphenol A type cyanate ester resin and 40 parts of XiranEF 3015 parts of bisphenol A type cyanate ester resin, and stirring at the rotating speed of 1300r/min for 3 hours to obtain a mixed solution of the thermosetting resin composition;
s2, adding 0.05 part of 1-benzyl benzene-2-ethylimidazole, 8 parts of diphenyl cresyl phosphate and 27 parts of magnesium hydroxide into the mixed solution, stirring at the rotating speed of 800r/min for 4 hours, then stirring at the rotating speed of 400r/min for 3 hours, and obtaining the glue solution after the gelation time of the glue solution is qualified.
Comparative example 2
S1, cleaning a glue mixing tank by using acetone, adding 40 parts of propylene glycol methyl ether, adding 3 parts of bisphenol F epoxy resin, 5 parts of NPPN442K80 multifunctional group epoxy resin of south Taiwan Asia, 10 parts of dicyclopentadiene phenol epoxy resin, BMI-510020 parts and XiranEF 3015 parts, and stirring at the rotating speed of 1300r/min for 3 hours to obtain a mixed solution of the thermosetting resin composition;
s2, adding 0.05 part of 1-benzyl benzene-2-ethylimidazole, 8 parts of diphenyl cresyl phosphate and 27 parts of magnesium hydroxide into the mixed solution, stirring at the rotating speed of 800r/min for 4 hours, then stirring at the rotating speed of 400r/min for 3 hours, and obtaining the glue solution after the gelation time of the glue solution is qualified.
Comparative example 3
S1, cleaning a glue mixing tank by using acetone, adding 35 parts of propylene glycol methyl ether, adding 3 parts of bisphenol F epoxy resin, 5 parts of NPPN442K80 multifunctional group epoxy resin of south Taiwan Asia, 10 parts of dicyclopentadiene phenol epoxy resin, 20 parts of bisphenol A cyanate ester resin and XiranEF 3015 parts, and stirring at the rotating speed of 1300r/min for 3 hours to obtain a mixed solution of the thermosetting resin composition;
s2, adding 0.05 part of 1-benzyl benzene-2-ethylimidazole, 8 parts of diphenyl cresyl phosphate and 27 parts of magnesium hydroxide into the mixed solution, stirring at the rotating speed of 800r/min for 4 hours, then stirring at the rotating speed of 400r/min for 3 hours, and obtaining the glue solution after the gelation time of the glue solution is qualified.
And (3) preparing the prepared glue solution into a prepreg according to a conventional mode, wherein the glue content is controlled to be 50%, the fluidity is controlled to be 38%, the gelling time is controlled to be 150s, and the volatile matter is less than 0.5%.
And (3) taking 2 prepregs, covering a copper foil on each prepreg to form a combined structure, putting the combined structure into a hot press, and pressing for 4 hours under the conditions that the temperature is 230 ℃ and the pressure is 420psi to obtain the copper-clad plate.
The copper-clad plate is detected by adopting the following method, wherein the table 1 shows the raw material proportion of the glue solution for the copper-clad plate of the embodiment 1-5, the table 2 shows the raw material proportion of the glue solution for the copper-clad plate of the comparative example 1-3, the table 3 shows the performance result of the copper-clad plate of the embodiment 1-5, and the table 4 shows the performance result of the copper-clad plate of the comparative example 1-3:
glass transition temperature (Tg): measured by Differential Scanning Calorimetry (DSC) according to the DSC method defined by IPC-TM-6502.4.25;
thermal stratification time T-288: measured by the method specified in IPC-TM-6502.4.24.1;
thermal cracking temperature (Td): measured by the method specified in IPC-TM-6502.4.25.6;
flame retardancy: measured by reference to the UL94 vertical burning method;
PCT + wicking: and (3) steaming the PCT for 2h, then placing the PCT into a tin furnace at 288 ℃, and testing whether the substrate has white spots, delamination and blistering.
Table 1 example 1-5 raw material ratio of glue solution for copper-clad plate
Table 2 raw material ratio of glue solution for comparative examples 1-3 copper-clad plate
Table 3 performance results for copper clad laminates of examples 1-5
Table 4 performance results for comparative examples 1-3 copper clad laminates
By comparing examples 1-5 and comparative examples 1-3, it can be seen that when the thermosetting resin prepared by the formulation of the present invention is used for preparing a copper-clad plate, the copper-clad plate has good heat resistance, dielectric properties, low water absorption and low expansion coefficient.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The thermosetting resin composition for the copper-clad plate is characterized by comprising the following components in parts by weight:
5-30 parts of epoxy resin, 5-20 parts of cyanate ester resin, 5-20 parts of bismaleimide resin and 2-10 parts of polystyrene-maleic anhydride resin.
2. The thermosetting resin composition claimed in claim 1, wherein the epoxy resin comprises any one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, multifunctional group epoxy resin or dicyclopentadiene phenol epoxy resin.
3. The thermosetting resin composition of claim 1, wherein the cyanate ester resin comprises one or both of bisphenol a cyanate ester resin and bisphenol a cyanate ester prepolymer resin.
4. The thermosetting resin composition of claim 1, wherein the bismaleimide resin comprises either or both of BMI-5100 or BMI-4000.
5. The thermosetting resin composition of claim 1, wherein the polystyrene-maleic anhydride resin comprises any one or more of XiranEF 30, XiranEF 40, XiranEF 60, or XiranEF 80.
6. The glue solution for the copper-clad plate is characterized by comprising the following components in parts by weight:
0.05 to 1.5 parts of catalyst, 3 to 10 parts of flame retardant, 15 to 45 parts of filler, 35 to 60 parts of solvent and 17 to 80 parts of thermosetting resin composition as claimed in any one of claims 1 to 5.
7. The dope according to claim 7, wherein the catalyst comprises any one or more of 1-benzylbenzene-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole or 1-cyanoethylimidazole.
8. The glue solution of claim 7, wherein the flame retardant comprises any one or two of a phosphorus flame retardant or a nitrogen flame retardant;
wherein the phosphorus flame retardant comprises any one or more of diphenyl cresyl phosphate, trichloropropyl phosphate, hexaphenoxycyclotriphosphazene, 1, 3-phenylene phosphoric acid (2, 6-xylyl) tetraester or DOPO;
the nitrogen-based flame retardant comprises one or two of melamine or melamine phosphate.
9. The glue solution of claim 7, wherein the inorganic filler comprises one or more of magnesium hydroxide, aluminum hydroxide monohydrate, fused silica micropowder, talcum powder or barium sulfate;
the solvent comprises any one or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, butanone, acetone, methanol or xylene.
10. The process for preparing the glue solution of any one of claims 6 to 9, characterized by comprising the following steps:
s1, adding the thermosetting resin composition into a solvent, and stirring for 1-3h at the rotating speed of 1300-1700r/min to obtain a mixed solution of the thermosetting resin composition;
s2, adding the rest components into the mixed solution, stirring for 2-4h at the rotation speed of 800-1200r/min, and then stirring for 1-3h at the rotation speed of 400-600r/min to obtain the glue solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7526235B2 (en) | 2021-11-26 | 2024-07-31 | 南亞塑膠工業股▲分▼有限公司 | Resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199351A (en) * | 2011-04-08 | 2011-09-28 | 苏州生益科技有限公司 | Thermosetting resin composition, prepreg and laminated board |
| CN110776739A (en) * | 2019-09-05 | 2020-02-11 | 艾蒙特成都新材料科技有限公司 | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate |
| US20200123307A1 (en) * | 2018-10-23 | 2020-04-23 | Taiwan Union Technology Corporation | Thermal-curable resin composition, and pre-preg, metal-clad laminate and printed circuit board manufactured using the same |
-
2021
- 2021-02-05 CN CN202110160568.XA patent/CN113025263A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199351A (en) * | 2011-04-08 | 2011-09-28 | 苏州生益科技有限公司 | Thermosetting resin composition, prepreg and laminated board |
| US20200123307A1 (en) * | 2018-10-23 | 2020-04-23 | Taiwan Union Technology Corporation | Thermal-curable resin composition, and pre-preg, metal-clad laminate and printed circuit board manufactured using the same |
| CN111087809A (en) * | 2018-10-23 | 2020-05-01 | 台燿科技股份有限公司 | Thermosetting resin composition, prepreg, metal foil laminate and printed wiring board using the same |
| CN110776739A (en) * | 2019-09-05 | 2020-02-11 | 艾蒙特成都新材料科技有限公司 | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7526235B2 (en) | 2021-11-26 | 2024-07-31 | 南亞塑膠工業股▲分▼有限公司 | Resin composition |
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Application publication date: 20210625 |