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

Abstract

The present invention provides a metal foil laminate, a printed circuit board, and a method for manufacturing the same. The metal foil laminate comprises: a substrate coated with a toughened resin composition; and a metal foil; the resin composition includes a toughened and modified compound comprising a styrene maleic anhydride compound, an anhydride-grafted olefin polymer, and a diisocyanate compound; the diisocyanate in the toughened and modified compound forms polyimide bonds with the styrene maleic anhydride compound and the anhydride-grafted olefin polymer, respectively. The present invention exhibits high toughness and excellent mechanical properties, and therefore has broad application in electronics, aerospace, and other fields.

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 with olefin polymer toughening and modified styrene maleic anhydride, a printed circuit board and a manufacturing method thereof. Background Art

[0002] Styrene maleic anhydride (SMA) is a copolymer formed by the polymerization of styrene and maleic anhydride. SMA polymers are characterized by excellent electrical properties, high heat resistance, and high dimensional stability, making them widely used in industry and commerce.

[0003] However, styrene maleic anhydride polymers also have some drawbacks. For example, after curing and crosslinking, the polymer becomes hard and brittle, resulting in poor mechanical properties. When used in copper-clad laminates (CCLs), this hard and brittle nature of crosslinking can cause cracks and white streaks in the CCLs during drilling of printed circuit boards (PCBs), leading to short-circuit failure. To improve this processing problem, rubber or toughening agents are generally added to increase toughness and improve cracks and white streaks. If the improvement is not effective, large amounts of rubber or toughening agents may be required to achieve the desired effect. However, adding large amounts of rubber or toughening agents may affect the physical and dielectric properties of the polymer. Summary of the Invention

[0004] In view of this, one of the problems to be solved by the present invention is how to improve the properties of styrene maleic anhydride polymer so that it has high toughness and excellent mechanical properties when applied to metal foil laminates and printed circuit boards.

[0005] The main object of the present invention is to provide a metal foil laminate comprising: a substrate coated with a toughened resin composition; and a metal foil; wherein the resin composition includes a toughened modified compound comprising a styrene maleic anhydride compound, an anhydride-grafted olefin polymer, and a diisocyanate compound; wherein the diisocyanate in the toughened modified compound forms polyimide bonds with the styrene maleic anhydride compound and the anhydride-grafted olefin polymer, respectively.

[0006] In a preferred embodiment, the resin composition further includes a thermosetting polymer.

[0007] In a preferred embodiment, the anhydride-grafted olefin polymer comprises: styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride, polypropylene grafted with maleic anhydride, or polyethylene grafted with maleic anhydride.

[0008] In a preferred embodiment, the diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl diisocyanate, 1,3-butyl 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 diphenyl The group consisting of: methylmethane 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'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.

[0009] In a preferred embodiment, the substrate is a fiber material.

[0010] In a preferred embodiment, the metal foil laminate includes two layers of the metal foil, and multiple layers of the substrate are laminated between the two layers of the metal foil.

[0011] Another object of the present invention is to provide a printed circuit board comprising the metal foil laminate as described above.

[0012] Furthermore, another object of the present invention is to provide a method for manufacturing the metal foil laminate as described above, which comprises: (a) preparing a toughened and modified compound: adding a styrene maleic anhydride compound and a solvent, heating to dissolve them, adding an anhydride-grafted olefin polymer, heating to dissolve them, and then adding a diisocyanate compound, heating and gradually raising the temperature of the synthetic solution to 120 to 150° C., and reacting for 0.5 to 2 hours, stopping heating and cooling to room temperature; (b) preparing a resin composition: adding a thermosetting resin to the toughened and modified compound solution, stirring and dissolving it; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, drying the substrate to obtain a semi-cured prepreg; and (d) preparing a metal foil laminate: laminating multiple layers of the prepreg, and laminating a metal foil on each of the outermost layers on both sides, and then hot-pressing and curing at high temperature to obtain a metal foil laminate.

[0013] In a preferred embodiment, step (b) further includes adding a material selected from the group consisting of a polybenzoxazine compound, an epoxy resin, a toughening resin, a solvent, a filler, and combinations thereof.

[0014] In a preferred embodiment, the hot pressing conditions of step (d) are to increase the temperature to 200°C to 220°C at a heating rate of 3.0°C / min, and to hot press at this temperature for 180 minutes with an initial pressure of 8 kg / cm2 and a total pressure of 15 kg / cm2.

[0015] Therefore, the metal foil laminates and printed circuit boards provided by the present invention include a toughened and modified compound. This compound uses an olefin polymer to toughen and modify a styrene maleic anhydride compound, and a diisocyanate compound to form a polyimide bond. This effectively improves the mechanical and electrical properties of the substrate, resulting in excellent mechanical and electrical properties and low water absorption. The high toughness and excellent mechanical properties of the present invention make it more suitable for applications in the electrical and electronic fields than existing technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The following drawings and description set forth details of one or more embodiments of the subject matter described in this specification. Other features, aspects, and advantages of the subject matter of this specification will become apparent from the description, drawings, and claims, including:

[0017] Figure 1 It is a reaction diagram of a preferred embodiment of the present invention.

[0018] Wherein, the reference numerals:

[0019] 100: Toughened modified compound

[0020] 110: Styrene maleic anhydride compound

[0021] 120: Styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride

[0022] 130:Isophorone diisocyanate DETAILED DESCRIPTION

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention pertains. As used in this application, the following terms have the following meanings.

[0024] As used herein, terms such as "first," "second," "third," "fourth," and "fifth" describe various elements, components, regions, layers, and / or sections, and these elements, components, regions, layers, and / or sections should not be 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, the use of terms such as "first," "second," "third," "fourth," and "fifth" herein does not imply a sequence or order.

[0025] Unless otherwise specified, "or" as used herein means "and / or". "Include" or "comprising" as used herein does not exclude the existence of or addition to the described components, steps, operations and / or elements; similarly, "include", "include", "contain", "includes", and "have" as used herein are interchangeable without limitation. "A" means that the grammatical object of the thing is one or more (i.e., at least one). The singular formats "a", "an", "an", and "the" used herein and in the claims include plural references.

[0026] The present invention relates to a metal foil laminate and a printed circuit board containing the same. The metal foil laminate comprises: a substrate coated with a toughened resin composition; and a metal foil; wherein the resin composition includes a toughened modified compound comprising a styrene maleic anhydride compound, an anhydride-grafted olefin polymer, and a diisocyanate compound; wherein the diisocyanate in the toughened modified compound forms polyimide bonds with the styrene maleic anhydride compound and the anhydride-grafted olefin polymer, respectively.

[0027] The "styrene maleic anhydride compound" described herein includes a copolymer (styrene maleic anhydride, SMA) formed by polymerization of styrene monomers and maleic anhydride monomers. In a preferred embodiment, the ratio of styrene to maleic anhydride in the styrene maleic anhydride compound is 3:1 to 6:1, such as, but not limited to, 3:1 to 6:1, 3:1 to 5:1, 3:1 to 4:1, 4:1 to 6:1, 5:1 to 6:1, or any ratio between any two of the foregoing. In a more preferred embodiment, the ratio of styrene to maleic anhydride in the styrene maleic anhydride compound is 3:1, 4:1, 5:1, or 6:1.

[0028] The anhydride-grafted olefin polymers described herein possess excellent electrical properties and good impact resistance. Preferably, the olefin polymers of the present invention are grafted with maleic anhydride, which improves compatibility with the substrate resin and achieves a modified effect. In a preferred embodiment, the anhydride-grafted olefin polymers include, but are not limited to, styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride (SEBS-g-MA), polypropylene grafted with maleic anhydride (PP (Poly Propylene)-g-MA), or polyethylene grafted with maleic anhydride (PE (Poly Ethylene)-g-MA).

[0029] In the diisocyanate compounds described herein, the diisocyanate groups form polyimide bonds with the anhydride of the styrene maleic anhydride compound and the anhydride of the olefin polymer grafted with the anhydride, achieving chemical modification. Cyanate compounds can increase the reactive functional groups in the resin structure, thereby increasing the crosslink density and heat resistance of the epoxy cured product. For example, the cyanate compound can be a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl diisocyanate, 1,3-butyl diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene diisocyanate, 1,2-butylene ... 1,2-butylene diisocyanate, 1,2-butylene diisocyanate, 1,2-butylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-methylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-methylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, Cyclohexyl 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 diisocyanate compound includes isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (methylene dicyclohexyl diisocyanate or hydrogenated MDI, HMDI), or hexamethylene diisocyanate (hexamethylene diisocyanate, HDI).

[0030] In a preferred embodiment, the toughened modified compound of the present invention comprises a styrene maleic anhydride compound selected from the group consisting of styrene-ethylene / butylene-styrene copolymers modified with isophorone diisocyanate and grafted with maleic anhydride toughened styrene maleic anhydride compound (IPDI / SEBS-g-MA / SMA), styrene-ethylene / butylene-styrene copolymers modified with methylene dicyclohexyl diisocyanate and grafted with maleic anhydride toughened styrene maleic anhydride compound (HMDI / SEBS-g-MA / SMA), styrene-ethylene / butylene-styrene copolymers modified with hexamethylene diisocyanate and grafted with maleic anhydride toughened styrene maleic anhydride compound (HDI / SEBS-g-MA / SMA), isophorone diisocyanate modified polypropylene grafted with maleic anhydride toughened styrene maleic anhydride compound (IPDI / PP-g-M The present invention relates to a group consisting of a maleic anhydride toughened styrene maleic anhydride compound toughened by polypropylene grafted with maleic anhydride modified with methylene dicyclohexyl diisocyanate (HMDI / PP-g-MA / SMA), a maleic anhydride toughened styrene maleic anhydride compound toughened by polypropylene grafted with maleic anhydride modified with hexamethylene diisocyanate (HDI / PP-g-MA / SMA), a maleic anhydride toughened styrene maleic anhydride compound toughened by polyethylene grafted with maleic anhydride modified with isophorone diisocyanate (IPDI / PE-g-MA / SMA), a maleic anhydride toughened styrene maleic anhydride compound toughened by polyethylene grafted with maleic anhydride modified with methylene dicyclohexyl diisocyanate (HMDI / PE-g-MA / SMA), and a maleic anhydride toughened styrene maleic anhydride compound toughened by polyethylene grafted with maleic anhydride modified with hexamethylene diisocyanate (HDI / PE-g-MA / SMA).

[0031] In a preferred embodiment, the resin composition includes (A) a toughened modified compound; (B) a thermosetting polymer; and / or (C) a toughening resin. In a preferred embodiment, in the toughened resin composition of the present invention, the composition ratio of (A) toughened modified compound: (B) thermosetting polymer: (C) toughening resin is 15 to 30: 20 to 35: 0.1 to 5. For example: (A) the toughened modified compound accounts for 15% to 30% of the overall resin composition, such as: 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or between any two of the foregoing values; (B) the thermosetting polymer accounts for 20% to 35% of the overall resin composition, such as: 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or between any two of the foregoing values; %, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% or between any two of the foregoing values; (C) the toughening resin accounts for 0.1% to 5% of the entire resin composition, such as 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or between any two of the foregoing values.

[0032] In a preferred embodiment, the toughening resin of the present invention is 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.

[0033] The thermosetting polymer of the present invention may also be bismaleimide tris(III) In a preferred embodiment, the thermosetting polymer of the present invention is a bismaleimide (BMI) resin, which has a carbonyl group and a nitrogen-containing epoxy resin. During processing and molding, the unsaturated end groups are used for curing, and the curing process does not produce volatile substances, which is conducive to the processing and molding of composite materials.

[0034] In a preferred embodiment, the substrate is a fiber material, such as fiberglass cloth. In a preferred embodiment, the metal foil laminate comprises two layers of metal foil, with multiple layers of substrate laminated between the two layers of metal foil, such as two, three, four, five, six, seven, eight, nine, ten, or more layers.

[0035] The toughened resin composition of the present invention may further include: a filler, a polybenzoxazine compound and / or a solvent.

[0036] In a preferred embodiment, the filler is an inorganic filler, for example, selected from the group consisting of silica, alumina, 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.

[0037] In a preferred embodiment, the polybenzoxazine compound is a bisphenol polybenzoxazine or a bisamine polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is at least one selected from the group consisting of bisphenol A benzoxazine (BPA-BZ), bisphenol F benzoxazine (BPF-BZ), bisphenol S benzoxazine (BPS-BZ), diaminodiphenylmethane benzoxazine (DDM-BZ), diaminodiphenyl ether benzoxazine (ODA-BZ), and polybenzoxazine with polyimide.

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

[0039] Furthermore, the method for manufacturing a metal foil laminate of the present invention comprises: (a) preparing a toughened and modified compound: adding a styrene maleic anhydride compound and a solvent, heating to dissolve them, adding an anhydride-grafted olefin polymer, heating to dissolve them, and then adding a diisocyanate compound, heating and gradually raising the temperature of the synthetic solution to 120 to 150°C, and reacting for 0.5 to 2 hours, stopping heating and cooling to room temperature; (b) preparing a resin composition: adding a thermosetting resin to the toughened and modified compound solution, stirring and dissolving it; (c) preparing a prepreg: impregnating or coating a substrate with the resin composition, drying the substrate to obtain a semi-cured prepreg; and (d) preparing a metal foil laminate: laminating multiple layers of the prepreg, and laminating a metal foil on the outermost layers on each side thereof, and then hot-pressing and curing at high temperature to obtain a metal foil laminate.

[0040] In a preferred embodiment, step (a) comprises adding a styrene maleic anhydride compound and a solvent to a reaction flask, heating the temperature to approximately 50-80°C, and stirring uniformly. The reaction is performed by heating the temperature to 50-80°C, for example, but not limited to, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or any two values ​​in between. In a preferred embodiment, step (a) comprises gradually (e.g., over 20 minutes) adding an anhydride-grafted olefin polymer to the solution while stirring, then heating the temperature to 80-100°C to allow complete dissolution, thereby forming a synthetic solution. The reaction is performed by heating the temperature to 80-100°C, for example, but not limited to, 80°C, 85°C, 90°C, 95°C, 100°C, or any two values ​​in between. In a preferred embodiment, step (a) comprises adding a diisocyanate compound, heating and gradually raising the temperature of the resulting solution to 120 to 150° C., and reacting for 0.5 to 2 hours. The reaction temperature is raised to 120 to 150° C., for example, but not limited to, 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., or any two values ​​therebetween. The reaction time is 0.5 to 2 hours, for example, but not limited to, 0.5 hour, 1 hour, 1.5 hours, 2 hours, or a range between the two time points.

[0041] In a preferred embodiment, step (b) further comprises adding a compound selected from the group consisting of a polybenzoxazine compound, 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 to increase the temperature to 200°C to 220°C at a heating rate of about 3.0°C / min, and to hot press at this temperature for about 180 minutes with an initial pressure of about 8 kg / cm2 and a total pressure of about 15 kg / cm2.

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

[0044] Example

[0045] Hereinafter, the present invention will be further described with detailed descriptions and embodiments. However, it should be understood that these embodiments are only used to help make the present invention more easily understood and to illustrate various aspects of the present invention and the benefits achieved thereby, and are not intended to limit the scope of the present invention.

[0046] Example 1

[0047] Seven toughened and modified compounds (Example Compounds AG) were prepared according to the present invention. Metal foil laminates were then prepared using Example Compounds AG.

[0048] Example Compound A

[0049] Please also refer to Figure 1 An exemplary reaction formula, Figure 1 Where m, n, X, and Y are identical or different positive integers. 200 grams of styrene-maleic anhydride compound 110 (styrene / maleic anhydride ratio of 3 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The temperature was raised to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride 120 was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C and completely dissolved. Next, approximately 5 grams of isophorone diisocyanate 130 was added, and the resulting solution was heated and gradually heated to approximately 130°C and allowed to react for 1 hour. Heating was then stopped and the temperature was allowed to cool to room temperature to obtain Example Compound A, i.e., the toughened and modified Compound 100.

[0050] Example Compound B

[0051] 200 grams of styrene-maleic anhydride (styrene / maleic anhydride ratio of 3 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of polypropylene-grafted maleic anhydride was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C, allowing it to completely dissolve. Next, approximately 5 grams of isophorone diisocyanate was added, and the resulting solution was heated and gradually heated to approximately 130°C. The reaction was allowed to proceed for 1 hour. Heating was then stopped and the solution was cooled to room temperature to obtain Example Compound B.

[0052] Example Compound C

[0053] 200 grams of styrene-maleic anhydride (styrene / maleic anhydride ratio of 3 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of polyethylene-grafted maleic anhydride was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C, allowing it to completely dissolve. Next, approximately 5 grams of isophorone diisocyanate was added, and the resulting solution was heated and gradually heated to approximately 130°C. The reaction was allowed to proceed for 1 hour. Heating was then stopped and the solution was cooled to room temperature to obtain Example Compound C.

[0054] Example Compound D

[0055] 200 grams of styrene-maleic anhydride (styrene / maleic anhydride ratio of 4 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C, allowing complete dissolution. Next, approximately 5 grams of isophorone diisocyanate was added, and the resulting solution was heated and gradually heated to approximately 130°C. The reaction was allowed to proceed for 1 hour. Heating was then stopped and the solution was cooled to room temperature to obtain Example Compound D.

[0056] Example Compound E

[0057] 200 grams of styrene-maleic anhydride (styrene / maleic anhydride ratio of 6 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C, allowing complete dissolution. Next, approximately 5 grams of isophorone diisocyanate was added, and the resulting solution was heated and gradually heated to approximately 130°C. The reaction was allowed to proceed for 1 hour. Heating was then stopped and the solution was cooled to room temperature to obtain Example Compound E.

[0058] Example Compound F

[0059] 200 grams of styrene-maleic anhydride (styrene / maleic anhydride ratio of 3 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C, allowing complete dissolution. Next, approximately 5 grams of methylene dicyclohexyl diisocyanate was added, and the resulting solution was heated and gradually heated to approximately 130°C. The reaction was allowed to proceed for 1 hour. Heating was then stopped and the solution was cooled to room temperature to obtain Example Compound F.

[0060] Example Compound G

[0061] 200 grams of styrene-maleic anhydride (styrene / maleic anhydride ratio of 3 / 1) and 600 grams of toluene were added to a 3-liter, four-necked, separable reaction flask equipped with a heater, thermometer, stirrer, and cooling tube. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride was gradually added to the toluene solution over 20 minutes. The temperature of the resulting solution was raised to 90°C, allowing complete dissolution. Next, approximately 5 grams of hexamethylene diisocyanate was added, and the resulting solution was heated and gradually heated to approximately 130°C. The reaction was allowed to proceed for 1 hour. Heating was then stopped and the temperature was allowed to cool to room temperature, yielding Example Compound G.

[0062] Material

[0063] Styrene-maleic anhydride compounds with styrene / maleic anhydride ratios of 3 / 1, 4 / 1, and 6 / 1 are produced by Polyscope; styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride is produced by Lee Chang-jung Co., Ltd. in Taiwan, China; polypropylene grafted with maleic anhydride is produced by ExxonMobil Chemical Company under the product model Exxelor TM PO1015; Polyethylene grafted maleic anhydride is produced by ExxonMobil Chemical Company, product model Exxelor TM PE1040.

[0064] Table 1 below shows the preparation ingredients and contents of Example Compounds AG.

[0065] Table 1

[0066]

[0067] Note: In the table, SMA (3 / 1) indicates a styrene-maleic anhydride compound having a styrene-maleic anhydride ratio of 3 / 1; SMA (4 / 1) indicates a styrene-maleic anhydride compound having a styrene-maleic anhydride ratio of 4 / 1; and SMA (6 / 1) indicates a styrene-maleic anhydride compound having a styrene-maleic anhydride ratio of 6 / 1.

[0068] Example 2

[0069] The following provides a non-limiting method for preparing metal foil laminates from the toughened and modified compounds of the present invention. Ten non-limiting example laminates (Example Laminates 1-10) and six comparative example laminates (Comparative Example Laminates 1-6) were prepared using methods similar to those disclosed below. However, the specific methods for preparing Example Laminates 1-10 and Comparative Example Laminates 1-6 will generally differ from the methods disclosed below in one or more aspects.

[0070] Example laminate 1

[0071] To prepare a resin composition, 30 grams of the solution of Compound A from the above example was added to 10 grams of bisphenol A-type polybenzoxazine (BPA-BZ), 5 grams of thermosetting resin (BMI), 25 grams of brominated epoxy resin, 1 gram of toughening resin (Ricon 100), and 40 grams of solvent (methyl ethyl ketone, MEK). The mixture was uniformly mixed and dissolved using a homogenizer. After complete dissolution, 30 grams of silica was added and continued to be uniformly mixed and dispersed in the solvent using a homogenizer to form a varnish-like liquid resin composition.

[0072] Preparation of prepreg: The reinforcing fiberglass cloth (substrate E-Glass) is impregnated or coated with the above-mentioned varnish liquid resin composition. The impregnated or coated substrate is dried at 80°C for 3 minutes and 180°C for 7 minutes to obtain a semi-cured (B-stage) prepreg.

[0073] Preparation of Metal Foil Laminates: Four prepreg sheets were laminated together, and a 0.5-ounce sheet of metal foil (copper foil) was laminated on each outermost layer. The sheets were then placed in a hot press for high-temperature curing. The hot press conditions were: heating at a rate of 3.0°C / minute to a temperature between 200°C and 220°C. At this temperature, the sheets were hot pressed at a full pressure of 15 kg / cm² (initial pressure of 8 kg / cm²) for 180 minutes to produce the copper foil laminates.

[0074] Example laminate 2-10

[0075] Example laminates 2-10 were prepared using a method similar to that of Example laminate 1. However, Example laminates 2-10 differed in one or more aspects, as shown in Table 2 below.

[0076] Table 2 shows the preparation components and contents of the laminates 1-10 of the examples, as well as the physical property measurement results such as strength, thermal expansion coefficient in the Z-axis direction, heat resistance, dielectric properties and drilling white line test.

[0077] Table 2

[0078]

[0079]

[0080]

[0081] Note: In the table, SMA (3 / 1) represents a styrene-maleic anhydride compound with a styrene / maleic anhydride ratio of 3 / 1; SMA (4 / 1) represents a styrene-maleic anhydride compound with a styrene / maleic anhydride ratio of 4 / 1; and SMA (6 / 1) represents a styrene-maleic anhydride compound with a styrene / maleic anhydride ratio of 6 / 1. CSR stands for core-shell rubber. Ricon 100 stands for butadiene-styrene copolymer. EG stands for E-Glass. The unit of addition for each ingredient in the table is grams.

[0082] Comparative Example Laminated Board 1

[0083] To prepare the resin composition, 7.5 grams of untoughened styrene maleic anhydride (styrene / maleic anhydride ratio of 3:1) was dissolved in 22.5 grams of toluene. Then, 10 grams of BPA-BZ, 5 grams of thermosetting resin (BMI), 25 grams of brominated epoxy resin, 2.5 grams of toughening resin (Ricon 100), and 40 grams of solvent (methyl ethyl ketone, MEK) were added. The mixture was uniformly mixed and dissolved using a homogenizer. After complete dissolution, 30 grams of silica was added and continuously mixed and dispersed in the solvent using a homogenizer to form a varnish-like liquid resin composition.

[0084] Preparation of prepreg: The reinforcing fiberglass cloth (substrate E-Glass) is impregnated or coated with the above-mentioned varnish liquid resin composition. The impregnated or coated substrate is dried at 80°C for 3 minutes and 180°C for 7 minutes to obtain a semi-cured (B-stage) prepreg.

[0085] To prepare a metal foil laminate, four prepreg sheets were laminated together, and a 0.5-ounce copper foil was laminated on each outermost layer. The laminate was then placed in a hot press for high-temperature curing. The hot press conditions were: heating at a rate of 3.0°C / minute to a temperature between 200°C and 220°C. At this temperature, the laminate was hot-pressed at a full pressure of 15 kg / cm² (initial pressure of 8 kg / cm²) for 180 minutes. This produced a copper foil laminate.

[0086] Comparative Example Laminated Boards 2-6

[0087] Comparative Example laminates 2-6 were prepared using a method similar to that of Comparative Example laminate 1. However, Comparative Example laminates 2-6 differ in one or more aspects, as shown in Table 3 below.

[0088] Table 3 shows the preparation components and contents of comparative example laminates 1-6, as well as the physical property measurement results such as bonding strength, thermal expansion coefficient in the Z-axis direction, heat resistance, dielectric properties, and drilling white line test.

[0089] Table 3

[0090]

[0091]

[0092] Note: In the table, SMA (3 / 1) represents a styrene-maleic anhydride compound with a styrene / maleic anhydride ratio of 3 / 1; SMA (4 / 1) represents a styrene-maleic anhydride compound with a styrene / maleic anhydride ratio of 4 / 1; and SMA (6 / 1) represents a styrene-maleic anhydride compound with a styrene / maleic anhydride ratio of 6 / 1. CSR stands for core-shell rubber. Ricon 100 stands for butadiene-styrene copolymer. EG stands for E-Glass. The unit of addition for each ingredient in the table is grams.

[0093] Material

[0094] BPA-BZ is produced by Yuanhong Company; the filler SiO2 is a 10um cut product produced by Sibico; the thermosetting resin BMI is produced by Yamato Chemical Company; the brominated epoxy resin is produced by Changchun Artificial Resin Company; the reinforcement material is E-Glass cloth 2116 produced by Taiwan Glass Corporation; the toughening resin is CSR produced by Kaneka Corporation and Ricon 100 produced by Polyscope; and the copper foil is H1 0.5OZ produced by Nan Ya Company.

[0095] Characteristic testing

[0096] Drilling white lines: Use a mechanical drill bit to drill 100 mechanical holes on the sample with an inner diameter of 0.3mm. Observe the number of drilling white lines and hole cracks. White lines and hole cracks will affect the resin filling effect and thus cause the board to explode.

[0097] CTE testing: According to IPC-TM-650 2.4.24.5, a thermal mechanical analyzer (TMA) is used to measure the coefficient of thermal expansion (CTE) of the sample in the Z-axis direction (total z-CTE) at temperatures below the glass transition temperature (Tg). Z-CTE is measured over a temperature range of 50°C to 260°C and is expressed in %.

[0098] Adhesion Strength Test: Adhesion strength refers to the adhesion of the metal foil to the laminated prepreg. In this test, the strength of adhesion is expressed by the force required to tear a 1 / 8-inch wide copper foil vertically from the board surface. The unit of tear strength is lbf / in.

[0099] Heat resistance test: Immerse the dried metal foil laminate in a 288°C solder bath for 100 seconds and repeat this process three times. Excellent heat resistance is recorded as "○". If there are bubbling or protrusions on the surface, poor heat resistance is recorded as "×".

[0100] The above results demonstrate that compared to Comparative Examples 1-6, which comprise untoughened styrene maleic anhydride and exhibit poor mechanical properties due to their brittleness after crosslinking, and which cannot be improved even with the addition of large amounts of toughening agents or rubber, Example 1-10, comprising toughened and modified compounds, exhibits excellent mechanical and electrical properties, low water absorption, and can reduce the amount of toughening agents or rubber added. Therefore, the present invention is more suitable for a wide range of applications, including composite materials and electronic circuit materials.

[0101] In summary, the present invention provides a metal foil laminate and printed circuit board, as well as methods for manufacturing the same. These methods utilize an olefin polymer to toughen and modify a styrene maleic anhydride compound, and employ a diisocyanate compound to form a polyimide bond therewith. These materials exhibit excellent mechanical and electrical properties, along with low water absorption. Consequently, compared to prior art styrene maleic anhydride polymers that are hard and brittle after cross-linking and exhibit poor mechanical properties, the present invention is more suitable for applications in the electrical and electronic fields.

[0102] As used herein and not otherwise defined, the terms "substantially" and "approximately" are used to describe and describe small variations. When applied to an event or circumstance, the terms may include the exact moment the event or circumstance occurred, as well as the point at which the event or circumstance occurred to a close approximation. For example, when applied to a numerical value, the terms may include 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%.

[0103] The above summarizes the components of several embodiments so that those with ordinary knowledge in the technical field to which the present invention belongs can better understand the concepts of the embodiments of the present invention. Those with ordinary knowledge in the technical field to which the present invention belongs should understand that the embodiments of the present invention can be used as a basis to design or modify other processes and structures to achieve the same purpose and / or achieve the same benefits as the embodiments introduced herein. Those with ordinary knowledge in the technical field to which the present invention belongs should also understand that these equivalent structures do not depart from the spirit and scope of the present invention, and various changes, substitutions and other options can be made here without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be defined as the scope of the patent application attached hereto.

Claims

1. A metal foil laminate, characterized in that: Include: a substrate, the exterior of which is coated with a toughened resin composition, wherein the substrate is a fiber material; and a metal foil; The resin composition includes a toughened modified compound, a thermosetting polymer and / or a toughening resin, and the composition ratio of the toughened modified compound, the thermosetting polymer and the toughening resin is 15 to 30:20 to 35:0.1 to 5. The toughened modified compound includes a styrene maleic anhydride compound, an anhydride-grafted olefin polymer and a diisocyanate compound; wherein the diisocyanate in the toughened modified compound forms a polyimide bond with the styrene maleic anhydride compound and the anhydride-grafted olefin polymer respectively.

2. The metal foil laminate according to claim 1, wherein the anhydride-grafted olefin polymer comprises: styrene-ethylene / butylene-styrene copolymer grafted with maleic anhydride, polypropylene grafted with maleic anhydride, or polyethylene grafted with maleic anhydride.

3. The metal foil laminate according to claim 1, wherein the diisocyanate compound is selected from 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-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, The group consisting of esters, 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'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.

4. The metal foil laminate as claimed in claim 1, wherein the metal foil laminate comprises two layers of the metal foil, and multiple layers of the substrate are laminated between the two layers of the metal foil.

5. A printed circuit board, characterized in that: A metal foil laminate according to any one of claims 1 to 4.

6. A method for producing a metal foil laminate according to any one of claims 1 to 4, characterized in that: Include: (a) preparing a toughened and modified compound: adding a styrene maleic anhydride compound and a solvent, heating to dissolve them, adding an anhydride-grafted olefin polymer, heating to dissolve them, then adding a diisocyanate compound, heating and gradually raising the temperature of the resulting solution to 120 to 150° C., reacting for 0.5 to 2 hours, stopping heating, and cooling to room temperature; (b) preparing a resin composition: adding bismaleimide resin to the toughened and modified compound solution and stirring to dissolve; (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) Preparation of metal foil laminate: laminating a plurality of prepreg sheets, and laminating a metal foil on each of the outermost layers on both sides thereof, followed by hot pressing and curing at high temperature to prepare a metal foil laminate.

7. The manufacturing method according to claim 6, wherein step (b) further comprises adding a compound selected from the group consisting of a polybenzoxazine compound, an epoxy resin, a toughening resin, a solvent, a filler, and a combination thereof.

8. The manufacturing method according to claim 6, wherein the hot pressing conditions in step (d) are to increase the temperature to 200°C to 220°C at a heating rate of 3.0°C / min, and then hot press at this temperature for 180 minutes at an initial pressure of 8 kg / cm2 and a total pressure of 15 kg / cm2.

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