CN117002110A

CN117002110A - Metal foil laminate, printed circuit board and method for manufacturing the same

Info

Publication number: CN117002110A
Application number: CN202210475678.XA
Authority: CN
Inventors: 巫胜彦; 陈子方; 曾柏凯; 余骏; 刘明
Original assignee: ITEQ Corp
Current assignee: ITEQ Corp
Priority date: 2022-04-29
Filing date: 2022-04-29
Publication date: 2023-11-07

Abstract

The application provides a metal foil laminated plate, a printed circuit board and a manufacturing method thereof. The metal foil laminate comprises: a substrate coated with a toughened resin composition; a metal foil; wherein the resin composition comprises a toughening modification compound which comprises a polybenzoxazine compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms bonding with the polybenzoxazine compound and the alkene polymer grafted by the anhydride respectively. The application has high toughness and excellent mechanical property, thus having wide application range in the fields of electronics, aerospace and the like.

Description

Metal foil laminate, printed circuit board and method for manufacturing the same

Technical Field

The present application relates to a metal foil laminate, a printed circuit board and a method for manufacturing the same, and more particularly, to a metal foil laminate, a printed circuit board and a method for manufacturing the same with an olefin polymer toughened and modified polybenzoxazine.

Background

Polybenzoxazines are thermosetting resins containing nitrogen and having a phenolic resin-like structure, and are superior in performance to conventional phenolic resins, and benzoxazine compounds are generally compounds prepared from phenolic compounds, primary amines and formaldehyde compounds by Mannich (Mannich) reaction, which is heated or catalyzed to ring-open polymerize a phenolic resin-like network, called benzoxazine resin (benzoxazine resin).

Benzoxazine resins have many superior properties compared to traditional phenolic resins, such as: the polymerization process has no release of small molecule byproducts and low volume shrinkage; the moisture absorption rate is low; the heat resistance, mechanical property, electrical property and flame retardant property are all good. Therefore, benzoxazine resins are widely used in the fields of composite matrix resins, solvent-free impregnating varnishes, electronic packaging materials, flame-retardant materials, electrical insulating materials and the like.

Although benzoxazine resins have many of the above advantages, benzoxazines have brittle mechanical properties after thermal ring-opening polymerization, which is a barrier to be overcome in application development.

Disclosure of Invention

In view of this, it is one of the problems to be solved by the present application how to improve the mechanical properties of the existing polybenzoxazine, so that it has high toughness and excellent mechanical properties when applied to metal foil laminate and printed circuit boards.

The main object of the present application is to provide a metal foil laminate comprising: a substrate coated with a toughened resin composition; a metal foil; wherein the resin composition comprises a toughening modification compound which comprises a polybenzoxazine compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms bonding with the polybenzoxazine compound and the alkene polymer grafted by the anhydride respectively.

In a preferred embodiment, the resin composition further comprises a thermosetting polymer.

In a preferred embodiment, the anhydride grafted olefin polymer comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.

In a preferred embodiment of the present application, the diisocyanate is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, and the like hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.

In a preferred embodiment, the substrate is a fibrous material.

In a preferred embodiment, the metal foil laminate comprises two layers of the metal foil, with a plurality of layers of the substrate laminated therebetween.

Another object of the present application is to provide a printed circuit board comprising the metal foil laminate as described above.

Another object of the present application is to provide a method for producing the metal foil laminate described above, comprising: (a) preparing a toughened and modified compound: adding a polybenzoxazine compound and a solvent, heating to dissolve the polybenzoxazine compound and the solvent, adding an anhydride grafted olefin polymer, heating to dissolve the olefin polymer, adding a diisocyanate compound, heating and gradually heating the synthetic solution to 120-150 ℃, reacting for 0.5-2 hours, stopping heating and cooling to room temperature; (b) preparing a resin composition: adding thermosetting resin into the toughened and modified compound solution, stirring and dissolving; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; (d) preparing a metal foil laminate: the prepreg was laminated with a metal foil laminated on each of the outermost layers on both sides thereof, followed by high-temperature hot-press curing to obtain a metal foil laminated plate.

In a preferred embodiment, step (b) further comprises adding a filler selected from the group consisting of epoxy, toughening resin, solvent, filler, and combinations thereof.

In a preferred embodiment, the hot-pressing conditions of step (d) are elevated to 200 ℃ to 220 ℃ at an elevated rate of 3.0 ℃/min, and hot-pressing for 180 minutes at the temperature at a pressure of 8 kg/cm at initial pressure and 15 kg/cm at full pressure.

Therefore, the metal foil laminated plate and the printed circuit board provided by the application comprise a toughening modification compound which toughens and modifies the polybenzoxazine compound by using olefin polymer polymers, and the diisocyanate compound is used for bonding with the toughening modification compound, so that the metal foil laminated plate and the printed circuit board have good heat resistance and mechanical property and low water absorption. The application has excellent heat resistance, low expansion, high dimensional stability, high mechanical strength and high toughness, and therefore, compared with the prior art, the application is more suitable for the application in the field of electronic motors.

Drawings

The details of one or more embodiments of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the subject matter of the present description will become apparent from the description, the drawings, and the claims, wherein:

FIG. 1 is a schematic representation of the reaction scheme of a preferred embodiment of the present application.

Wherein, the reference numerals:

100 toughened and modified compound

110 bisphenol A type polybenzoxazine

120 styrene-ethylene/butene-styrene copolymer grafted maleic anhydride

130 isophorone diisocyanate

Detailed Description

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. As used in the present application, the following terms have the following meanings.

As used herein, terms such as "first," "second," "third," "fourth," and "fifth," etc., describe various elements, components, regions, layers and/or sections that are not limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another. Unless the context clearly indicates otherwise, terms such as "first", "second", "third", "fourth" and "fifth" as used herein do not imply a sequence or order.

The term "or" as used herein means "and/or" unless otherwise indicated. The terms "comprises" or "comprising" when used herein are intended to exclude the presence of, or the addition to, one or more other elements, steps, operations, and/or components; similarly, the terms "include", "contain", "include", "have" and "have" as used herein are interchangeable and are not limiting. "a" or "an" means that the grammatical object of the article is one or more (i.e., at least one). As used herein and in the claims, the singular forms "a", "an", and "the" include plural referents.

The application relates to a metal foil laminated plate and a printed circuit board comprising the same. The metal foil laminate comprises: a substrate coated with a toughened resin composition; a metal foil; wherein the resin composition comprises a toughening modification compound which comprises a polybenzoxazine compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms bonding with the polybenzoxazine compound and the alkene polymer grafted by the anhydride respectively.

The "polybenzoxazine compound (abbreviated herein as BZ)" described herein is a thermosetting resin containing nitrogen and having a phenolic resin-like structure, and the benzoxazine compound is a six-membered heterocyclic compound system composed of an oxygen atom and a nitrogen atom, typically a compound obtained by Mannich (Mannich) reaction of a phenol compound, a primary amine and a formaldehyde compound, which is ring-opening polymerized under the action of heat or a catalyst to form a phenolic resin-like network structure, which may also be referred to as a benzoxazine resin. In a preferred embodiment, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a diamine type polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is at least one selected from the group consisting of bisphenol A type benzoxazine (BPA-BZ), bisphenol F type benzoxazine (BPF-BZ), bisphenol S type benzoxazine (BPS-BZ), diaminodiphenyl methane type benzoxazine (DDM-BZ), diaminodiphenyl ether type benzoxazine (ODA-BZ) and polyimide type benzoxazine (polybenzoxazine with polyimide).

The anhydride grafted olefin polymer described herein has excellent electrical properties and good impact resistance; preferably, the olefin polymer of the toughening agent is grafted with maleic anhydride, has good compatibility with base material resin, and achieves the modification effect. In a preferred embodiment, the toughening agent is such as, but not limited to: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA), polypropylene grafted maleic anhydride (PP (Poly Propylene) -g-MA) or polyethylene grafted maleic anhydride (PE (Poly Ethylene) -g-MA).

In the diisocyanate compounds described herein, the diisocyanate forms a bond with the polybenzoxazine compound and the anhydride of the toughening agent, respectively, to achieve chemical modification. The cyanate ester compound can increase the reactive functional groups in the resin structure, thereby improving the crosslinking density of the epoxy cured product and improving the heat resistance. For example, the cyanate ester compound may be a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, for example: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate and the like, 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, and the like. In a preferred embodiment, the modifier comprises: isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (Methylene dicyclohexyldiisocyanate or hydrogenated MDI, HMDI), or hexamethylene diisocyanate (Hexamethylene diisocyanate, HDI)).

In a preferred embodiment, the toughened and modified compound of the present application is a composition comprising a polymer selected from the group consisting of a modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound (IPDI/SEBS-g-MA/BZ), a modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound (HMDI/SEBS-g-MA/BZ), a modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound (HDI/SEBS-g-MA/BZ), a modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound (IPDI/PP-g-MA/BZ), a modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound (HMDI/PP-g-MA/BZ), a modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound (HDI/PP-g-MA/BZ), a modified polypropylene toughened polystyrene/PP-g-MA/BZ, and a modified polypropylene toughened polybenzoxazine compound (HDI/PP-g-MA/BZ), the group consisting of a methylene dicyclohexyl diisocyanate modified polyethylene grafted maleic anhydride toughened polybenzoxazine compound (HMDI/PE-g-MA/BZ) and a hexamethylene diisocyanate modified polyethylene grafted maleic anhydride toughened polybenzoxazine compound (HDI/PE-g-MA/BZ).

In a preferred embodiment, the resin composition comprises (A) a toughening modifier compound; and (B) a thermosetting polymer. In a preferred embodiment, the toughened resin composition of the present application comprises (A) 30 to 50 parts by weight of a toughening modifying compound, such as but not limited to: 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, or between any two of the foregoing; (B) The thermosetting polymer is 8 to 15 parts by weight, such as but not limited to: 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight or a range between any two of the foregoing.

The thermosetting polymer of the application may also be bismaleimide trimethamidePolymers, cyanate ester polymers, benzocyclobutene (benzocyclobutene) polymers, or phenolic resins (phenolic). In a preferred embodiment, the thermosetting polymer of the present application is a Bismaleimide (BMI) resin having carbonyl groups, a nitrogen-containing epoxy resin, and is cured by unsaturation of the end groups during processing without generating volatile materials during curing, which facilitates processing into composite materials.

In a preferred embodiment, the substrate is a fibrous material, such as: glass fiber cloth. In a preferred embodiment, the metal foil laminate comprises two layers of the metal foil, a plurality of layers of the substrate being laminated therebetween, the plurality of layers being, for example: two, three, four, five, six, seven, eight, nine, ten or more than ten layers.

The toughened resin composition of the present application may further comprise: a filler, a toughening resin and/or a solvent.

In a preferred embodiment, the filler is an inorganic filler, such as: selected from the group consisting of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene. In a preferred embodiment, the filler is 40 to 60 parts by weight, such as, but not limited to: 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, or between any two of the foregoing.

In a preferred embodiment, the resin composition further comprises: toughening resins such as: a core-shell polymer and/or polybutadiene resin. Core-shell polymers such as core-shell rubbers (core shell rebber, CSR). Such as polybutadiene homopolymer or butadiene-styrene copolymer. In a preferred embodiment, the toughening resin is 10 to 15 parts by weight, such as but not limited to: 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight or a range between any two of the foregoing.

In a preferred embodiment, the solvent is selected from the group consisting of toluene, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

Further, the method for manufacturing a metal foil laminate of the present application comprises: (a) preparing a toughened and modified compound: adding a polybenzoxazine compound and a solvent, heating to dissolve the polybenzoxazine compound and the solvent, adding an anhydride grafted olefin polymer, heating to dissolve the olefin polymer, adding a diisocyanate compound, heating and gradually heating the synthetic solution to 120-150 ℃, reacting for 0.5-2 hours, stopping heating and cooling to room temperature; (b) preparing a resin composition: adding thermosetting resin into the toughened and modified compound solution, stirring and dissolving; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; (d) preparing a metal foil laminate: the prepreg was laminated with a metal foil laminated on each of the outermost layers on both sides thereof, followed by high-temperature hot-press curing to obtain a metal foil laminated plate.

In a preferred embodiment, step (a) is to add a polybenzoxazine compound and a solvent to a reaction flask, heat to about 50 to 80 ℃ and stir well; the reaction is warmed to 50 to 80 ℃, such as but not limited to: 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any two values between the two. In a preferred embodiment, step (a) is to gradually (e.g., within 20 minutes) add an anhydride grafted olefin polymer to the solution under stirring, and then raise the temperature to 80 to 100 ℃ to dissolve the polymer completely, thereby forming a synthetic solution; the reaction is raised to 80 to 100 ℃, such as but not limited to: 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or any two values between the two values. In a preferred embodiment, step (a) is to add diisocyanate compound, heat and gradually raise the temperature of the synthesized solution to 120 to 150 ℃ and react for 0.5 to 2 hours; the reaction is raised to 120 to 150 ℃, such as but not limited to: 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or any two values between the two values; the reaction time is 0.5 to 2 hours, such as but not limited to: 0.5 hours, 1 hour, 1.5 hours, 2 hours or between the two time points.

In a preferred embodiment, step (b) further comprises adding a material selected from the group consisting of epoxy resins, toughening resins, solvents, fillers, and combinations thereof.

In a preferred embodiment, the hot pressing conditions of step (d) are elevated to a temperature of 200 ℃ to 220 ℃ at a rate of about 3.0 ℃/min and hot pressing at that temperature for about 180 minutes at a pressure of about 8 kg/cm at initial pressure and about 15 kg/cm at full pressure.

The application not only forms the chemical modification of polyimide bond by the reaction of isocyanate and anhydride, but also achieves the effect of toughening and improving by the modification of olefin polymer and polybenzoxazine compound, so that the application has high toughness and excellent mechanical property.

Examples

The present application will be further described in terms of detailed description and embodiments, however, it should be understood that these embodiments are merely used to facilitate easier understanding of the present application and to clarify aspects of the present application and the benefits achieved thereby, and are not intended to limit the scope of the present application.

Example 1

6 toughened and modified compounds (example compounds A-F) were prepared according to the present application. Metal foil laminates were then prepared using the example compounds a-F.

Examples Compound A

Referring to the exemplary reaction scheme of fig. 1, m, n, X, Y in fig. 1 is the same or different positive integer. 200 g of bisphenol A benzoxazine (BPA-BZ) 110 and 600 g of toluene were added to a 3 liter four port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA) 120 was gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate (IPDI) 130 was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound A of the embodiment, namely the toughened and modified compound 100.

Examples compound B

200 g of ODA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of SEBS-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of IPDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound B of the example.

Examples compound C

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of PP-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of IPDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound C of the example.

Examples compound D

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of PE-g-MA were gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of IPDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound D of the example.

Examples Compound E

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of SEBS-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 grams of HMDI was added, the synthesis solution was heated and gradually warmed to about 130 ℃, and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound E of the example.

Examples compound F

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of SEBS-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of HDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound F of the example.

Material

BPA-BZ and ODA-BZ are manufactured by Yuanhong corporation; SEBS-g-MA is produced by Taiwan Li Changrong company; PP-g-MA is produced by ExxonMobil chemical company, product model Exxelor ^TM PO1015; PE-g-MA is produced by Exxelor, product model Exxelor ^TM PE1040。

Table 1 below shows the preparation ingredients and contents of the compounds A to F of the examples.

TABLE 1

Example 2

The following provides a non-limiting method of preparing the toughened and modified compounds of the present application into metal foil laminate. Ten non-limiting example laminates (example laminates 1-10) and six comparative example laminates (comparative example laminates 1-6) were prepared with example compounds according to a method similar to the method disclosed below. However, the specific methods of preparing the example laminate plates 1 to 10 and the comparative example laminate plates 1 to 6 will generally differ in one or more respects from the methods disclosed below.

Example laminate 1

Preparation of a resin composition: the solution of compound a of the above example was taken at 30 g, 5 g of thermosetting resin (BMI), 25 g of CNE epoxy resin and 40 g of solvent (butanone, MEK) were added, and the mixture was uniformly mixed with a homogenizing mixer to dissolve the components. After the resin was completely dissolved, 40 g of silica was added, and the mixture was uniformly mixed with a homogenizing mixer and dispersed in a solvent to prepare a varnish-like resin composition.

Preparing a prepreg: the reinforcing material Glass fiber cloth (base material E-Glass) is impregnated or coated with the varnish liquid resin composition, and the impregnated or coated base material is dried at 80 ℃ for 3 minutes and 180 ℃ for 7 minutes to obtain a prepreg in a semi-cured state (B-stage).

Preparing a metal foil laminated plate: four prepregs were laminated, and 0.5oz of metal foil (copper foil) was laminated on each of the outermost layers on both sides, followed by hot press curing at high temperature. The hot pressing conditions are as follows: the temperature is raised to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and the copper foil laminate is prepared by hot pressing at the temperature for 180 minutes at a pressure of 15 kg/square centimeter (8 kg/square centimeter at initial pressure).

Examples laminate panels 2-10

The example laminate sheets 2-10 were prepared according to a method similar to that of example laminate sheet 1, however, example laminate sheets 2-10 may differ in one or more respects, with the specific differences shown in table 2 below.

Table 2 shows the results of measuring the preparation components and contents of the laminate sheets 1 to 10, and the adhesion strength, the thermal expansion coefficient in the Z-axis direction, and the heat resistance.

TABLE 2

Remarks: EG in the Table represents E-Glass. The units of addition of each component in the table are grams.

Comparative example laminate 1

Preparation of a resin composition: 30 g of non-toughened and modified BPA-BZ was added with 5 g of thermosetting resin (BMI), 25 g of epoxy resin, 2 g of toughening resin and 40 g of solvent (butanone, MEK) and mixed uniformly by a homogenizing mixer to dissolve the components. After the resin was completely dissolved, 40 g of silica was added, and the mixture was uniformly mixed with a homogenizing mixer and dispersed in a solvent to prepare a varnish-like resin composition.

Preparing a metal foil laminated plate: four prepregs were laminated, and 0.5oz of copper foil was laminated on each of the outermost layers on both sides, followed by hot press curing at high temperature. The hot pressing conditions are as follows: heating to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and hot-pressing at the temperature for 180 minutes at a pressure of 15 kg/square centimeter (8 kg/square centimeter at initial pressure). To obtain a copper foil laminate.

Comparative example laminate 2-6

Comparative example laminate sheets 2-6 were prepared in a similar manner to comparative example laminate sheet 1, however comparative example laminate sheets 2-6 may differ in one or more respects, the specific differences being disclosed in Table 3 below.

Table 3 shows the results of measuring the preparation components and contents of the laminate sheets 1 to 6 of comparative examples, and the adhesion strength, the thermal expansion coefficient in the Z-axis direction, and the heat resistance.

TABLE 3 Table 3

Remarks: CSR in the table is core-shell rubber. Ricon100 is a butadiene-styrene copolymer. EG represents E-Glass. The units of addition of each component in the table are grams.

Material

BPA-BZ and ODA-BZ are manufactured by Yuanhong corporation; filler SiO ₂ Is 10um cut manufactured by Sibiraex; the thermosetting resin BMI (KI-70) is produced by Dai and Chemie; CNE epoxy resin is produced by vinca resin company; the reinforcement material is E-Glass cloth 2116 produced by Taibo Glass company; the toughening resin is Ricon100 manufactured by CSR, polyscope company of Kaneka company; the copper foil was H1.5 OZ from Nanya.

Characterization test

CTE test: according to IPC-TM-650.2.4.24.5 specifications, the coefficient of thermal expansion (coefficient of thermal exapansion, CTE) change rate (total Z-CTE) in the Z-axis direction of a thermal expansion Coefficient (CTE) of a sample to be measured at a temperature lower than the glass transition temperature (Tg) is measured using a thermo-mechanical analyzer (thermal mechanical analyzer, TMA). Z-CTE is measured in% at a temperature in the range of 50 ℃ to 260 ℃.

And (3) adhesive strength test: the adhesion strength refers to the adhesion of the metal foil to the laminated prepreg, and in this test, the adhesion is expressed by the amount of force required by a 1/8 inch wide copper foil that is peeled vertically from the board surface. Tear strength is in pounds force per inch (lbf/in).

Heat resistance test: immersing the dried metal foil laminate in a soldering bath at 288 ℃ and 300 ℃ for 100 seconds, repeating the process 3 times, showing excellent heat resistance, and recording as ""; when the appearance had a bubbling bulge, it was recorded as "×" indicating that the heat resistance was poor.

From the above results, it is understood that the crosslinked and brittle mechanical properties are poor and cannot be improved even if a large amount of toughening agent or rubber is added externally, compared with the comparative example laminate sheets 1 to 6 containing the non-toughened and modified polybenzoxazine compound, and the example laminate sheets 1 to 10 containing the toughened and modified compound exhibit good mechanical properties and heat resistance. Therefore, the application is more suitable for being applied to the wide fields of composite materials, electronic circuit materials and the like.

In summary, the present application provides a metal foil laminate, a printed circuit board and a method for manufacturing the same, wherein an olefin polymer is used to toughen and modify a polybenzoxazine compound, and a diisocyanate compound is used to form a chemical bond with the polybenzoxazine compound, so that the compound has good mechanical properties and heat resistance. Therefore, compared with the mechanical property of the prior art of the polybenzoxazine compound after the thermal ring-opening polymerization reaction, the application is more suitable for the application in the field of electronic motors.

The terms "substantially" and "about" are used herein and are not otherwise defined as describing or claiming small variations. When combined with an event or circumstance, the term can include the exact whereabouts of the event or circumstance and the whereabouts of the event or circumstance to a close approximation. For example, when combined with a numerical value, the term can include a variation of less than or equal to + -10%, such as less than or equal to + -5%, less than or equal to + -4%, less than or equal to + -3%, less than or equal to + -2%, less than or equal to + -1%, less than or equal to + -0.5%, less than or equal to + -0.1%, or less than or equal to + -0.05% of the numerical value.

The foregoing has outlined the components of several embodiments so that those skilled in the art may better understand the concepts of the embodiments of the application. It will be appreciated by those skilled in the art that the embodiments of the application may be used as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art to which the application pertains will also appreciate that such equivalent constructions do not depart from the spirit and scope of the application and that they may make various changes, substitutions and other selections herein without departing from the spirit and scope of the application. Accordingly, the scope of the application is defined by the appended claims.

Claims

1. A metal foil laminate, comprising:

a substrate coated with a toughened resin composition; and

A metal foil;

wherein the resin composition comprises a toughening modification compound which comprises a polybenzoxazine compound, an anhydride grafted olefin polymer and a diisocyanate compound; wherein, in the toughened and modified compound, the diisocyanate forms bonding with the polybenzoxazine compound and the alkene polymer grafted by the anhydride respectively.

2. The metal foil laminate of claim 1 wherein the resin composition further comprises a thermosetting polymer.

3. The metal foil laminate of claim 1 wherein the anhydride grafted olefinic polymeric macromolecule comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.

4. The metal foil laminate of claim 1, wherein the diisocyanate is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, etc., 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.

5. The metal foil laminate of claim 1 wherein the substrate is a fibrous material.

6. The metal foil laminate of claim 1, wherein the metal foil laminate comprises two layers of the metal foil, the two layers of metal foil sandwiching the substrate.

7. A printed circuit board comprising the metal foil laminate of any one of claims 1 to 6.

8. A method of manufacturing the metal foil laminate according to any one of claims 1 to 6, comprising:

(a) Preparing a toughened and modified compound: adding a polybenzoxazine compound and a solvent, heating to dissolve the polybenzoxazine compound and the solvent, adding an anhydride grafted olefin polymer, heating to dissolve the olefin polymer, adding a diisocyanate compound, heating and gradually heating the synthetic solution to 120-150 ℃, reacting for 0.5-2 hours, stopping heating and cooling to room temperature;

(b) Preparation of a resin composition: adding thermosetting resin into the toughened and modified compound solution, stirring and dissolving;

(c) Preparing a prepreg: impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; and

(d) Preparing a metal foil laminated plate: the prepreg was laminated with a metal foil laminated on each of the outermost layers on both sides thereof, followed by high-temperature hot-press curing to obtain a metal foil laminated plate.

9. The method of manufacturing of claim 8, wherein step (b) further comprises adding a material selected from the group consisting of epoxy, toughening resin, solvent, filler, and combinations thereof.

10. The manufacturing method according to claim 8, wherein the hot pressing condition of step (d) is to heat up to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and to heat press at the temperature for 180 minutes at a pressure of 8 kg/cm at initial pressure and 15 kg/cm at full pressure.