Toughening modified compounds and their manufacturing methods

Abstract

This invention provides a toughened modified compound and its manufacturing method. The toughened modified compound comprises: a styrene-maleic anhydride compound, including a polymer of styrene and maleic anhydride; a toughening agent, including an anhydride-grafted olefin polymer; and a modifier, including a diisocyanate compound; wherein the diisocyanate of the modifier forms polyimide bonds with the anhydride of the styrene-maleic anhydride compound and the anhydride of the toughening agent, respectively. This invention possesses high toughness and excellent mechanical properties, and therefore has a wide range of applications in electronics, aerospace, and other fields.

Description

Technical Field

[0001] This invention relates to a toughened and modified compound and its manufacturing method, particularly to a styrene-maleic anhydride compound modified with an olefin polymer. Background Technology

[0002] Styrene maleic anhydride (SMA) is a copolymer formed by polymerizing styrene monomers and maleic anhydride monomers. The main characteristics of styrene maleic anhydride polymers are their excellent electrical properties, high heat resistance, and high dimensional stability, leading to their widespread use in industrial and commercial applications.

[0003] However, styrene-maleic anhydride polymers also have some drawbacks. For example, after curing and crosslinking, the polymer is relatively hard and brittle, resulting in poor mechanical properties. When applied to copper-clad laminates (CCLs), its hard and brittle nature after crosslinking can cause hole cracks and white streaks during PCB drilling, leading to short circuit failures. To improve this processing defect, rubber or toughening agents are usually added to increase toughness and improve hole cracks and white streaks. If the improvement effect is not good, a large amount needs to be added to achieve the desired effect. However, adding large amounts of rubber or toughening agents may affect the physical or dielectric properties of the polymer. Summary of the Invention

[0004] In view of this, how to improve the properties of styrene-maleic anhydride polymer is one of the problems that this invention aims to solve.

[0005] The main objective of this invention is to provide a toughened and modified compound comprising: a styrene-maleic anhydride compound, including a polymer of styrene and maleic anhydride; a toughening agent, including an anhydride-grafted olefin polymer; and a modifier, including a diisocyanate compound; wherein the diisocyanate of the modifier forms polyimide bonds with the anhydride of the styrene-maleic anhydride compound and the anhydride of the toughening agent, respectively.

[0006] In a preferred embodiment, the toughening agent comprises: a styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride, a polypropylene grafted with maleic anhydride, or a polyethylene grafted with maleic anhydride.

[0007] In a preferred embodiment, the modifier is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-epoxypropyl diisocyanate, 1,3-epoxybutyl 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.

[0008] In a preferred embodiment, the ratio of styrene to maleic anhydride in the styrene-maleic anhydride compound is 3:1 to 6:1.

[0009] In a 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.

[0010] In a preferred embodiment, the toughening modified compound includes a styrene-maleic anhydride compound toughened with maleic anhydride and modified with isoflurane diisocyanate to styrene-ethylene / butene-styrene copolymer, a styrene-maleic anhydride compound toughened with maleic anhydride and modified with methylene dicyclohexyl diisocyanate to styrene-ethylene / butene-styrene copolymer, a styrene-maleic anhydride compound toughened with maleic anhydride and modified with hexamethylene diisocyanate to styrene-ethylene / butene-styrene copolymer, and a styrene-maleic anhydride compound toughened with maleic anhydride and modified with isoflurane diisocyanate to polypropylene. The group consisting of styrene-maleic anhydride compounds, styrene-maleic anhydride compounds toughened by grafting maleic anhydride onto methylene dicyclohexyl diisocyanate-modified polypropylene, styrene-maleic anhydride compounds toughened by grafting maleic anhydride onto hexamethylene diisocyanate-modified polypropylene, styrene-maleic anhydride compounds toughened by grafting maleic anhydride onto isoflavone diisocyanate-modified polyethylene, styrene-maleic anhydride compounds toughened by grafting maleic anhydride onto methylene dicyclohexyl diisocyanate-modified polyethylene, and styrene-maleic anhydride compounds toughened by grafting maleic anhydride onto hexamethylene diisocyanate-modified polyethylene.

[0011] Another object of the present invention is to provide a method for preparing the toughened modified compound as described above, comprising: (a) adding a styrene maleic anhydride compound and a solvent into a reaction flask, heating to approximately 50 to 80°C, and stirring until homogeneous; (b) while stirring, gradually adding an anhydride-grafted olefin polymer to the solution of step (a), at which point the temperature rises to 80 to 100°C to completely dissolve it, thereby forming a synthetic solution; (c) adding a diisocyanate compound, heating and gradually increasing the temperature of the synthetic solution to 120 to 150°C, and reacting for 0.5 to 2 hours; and (d) stopping the heating and cooling to room temperature to obtain the toughened modified compound.

[0012] 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.

[0013] In a preferred embodiment, step (a) involves heating to 55 to 65°C, and step (b) involves heating to 85 to 95°C.

[0014] In a preferred embodiment, step (c) involves heating to 130°C and reacting for 1 hour.

[0015] Therefore, the toughened and modified compound and its manufacturing method provided by this invention use olefin polymers to toughen and modify styrene-maleic anhydride compounds, and use diisocyanate compounds to form polyimide bonds with them. This gives the compound of this invention excellent mechanical and electrical properties, and low water absorption. Therefore, this invention is more suitable for application in composite materials and electronic circuit materials, and the resin materials using this invention can be used in a wide range of fields such as aerospace, electronics and electrical engineering, and the automotive industry. Attached Figure Description

[0016] 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:

[0017] Figure 1 This is a schematic diagram of a reaction scheme according to a preferred embodiment of the present invention.

[0018] In the attached figures, the following labels are used:

[0019] 100: Toughened and modified compounds

[0020] 110: Styrene-maleic anhydride compounds

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

[0022] 130: Isophorone diisocyanate Detailed Implementation

[0023] 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.

[0024] 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.

[0025] 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 "a", "an", "a", and "the" as used herein and in the claims include plural references.

[0026] The present invention relates to a toughened and modified compound comprising: a styrene-maleic anhydride compound; a toughening agent; and a modifier.

[0027] The term "styrene maleic anhydride compound" as used herein refers to copolymers (styrene maleic anhydride, SMA) polymerized from styrene monomers and maleic anhydride monomers. In a preferred embodiment, the ratio of styrene to maleic anhydride in the styrene maleic anhydride compound is from 3:1 to 6:1, for example, 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 two of the foregoing ratios. 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 "toughening agent" described herein is an olefin polymer grafted with anhydride, which possesses excellent electrical properties and good impact resistance. Preferably, the olefin polymer of 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).

[0029] The "modifier" described in this article includes diisocyanate compounds, wherein the diisocyanate forms polyimide bonds with the anhydrides of the styrene maleic anhydride compound and the toughening agent, respectively, to achieve chemical modification. Diisocyanate 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).

[0030] In a preferred embodiment, the toughened modified compound of the present invention comprises a styrene-maleic anhydride compound toughened with maleic anhydride and modified with isoflurane diisocyanate-modified styrene-ethylene / butene-styrene copolymer (IPDI / SEBS-g-MA / SMA), a styrene-maleic anhydride compound toughened with maleic anhydride and modified with methylene dicyclohexyl diisocyanate-modified styrene-ethylene / butene-styrene copolymer (HMDI / SEBS-g-MA / SMA), a styrene-maleic anhydride compound toughened with maleic anhydride and modified with hexamethylene diisocyanate-modified styrene-ethylene / butene-styrene copolymer (HDI / SEBS-g-MA / SMA), and a styrene-maleic anhydride compound toughened with maleic anhydride and modified with isoflurane diisocyanate-modified polypropylene (IPDI / PP-g-M... The group consisting of (A / SMA), styrene-maleic anhydride compounds toughened with maleic anhydride by methylene dicyclohexyl diisocyanate-modified polypropylene (HMDI / PP-g-MA / SMA), styrene-maleic anhydride compounds toughened with maleic anhydride by hexamethylene diisocyanate-modified polypropylene (HDI / PP-g-MA / SMA), styrene-maleic anhydride compounds toughened with maleic anhydride by isoflavone diisocyanate-modified polyethylene (IPDI / PE-g-MA / SMA), styrene-maleic anhydride compounds toughened with maleic anhydride by methylene dicyclohexyl diisocyanate-modified polyethylene (HMDI / PE-g-MA / SMA), and styrene-maleic anhydride compounds toughened with maleic anhydride by hexamethylene diisocyanate-modified polyethylene (HDI / PE-g-MA / SMA).

[0031] Furthermore, the present invention also relates to a method for preparing the toughened and modified compound as described above, comprising the steps (a) to (d).

[0032] Step (a): A styrene-maleic anhydride compound and a solvent are added to a reaction flask, heated to approximately 50 to 80°C, and stirred until homogeneous. In step (a), the reaction is carried out at a temperature of 50 to 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 of the aforementioned values. In a preferred embodiment, step (a) is carried out at a temperature of 55 to 65°C, for example, but not limited to: 55°C, 57°C, 59°C, 61°C, 63°C, 65°C, or any two of the aforementioned values.

[0033] The term "solvent" as used herein refers to any solvent that can dissolve or disperse the components in a solution without reacting with them. In a preferred embodiment, the solvent may be 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.

[0034] Step (b): Under stirring, an anhydride-grafted olefin polymer is gradually added (e.g., over 20 minutes) to the solution from step (a), while the temperature is raised to 80 to 100°C to ensure complete dissolution and form a synthetic solution. In step (b), the reaction is carried out at a temperature of 80 to 100°C, for example, but not limited to: 80°C, 85°C, 90°C, 95°C, 100°C, or any two of the aforementioned values. In a preferred embodiment, step (b) involves raising the temperature to 85 to 95°C, for example, but not limited to: 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, or any two of the aforementioned values.

[0035] Step (c): Add the diisocyanate compound, heat and gradually increase the temperature of the synthetic solution to 120 to 150°C, and react for 0.5 to 2 hours. In step (c), the reaction is carried out at a temperature of 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 of the aforementioned values; the reaction time is 0.5 to 2 hours, for example, but not limited to: 0.5 hours, 1 hour, 1.5 hours, 2 hours, or between the aforementioned two time points. In a preferred embodiment, step (c) involves heating to 130°C and reacting for 1 hour.

[0036] Step (d): Stop heating and cool to room temperature to obtain the toughened and modified compound.

[0037] This invention not only achieves chemical modification by reacting isocyanate with acid anhydride to form polyimide bonds, but also by modifying toughening agents with styrene-maleic anhydride compounds to achieve toughening and improvement effects. This gives the invention high toughness and excellent mechanical properties. If blended with other materials, it can form composite materials with even better properties.

[0038] Example

[0039] 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.

[0040] Example 1

[0041] Seven toughened and modified compounds (Example compound AG) were prepared according to the present invention. Subsequently, metal foil laminates were prepared using Example compound AG.

[0042] Example Compound A

[0043] Please refer to the following: Figure 1 An example reaction formula, Figure 1 In this context, m, n, X, and Y are the same 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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butene-styrene copolymer grafted maleic anhydride 120 were 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 completely dissolve. Next, approximately 5 grams of isophorone diisocyanate 130 were 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.

[0044] Example Compound B

[0045] 200 grams of styrene-maleic anhydride compound (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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of polypropylene-grafted maleic anhydride were 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 grams of isophorone diisocyanate were 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.

[0046] Example Compound C

[0047] 200 grams of styrene-maleic anhydride compound (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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of polyethylene-grafted maleic anhydride were 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 grams of isophorone diisocyanate were 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.

[0048] Example Compound D

[0049] 200 grams of a styrene-maleic anhydride compound (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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of a styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride 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 grams of isophorone diisocyanate were 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.

[0050] Example Compound E

[0051] 200 grams of a styrene-maleic anhydride compound (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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride 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 grams of isophorone diisocyanate were 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.

[0052] Example Compound F

[0053] 200 grams of a styrene-maleic anhydride compound (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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of a styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride 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 grams of methylene dicyclohexyl diisocyanate were 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.

[0054] Example Compound G

[0055] 200 grams of a styrene-maleic anhydride compound (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 heating device, thermometer, stirrer, and cooling pipe. The mixture was heated to approximately 60°C and stirred until completely dissolved. While stirring, 5 grams of a styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride 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 grams of hexamethylene diisocyanate were 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 G of Example.

[0056] Material

[0057] Styrene-maleic anhydride compounds with styrene / maleic anhydride ratios of 3 / 1, 4 / 1, and 6 / 1 are manufactured by Polyscope; styrene-ethylene / butene-styrene copolymers grafted with maleic anhydride are manufactured by Lee Chang Yung Chemical Co., Ltd. (Taiwan); polypropylene grafted with maleic anhydride is manufactured by ExxonMobil Chemical Co., Ltd., product model Exxelor. TM PO1015; Polyethylene grafted with maleic anhydride is manufactured by ExxonMobil Chemical Company, product model Exxelor TM PE1040.

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

[0059] Table 1

[0060]

[0061]

[0062] 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.

[0063] Example 2

[0064] 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.

[0065] Example 1: Laminated Plate

[0066] Preparation of the resin composition: Take 30 grams of the solution of compound A from the above examples, add 10 grams of bisphenol A-based polybenzoxazine (BPA-BZ), 5 grams of thermosetting resin (BMI), 25 grams of epoxy resin (brominated epoxy), 1 gram of toughening resin (Ricon 100), and 40 grams of solvent (butanone, MEK). Mix evenly with a homogenizer until all components are dissolved. After complete dissolution, add 30 grams of silica, and continue to mix evenly with a homogenizer and disperse in the solvent to prepare a varnish-like liquid resin composition.

[0067] 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.

[0068] 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.

[0069] Example 2-10 Laminated Plate

[0070] 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.

[0071] 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, heat resistance, dielectric properties, and drilling white lines test.

[0072] Table 2

[0073]

[0074]

[0075] Notes: 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 is a butadiene-styrene copolymer. EG stands for E-Glass. All components in the table are listed in grams.

[0076] Comparative example laminate 1

[0077] Preparation of the resin composition: 7.5 g of untoughened and unmodified styrene-maleic anhydride (styrene / maleic anhydride ratio of 3 / 1) was dissolved in 22.5 g of toluene. 10 g of BPA-BZ, 5 g of thermosetting resin (BMI), 25 g of epoxy resin (brominated epoxy), 2.5 g of toughening resin (Ricon 100), and 40 g of solvent (methyl ethyl ketone, MEK) were added. The mixture was homogenized and stirred until all components were dissolved. After complete dissolution, 30 g of silica was added, and the mixture was continuously homogenized 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 prepreg sheet in a semi-cured state (B-stage).

[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 preparation 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, heat resistance, dielectric properties, and drilling white lines test.

[0083] Table 3

[0084]

[0085]

[0086] Notes: 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 is a butadiene-styrene copolymer. EG stands for E-Glass. All components in the table are listed in grams.

[0087] Material

[0088] BPA-BZ was manufactured by Yuan Hung Corporation; the filler SiO2 was 10µm cut manufactured by Silicon Power Corporation; the thermosetting resin BMI was manufactured by Daiwa Chemical Corporation; the brominated epoxy resin was manufactured by Chang Chun Artificial 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.

[0089] Feature testing

[0090] White streaks in drilling: Drill 100 mechanical holes with an inner diameter of 0.3 mm into the sample using a mechanical drill bit. Observe the number of white streaks and hole cracks. White streaks and hole cracks will affect the resin filling effect and thus cause the board to burst.

[0091] 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.

[0092] 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).

[0093] Heat resistance test: Immerse the dried metal foil laminate in a solder bath at 288°C for 100 seconds. Repeat this process 3 times. If the heat resistance is excellent, it is recorded as "○". If there are bubbles or bulges on the surface, it indicates poor heat resistance and is recorded as "×".

[0094] The results above show that, compared to comparative examples 1 to 6, which contain untoughened styrene-maleic anhydride and exhibit poor mechanical properties after crosslinking, which cannot be improved even with the addition of large amounts of toughening agents or rubber, the laminates of embodiments 1 to 10, which contain the toughened modified compound of the present invention, demonstrate good 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 applications in a wide range of fields such as composite materials and electronic circuit materials.

[0095] In summary, this invention provides a toughened and modified compound and its manufacturing method. It uses olefin-based polymers to toughen and modify styrene-maleic anhydride compounds, and employs diisocyanate compounds to form polyimide bonds with them. This results in compounds with excellent mechanical and electrical properties and low water absorption. Therefore, compared to the poor mechanical properties of existing styrene-maleic anhydride polymers after crosslinking, 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, including aerospace, electronics, and the automotive industry.

[0096] 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%.

[0097] The foregoing outlines 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 determined by the appended claims.

Claims

1. A toughened and modified compound, characterized in that, Include: Styrene-maleic anhydride compounds, including polymers of styrene and maleic anhydride; Toughening agents, including anhydride-grafted olefin polymers; and Modifiers include diisocyanate compounds 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, and isoflavone. 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; The diisocyanate of the modifier forms polyimide bonds with the anhydride of the styrene-maleic anhydride compound and the anhydride of the toughening agent, respectively.

2. The toughened modified compound of claim 1, wherein the toughening agent comprises: styrene-ethylene / butene-styrene copolymer grafted with maleic anhydride, polypropylene grafted with maleic anhydride, or polyethylene grafted with maleic anhydride.

3. The toughened and modified compound according to claim 1, wherein the ratio of styrene to maleic anhydride in the styrene-maleic anhydride compound is 3:1 to 6:

1.

4. The toughened and modified compound according to claim 1, wherein the ratio of styrene to maleic anhydride in the styrene-maleic anhydride compound is 3:1, 4:1, 5:1 or 6:

1.

5. The toughened modified compound of claim 1, wherein the toughened modified compound comprises a styrene-maleic anhydride compound toughened by maleic anhydride grafted onto a styrene-ethylene / butene-styrene copolymer modified with isoflurane diisocyanate, a styrene-maleic anhydride compound toughened by maleic anhydride grafted onto a styrene-ethylene / butene-styrene copolymer modified with methylene diisocyanate, a styrene-maleic anhydride compound toughened by maleic anhydride grafted onto a styrene-ethylene / butene-styrene copolymer modified with hexamethylene diisocyanate, or a styrene-maleic anhydride compound toughened by maleic anhydride grafted onto a polypropylene copolymer modified with isoflurane diisocyanate. The group consisting of styrene-maleic anhydride-toughened compounds, styrene-maleic anhydride-toughened compounds grafted onto methylene dicyclohexyl diisocyanate-modified polypropylene, styrene-maleic anhydride-toughened compounds grafted onto hexamethylene diisocyanate-modified polypropylene, styrene-maleic anhydride-toughened compounds grafted onto isoflavone diisocyanate-modified polyethylene, styrene-maleic anhydride-toughened compounds grafted onto methylene dicyclohexyl diisocyanate-modified polyethylene, and styrene-maleic anhydride-toughened compounds grafted onto hexamethylene diisocyanate-modified polyethylene.

6. A method for manufacturing the toughened modified compound according to any one of claims 1 to 5, characterized in that, Include: (a) Add the styrene maleic anhydride compound and solvent to a reaction flask, heat to 50 to 80°C, and stir until homogeneous; (b) Under stirring, the anhydride-grafted olefin polymer is gradually added to the solution of step (a), while the temperature rises to 80 to 100°C to completely dissolve it and form a synthesis solution. (c) Add a diisocyanate compound, heat and gradually increase the temperature of the synthetic solution to 120 to 150°C, and react for 0.5 to 2 hours; and (d) Stop heating and cool to room temperature to obtain the toughened and modified compound.

7. The manufacturing method of claim 6, wherein 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.

8. The manufacturing method of claim 6, wherein step (a) is heating to 55 to 65°C and step (b) is heating to 85 to 95°C.

9. The manufacturing method of claim 6, wherein step (c) involves heating to 130°C and reacting for 1 hour.

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