CN117363141A - Method for producing cured product and metal foil layer substrate - Google Patents

Method for producing cured product and metal foil layer substrate Download PDF

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Publication number
CN117363141A
CN117363141A CN202210759810.XA CN202210759810A CN117363141A CN 117363141 A CN117363141 A CN 117363141A CN 202210759810 A CN202210759810 A CN 202210759810A CN 117363141 A CN117363141 A CN 117363141A
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resin
fluorine
weight
metal foil
parts
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Inventor
巫胜彦
多手能
刘亚萍
张淳浩
赖珮淳
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Jiangxi Lianmao Electronic Technology Co ltd
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Jiangxi Lianmao Electronic Technology Co ltd
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a method for manufacturing a cured product and a metal foil layer substrate. The method for producing the cured product comprises: preparing a resin composition; coating the resin composition onto a metal substrate; curing the resin composition at a temperature of 70 ℃ to 200 ℃ to form a half-cured film; the semi-cured film is hot-pressed to form a cured product. The resin composition comprises: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler. The content of fluorine atoms in the maleimide resin is 10 to 50% by weight. The cured product and the metal foil layer substrate have the characteristics of low thermal expansion coefficient, low water absorption, low dielectric constant and low dielectric loss.

Description

Method for producing cured product and metal foil layer substrate
Technical Field
The present invention relates to a method for producing a cured product and a metal foil substrate, and more particularly, to a method for producing a cured product and a metal foil substrate having a low thermal expansion coefficient, a low water absorption, a low dielectric constant, and a low dielectric loss.
Background
The benzoxazine resin is a thermosetting resin with a phenolic resin-like structure, and the characteristics of the benzoxazine resin are superior to those of the traditional phenolic resin. For example: benzoxazine resins have low moisture absorption and good mechanical and dielectric properties. In the curing process, the benzoxazine resin does not release small molecule byproducts, and the volume shrinkage rate after curing is low.
Therefore, the benzoxazine resin has wide application, and can be particularly applied to manufacturing metal foil layer substrates. Specifically, the benzoxazine resin may be mixed with other kinds of resins and used to form a cured product between a metal substrate and a printed circuit board.
However, with the advancement of technology, the requirements for the characteristics of metal foil substrates are gradually increasing. The characteristic specification of the benzoxazine resin which is circulated in the market at present cannot meet the product requirement gradually.
Therefore, it has been an important issue to be solved by the industry to overcome the above-mentioned drawbacks by improving the characteristics of the benzoxazine resin as a whole by improving the components.
Disclosure of Invention
The invention aims to provide a method for manufacturing a cured product and a metal foil layer substrate, which aims to overcome the defects of the prior art.
In order to solve the above-mentioned problems, one of the technical solutions adopted in the present invention is to provide a method for manufacturing a cured product. The method for producing the cured product comprises: preparing a resin composition; coating the resin composition onto a metal substrate; curing the resin composition at a temperature of 70 ℃ to 200 ℃ to form a half-cured film; the semi-cured film is hot-pressed to form a cured product. The resin composition comprises: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler. The content of fluorine atoms in the maleimide resin is 10 to 50% by weight.
Further, the maleimide resin comprises a fluorine-containing maleimide compound, and in the step of curing the resin composition: the fluorine-containing maleimide compound is grafted on the molecular side chain of the benzoxazine resin in a reaction way.
Further, the maleimide resin comprises a fluorine-containing maleimide compound represented by the formula (I):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ，R 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
Further, the fluorine-containing maleimide compound is produced by imidizing (imidizing) a maleic anhydride with a fluorine-containing aniline; wherein the fluoroaniline is represented by formula (II):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ，R 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
Further, the fluoroaniline is selected from the group consisting of:
is->
Still further, the step of producing a maleimide resin further comprises: drying maleic anhydride and fluoroaniline to remove water; under inert atmosphere, maleic anhydride reacts with fluorine-containing aniline to generate maleimide resin.
Still further, the step of producing a maleimide resin further comprises: dissolving fluorine-containing aniline with a solvent at a temperature of 50 ℃ to 70 ℃ to form a reactant solution; adding maleic anhydride to the reactant solution at a temperature of 80 ℃ to 100 ℃; the reactant solution is heated to a temperature of 130 ℃ to 150 ℃ to react to form the maleimide resin.
In order to solve the above-mentioned problems, another technical solution adopted by the present invention is to provide a method for manufacturing a metal foil layer substrate. The method for manufacturing the metal foil layer substrate comprises preparing a resin composition; coating the resin composition onto a metal substrate; curing the resin composition at a temperature of 70 ℃ to 200 ℃ to form a half-cured film; and arranging a printed circuit board on the semi-solidified film, and hot-pressing to obtain the metal foil layer substrate. The resin composition comprises: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler. The maleimide resin has a fluorine atom content of 10 to 50% by weight.
Further, the maleimide resin comprises a fluorine-containing maleimide compound represented by the formula (I):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ，R 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
Further, in the step of curing the resin composition, the fluorine-containing maleimide compound is reacted and grafted to the molecular side chains of the benzoxazine resin.
One of the advantages of the present invention is that the method for manufacturing a cured product and a metal foil layer substrate according to the present invention can be achieved by: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler, and the technical proposal of the fluorine atom content of the maleimide resin being 10 to 50 weight percent, so as to reduce the thermal expansion coefficient, the water absorption, the dielectric constant and the dielectric loss of the metal foil layer substrate.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for purposes of reference only and are not intended to limit the invention.
Drawings
FIG. 1 is a flow chart showing the steps for synthesizing a fluorine-containing maleimide compound according to the present invention.
FIG. 2 is a schematic diagram showing the production of a cured product of the present invention.
FIG. 3 is a flow chart showing the steps of the method for producing a cured product according to the present invention.
Fig. 4 is a schematic view of the manufacture of the metal foil layer substrate of the present invention.
Fig. 5 is a flowchart showing steps of a method for manufacturing a metal foil layer substrate according to the present invention.
Detailed Description
The following is a description of embodiments of the present invention related to "method for manufacturing a cured product and a metal foil layer substrate", and those skilled in the art will appreciate the advantages and effects of the present invention from the disclosure of the present invention. The invention is capable of other and different embodiments and its several details are capable of modification and variation in various respects, all from the point of view and application, all without departing from the spirit of the present invention. The drawings of the present invention are merely schematic illustrations, and are not intended to be drawn to actual dimensions. The following embodiments will further illustrate the related art content of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention. In addition, the term "or" as used herein shall include any one or combination of more of the associated listed items as the case may be.
The cured product and the metal foil layer substrate of the present invention are made of a resin composition. The cured product of the resin composition has low thermal expansion coefficient, low water absorption, low dielectric constant and low dielectric loss, and is suitable for manufacturing metal foil layer substrates.
In the present invention, the resin composition contains 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler.
It is worth noting that the maleimide resin added in the invention has fluorine-containing functional groups. The fluorine-containing functional group on the maleimide resin can reduce the thermal expansion coefficient, the water absorption rate, the dielectric constant and the dielectric loss of the resin composition, thereby achieving the effect of improving the characteristics of the cured product and the metal foil layer substrate. Specifically, the maleimide resin contains 10 to 50 weight percent of fluorine atoms. In some embodiments, the maleimide resin may contain 15, 20, 25, 30, 35, 40, or 45 weight percent fluorine atoms.
In some embodiments, the maleimide resin comprises a fluorine-containing maleimide compound having the structure represented by formula (I):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ，R 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
In some embodiments, the fluorine-containing maleimide compound may be synthesized from maleic anhydride and fluorine-containing aniline by a closed-loop polyimide reaction. The fluorine-containing functional group (trifluoromethyl group or fluorine atom) in the fluorine-containing maleimide compound is contributed by the fluorine-containing aniline.
In some embodiments, the fluoroaniline has a structure represented by formula (II):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ，R 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
In some embodiments, R 2 And R is R 4 Having the same substituents, for example: r is R 2 And R is R 4 Can be simultaneously-F. In other embodiments, R 3 And R is R 5 Having the same substituents, for example: r is R 3 And R is R 5 Can be simultaneously-F or-CF 3 。
In a preferred embodiment, the fluoroaniline is selected from the group consisting of:
is->
In a preferred embodiment, the structure of the fluorine-containing aniline has symmetry, so that the dielectric constant and dielectric loss of the metal foil layer substrate can be effectively reduced. That is, the fluoroaniline is preferably:
in the synthesis of the fluorine-containing maleimide compound, moisture causes hydrolysis reaction of the intermediate product (polyimide acid) and does not produce the fluorine-containing maleimide compound.
Thus, in order to exclude the influence of moisture, maleic anhydride and fluoroaniline are dried before the reaction is carried out. And, during the reaction, maleic anhydride and fluorine-containing aniline are maintained to react under an inert atmosphere. Thus, the moisture in the reactant or the water vapor in the air can be prevented from negatively affecting the imidization reaction.
For a specific synthesis procedure of the fluorine-containing maleimide compound, please refer to fig. 1. The maleic anhydride and the fluorine-containing aniline are dried to achieve the effect of removing the water (step S1). Fluorine-containing aniline is added to a solvent at a temperature of 50 ℃ to 70 ℃ to form a reactant solution (step S2). Maleic anhydride is added to the reactant solution at a temperature of 80 ℃ to 100 ℃ (step S3). The reactant solution is heated to 130 ℃ to 150 ℃ under an inert atmosphere to produce a fluorine-containing maleimide compound (step S4).
The following synthesis examples 1 to 5 specifically illustrate the synthesis of the fluorine-containing maleimide compound. In synthesis examples 1 to 5, different kinds of fluorine-containing anilines were used to synthesize fluorine-containing maleimide compounds having different fluorine atom contents.
Synthesis example 1
In a separable reaction flask were added 19.7 g of 4-amino-2,6-difluorobenzotrifluoride (4-amino-2, 6-difluoroobenz-trifluoride) and 150 g of Dimethylacetamide (DMAC) to form a reactant solution. The reaction flask was heated to 60℃and stirred until the 4-amino-2,6-difluorobenzotrifluoride was completely dissolved.
During the continuous stirring, 10 grams of maleic anhydride were gradually added to the reactant solution and the addition was completed within 20 minutes. Next, the temperature of the reaction flask was raised to 90℃and 1 g of 5-ethyl-2-methylpyridine (5-methyl-2-methylpyridine) was added as a catalyst. Finally, the temperature of the reaction flask was raised to 140℃and reacted for 1 hour.
After the reaction was completed and the reaction flask was cooled to room temperature, 400 g of methanol was added to precipitate a product. After collecting the product, the resultant was washed three times with methanol to obtain a fluorine-containing maleimide compound (hereinafter abbreviated as MA-1). In synthesis example 1, the fluorine atom content of the fluorine-containing maleimide compound was 31.95% by weight.
Synthesis example 2
A separable reaction flask was charged with 17.9 g of 4-amino-2-fluorobenzotrifluoride (4-amino-2-fluoroobenzotrifluoride) and 150 g of Dimethylacetamide (DMAC) to form a reactant solution. The reaction flask was heated to 60℃and stirred until the 4-amino-2-fluorobenzotrifluoride was completely dissolved.
During the continuous stirring, 10 grams of maleic anhydride were gradually added to the reactant solution and the addition was completed within 20 minutes. Next, the temperature of the reaction flask was raised to 90℃and 1 g of 5-ethyl-2-methylpyridine was added as a catalyst. Finally, the temperature of the reaction flask was raised to 140℃and reacted for 1 hour.
After the reaction was completed and cooled to room temperature, 400 g of methanol was added to precipitate a product. After collecting the product, the resultant was washed three times with methanol to obtain a fluorine-containing maleimide compound (hereinafter abbreviated as MA-2). In synthesis example 2, the fluorine atom content of the fluorine-containing maleimide compound was 27.21% by weight.
Synthesis example 3
To a separable reaction flask was added 12.9 grams of 2,4-difluoroaniline (2, 4-difluoroaniline) and 150 grams of Dimethylacetamide (DMAC) to form a reactant solution. The reaction flask was heated to 60℃and stirred until the 2,4-difluoroaniline was completely dissolved.
During the continuous stirring, 10 grams of maleic anhydride were gradually added to the reactant solution and the addition was completed within 20 minutes. Next, the temperature of the reaction flask was raised to 90℃and 1 g of 5-ethyl-2-methylpyridine was added as a catalyst. Finally, the temperature of the reaction flask was raised to 140℃and reacted for 1 hour.
After the reaction was completed and cooled to room temperature, 400 g of methanol was added to precipitate a product. After collecting the product, the resultant was washed three times with methanol to obtain a fluorine-containing maleimide compound (hereinafter abbreviated as MA-3). In synthesis example 3, the fluorine atom content of the fluorine-containing maleimide compound was 16.57% by weight.
Synthesis example 4
14.7 g of 2,4,6-trifluoroaniline (2, 4, 6-trifluoroaniline) and 150 g of Dimethylacetamide (DMAC) were added to a separable reaction flask to form a reactant solution. The reaction flask was heated to 60℃and stirred until the 2,4,6-trifluoroaniline was completely dissolved.
During the continuous stirring, 10 grams of maleic anhydride were gradually added to the reactant solution and the addition was completed within 20 minutes. Next, the temperature of the reaction flask was raised to 90℃and 1 g of 5-ethyl-2-methylpyridine was added as a catalyst. Finally, the temperature of the reaction flask was raised to 140℃and reacted for 1 hour.
After the reaction was completed and cooled to room temperature, 400 g of methanol was added to precipitate a product. After collecting the product, the resultant was washed three times with methanol to obtain a fluorine-containing maleimide compound (hereinafter abbreviated as MA-4). In synthesis example 4, the fluorine atom content in the fluorine-containing maleimide compound was 25.1% by weight.
Synthesis example 5
29.7 grams of 2,4,6-tris (trifluoromethyl) aniline (2, 4,6-tris (trifluoromethyl) aniline) and 150 grams of Dimethylacetamide (DMAC) were added to a separable reaction flask to form a reactant solution. The reaction flask was heated to 60 ℃ and stirred until the 2,4,6-tris (trifluoromethyl) aniline was completely dissolved.
During the continuous stirring, 10 grams of maleic anhydride were gradually added to the reactant solution and the addition was completed within 20 minutes. Next, the temperature of the reaction flask was raised to 90℃and 1 g of 5-ethyl-2-methylpyridine was added as a catalyst. Finally, the temperature of the reaction flask was raised to 140℃and reacted for 1 hour.
After the reaction was completed and cooled to room temperature, 400 g of methanol was added to precipitate a product. After collecting the product, the resultant was washed three times with methanol to obtain a fluorine-containing maleimide compound (hereinafter abbreviated as MA-5). In synthesis example 5, the fluorine atom content of the fluorine-containing maleimide compound was 45.3% by weight.
The above-mentioned fluorine-containing maleimide compound may be used as a maleimide resin as it is, or may be further mixed with another fluorine-free maleimide compound to be used as a maleimide resin.
For the manner of producing the cured product, please refer to fig. 2. The resin composition containing the maleimide resin is prepared first, and the resin composition is coated on a metal substrate 10 to form a resin film 20. Next, the resin film 20 is cured at a temperature of 70 ℃ to 200 ℃ to form a semi-cured film 20'. After the semi-cured film 20' is hot-pressed, a cured product 20 "can be obtained.
The specific steps for producing the cured product are shown in FIG. 3. A resin composition is prepared, which includes a maleimide resin, a benzoxazine resin, an epoxy resin and a filler (step S5). Coating the resin composition onto the metal substrate (step S6). The resin composition is cured at a temperature of 70 ℃ to 200 ℃ to form a semi-cured film (step S7). The semi-cured film is hot-pressed to form a cured product (step S8).
For a manner of manufacturing a metal foil layer substrate, refer to fig. 4. A resin composition containing the foregoing maleimide resin is prepared first, and the resin composition is coated on a metal substrate 10 to form a resin film 20. Next, the resin film 20 is cured at a temperature of 70 ℃ to 200 ℃ to form a semi-cured film 20'. A printed circuit board 30 is disposed on the semi-cured film 20 'and hot-pressed, so that the semi-cured film 20' forms a cured product 20″ and a metal foil layer substrate can be obtained.
In a specific manufacturing step of the metal foil substrate, please refer to fig. 5. Steps S5 to S7 in the manufacturing steps of the metal foil layer substrate are the same as steps S5 to S7 in the manufacturing steps of the cured product, and thus, a description thereof will not be repeated. After the semi-cured film is formed (step S7), a printed circuit board is disposed on the semi-cured film to form a laminated structure (step S8'). The laminated structure is hot-pressed so that the semi-cured film forms a cured product, and a metal foil layer substrate is produced (step S9').
In either the above-mentioned method for producing a cured product or a metal foil-layered substrate, the resin composition is cured and hot-pressed to form a cured product. It is worth noting that in the process of curing the resin composition, the fluorine-containing maleimide compound reacts and grafts on the molecular side chain of the benzoxazine resin, so that the effect of modifying the benzoxazine resin is achieved. The invention controls the content of fluorine atoms in the maleimide resin, and can improve the dielectric constant and hygroscopicity of the benzoxazine resin through a proper amount of fluorine atoms.
To illustrate the characteristic advantages of the cured product and the metal foil layer substrate of the present invention, metal foil layer substrates of examples 1 to 9 (E1 to E9) and comparative examples 1 to 4 (C1 to C4) were manufactured according to the foregoing procedure.
The resin compositions of examples 1 to 9 and comparative examples 1 to 4 contained different kinds and amounts of resins (specific components and amounts are shown in Table 1) to compare the influence of the different resin compositions on the characteristics of the metal foil layer substrate. Examples 1 to 9 differ from comparative examples 1 to 4 in that: the bismaleimide resins (manufacturer: KI CHEMICAL, model: BMI-70) added in comparative examples 1 to 4 did not contain fluorine atoms.
Examples 1 to 9
Examples 1 to 9 (E1 to E9) were prepared by adding a maleimide resin (at least one of MA-1 to MA-5, and optionally including BMI-70) and a benzoxazine resin (bisphenol A type benzoxazine resin, diamine type benzoxazine resin) to 40 g of a solvent (butanone) according to the component contents listed in Table 1, and allowing them to dissolve completely. Next, epoxy resin (o-methyl novolac epoxy resin, bisphenol a type epoxy resin, long chain type epoxy resin), toughening agent (liquid polybutadiene) and flame retardant are added, uniformly mixed and dissolved by a homogenizing mixer. After complete dissolution, the filler (silica) was added and dispersed with continuous stirring by a homogenizing mixer, to complete the preparation of the resin composition.
The resin composition was coated on a metal substrate (copper foil) using a doctor blade, baked at 80℃for 3 minutes, and baked at 180℃for 7 minutes. After drying, a semi-cured film can be obtained. Then, a printed circuit board is arranged on the semi-cured film to form a laminated structure. After the lamination structure is hot pressed, a metal foil layer substrate can be obtained.
Comparative examples 1 to 4
Comparative examples 1 to 4 (C1 to C4) were prepared by adding a maleimide resin (BMI-70) and a benzoxazine resin (bisphenol A type benzoxazine resin, diamine type benzoxazine resin) to 40 g of a solvent (butanone) according to the component contents listed in Table 1, and allowing them to dissolve completely. Next, epoxy resin (o-methyl novolac epoxy resin, bisphenol a type epoxy resin, long chain type epoxy resin), toughening agent (liquid polybutadiene) and flame retardant are added, uniformly mixed and dissolved by a homogenizing mixer. After complete dissolution, the filler (silica) was added and dispersed with continuous stirring by a homogenizing mixer, to complete the preparation of the resin composition.
The resin composition was coated on a metal substrate (copper foil) using a doctor blade, baked at 80℃for 3 minutes, and baked at 180℃for 7 minutes. After drying, a semi-cured film can be obtained. Then, a printed circuit board is arranged on the semi-cured film to form a laminated structure. After the lamination structure is hot pressed, a metal foil layer substrate can be obtained.
[ Property test ]
Glass transition temperature (transition glass temperature, tg): glass transition temperatures of the metal foil layer substrates were measured using a thermo-mechanical analyzer (thermal mechanical analyzer, TMA).
Coefficient of thermal expansion (coefficient of thermal expansion, CTE): according to the specifications of IPC-TM-6502.4.24.5, the coefficient of thermal expansion (z-CTE) of a metal foil layer substrate in the z-axis direction is measured with a thermo-mechanical analyzer over a temperature range of 50 ℃ to 260 ℃.
Peel strength: the metal foil base material was dried and then the magnitude of the external force required to vertically tear the 1/8 inch wide copper foil (metal substrate) was measured to quantify the peel strength of the metal foil base material.
Heat resistance: the metal foil substrate was dried and then immersed in a 300 c solder bath for 100 seconds and repeated 3 times. When the appearance of the metal foil layer substrate is unchanged, the appearance is indicated by "O". If the appearance of the metal foil layer substrate has a blister, the appearance is indicated by "X".
Water absorption rate: the metal foil layer substrate was cut into samples having a side length of 10 cm and a thickness of 25 microns. Baking in an oven at 120deg.C for 1 hr, taking out, weighing to obtain W1, soaking in 25deg.C water for 24 hr, taking out, wiping water on the surface of the sample, and weighing to obtain W2. The water absorption is calculated by the following formula: (W2-W1)/W1X 100%.
Dielectric properties: the metal foil layer substrate was cut into samples having a side length of 6 cm and a thickness of 25 microns. After baking in an oven at 120 ℃ for 1 hour, the oven was placed in a resonant cavity, and dielectric constant and dielectric loss were measured.
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As can be seen from the results of table 1, the metal foil layer substrates of examples 1 to 9 have lower thermal expansion coefficients, water absorption, dielectric constants, and dielectric losses than those of comparative examples 1 to 4. From these results, it is apparent that the use of the maleimide resin containing fluorine atoms in the present invention can improve the characteristics of the metal foil layer substrate.
Specifically, the glass transition temperature of the metal foil layer substrate is 165 ℃ to 180 ℃, and the thermal expansion coefficient of the metal foil layer substrate in the z direction is 1.0% to 1.5%. Therefore, the metal foil layer substrate has good heat resistance.
The peel strength of the metal foil layer substrate is 5.2lbf/in to 6.0lbf/in, and meets the use requirement. The water absorption of the metal foil layer substrate is 0.20% to 0.35%, and excessive water vapor can be prevented from adhering to the metal foil layer substrate.
The dielectric constant of the metal foil layer substrate is 3.8 to 4.0, and the dielectric loss of the metal foil layer substrate is 0.0075 to 0.0090 in terms of dielectric characteristics.
As can be seen from the results of table 1, the epoxy resins of the present invention may include ortho-methyl novolac epoxy resin (cresol novolac epoxy resin, CNE resin), bisphenol a novolac epoxy resin (bisphenol A novolac epoxy resin, BNE resin), bisphenol a type epoxy resin (bisphenol A epoxy resin) and long chain type epoxy resin. The total weight of the epoxy resin is 100 weight percent, the content of the o-methyl phenolic epoxy resin is 12 weight percent to 20 weight percent, the content of the bisphenol A phenolic epoxy resin is 18 weight percent to 25 weight percent, the content of the bisphenol A epoxy resin is 20 weight percent to 25 weight percent, and the content of the long chain epoxy resin is 35 weight percent to 45 weight percent.
As can be seen from the results of Table 1, the benzoxazine resins of the present invention may include bisphenol A type benzoxazine resins as well as diamine type benzoxazine resins. In a preferred embodiment, the content of bisphenol A type benzoxazine resin is greater than the content of diamine type benzoxazine resin. More preferably, the content of the phenol A type benzoxazine resin is 1.5 to 2.5 times the content of the diamine type benzoxazine resin.
As can be seen from the results in Table 1, the content of the benzoxazine resin in the resin composition of the present invention is 1.3 to 1.8 times the content of the maleimide resin. Preferably, the benzoxazine resin content is 1.4 to 1.6 times the maleimide resin content. Thus, a better modifying effect can be achieved, and the dielectric constant and hygroscopicity of the benzoxazine resin can be reduced.
As can be seen from the results of table 1, when comparing examples 1, 2, 3, 8 and 9, the metal foil substrate can have a low dielectric constant and dielectric loss when the structure of the fluorine-containing maleimide compound (fluorine-containing aniline) in the maleimide resin has symmetry.
Advantageous effects of the embodiment
One of the advantages of the present invention is that the method for manufacturing a cured product and a metal foil layer substrate according to the present invention can be achieved by: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler, and the technical proposal of the fluorine atom content of the maleimide resin being 10 to 50 weight percent, so as to reduce the thermal expansion coefficient, the water absorption, the dielectric constant and the dielectric loss of the metal foil layer substrate.
Furthermore, by the technical scheme of grafting the fluorine-containing maleimide compound to the molecular side chain of the benzoxazine resin, the cured product and the metal foil layer substrate can have low thermal expansion coefficient, water absorption rate, dielectric constant and dielectric loss.
The foregoing disclosure is only a preferred embodiment of the present invention and is not intended to limit the scope of the claims, so that all equivalent technical changes made by the application of the present invention and the accompanying drawings are included in the scope of the claims.

Claims (10)

1. A method for producing a cured product of a metal foil-layered substrate, the method comprising:
preparing a resin composition comprising: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler; wherein the content of fluorine atoms in the maleimide resin is 10 to 50 weight percent;
coating the resin composition on a metal substrate;
curing the resin composition at a temperature of 70 ℃ to 200 ℃ to form a half-cured film; and
and hot-pressing the semi-cured film to form a cured product.
2. The method of claim 1, wherein the maleimide resin comprises a fluorine-containing maleimide compound, and wherein the step of curing the resin composition comprises: the fluorine-containing maleimide compound is grafted on the molecular side chain of the benzoxazine resin in a reaction way.
3. The method of claim 1, wherein the maleimide resin comprises a fluorine-containing maleimide compound represented by formula (I):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ；
Wherein R is 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
4. The method according to claim 3, wherein the fluorine-containing maleimide compound is produced by imidizing a maleic anhydride with a fluorine-containing aniline; wherein the fluoroaniline is represented by formula (II):
；
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ；
Wherein,R 2 、R 3 、R 4 and R is R 5 At least one of them is-F or-CF 3 。
5. The method of claim 4, wherein the fluoroaniline is selected from the group consisting of:
is->
6. The method of producing according to claim 4, wherein the step of producing the fluorine-containing maleimide compound further comprises:
drying the maleic anhydride and the fluoroaniline to remove moisture; and
and reacting the maleic anhydride with the fluorine-containing aniline under an inert atmosphere to generate the fluorine-containing maleimide compound.
7. The method of producing according to claim 4, wherein the step of producing the fluorine-containing maleimide compound further comprises:
dissolving the fluoroaniline with a solvent at a temperature of 50 ℃ to 70 ℃ to form a reactant solution;
adding the maleic anhydride to the reactant solution at a temperature of 80 ℃ to 100 ℃; and
heating the reactant solution to a temperature of 130 ℃ to 150 ℃ to react to form the fluorine-containing maleimide compound.
8. A method for manufacturing a metal foil layer substrate, the method comprising:
preparing a resin composition comprising: 5 to 15 parts by weight of a maleimide resin, 5 to 30 parts by weight of a benzoxazine resin, 40 to 70 parts by weight of an epoxy resin and 40 to 60 parts by weight of a filler; wherein the content of fluorine atoms in the maleimide resin is 10 to 50 weight percent;
coating the resin composition on a metal substrate;
curing the resin composition at a temperature of 70 ℃ to 200 ℃ to form a half-cured film; and
and arranging a printed circuit board on the semi-cured film, and hot-pressing to obtain the metal foil layer substrate.
9. The method of claim 8, wherein the maleimide resin comprises a fluorine-containing maleimide compound represented by formula (I):
wherein R is 1 Is selected from the group consisting of: -F and-CF 3 ；
Wherein R is 2 、R 3 、R 4 And R is R 5 At least one of them is-F or-CF 3 。
10. The method according to claim 9, wherein in the step of curing the resin composition, the fluorine-containing maleimide compound is reaction-grafted to a molecular side chain of the benzoxazine resin.
CN202210759810.XA 2022-06-29 2022-06-29 Method for producing cured product and metal foil layer substrate Pending CN117363141A (en)

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CN202210759810.XA CN117363141A (en) 2022-06-29 2022-06-29 Method for producing cured product and metal foil layer substrate

Applications Claiming Priority (1)

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Publications (1)

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CN117363141A true CN117363141A (en) 2024-01-09

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