Toughened resin composition

Abstract

The present application provides a toughened resin composition, which comprises: (A) a toughening modifier compound, comprising a polybenzoxazine compound, an anhydride grafted olefin polymer and a diisocyanate compound; and (B) a thermosetting polymer; wherein the diisocyanate is bonded to the polybenzoxazine compound and the anhydride grafted olefin polymer, respectively. The present application has high toughness and excellent mechanical properties, and thus can be widely applied in the fields of electronics, aerospace, etc.

Description

Technical Field

[0001] This invention relates to a toughened resin composition, and more particularly to a resin composition having an olefin-based polymer toughened modified polybenzoxazine compound. Background Technology

[0002] Polybenzoxazine is a type of nitrogen-containing thermosetting resin with a structure similar to phenolic resin. Its performance is superior to that of traditional phenolic resin. Benzoxazine compounds are generally produced by the Mannich reaction of phenolic compounds, primary amines and formaldehyde compounds. Under the action of heating or a catalyst, the ring-opening polymerization produces a network structure similar to phenolic resin, which is called benzoxazine resin.

[0003] Compared with traditional phenolic resins, benzoxazine resins possess many superior properties, such as: no small molecule byproducts are released during polymerization, low volume shrinkage, low moisture absorption, and good heat resistance, mechanical properties, electrical properties, and flame retardant properties. Therefore, benzoxazine resins are widely used in composite matrix resins, solvent-free impregnating varnishes, electronic packaging materials, flame retardant materials, and electrical insulation materials.

[0004] Although benzoxazine resins have many advantages, their mechanical properties are brittle after thermal ring-opening polymerization, which is an obstacle that needs to be overcome in their application development. Summary of the Invention

[0005] In view of this, how to improve the mechanical properties of existing polybenzoxazine resins so that the resin composition has high toughness and excellent mechanical properties is one of the problems that this invention aims to solve.

[0006] The main objective of this invention is to provide a toughened resin composition comprising: (A) a toughened modified compound comprising a polybenzoxazine compound, an anhydride-grafted olefin polymer and a diisocyanate compound; and (B) a thermosetting polymer; wherein, in the toughened modified compound, the diisocyanate is bonded to the polybenzoxazine compound and the anhydride-grafted olefin polymer, respectively.

[0007] In a preferred embodiment, (A) the toughening modified compound is 30 to 50 parts by weight; and (B) the thermosetting polymer is 8 to 15 parts by weight.

[0008] In a preferred embodiment, the thermosetting polymer is a bismaleimide (BMI) resin or a bismaleimide tripolymer. Polymers, cyanate ester polymers, benzocyclobutene polymers, or phenolic resins.

[0009] In a preferred embodiment, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a diamine type polybenzoxazine.

[0010] In a preferred embodiment, the polybenzoxazine compound is selected from the group consisting of bisphenol A type benzoxazine, bisphenol F type benzoxazine, bisphenol S type benzoxazine, diaminodiphenylmethane type benzoxazine, diaminodiphenyl ether type benzoxazine and polyimide-modified benzoxazine.

[0011] In a preferred embodiment, the anhydride-grafted olefin polymer comprises: a styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride, a polypropylene grafted with maleic anhydride, or a polyethylene grafted with maleic anhydride.

[0012] In a preferred embodiment, the diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-epoxypropyl diisocyanate, 1,3-epoxybutyl diisocyanate, dodecamethyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isoflavone diisocyanate, and hydrogenated diphenylene oxide. The group consisting of methyl methane diisocyanate, hydrogenated phenyl diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl phenyl diisocyanate, phenyl 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 phenyl diisocyanate.

[0013] In a preferred embodiment, the resin composition further comprises: a filler selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.

[0014] In a preferred embodiment, the filler is 40 to 60 parts by weight.

[0015] In a preferred embodiment, the resin composition further comprises 10 to 15 parts by weight of toughening resin.

[0016] Therefore, the toughened resin composition provided by this invention comprises a toughened modified compound, which uses an olefin polymer to toughen and modify a polybenzoxazine compound, and uses a diisocyanate compound to form a bond with it. This gives the compound of this invention excellent heat resistance and mechanical properties, and low water absorption. This invention exhibits excellent heat resistance, low swelling, high dimensional stability, high mechanical strength, and high toughness. It can be blended with other thermosetting polymers, inorganic fillers, or fibers to form composite materials. Therefore, this invention has a wide range of applications in the electronics, aerospace, and other fields.

[0017] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the present invention. Attached Figure Description

[0018] 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:

[0019] Figure 1 This is a schematic diagram of a reaction scheme according to a preferred embodiment of the present invention.

[0020] In the attached figures, the following labels are used:

[0021] 100: Toughened and modified compounds

[0022] 110: Bisphenol A type polybenzoxazine

[0023] 120: Styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride

[0024] 130: Isophorone diisocyanate Detailed Implementation

[0025] 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.

[0026] 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.

[0027] Unless otherwise stated, the word "or" as used herein means "and / or". The terms "comprising" or "including" as used herein mean that the presence or addition of one or more other components, steps, operations, and / or elements is not excluded; similarly, the terms "comprising", "including", "containing", "encompassing", and "having" as used herein are interchangeable without limitation. "A" means that the syntactic object of the thing is one or more (i.e., at least one). The singular forms of "a", "an", "a", and "the" in this document and the claims include plural references.

[0028] The present invention is a toughened resin composition comprising: (A) a toughened modified compound comprising a polybenzoxazine compound, an anhydride-grafted olefin polymer and a diisocyanate compound; and (B) a thermosetting polymer; wherein, in the toughened modified compound, the diisocyanate is bonded to the polybenzoxazine compound and the anhydride-grafted olefin polymer respectively.

[0029] The "polybenzoxazine (BZ)" described herein is a class of nitrogen-containing thermosetting resins with a structure similar to phenolic resins. Benzoxazine compounds are six-membered heterocyclic compound systems composed of oxygen and nitrogen atoms. They are generally produced by the Mannich reaction of phenolic compounds, primary amines, and formaldehyde compounds. Under heating or with a catalyst, this reaction involves ring-opening polymerization to generate a network structure similar to phenolic resins, which can also be called benzoxazine resin. In a preferred embodiment, the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a diamine-type polybenzoxazine. In a preferred embodiment, the polybenzoxazine compound is selected from at least one of 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.

[0030] The anhydride-grafted olefin polymers described herein possess excellent electrical properties and good impact resistance. Preferably, the toughening agent of this invention is grafted with maleic anhydride, exhibiting good compatibility with the substrate resin and achieving a modification effect. In a preferred embodiment, the toughening agent is, for example, but not limited to: styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride (SEBS-g-MA), polypropylene grafted with maleic anhydride (PP(PolyPropylene)-g-MA), or polyethylene grafted with maleic anhydride (PE(PolyEthylene)-g-MA).

[0031] In the diisocyanate compounds described herein, the diisocyanate forms bonds with both the polybenzoxazine compound and the anhydride of the toughening agent to achieve chemical modification. Cyanate compounds can increase the reactive functional groups in the resin structure, thereby increasing the crosslinking density of the epoxy cured product and improving its heat resistance. For example, cyanate compounds can be polyfunctional aliphatic isocyanates, polyfunctional alicyclic isocyanates, or polyfunctional aromatic isocyanates, such as: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-endenylpropyl diisocyanate, 1,3-endenylbutyl diisocyanate, dodecanethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc., 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene diisocyanate, etc. Cyclohexyl diisocyanate, isoflavone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated phenyldimethyl diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylphenyldimethyl diisocyanate, phenyl 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, phenyldimethyl diisocyanate, etc. In a preferred embodiment, the modifier includes isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (HMDI) or hexamethylene diisocyanate (HDI).

[0032] In a preferred embodiment, the toughened modified compound of the present invention comprises a polybenzoxazine compound toughened with maleic anhydride and selected from isoflurane diisocyanate-modified styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride (IPDI / SEBS-g-MA / BZ), a polybenzoxazine compound toughened with maleic anhydride and selected from isoflurane diisocyanate-modified styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride (HMDI / SEBS-g-MA / BZ), a polybenzoxazine compound toughened with maleic anhydride and selected from hexamethylene diisocyanate-modified styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride (HDI / SEBS-g-MA / BZ), and a polybenzoxazine compound toughened with maleic anhydride and selected from isoflurane diisocyanate-modified polypropylene grafted with maleic anhydride (IPDI / PP- The group consisting of g-MA / BZ), methylene dicyclohexyl diisocyanate modified polypropylene grafted with maleic anhydride toughening polybenzoxazine compound (HMDI / PP-g-MA / BZ), hexamethylene diisocyanate modified polypropylene grafted with maleic anhydride toughening polybenzoxazine compound (HDI / PP-g-MA / BZ), isoflavone diisocyanate modified polyethylene grafted with maleic anhydride toughening polybenzoxazine compound (IPDI / PE-g-MA / BZ), methylene dicyclohexyl diisocyanate modified polyethylene grafted with maleic anhydride toughening polybenzoxazine compound (HMDI / PE-g-MA / BZ), and hexamethylene diisocyanate modified polyethylene grafted with maleic anhydride toughening polybenzoxazine compound (HDI / PE-g-MA / BZ).

[0033] In a preferred embodiment, in the toughened resin composition of the present invention, (A) the toughening modified compound is 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) the thermosetting polymer is 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.

[0034] The thermosetting polymer of the present invention can also be bismaleimide trioxide. The polymer can be a cyanate ester polymer, a benzocyclobutene polymer, or a phenolic resin. In a preferred embodiment, the thermosetting polymer of the present invention is a bismaleimide (BMI) resin having carbonyl groups, a nitrogen-containing epoxy resin, which is cured during processing and molding through the unsaturation of the end groups, and the curing process does not produce volatile substances, which is beneficial for processing and molding composite materials.

[0035] The toughened resin composition of the present invention may 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, silicon aluminum 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, for example, 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 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.

[0038] In a preferred embodiment, the resin composition further comprises: a toughening resin, such as a core-shell polymer and / or polybutadiene resin. The core-shell polymer is, for example, core-shell rebber (CSR). The polybutadiene resin is, for example, polybutadiene homopolymer or butadiene-styrene copolymer. In a preferred embodiment, the toughening resin is 10 to 15 parts by weight, for example, 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.

[0039] This invention not only achieves toughening and improvement through chemical modification by reacting isocyanates with acid anhydrides to form polyimide bonds, but also through modification with olefin polymers and polybenzoxazine compounds, giving the invention high toughness and excellent mechanical properties. Furthermore, if this invention is blended with other materials, it can form composite materials with even better properties.

[0040] Example

[0041] The present invention will be further described in detail and with embodiments below. However, it should be understood that these embodiments are only intended to help to make the present invention easier to understand and to illustrate various aspects of the present invention and the benefits achieved thereto, and are not intended to limit the scope of the present invention.

[0042] Example 1

[0043] Six toughened and modified compounds (Example compound AF) were prepared according to the present invention. Subsequently, metal foil laminates were prepared using Example compound AF.

[0044] Example Compound A

[0045] Please refer to the following: Figure 1 An exemplary reaction formula, Figure 1 In this context, m, n, X, and Y are the same or different positive integers. 200 g of bisphenol A type benzoxazine (BPA-BZ) 110 and 600 g of toluene were added to a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until homogeneous. While stirring, 20 g of styrene-ethylene / butene-styrene copolymer grafted maleic anhydride (SEBS-g-MA) 120 was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution rose to 90°C, allowing it to dissolve completely. Next, approximately 5 g of isophorone diisocyanate (IPDI) 130 was added, and the temperature of the synthesis solution was heated and gradually increased to approximately 130°C, and the reaction was carried out for 1 hour. Heating was then stopped, and the mixture was cooled to room temperature to obtain compound A of Example, namely, toughened and modified compound 100.

[0046] Example Compound B

[0047] 200 g of ODA-BZ and 600 g of toluene were added to a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until homogeneous. While 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 rose to 90°C, allowing it to dissolve completely. Next, approximately 5 g of IPDI was added, and the temperature of the synthesis solution was heated and gradually increased to approximately 130°C, and the reaction was carried out for 1 hour. Heating was then stopped, and the mixture was cooled to room temperature to obtain compound B of Example.

[0048] Example Compound C

[0049] 200 g of BPA-BZ and 600 g of toluene were added to a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until homogeneous. While 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 rose to 90°C, allowing it to dissolve completely. Next, approximately 5 g of IPDI was added, and the temperature of the synthesis solution was heated and gradually increased to approximately 130°C, and the reaction was carried out for 1 hour. Heating was then stopped, and the mixture was cooled to room temperature to obtain compound C of Example.

[0050] Example Compound D

[0051] 200 g of BPA-BZ and 600 g of toluene were added to a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until homogeneous. While stirring, 20 g of PE-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution rose to 90°C, allowing it to dissolve completely. Next, approximately 5 g of IPDI was added, and the temperature of the synthesis solution was heated and gradually increased to approximately 130°C, and the reaction was carried out for 1 hour. Heating was then stopped, and the mixture was cooled to room temperature to obtain compound D of Example.

[0052] Example Compound E

[0053] 200 g of BPA-BZ and 600 g of toluene were added to a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until homogeneous. While 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 rose to 90°C, allowing it to dissolve completely. Next, approximately 5 g of HMDI was added, and the temperature of the synthesis solution was heated and gradually increased to approximately 130°C, and the reaction was carried out for 1 hour. Heating was then stopped, and the mixture was cooled to room temperature to obtain compound E of Example.

[0054] Example Compound F

[0055] 200 g of BPA-BZ and 600 g of toluene were added to a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until homogeneous. While 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 rose to 90°C, allowing it to dissolve completely. Next, approximately 5 g of HDI was added, and the temperature of the synthesis solution was heated and gradually increased to approximately 130°C, and the reaction was carried out for 1 hour. Heating was then stopped, and the mixture was cooled to room temperature to obtain compound F of Example.

[0056] Material

[0057] BPA-BZ and ODA-BZ are manufactured by Yuan Hung Corporation; SEBS-g-MA is manufactured by Lee Chang Yung Corporation of Taiwan, China; PP-g-MA is manufactured by ExxonMobil Chemical Company, product model Exxelor™ PO1015; PE-g-MA is manufactured by ExxonMobil Chemical Company, product model Exxelor™ PE1040.

[0058] Table 1 below shows the composition and content of compound AF in the examples.

[0059] Table 1

[0060]

[0061]

[0062] Example 2

[0063] The following provides a non-limiting method for preparing metal foil laminates using the toughening 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) having the example compounds are prepared according to a method similar to that disclosed below. However, the specific methods for preparing Example Laminates 1-10 and Comparative Example Laminates 1-6 generally differ from the methods disclosed below in one or more aspects.

[0064] Example 1: Laminated Plate

[0065] Preparation of the resin composition: Take 30 grams of the compound A solution from the above examples, add 5 grams of thermosetting resin (BMI), 25 grams of CNE epoxy resin, and 40 grams of solvent (butanone, MEK), and mix evenly with a homogenizer until all components are dissolved. After complete dissolution, add 40 grams of silica, and continue to mix evenly with a homogenizer and disperse in the solvent to prepare a varnish-like liquid resin composition.

[0066] Preparation of prepreg sheet: Impregnate or coat the reinforcing glass fiber cloth (substrate E-Glass) with the above-mentioned clear varnish liquid resin composition, and dry the impregnated or coated substrate at 80°C for 3 minutes and at 180°C for 7 minutes to obtain a semi-cured (B-stage) prepreg sheet.

[0067] Preparation of metal foil laminate: Four pre-impregnated sheets are laminated, and a 0.5 ounce metal foil (copper foil) is laminated on the outermost layer of each of the two sides. The laminate is then placed in a hot press for high-temperature hot pressing and curing. The hot pressing conditions are: heating to 200°C to 220°C at a rate of 3.0°C / min, and then hot pressing at this temperature with a total pressure of 15 kg / cm² (initial pressure 8 kg / cm²) for 180 minutes to obtain the copper foil laminate.

[0068] Example 2-10 Laminated Plate

[0069] The laminates of embodiments 2-10 are prepared according to a method similar to that of laminate 1 of embodiment 2; however, laminates of embodiments 2-10 may differ in one or more aspects, as shown in Table 2 below.

[0070] Table 2 shows the preparation composition and content of laminates 1-10 in Examples, as well as the measurement results of physical properties such as adhesion strength, coefficient of thermal expansion in the Z-axis direction, and heat resistance.

[0071] Table 2

[0072]

[0073]

[0074]

[0075] Note: EG in the table represents E-Glass. The unit for each ingredient in the table is grams.

[0076] Comparative example laminate 1

[0077] Preparation of the resin composition: 30 grams of untoughened BPA-BZ, 5 grams of thermosetting resin (BMI), 25 grams of epoxy resin, 2 grams of toughening resin, and 40 grams of solvent (methyl ethyl ketone, MEK) were added and mixed evenly with a homogenizer until all components were dissolved. After complete dissolution, 40 grams of silica were added, and the mixture was continuously mixed evenly with a homogenizer and dispersed in the solvent to prepare a varnish-like liquid resin composition.

[0078] Preparation of prepreg sheet: Impregnate or coat the reinforcing glass fiber cloth (substrate E-Glass) with the above-mentioned clear varnish liquid resin composition, and dry the impregnated or coated substrate at 80°C for 3 minutes and at 180°C for 7 minutes to obtain a semi-cured (B-stage) prepreg sheet.

[0079] Preparation of the metal foil laminate: Four pre-impregnated sheets are laminated, and a 0.5 oz copper foil is laminated on the outermost layer of each of the two sides. The laminate is then placed in a hot press for high-temperature hot pressing and curing. The hot pressing conditions are: heating to 200°C to 220°C at a rate of 3.0°C / min, and then hot pressing at this temperature with a total pressure of 15 kg / cm² (initial pressure 8 kg / cm²) for 180 minutes. The resulting copper foil laminate is obtained.

[0080] Comparative Examples of Laminated Plates 2-6

[0081] Comparative example laminates 2-6 were prepared using a method similar to that used for comparative example laminate 1. However, comparative example laminates 2-6 differ in one or more aspects, as detailed in Table 3 below.

[0082] Table 3 shows the composition and content of comparative laminates 1-6, as well as the measurement results of physical properties such as adhesion strength, coefficient of thermal expansion in the Z-axis direction, and heat resistance.

[0083] Table 3

[0084]

[0085] Note: CSR in the table refers to core-shell rubber. Ricon 100 is butadiene-styrene copolymer. EG indicates E-Glass. The units for each component in the table are grams.

[0086] Material

[0087] BPA-BZ and ODA-BZ were manufactured by Yuan Hung Corporation; the filler SiO2 was 10µm cut manufactured by Silicon Power Corporation; the thermosetting resin BMI (KI-70) was manufactured by Daiwa Chemical Corporation; the CNE epoxy resin was manufactured by Chang Chun Resin Corporation; the reinforcing material was E-Glass 2116 manufactured by Taiwan Glass Corporation; the toughening resin was CSR manufactured by Kaneka Corporation and Ricon 100 manufactured by Polyscope Corporation; and the copper foil was H1 0.5OZ manufactured by Nan Ya Plastics Corporation.

[0088] Feature testing

[0089] CTE Test: According to IPC-TM-650 2.4.24.5, the change rate of the coefficient of thermal expansion (CTE) of the sample under test in the Z-axis direction (total z-CTE) at temperatures below the glass transition temperature (Tg) is measured using a thermal mechanical analyzer (TMA). Z-CTE is measured within a temperature range of 50℃ to 260℃ and is expressed as a percentage.

[0090] Next, the tear strength test: Tear strength refers to the adhesion of the metal foil to the laminated prepreg sheet. In this test, a 1 / 8-inch wide copper foil is torn vertically from the board surface, and the strength required to express the adhesion is measured by the force required. The unit of tear strength is pounds-force per inch (lbf / in).

[0091] Heat resistance test: Immerse the dried metal foil laminate in a solder bath at 288°C and 300°C for 100 seconds, and repeat the process 3 times. If the heat resistance is excellent, it is recorded as "○"; if there are bubbles or protrusions on the surface, it indicates poor heat resistance and is recorded as "×".

[0092] The results above show that, compared to comparative examples 1 to 6 which contain untoughened polybenzoxazine compounds, their crosslinked, brittle mechanical properties are poor and cannot be improved even with the addition of large amounts of toughening agents or rubber. In contrast, example laminates 1 to 10, which contain the toughened resin composition of this invention, exhibit excellent mechanical and heat resistance properties. Therefore, this invention is more suitable for applications in a wide range of fields, including composite materials and electronic circuit materials.

[0093] In summary, this invention provides a toughened and modified compound and its manufacturing method. It uses olefin-based polymers to toughen and modify polybenzoxazine compounds, and employs diisocyanate compounds to form chemical bonds with them, giving the compound excellent mechanical and heat resistance properties. Therefore, compared to the brittle mechanical properties of conventional polybenzoxazine compounds after thermal ring-opening polymerization, this invention is more suitable for applications in composite materials and electronic circuit materials. Resin materials using the toughened and modified compound of this invention can be used in a wide range of fields such as aerospace, electronics, and the automotive industry.

[0094] Unless otherwise defined, the terms "substantially" and "approximately" are used to describe and narrate small changes. When combined with an event or situation, the term may include the exact moment the event or situation occurred, or an approximate point in time. For example, when combined with a numerical value, the term may include a range of variation less than or equal to ±10% of that 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%.

[0095] The foregoing has outlined components of several embodiments to enable those skilled in the art to better understand the concepts of the embodiments of the present invention. Those skilled in the art 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 benefits as the embodiments described herein. Those skilled in the art 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 therein without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be defined by the appended claims.

[0096] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A metal foil laminate, characterized in that, It comprises a toughened resin composition, the toughened resin composition comprising: (A) A toughened and modified compound comprising a polybenzoxazine compound, an anhydride-grafted olefin polymer, and a diisocyanate compound; and (B) Thermosetting polymers; In the toughened and modified compound, the diisocyanate is bonded to the polybenzoxazine compound and the anhydride-grafted olefin polymer, respectively. The polybenzoxazine compound is selected from the group consisting of bisphenol A type benzoxazine, bisphenol F type benzoxazine, bisphenol S type benzoxazine, diaminodiphenylmethane type benzoxazine, diaminodiphenyl ether type benzoxazine and polyimide benzoxazine. The diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-endenylpropyl diisocyanate, 1,3-endenylbutyl diisocyanate, dodecanethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isoflavone diisocyanate, and hydrogenated diphenylmethane. The group consisting of diisocyanates, hydrogenated phenyl diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl phenyl diisocyanate, phenyl 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 phenyl diisocyanate.

2. The metal foil laminate according to claim 1, characterized in that, (A) 30 to 50 parts by weight of the toughened and modified compound; (B) 8 to 15 parts by weight of the thermosetting polymer.

3. The metal foil laminate according to claim 1, characterized in that, The thermosetting polymer is a bismaleimide resin, a cyanate polymer, a benzocyclobutene polymer, or a phenolic resin.

4. The metal foil laminate according to claim 1, characterized in that, The anhydride-grafted olefin polymers include: styrene-ethylene / butene-styrene copolymers grafted with maleic anhydride, polypropylene grafted with maleic anhydride, or polyethylene grafted with maleic anhydride.

5. The metal foil laminate according to any one of claims 1 to 4, characterized in that, It further includes: a filler selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene.

6. The metal foil laminate according to claim 5, characterized in that, The filler is available in quantities of 40 to 60 parts by weight.

7. The metal foil laminate according to any one of claims 1 to 4, characterized in that, It further includes: 10 to 15 parts by weight of toughening resin.

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