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

Abstract

The present application provides a kind of metal foil laminate, printed circuit board and its manufacturing method.The metal foil laminate includes: a substrate, which is covered with a toughened resin composition outside;And a metal foil;Wherein, the resin composition includes a toughened modified compound, which includes a polybenzoxazine compound, an anhydride grafted olefin polymer and a diisocyanate compound;Wherein, the diisocyanate in the toughened modified compound is bonded to the polybenzoxazine compound and the anhydride grafted olefin polymer respectively.The present application has high toughness and excellent mechanical properties, so it can be widely used in the field of electronics, aerospace, etc.

Description

TECHNICAL FIELD

[0001] The present invention relates to a metal foil laminate, a printed circuit board and a manufacturing method thereof, and in particular, to a metal foil laminate having an olefin-based polymeric high molecule toughened and modified polybenzoxazine, a printed circuit board and a manufacturing method thereof. BACKGROUND

[0002] Polybenzoxazine is a kind of thermosetting resin containing nitrogen and having a structure similar to that of phenolic resin, and has better performance than conventional phenolic resin. Benzoxazine compounds are generally prepared by Mannich reaction of phenolic compounds, primary amines and formaldehyde compounds. The reaction generates a network structure similar to that of phenolic resin through ring-opening polymerization under the action of heat or catalyst, and is referred to as benzoxazine resin.

[0003] Compared with conventional phenolic resin, benzoxazine resin has many excellent properties, such as no small molecule by-product being released during polymerization, low volume shrinkage, low moisture absorption, good heat resistance, mechanical properties, electrical properties and flame retardancy. Therefore, benzoxazine resin is widely used in the fields of composite matrix resin, solvent-free impregnating varnish, electronic packaging material, flame-retardant material and electrical insulation material.

[0004] Although benzoxazine resin has many advantages, the mechanical properties of benzoxazine are brittle after the ring-opening polymerization reaction, which is an obstacle to the development of its application. SUMMARY

[0005] Therefore, how to improve the mechanical properties of existing polybenzoxazine so as to apply it to metal foil laminates and printed circuit boards with high toughness and excellent mechanical properties is one of the problems to be solved by the present invention.

[0006] The main purpose of the present invention is to provide a metal foil laminate, which comprises a substrate coated with a toughened resin composition on the outside and a metal foil, wherein the resin composition comprises a toughened and modified compound, which comprises a polybenzoxazine compound, an anhydride-grafted olefin-based polymeric high molecule and a diisocyanate compound, and wherein the diisocyanate is bonded to the polybenzoxazine compound and the anhydride-grafted olefin-based polymeric high molecule, respectively.

[0007] In a preferred embodiment, the resin composition further comprises a thermosetting polymer.

[0008] In a preferred embodiment, the anhydride-grafted olefin-based polymeric high molecule comprises styrene-ethylene / butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.

[0009] In a preferred embodiment, the diisocyanate compound is selected from the group consisting of triethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4- trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylene diisocyanate.

[0010] In a preferred embodiment, the substrate is a fiber material.

[0011] In a preferred embodiment, the metal foil laminate includes two layers of the metal foil, and the two layers of the metal foil are interlayered with a plurality of layers of the substrate.

[0012] Another object of the present application is to provide a printed circuit board including the metal foil laminate as described above.

[0013] Further, another object of the present application is to provide a method of manufacturing the metal foil laminate as described above, which includes: (a) preparing a toughened modified compound by adding a polybenzoxazine compound and a solvent, dissolving the same by heating, adding an anhydride-grafted olefin-based polymeric macromolecule, dissolving the same by heating, further adding a diisocyanate compound, heating and gradually increasing the temperature of the resultant solution to 120 to 150°C, and reacting for 0.5 to 2 hours, and stopping the heating and decreasing the temperature to room temperature; (b) preparing a resin composition by adding the toughened modified compound solution to a thermosetting resin, and stirring and dissolving the same; (c) preparing a prepreg by impregnating or coating the resin composition to a substrate, and drying the substrate to obtain a semi-cured prepreg; and (d) preparing a metal foil laminate by layering a plurality of the prepreg, and layering a metal foil to each of the outermost layers on both sides of the prepreg, and then high-temperature hot-pressing and curing to manufacture the metal foil laminate.

[0014] In a preferred embodiment, step (b) further includes adding a member selected from the group consisting of an epoxy resin, a toughening resin, a solvent, a filler, and a combination thereof.

[0015] In a preferred embodiment, the hot pressing conditions in step (d) are to heat the temperature to 200°C to 220°C at a heating rate of 3.0°C / min, and at this temperature, to hot press for 180 minutes with an initial pressure of 8 kg / cm² and a total pressure of 15 kg / cm².

[0016] Therefore, the metal foil laminate and printed circuit board provided by the present invention include a toughened and modified compound, which is a polybenzoxazine compound toughened and modified by an olefin polymer and bonded to it using a diisocyanate compound. This gives the present invention excellent heat resistance and mechanical properties, and low water absorption. The present invention has excellent heat resistance, low expansion, high dimensional stability, high mechanical strength and high toughness. Therefore, the present invention is more suitable for applications in the field of electronics and electrical engineering compared to the prior art. Attached Figure Description

[0017] Details of one or more embodiments of the subject matter described herein are set forth in the following drawings and description. Other features, aspects, and advantages of the subject matter of this specification will become apparent from the description, drawings, and claims, wherein:

[0018] Figure 1 This is a schematic diagram of a reaction scheme according to a preferred embodiment of the present invention.

[0019] In the attached figures, the following labels are used:

[0020] 100: Toughened and modified compounds

[0021] 110: Bisphenol A type polybenzoxazine

[0022] 120: Styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride

[0023] 130: Isophorone diisocyanate Detailed Implementation

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as understood by one of ordinary skill in the art to which this invention pertains. As used in this application, the following terms have the following meanings.

[0025] As used herein, terms such as "first," "second," "third," "fourth," and "fifth" describe various elements, components, regions, layers, and / or parts, which should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer, or part from another. Unless the context clearly indicates otherwise, the use of terms such as "first," "second," "third," "fourth," and "fifth" herein does not imply order or sequence.

[0026] Unless otherwise indicated herein, "or" as used in a phrase such as "A or B" is to be interpreted as "A, B, or both A and B." As used herein, "includes" or "including" means, and is used to mean, the inclusion of one or more other components, steps, operations, and / or elements not recited. As used herein, "including," "includes," "include," "contain," "containing," "has," "have," "has," "having," or the like are not limited to an open-ended reading, but rather should be interpreted to mean and cover one or more components, steps, operations, and / or elements not recited. As used herein, "a" or "an" means one or more (i.e., at least one).

[0027] The present invention is a metal foil laminate and a printed circuit board comprising the same. The metal foil laminate comprises: a substrate, an outer portion of which is covered with a toughened resin composition; and a metal foil; wherein the resin composition includes a toughening modifier compound comprising a polybenzoxazine compound, an anhydride-grafted olefin-based polymeric high molecule, and a diisocyanate compound; wherein the diisocyanate is bonded to the polybenzoxazine compound and the anhydride-grafted olefin-based polymeric high molecule, respectively.

[0028] As used herein, "polybenzoxazine" (also referred to herein simply as "BZ") is a class of nitrogen-containing thermoset resins having a structure similar to that of phenol-formaldehyde resins. Benzoxazine compounds are six-membered heterocyclic compound systems composed of oxygen and nitrogen atoms, and are generally compounds prepared by Mannich reaction of a phenolic compound, a primary amine, and a formaldehyde compound. The reaction, which is carried out with or without a catalyst, undergoes ring-opening polymerization to form a network structure similar to that of a phenol-formaldehyde resin, and can also be referred to as a benzoxazine resin. In a preferred embodiment, the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a bisamine-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), diamine-based diphenylmethane-type benzoxazine (DDM-BZ), diamine-based diphenyl ether-type benzoxazine (ODA-BZ), and polybenzoxazine with polyimide.

[0029] The anhydride grafted olefinic polymer described herein has excellent electrical properties and good impact resistance; preferably, the olefinic polymer of the present application is grafted with maleic anhydride, which is compatible with the base resin and achieves the modification effect. In a preferred embodiment, the toughener is, for example but not limited to: styrene-ethylene / butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA), polypropylene grafted maleic anhydride (PP-g-MA) or polyethylene grafted maleic anhydride (PE-g-MA).

[0030] In the diisocyanate compound described herein, the diisocyanate is bonded to the polybenzoxazine compound and the anhydride of the toughener, respectively, to achieve chemical modification. The cyanate compound can increase the reactive functional groups in the resin structure, thereby increasing the crosslinking density of the epoxy cured product and improving heat resistance. For example, the cyanate compound can be a multifunctional aliphatic isocyanate compound, a multifunctional alicyclic isocyanate, a multifunctional aromatic isocyanate compound, such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentylene 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, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, etc. In a preferred embodiment, the modifier includes isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (HMDI) or hexamethylene diisocyanate (HDI).

[0031] In a preferred embodiment, the toughened modified compound of the present application is selected from the group consisting of isophorone diisocyanate modified styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride toughened polybenzoxazine (IPDI / SEBS-g-MA / BZ), methylene dicyclohexyl diisocyanate modified styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride toughened polybenzoxazine (HMDI / SEBS-g-MA / BZ), hexamethylene diisocyanate modified styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride toughened polybenzoxazine (HDI / SEBS-g-MA / BZ), isophorone diisocyanate modified polypropylene grafted with maleic anhydride toughened polybenzoxazine (IPDI / PP-g-MA / BZ), methylene dicyclohexyl diisocyanate modified polypropylene grafted with maleic anhydride toughened polybenzoxazine (HMDI / PP-g-MA / BZ), hexamethylene diisocyanate modified polypropylene grafted with maleic anhydride toughened polybenzoxazine (HDI / PP-g-MA / BZ), isophorone diisocyanate modified polyethylene grafted with maleic anhydride toughened polybenzoxazine (IPDI / PE-g-MA / BZ), methylene dicyclohexyl diisocyanate modified polyethylene grafted with maleic anhydride toughened polybenzoxazine (HMDI / PE-g-MA / BZ), and hexamethylene diisocyanate modified polyethylene grafted with maleic anhydride toughened polybenzoxazine (HDI / PE-g-MA / BZ).

[0032] In a preferred embodiment, the resin composition comprises (A) a toughened modified compound; and (B) a thermoset polymer. In a preferred embodiment, the toughened resin composition of the present application comprises (A) a toughened modified compound in an amount of 30 to 50 parts by weight, for example 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 aforementioned values; and (B) a thermoset polymer in an amount of 8 to 15 parts by weight, for example 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 between any two of the aforementioned values.

[0033] The thermoset polymer of the present application can also be a bismaleimide tri polymer, cyanate ester polymer, benzocyclobutene polymer, or phenolic. In a preferred embodiment, the thermoset polymer of the present application is a bismaleimide (BMI) resin, which has carbonyl groups, nitrogen-containing epoxy resin, and is cured by the unsaturation of the end groups during processing, and the curing process does not generate volatile substances, which will facilitate the processing of the composite material.

[0034] In a preferred embodiment, the substrate is a fibrous material, such as a glass fiber cloth. In a preferred embodiment, the metal foil laminate includes two layers of the metal foil, and the two layers of the metal foil are laminated with a plurality of layers of the substrate, such as two layers, three layers, four layers, five layers, six layers, seven layers, eight layers, nine layers, ten layers, or more than ten layers.

[0035] The toughened resin composition of the present application can further include a filler, a toughening resin, and / or a solvent.

[0036] In a preferred embodiment, the filler is an inorganic filler, such as selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, 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 aforementioned values.

[0037] In a preferred embodiment, the resin composition further includes a toughening resin, such as a core-shell polymer and / or a polybutadiene resin. The core-shell polymer is, for example, a core shell rubber (CSR). The polybutadiene resin is, for example, a polybutadiene homopolymer or a 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 between any two of the aforementioned values.

[0038] In a preferred embodiment, the solvent is selected from the group consisting of toluene, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

[0039] Further, the present application provides a method for manufacturing a metal foil laminate, comprising: (a) preparing a toughening-modified compound by adding a polybenzoxazine compound and a solvent, heating to dissolve, adding an anhydride-grafted olefin-based polymer, heating to dissolve, and then adding a diisocyanate compound, heating and gradually heating the synthesis solution to 120 to 150°C, and reacting for 0.5 to 2 hours, and stopping heating and cooling to room temperature; (b) preparing a resin composition by adding the toughening-modified compound solution to a thermosetting resin, and stirring to dissolve; (c) preparing a prepreg by 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 laminate by laminating multiple layers of the prepreg, and laminating a metal foil on each of the outermost layers on both sides, and then high-temperature hot-pressing and curing to obtain a metal foil laminate.

[0040] In a preferred embodiment, step (a) is adding a polybenzoxazine compound and a solvent to a reaction bottle, heating to about 50 to 80°C, and stirring to uniform; the reaction is heating to 50 to 80°C, such as but not limited to: 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or between any two of the foregoing values. In a preferred embodiment, step (a) is gradually (such as within 20 minutes) adding an anhydride-grafted olefin-based polymer to the solution under stirring, at which time the temperature is raised to 80 to 100°C, to completely dissolve to form a synthesis solution; the reaction is heating to 80 to 100°C, such as but not limited to: 80°C, 85°C, 90°C, 95°C, 100°C, or between any two of the foregoing values. In a preferred embodiment, step (a) is adding a diisocyanate compound, heating and gradually heating the synthesis solution to 120 to 150°C, and reacting for 0.5 to 2 hours; the reaction is heating to 120 to 150°C, such as but not limited to: 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, or between any two of the foregoing values; and 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 any two of the foregoing values.

[0041] In a preferred embodiment, step (b) further adds a member selected from the group consisting of an epoxy resin, a toughening resin, a solvent, a filler, and combinations thereof.

[0042] In a preferred embodiment, the hot-pressing conditions of step (d) are heating to 200 to 220°C at a heating rate of about 3.0°C / min, and hot-pressing at a pressure of about 8 kg / cm2initial pressure and about 15 kg / cm2full pressure for about 180 minutes at the temperature.

[0043] The present application not only has the effect of toughening and improving by the chemical modification of the isocyanate and the anhydride to form the polyimide bond, but also has the effect of toughening and improving by the modification of the olefin polymer and the polybenzoxazine compound, so that the present application has high toughness and excellent mechanical properties.

[0044] Examples

[0045] Hereinafter, the present application will be described in detail and in the form of examples, however, it should be understood that these examples are only used to help more easily understand the present application, and to clarify aspects of the present application and the benefits achieved thereby, and are not used to limit the scope of the present application.

[0046] Example 1

[0047] Six toughened modified compounds (Example Compounds A-F) were prepared according to the present application. Subsequently, metal foil laminates were prepared using Example Compounds A-F.

[0048] Example Compound A

[0049] Please refer to Figure 1 the exemplary reaction formula, Figure 1 wherein m, n, X, and Y are the same or different positive integers. 200 grams of bisphenol A type benzoxazine (BPA-BZ) 110 and 600 grams of toluene were added to a 3 liter four-neck separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and heated to about 60°C and stirred uniformly. While stirring, 20 grams of styrene-ethylene / butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA) 120 in toluene solution was gradually added over 20 minutes, at which time the temperature of the synthesis solution rose to 90°C, and was allowed to completely dissolve. Next, about 5 grams of isophorone diisocyanate (IPDI) 130 was added, and the synthesis solution was heated and gradually heated to about 130°C, and reacted for 1 hour. Subsequently, the heating was stopped and cooled to room temperature, and Example Compound A, a toughened modified compound 100, was obtained.

[0050] Example Compound B

[0051] 200 grams of ODA-BZ and 600 grams of toluene were added to a 3 liter four-neck separable reaction flask equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and heated to about 60°C and stirred uniformly. While stirring, 20 grams of SEBS-g-MA in toluene solution was gradually added over 20 minutes, at which time the temperature of the synthesis solution rose to 90°C, and was allowed to completely dissolve. Next, about 5 grams of IPDI was added, and the synthesis solution was heated and gradually heated to about 130°C, and reacted for 1 hour. Subsequently, the heating was stopped and cooled to room temperature, and Example Compound B was obtained.

[0052] Example Compound C

[0053] Into a 3 liter 4-neck separable flask equipped with heating device, thermometer, stirrer, cooling tube, 200 grams of BPA-BZ and 600 grams of toluene were added, heated to about 60°C, and stirred uniformly. Under stirring, 20 grams of PP-g-MA in toluene solution was gradually added within 20 minutes, at which time the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of IPDI was added, heated and gradually heated the synthetic solution to about 130°C, and reacted for 1 hour. Then stop heating and cool to room temperature, to obtain Example Compound C.

[0054] Example Compound D

[0055] Into a 3 liter 4-neck separable flask equipped with heating device, thermometer, stirrer, cooling tube, 200 grams of BPA-BZ and 600 grams of toluene were added, heated to about 60°C, and stirred uniformly. Under stirring, 20 grams of PE-g-MA in toluene solution was gradually added within 20 minutes, at which time the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of IPDI was added, heated and gradually heated the synthetic solution to about 130°C, and reacted for 1 hour. Then stop heating and cool to room temperature, to obtain Example Compound D.

[0056] Example Compound E

[0057] Into a 3 liter 4-neck separable flask equipped with heating device, thermometer, stirrer, cooling tube, 200 grams of BPA-BZ and 600 grams of toluene were added, heated to about 60°C, and stirred uniformly. Under stirring, 20 grams of SEBS-g-MA in toluene solution was gradually added within 20 minutes, at which time the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of HMDI was added, heated and gradually heated the synthetic solution to about 130°C, and reacted for 1 hour. Then stop heating and cool to room temperature, to obtain Example Compound E.

[0058] Example Compound F

[0059] A 200-gram sample of BPA-BZ was added to 600 grams of toluene in a 3-liter, four-necked separable flask equipped with a heating device, thermometer, stirrer, and cooling tube, and the mixture was heated to about 60°C and stirred until uniform. While stirring, 20 grams of SEBS-g-MA in toluene was gradually added over a period of 20 minutes, and the temperature of the resulting solution rose to 90°C. The solution was heated to about 130°C and stirred for 1 hour. The heating was then stopped, and the solution was allowed to cool to room temperature to obtain Example Compound F.

[0060] Materials

[0061] BPA-BZ and ODA-BZ were produced by Yuanhong Co.; SEBS-g-MA was produced by Li Chang Rong Co., Taiwan; PP-g-MA was produced by ExxonMobil, product type Exxelor TM PO1015; PE-g-MA was produced by ExxonMobil, product type Exxelor TM PE1040.

[0062] Table 1 below shows the ingredients and amounts used to prepare Example Compounds A-F.

[0063] Table 1

[0064]

[0065] Example 2

[0066] A non-limiting method for preparing metal foil laminates using the toughened modified compounds of the present application is provided below. Ten non-limiting example laminates (Example Laminates 1-10) having Example Compounds and six comparative example laminates (Comparative Laminates 1-6) were prepared according to methods similar to the method disclosed below. However, the specific methods used to prepare Example Laminates 1-10 and Comparative Laminates 1-6 will generally differ from the method disclosed below in one or more aspects.

[0067] Example Laminate 1

[0068] Preparation of Resin Composition: 30 grams of the above-described solution of Example Compound A was added to 5 grams of thermosetting resin (BMI), 25 grams of CNE epoxy resin, and 40 grams of solvent (butanone, MEK), and the mixture was uniformly mixed and the components were dissolved using a homogenizer. After the components were completely dissolved, 40 grams of silica was added, and the mixture was uniformly mixed and dispersed in the solvent using a homogenizer to obtain a varnish liquid resin composition.

[0069] Preparation of prepreg: The reinforcing material glass fiber cloth (substrate E-Glass) was impregnated or coated with the above-mentioned varnish liquid resin composition, and the impregnated or coated substrate was dried at a temperature of 80°C for 3 minutes and at a temperature of 180°C for 7 minutes, thereby obtaining a prepreg in a semi-cured state (B-stage).

[0070] Preparation of metal foil laminate: Four pieces of prepreg were laminated, and one 0.5 ounce metal foil (copper foil) was laminated on each of the outermost layers on both sides, and then placed in a hot press for high-temperature hot-pressing and curing. The hot-pressing conditions were as follows: the temperature was raised to 200°C to 220°C at a temperature raising rate of 3.0°C / min, and the temperature was maintained at this temperature for 180 minutes under a pressure of 15 kg / cm2(full pressure, 8 kg / cm2(initial pressure)), thereby obtaining a copper foil laminate.

[0071] Example Laminates 2-10

[0072] Example laminates 2-10 were prepared according to a method similar to that of Example Laminates 1, but differed in one or more aspects, as shown in Table 2.

[0073] Table 2 shows the preparation components and amounts of Example Laminates 1-10, and the results of subsequent physical property measurements, such as tensile strength, coefficient of thermal expansion in the Z-axis direction, and heat resistance.

[0074] Table 2

[0075]

[0076]

[0077] Note: EG in the table represents E-Glass. The unit of addition of each component in the table is gram.

[0078] Comparative Laminates 1

[0079] Preparation of resin composition: 30 grams of BPA-BZ without toughening modification, 5 grams of thermosetting resin (BMI), 25 grams of epoxy resin, 2 grams of toughening resin, and 40 grams of solvent (butanone, MEK) were uniformly mixed and dissolved using a homogenizer. After complete dissolution, 40 grams of silica was continuously uniformly mixed and dispersed in the solvent using a homogenizer, thereby preparing a varnish liquid resin composition.

[0080] Preparation of prepreg: The reinforcing material glass fiber cloth (substrate E-Glass) was impregnated or coated with the above-mentioned varnish liquid resin composition, and the impregnated or coated substrate was dried at a temperature of 80°C for 3 minutes and at a temperature of 180°C for 7 minutes, thereby obtaining a prepreg in a semi-cured state (B-stage).

[0081] Preparation of Metal Foil Laminate: Four pieces of pre-impregnated sheets were laminated and one 0.5 ounce copper foil was laminated on each of the outermost layers on both sides, followed by high temperature hot-pressing curing in a hot press. The hot-pressing conditions were: temperature ramping up to 200-220°C at a rate of 3.0°C / min, and hot-pressing at a full pressure of 15 kg / cm2(initial pressure 8 kg / cm2) for 180 minutes at the temperature. A copper foil laminate was prepared.

[0082] Comparative Example Laminate 2-6

[0083] Comparative Example Laminate 2-6 was prepared according to a method similar to that of Comparative Example Laminate 1, however, Comparative Example Laminate 2-6 would differ in one or more aspects, the specific differences being revealed in Table 3 below.

[0084] Table 3 is a list of the ingredients and amounts used in the preparation of Comparative Example Laminates 1-6, as well as the results of the physical property measurements of strength, coefficient of thermal expansion in the Z-axis direction, and heat resistance, etc.

[0085] Table 3

[0086]

[0087]

[0088] Note: CSR in the table is a core-shell rubber. Ricon 100 is a butadiene-styrene copolymer. EG represents E-Glass. The unit of addition of each ingredient in the table is gram.

[0089] Materials

[0090] BPA-BZ and ODA-BZ were produced by Yuanhong Company; filler Si02was 10um cut produced by Silbione Company; thermosetting resin BMI (KI-70) was produced by Dawa Chemical Company; CNE epoxy resin was produced by Changchun Artificial Resin Company; reinforcing material was E-Glass cloth 2116 produced by Taibo Company; toughening resin was CSR produced by Kaneka Company, Ricon 100 produced by Polyscope Company; copper foil was H10.5OZ produced by Nanya Company.

[0091] Property Test

[0092] CTE test: The coefficient of thermal expansion (CTE) of the sample to be tested was measured in the Z-axis direction according to the IPC-TM-650 2.4.24.5 specification using a thermal mechanical analyzer (TMA) to measure the change in the coefficient of thermal expansion (total z-CTE) of the sample to be tested at a temperature below the glass transition temperature (Tg). The z-CTE was measured in the temperature range of 50°C to 260°C and was expressed in %.

[0093] Tack test: Tack is the adhesion of the metal foil to the laminated prepreg. In this test, the copper foil was pulled vertically from the surface of the board at a width of 1 / 8 inch, and the strength of the adhesion was expressed in terms of the amount of force required. The unit of the tear strength was pound force / inch (lbf / in).

[0094] Heat resistance test: The dried metal foil laminate was immersed in a solder bath at 288°C and 300°C for 100 seconds, and the process was repeated three times. Good heat resistance was indicated by a mark of "O", and poor heat resistance was indicated by a mark of "X" when there were bubbles on the surface.

[0095] From the above results, it can be seen that the comparative example laminates 1 to 6 containing the polybenzoxazine compound without toughening modification have poor mechanical properties after crosslinking, and even if a large amount of toughening agent or rubber is added, the properties cannot be improved. The example laminates 1 to 10 containing the toughened modified compound show good mechanical properties and heat resistance. Therefore, the present application is more suitable for application in the fields of composite materials and electronic circuit materials.

[0096] In summary, the present application provides a metal foil laminate and a printed circuit board and a method for manufacturing the same, in which an olefin-based polymer is used to toughen and modify a polybenzoxazine compound, and a diisocyanate compound is used to form a chemical bond with the compound, so that the compound of the present application has good mechanical properties and heat resistance. Therefore, compared with the prior art polybenzoxazine compound which has a brittle mechanical property after thermal ring-opening polymerization, the present application is more suitable for application in the field of electronic machines.

[0097] As used herein and otherwise, the terms "substantially" and "approximately" are used to describe and account for small variations. When used in connection with a description of an event or circumstance, the terms can encompass the event or circumstance occurring precisely as well as the event or circumstance occurring to a close approximation. For example, when used in connection with a numerical value, the terms can encompass a range of variation less than or equal to ±10% of the numerical value, 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%.

[0098] The foregoing summary of the components of the several embodiments is such that those having ordinary skill in the art can better understand the concepts of the embodiments of the present application. Those having ordinary skill in the art should understand that other processes and structures can be designed or modified using the embodiments of the present application as a basis, to achieve the same objectives and / or to attain the same benefits, as the embodiments described herein. Those having ordinary skill in the art should also understand that such equivalent structures do not depart from the spirit and scope of the present application, and that various changes, substitutions, and other alternatives can be made to the embodiments described herein without departing from the spirit and scope of the present application. Therefore, the scope of the present application is defined only by the following claims.

Claims

1. A metal foil laminate, characterized by, A metal foil laminate comprising: a substrate having an outer surface coated with a resin composition; and a metal foil; wherein the resin composition comprises 8 to 15 parts by weight of a thermosetting polymer and 30 to 50 parts by weight of a toughening modifier compound, the toughening modifier compound comprising a polybenzoxazine compound, an anhydride-grafted olefin-based polymeric high molecule, and a diisocyanate compound; wherein the diisocyanate is bonded to the polybenzoxazine compound and the anhydride-grafted olefin-based polymeric high molecule, respectively.

2. The metal foil laminate of claim 1, wherein the anhydride-grafted olefin-based polymeric high molecule comprises a styrene-ethylene / butylene-styrene copolymer grafted maleic anhydride, a polypropylene grafted maleic anhydride, or a polyethylene grafted maleic anhydride.

3. The metal foil laminate of claim 1, wherein the diisocyanate compound 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, 2,4,4- trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene 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, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.

4. The metal foil laminate of claim 1, wherein the substrate is a fiber material.

5. The metal foil laminate of claim 1, wherein the metal foil laminate comprises two layers of the metal foil, the two layers of the metal foil being interlayered with a plurality of the substrate.

6. A printed circuit board, characterized by A metal foil laminate comprising any one of claims 1 to 5.

7. A method of manufacturing the metal foil laminate according to any one of claims 1 to 5, characterized by, A method for manufacturing a metal foil laminate, the method comprising: (a) preparing a toughening modifier compound by adding a polybenzoxazine compound to a solvent, heating and dissolving the polybenzoxazine compound, adding an anhydride-grafted olefin-based polymeric high molecule, heating and dissolving the anhydride-grafted olefin-based polymeric high molecule, adding a diisocyanate compound, heating the resultant solution to a temperature of 120 to 150°C, and reacting the resultant solution for a period of 0.5 to 2 hours; (b) preparing a resin composition by adding the toughening modifier compound solution to a bismaleimide resin, and stirring and dissolving the bismaleimide resin; (c) preparing a prepreg by impregnating or coating a substrate with the resin composition, and drying the substrate to obtain a semi-cured prepreg; and (d) manufacturing the metal foil laminate by interlayering the prepreg with a metal foil. (d) preparing a metal foil laminate: laminating the plurality of layers of the prepreg, and laminating a metal foil to each of the outermost layers on both sides of the prepreg, and then heat-pressing and curing at a high temperature to obtain a metal foil laminate.

8. The manufacturing method of claim 7, wherein step (b) further comprises adding a member selected from the group consisting of a CNE epoxy resin, a toughening resin, a solvent, a filler, and combinations thereof.

9. The manufacturing method of claim 7, wherein the heat-pressing conditions of step (d) are to heat up to 200°C to 220°C at a temperature increasing rate of 3.0°C / min, and heat-press at a pressure of 8 kg / cm2 as an initial pressure and 15 kg / cm2 as a full pressure for 180 min at the temperature.

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