TWI808754B - Toughened resin composition - Google Patents

Abstract

The present invention provides a toughened resin composition, which comprises: (A) a toughened and modified compound, which comprises a styrene maleic anhydride compound, an anhydride grafted olefin polymer, and a diisocyanate compound; (B) a thermosetting polymer; and (C) a toughening resin; wherein, in the toughened and modified compound, the diisocyanate forms a polyimide bond with the styrene maleic anhydride compound and the anhydride grafted olefin polymer, respectively. The present invention has high toughness and excellent mechanical properties; thus, it can have a wide range of applications in the fields of electronics, aerospace and the like.

Description

toughened resin composition

The invention relates to a toughened resin composition, in particular to a resin composition with olefinic polymer toughened and modified styrene maleic anhydride.

Styrene maleic anhydride (SMA) is a copolymer formed by polymerization of styrene monomer and maleic anhydride monomer. The main characteristics of styrene maleic anhydride polymer are its excellent electrical properties, high heat resistance and high dimensional stability, and it is widely used in industry and commerce.

However, styrene maleic anhydride polymers also have some disadvantages. For example, after curing and cross-linking, the polymer is hard and brittle, so its mechanical properties are not good. When it is applied to copper clad substrates (CCL), it will be hard and brittle after crosslinking. When the base material is drilled on a printed circuit board (PCB), cracks and white lines will occur in the copper clad substrate, which will lead to short circuit failure. In order to improve this poor processing, rubber or toughener is generally added to increase the toughness in order to improve the cracks and white lines. If the improvement effect is not good, it needs to be added in large quantities to achieve the improvement effect. However, adding a large amount of rubber or toughener may affect the physical properties or dielectric properties of the polymer.

In view of this, how to improve the properties of styrene maleic anhydride polymer so that the resin composition has high toughness and excellent mechanical properties is one of the problems to be solved by the present invention.

The main purpose of the present invention is to provide a toughened resin composition, which comprises: (A) a toughened modified compound, which includes a styrene maleic anhydride compound, an anhydride-grafted olefinic polymer, and a diisocyanate compound; (B) a thermosetting polymer; amine bond.

In a preferred embodiment, the ratio of (A):(B):(C) in the resin composition is 15-30:20-35:0.1-5.

In a preferred embodiment, the toughened resin is a core-shell polymer and/or polybutadiene resin.

聚合物、氰酸酯(cyanate ester)聚合物、苯并環丁烯(benzocyclobutene)聚合物、或酚醛樹脂(phenolic)。 In a preferred embodiment, the thermosetting polymer is bismaleimide (BMI) resin, bismaleimide three

polymers, cyanate ester polymers, benzocyclobutene polymers, or phenolic resins.

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

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

In a preferred embodiment, the diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylidene 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, iso Foone 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, A group consisting of 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.

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

In a preferred embodiment, the resin composition further includes: a polybenzoxazine compound, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a bisamine type polybenzoxazine.

In a preferred embodiment, the resin composition further includes: a solvent, and 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.

Therefore, the toughened resin composition provided by the present invention includes a toughened modified compound, which uses olefinic polymers to toughen and modify styrene maleic anhydride compounds, and uses diisocyanate compounds to form polyimide bonds with it, which can effectively improve the mechanical properties and electrical properties of the resin composition, so that the resin composition of the present invention has good mechanical properties and electrical properties, and has low water absorption. The invention has high toughness and excellent mechanical properties, and can be combined with other thermosetting polymers, inorganic fillers or Fibers and the like are blended to form composite materials. Therefore, the invention has a wide range of applications in the fields of electronics, aerospace and other fields.

100: Toughened and modified compound

110: Styrene maleic anhydride compound

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

130: Isophorone diisocyanate

The details of one or more implementations of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects and advantages of the subject matter of this specification will be apparent from the description, drawings and scope of patent application, wherein: Fig. 1 is a schematic diagram of a reaction formula of a preferred embodiment of the present invention.

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

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. Terms such as "first," "second," "third," "fourth," and "fifth" when used herein do not imply a sequence or order unless clearly indicated by the context.

Unless otherwise stated, "or" mentioned herein means "and/or". The term "comprising" or "comprising" referred to herein means not excluding the existence of one or more other components, steps, operations and/or elements or adding to said components, steps, operations and/or elements; "Includes", "includes", "contains", "includes", and "has" are interchangeable without limitation. "One" means that the grammatical object of the thing is one or more than one (ie, at least one). The singular forms "a", "an", "an" and "the" mentioned herein and claims include plural referents.

The present invention is a toughened resin composition, which comprises: (A) a toughened modified compound, which includes a styrene maleic anhydride compound, an anhydride-grafted olefinic polymer, and a diisocyanate compound; (B) a thermosetting polymer; and (C) a toughened resin; wherein, in the toughened modified compound, the diisocyanate forms a polyimide bond with the styrene maleic anhydride compound and the anhydride-grafted olefinic polymer respectively.

The "styrene maleic anhydride compound" mentioned herein includes a copolymer (styrene maleic anhydride, SMA) polymerized from styrene monomer and maleic anhydride monomer. In a preferred embodiment, the ratio of styrene and 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 two ratios mentioned above. In a more preferred embodiment, the ratio of styrene and maleic anhydride in the styrene maleic anhydride compound is 3:1, 4:1, 5:1 or 6:1.

The anhydride-grafted olefinic polymers described herein have excellent electrical properties and good impact resistance; preferably, the olefinic polymers of the present invention are grafted with maleic anhydride, which has good compatibility with the substrate resin and achieves a modification effect. In a preferred embodiment, the anhydride-grafted olefinic polymer is for example but not limited to: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA), polypropylene grafted maleic anhydride (PP (Poly Propylene)-g-MA) or polyethylene grafted maleic anhydride (PE (Poly Ethylene)-g-MA).

In the diisocyanate compounds described herein, the diisocyanate group forms a polymer with the acid anhydride of the styrene maleic anhydride compound and the anhydride of the anhydride-grafted olefinic polymer respectively. imide bond to achieve chemical modification. Cyanate compounds can increase the reactive functional groups in the resin structure, thereby increasing the crosslinking density of epoxy cured products and improving heat resistance. For example, the cyanate compound may be a multifunctional aliphatic isocyanate compound, a multifunctional alicyclic isocyanate, or a multifunctional aromatic isocyanate compound, such as: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Cyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2,2'-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 or hydrogenated MDI (HMDI), or hexamethylene diisocyanate (Hexamethylene diisocyanate, HDI)).

In a preferred embodiment, the toughened modified compound of the present invention is selected from styrene maleic anhydride compound (IPDI/SEBS-g-MA/SMA) modified by isophorone diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride (IPDI/SEBS-g-MA/SMA), methylene dicyclohexyl diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride toughened styrene maleic anhydride compound (HMDI/SEBS- g-MA/SMA), hexamethylene diisocyanate modified styrene-ethylene/butylene-styrene Copolymer grafted maleic anhydride toughened styrene maleic anhydride compound (HDI/SEBS-g-MA/SMA), isophorone diisocyanate modified polypropylene grafted maleic anhydride toughened styrene maleic anhydride compound (IPDI/PP-g-MA/SMA), methylene dicyclohexyl diisocyanate modified polypropylene grafted maleic anhydride toughened styrene maleic anhydride compound (HMDI/PP-g-MA/SMA), hexaethylene Methyl diisocyanate modified polypropylene grafted maleic anhydride toughened styrene maleic anhydride compound (HDI/PP-g-MA/SMA), isophorone diisocyanate modified polyethylene grafted maleic anhydride toughened styrene maleic anhydride compound (IPDI/PE-g-MA/SMA), methylene dicyclohexyl diisocyanate modified polyethylene grafted maleic anhydride toughened styrene maleic anhydride compound (HMDI/PE-g-MA/SMA) and A group consisting of hexamethylene diisocyanate modified polyethylene grafted maleic anhydride toughened styrene maleic anhydride compound (HDI/PE-g-MA/SMA).

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) toughened resin is 15 to 30:20 to 35:0.1 to 5. For example: (A) the toughened and 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 values above; (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%, 31%, 32%, 33%, 34%, 35% or between any two values above; (C) the toughening resin accounts for 0.1% to 5% of the overall 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 values above.

In a preferred embodiment, the toughening resin of the present invention is a core-shell polymer and/or polybutadiene resin. Core-shell polymers such as core-shell rubber (core shell rebber, CSR). The polybutadiene resin is, for example, a polybutadiene homopolymer or a butadiene-styrene copolymer.

聚合物、氰酸酯(cyanate ester)聚合物、苯并環丁烯(benzocyclobutene)聚合物、或酚醛樹脂(phenolic)。於一較佳實施例中，本發明之該熱固性聚合物為雙馬來醯亞胺(BMI)樹脂，其具有羰基，含氮環氧樹脂，加工成型時通過端基的不飽和性進行固化，且固化過程不會產生揮發性的物質，將利於加工成型複合材料。 The thermosetting polymer of the present invention can also be bismaleimide tris

polymers, cyanate ester polymers, benzocyclobutene polymers, or phenolic resins. In a preferred embodiment, the thermosetting polymer of the present invention is a bismaleimide (BMI) resin, which has a carbonyl group, nitrogen-containing epoxy resin, and is cured through the unsaturation of the end group during processing and molding, and the curing process will not produce volatile substances, which will facilitate processing and molding composite materials.

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

In a preferred embodiment, the filler is an inorganic filler, for example: selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene.

In a preferred embodiment, the polybenzoxazine compound is bisphenol polybenzoxazine or diamine polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is selected from 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 polyimidized benzoxazine (polyben at least one member of the group consisting of zoxazine with polyimide).

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.

The present invention not only realizes the chemical modification of polyimide bonds through the reaction of isocyanate and acid anhydride, but also achieves toughening modification through the modification of olefinic polymers and styrene maleic anhydride compounds. The good effect makes the present invention have high toughness and excellent mechanical properties. If it is blended with other materials, it can form a composite material with excellent properties.

Example

Hereinafter, the present invention will be further described in detail and implementations. However, it should be understood that these implementations are only used to help understand the present invention more easily, and to clarify aspects of the present invention and the benefits achieved, but not to limit the scope of the present invention.

Example 1

Seven toughened and modified compounds (Example Compounds A-G) were prepared according to the present invention. Metal foil laminates were then prepared using Example compounds A-G.

Example Compound A

Please also refer to the exemplary reaction formula shown in FIG. 1 . In FIG. 1 , m, n, X, and Y are the same or different positive integers. Put 200 grams of styrene-maleic anhydride compound 110 (the ratio of styrene/maleic anhydride is 3/1) and 600 grams of toluene into a 3-liter four-necked separable reaction flask equipped with a heating device, a thermometer, a mixer, and a cooling tube. Heat up to about 60° C. and stir evenly to dissolve completely. While stirring, gradually add 5 grams of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride 120 into the toluene solution within 20 minutes, and the temperature of the synthesis solution rises to 90°C to completely dissolve it. Next, about 5 grams of isophorone diisocyanate 130 was added, and the synthesis solution was heated and gradually raised to about 130° C., and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound A, that is, the toughened and modified compound 100.

Example compound B

Put 200 grams of styrene maleic anhydride compound (styrene/maleic anhydride ratio is 3/1) and 600 grams of toluene into a 3 liter container equipped with heating device, thermometer, mixer and cooling tube In a four-necked separable reaction flask, heat up to about 60°C and stir evenly to dissolve completely. While stirring, gradually add 5 grams of polypropylene-grafted maleic anhydride to the toluene solution within 20 minutes. At this time, the temperature of the synthesis solution rises to 90° C. to completely dissolve it. Next, about 5 grams of isophorone diisocyanate was added, and the synthesis solution was heated and gradually raised to about 130° C., and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound B.

Example compound C

Put 200 grams of styrene-maleic anhydride compound (styrene/maleic anhydride ratio is 3/1) and 600 grams of toluene into a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, mixer, and cooling tube, raise the temperature to about 60°C, and stir evenly to dissolve completely. While stirring, gradually add 5 grams of polyethylene-grafted maleic anhydride to the toluene solution within 20 minutes. At this time, the temperature of the synthesis solution rises to 90° C. to completely dissolve it. Next, about 5 grams of isophorone diisocyanate was added, and the synthesis solution was heated and gradually raised to about 130° C., and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound C.

Example Compound D

Put 200 grams of styrene-maleic anhydride compound (styrene/maleic anhydride ratio is 4/1) and 600 grams of toluene into a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, mixer, and cooling tube, raise the temperature to about 60°C, and stir evenly to dissolve completely. While stirring, gradually add 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride to the toluene solution within 20 minutes. At this time, the temperature of the synthesis solution rises to 90° C. to completely dissolve it. Next, about 5 grams of isophorone diisocyanate was added, and the synthesis solution was heated and gradually raised to about 130° C., and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound D.

Example Compound E

Add 200 grams of styrene-maleic anhydride compound (styrene/maleic anhydride ratio: 6/1) and 600 grams of toluene into a 3-liter four-necked separable reaction bottle equipped with a heating device, thermometer, mixer, and cooling tube, raise the temperature to about 60°C, and stir evenly to dissolve completely. While stirring, gradually add 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride to the toluene solution within 20 minutes. At this time, the temperature of the synthesis solution rises to 90° C. to completely dissolve it. Next, about 5 grams of isophorone diisocyanate was added, and the synthesis solution was heated and gradually raised to about 130° C., and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound E.

Example compound F

Put 200 grams of styrene-maleic anhydride compound (styrene/maleic anhydride ratio is 3/1) and 600 grams of toluene into a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, mixer, and cooling tube, raise the temperature to about 60°C, and stir evenly to dissolve completely. While stirring, gradually add 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride to the toluene solution within 20 minutes. At this time, the temperature of the synthesis solution rises to 90° C. to completely dissolve it. Next, about 5 grams of methylene dicyclohexyl diisocyanate was added, and the synthesis solution was heated and gradually raised to about 130° C., and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound F.

Example Compound G

Put 200 grams of styrene-maleic anhydride compound (styrene/maleic anhydride ratio is 3/1) and 600 grams of toluene into a 3-liter four-necked separable reaction flask equipped with a heating device, thermometer, mixer, and cooling tube, raise the temperature to about 60°C, and stir evenly to dissolve completely. While stirring, gradually add 5 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride to the toluene solution within 20 minutes. At this time, the temperature of the synthesis solution rises to 90° C. to completely dissolve it. Next, add About 5 grams of hexamethylene diisocyanate, heated and gradually raised the temperature of the synthesis solution to about 130 ° C, and reacted for 1 hour. Then the heating was stopped and the temperature was lowered to room temperature to obtain Example Compound G.

Material

Styrene/maleic anhydride ratio is that the styrene maleic anhydride compound of 3/1, 4/1 and 6/1 is produced by Polyscope Company; Styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride is produced by Li Changrong Company of Taiwan; Polypropylene grafted maleic anhydride is produced by ExxonMobil Chemical Company (ExxonMobil), product model Exxelor ^TM PO1015; Model Exxelor( ^TM) PE1040.

The following table 1 shows the preparation ingredients and contents of the compounds A-G of the examples.

Example 2

The following provides a non-limiting method for preparing the toughened modified compound of the present invention into a metal foil laminate. Ten non-limiting example laminates (Example Laminates 1-10) and six comparative example laminates (Comparative Example Laminates 1-6) with example compounds were prepared according to methods similar to those disclosed below. However, the specific methods of making Example Laminates 1-10 and Comparative Example Laminates 1-6 generally differed in one or more ways from the methods disclosed below.

Example laminate 1

Preparation of resin composition: Take 30 grams of the compound A solution of the above example, add 10 grams of bisphenol A polybenzoxazine (BPA-Benzoxazine, 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 (methyl ethyl ketone, MEK). After it is completely dissolved, add 30 grams of silicon dioxide, continue to mix evenly with a homogeneous mixer and disperse in the solvent to prepare a varnish liquid resin composition.

Preparation of prepreg: impregnate or coat the reinforcing material glass fiber cloth (substrate E-Glass) with the above-mentioned 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.

Preparation of metal foil laminates: Laminate four prepregs, and laminate a piece of 0.5 oz metal foil (copper foil) on each of the outermost layers on both sides, and then place it in a hot press for high-temperature hot-press curing. The hot-pressing conditions are as follows: heat up to 200-220°C at a heating rate of 3.0°C/min, and at this temperature, press with a total pressure of 15 kg/cm2 (initial pressure of 8 kg/cm2) for 180 minutes to produce a copper foil laminate.

Example laminates 2-10

Example laminates 2-10 were prepared according to a method similar to that of Example laminate 1, however, Example laminates 2-10 differed in one or more aspects, and the specific differences are shown in Table 2 below.

Table 2 shows the composition and content of the laminates 1-10 of the examples, as well as the measurement results of physical properties such as bonding strength, thermal expansion coefficient in the Z-axis direction, heat resistance, dielectric properties, and drilling white streaks.

Comparative Example Laminate 1

Preparation of resin composition: Dissolve 7.5 grams of untoughened and modified styrene maleic anhydride (styrene/maleic anhydride ratio: 3/1) in 22.5 grams of toluene, add 10 grams of BPA-BZ, 5 grams of thermosetting resin (BMI), 25 grams of epoxy resin (brominated epoxy), 2.5 grams of toughening resin (Ricon 100) and 40 grams of solvent (methyl ethyl ketone, MEK), and stir homogeneously Mix well and dissolve ingredients. After it is completely dissolved, add 30 grams of silicon dioxide, continue to mix evenly with a homogeneous mixer and disperse in the solvent to prepare a varnish liquid resin composition.

Preparation of prepreg: impregnate or coat the reinforcing material glass fiber cloth (substrate E-Glass) with the above-mentioned 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.

Preparation of metal foil laminates: Laminate four prepregs, and laminate a piece of 0.5 oz copper foil on each of the outermost layers on both sides, and then place them in a hot press for high-temperature hot-press curing. The hot-pressing conditions are as follows: heat up to 200-220°C at a heating rate of 3.0°C/min, and at this temperature, press with a total pressure of 15 kg/cm2 (initial pressure of 8 kg/cm2) for 180 minutes. A copper foil laminate was produced.

Comparative Example Laminate 2-6

Comparative Laminates 2-6 were prepared according to a method similar to that of Comparative Laminate 1. However, Comparative Laminates 2-6 differed in one or more aspects, and the specific differences are disclosed in Table 3 below.

Table 3 shows the preparation ingredients and content of comparative laminates 1-6, as well as the measurement results of adhesive strength, thermal expansion coefficient in the Z-axis direction, heat resistance and other physical properties, dielectric properties and drilling white streak test.

Material

BPA-BZ is produced by Yuanhong Company; filler SiO ₂ is 10um cut produced by Sibelco; thermosetting resin BMI is produced by Daiwa Chemical Co.; brominated epoxy resin is produced by Changchun Artificial Resin Company; reinforcing material is E-Glass glass cloth 2116 produced by Taiwan Glass; toughening resin is CSR produced by Kaneka Company and Ricon 100 produced by Polyscope Company;

Characteristic test

Drilling white lines: use a mechanical drill to drill 100 mechanical holes on the sample, the inner diameter of the holes is 0.3mm, observe the number of drilling white lines and hole cracks, white lines and hole cracks will affect the resin filling effect and cause the phenomenon of plate explosion.

CTE test: According to the IPC-TM-650 2.4.24.5 specification, use a thermal mechanical analyzer (thermal mechanical analyzer, TMA) to measure the thermal expansion coefficient (coefficient of thermal exapansion, CTE) of the sample to be tested at a temperature lower than the glass transition temperature (Tg). Z-CTE is measured in the temperature range from 50°C to 260°C, and the unit is %.

Then the strength test: The next strength refers to the adhesion of the metal foil to the laminated prepreg. In this test, the 1/8 inch width of the copper foil is torn vertically from the board surface, and the strength of the adhesion is expressed by the required force. Tear strength is measured in pounds force per inch (lbf/in).

Heat resistance test: Soak the dried metal foil laminate in a tin soldering bath at 288°C for 100 seconds, repeat the process 3 times, if the heat resistance is excellent, record it as "○"; if there are bulges on the appearance, it indicates poor heat resistance, record it as "×".

From the above results, it can be seen that compared to the comparative example laminates 1 to 6 containing styrene maleic anhydride without toughening and modification, the mechanical properties of which are hard and brittle after crosslinking are not good and cannot be improved even if a large amount of toughening agent or rubber is added externally, the laminates of examples 1 to 10 contain the toughened resin composition of the present invention, which shows good mechanical properties and electrical properties, and low water absorption, and can also reduce the amount of external toughening agent or rubber. Therefore, the invention is more suitable to be applied in a wide range of fields such as composite materials and electronic circuit materials.

In summary, the present invention provides a toughened resin composition, which uses olefinic polymers to toughen and modify styrene maleic anhydride compounds, and uses diisocyanate compounds to form polyimide bonds with it, so that the resin composition of the present invention has good mechanical properties and electrical properties, and has low water absorption. Therefore, compared with the hard and brittle mechanical properties of the conventional styrene maleic anhydride polymer resin composition after crosslinking, the present invention is more suitable for composite materials and electronic circuit materials, etc. The toughened resin composition of the present invention can be used in a wide range of fields such as aerospace, electronic motors, and automobile industries.

As used herein and not otherwise defined, the terms "substantially" and "approximately" are used to describe and describe small variations. When used in connection with an event or circumstance, the term can include the exact moment at which the event or circumstance occurs, as well as the event or circumstance occurring to a close approximation point. For example, when in conjunction with a value, the term may include a range of variation less than or equal to ±10% of the 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%.

The components of several embodiments are outlined above, so that those skilled in the art of the present invention can better understand the concepts of the embodiments of the present invention. Those with ordinary knowledge in the technical field of the present invention 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 described herein. Those having ordinary knowledge in the technical field of the present invention should also understand that these equivalent structures do not depart from the spirit and scope of the present invention, and that various changes, substitutions and other choices can be made herein without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.

100: Toughened and modified compound

110: Styrene maleic anhydride compound

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

130: Isophorone diisocyanate

Claims (8)

A toughened resin composition, comprising: (A) a toughened and modified compound, which includes a styrene maleic anhydride compound, an anhydride-grafted olefin polymer, and a diisocyanate compound; (B) a thermosetting polymer; and (C) a toughened resin; wherein, in the toughened and modified compound, the diisocyanate forms a polyimide bond with the styrene maleic anhydride compound and the anhydride-grafted olefin polymer; The thermosetting polymer is bismaleimide (BMI) resin, bismaleimide three

polymer, the toughening resin is a core-shell polymer and/or polybutadiene resin. The resin composition according to claim 1, wherein (A):(B):(C) is 15 to 30: 20 to 35: 0.1 to 5. The resin composition according to claim 1, wherein the ratio of styrene and maleic anhydride in the styrene-maleic anhydride compound is 3:1 to 6:1. The resin composition according to claim 1, wherein the anhydride-grafted olefinic polymer comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride. The resin composition as described in 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, etc. Isocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl phenylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-methane A group consisting of aniline diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate. The resin composition according to any one of claims 1 to 5, further comprising: a filler, the filler is selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene. The resin composition according to any one of claims 1 to 5, further comprising: a polybenzoxazine compound, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a bisamine type polybenzoxazine. The resin composition according to any one of claims 1 to 5, further comprising: a solvent, and 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.