TWI867298B - 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 polybenzoxazine compound, an anhydride grafted olefin polymer, and a diisocyanate compound; and (B) a thermosetting polymer; wherein, in the toughened and modified compound, the diisocyanate forms a bond with the polybenzoxazine 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 present invention relates to a toughened resin composition, in particular to a resin composition having an olefin polymerized high molecular weight toughened and modified polybenzoxazine compound.

Polybenzoxazine is a type of thermosetting resin containing nitrogen and having a structure similar to phenolic resin. Its performance is superior to that of traditional phenolic resin. Benzoxazine compounds are generally prepared by the Mannich reaction of phenolic compounds, primary amines and formaldehyde compounds. Under the action of heat or catalyst, the reaction undergoes ring-opening polymerization to form a reticular structure similar to phenolic resin, called benzoxazine resin.

Compared with traditional phenolic resins, benzoxazine resins have many excellent properties, such as: no small molecular byproducts are released during the polymerization process, low volume shrinkage rate; low moisture absorption rate; good heat resistance, mechanical properties, electrical properties, and flame retardant properties. Therefore, benzoxazine resins are widely used in composite material matrix resins, solvent-free impregnation paints, electronic packaging materials, flame retardant materials, and electrical insulation materials.

Although benzoxazine resin has many of the above advantages, its mechanical properties are relatively brittle after the thermal ring-opening polymerization reaction, which is an obstacle that needs to be overcome in its application development.

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

The main purpose of the present invention is to provide a toughened resin composition, which comprises: (A) a toughened modified compound, which comprises 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 forms a bond with the polybenzoxazine compound and the anhydride grafted olefin polymer, respectively.

In a preferred embodiment, (A) the toughened and modified compound is 30 to 50 parts by weight; (B) the thermosetting polymer is 5 or 8 to 15 parts by weight.

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 tris(III)

polymer, cyanate ester polymer, benzocyclobutene polymer, or phenolic resin.

In a preferred embodiment, the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a bisamine-type polybenzoxazine.

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 polyimidized benzoxazine.

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

In a preferred embodiment, the diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl diisocyanate, 1,3-butyl diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, diphenyl diisocyanate, etc. The group consisting of methyl methane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.

In a preferred embodiment, the resin composition 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, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene.

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

In a preferred embodiment, the resin composition further includes: 10 to 15 parts by weight of toughening resin.

Therefore, the toughened resin composition provided by the present invention includes a toughened modified compound, which is a polybenzoxazine compound toughened and modified by an olefin polymer, and a diisocyanate compound is used to form a bond with it, so that the compound of the present invention has good heat resistance and mechanical properties, and low water absorption. The present invention has excellent heat resistance, low expansion, high dimensional stability, high mechanical strength and high toughness, and can be blended with other thermosetting polymers, inorganic fillers or fibers to form a composite material. Therefore, the present invention has a wide range of applications in the fields of electronics, aerospace, etc.

100: Toughened and modified compound

110: Bisphenol A type polybenzoxazine

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

130: Isophorone diisocyanate

The following figures and descriptions describe the details of one or more embodiments of the subject matter described in this specification. From the description, figures and patent application scope, other features, aspects and advantages of the subject matter of this specification will become apparent, among which: Figure 1 is a reaction diagram of a preferred embodiment of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those understood by persons of ordinary skill in the art to which the present 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 parts, which should not be limited by these terms. These terms may only be used to distinguish one element, component, region, layer, or part from another. Unless the context clearly indicates otherwise, the terms such as "first", "second", "third", "fourth", and "fifth" used herein do not imply a sequence or order.

Unless otherwise specified, the "or" mentioned in this article means "and/or". The "include" or "comprising" mentioned in this article does not exclude the existence of one or more other components, steps, operations and/or elements or addition to the components, steps, operations and/or elements described; similarly, the "include", "include", "contain", "include", "have" mentioned in this article can be interchanged without limitation. "One" means that the grammatical object of the thing is one or more (that is, at least one). The singular formats of "one", "one", "a kind" and "the" described in this article and the scope of the patent application include plural references.

The present invention is a toughened resin composition, which comprises: (A) a toughened modified compound, which comprises 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 forms a bond with the polybenzoxazine compound and the anhydride grafted olefin polymer, respectively.

The "polybenzoxazine compound (hereinafter referred to as BZ)" described herein is a type of thermosetting resin containing nitrogen and having a structure similar to that of phenolic resin. The benzoxazine compound is a six-membered heterocyclic compound system composed of oxygen atoms and nitrogen atoms, and is generally a compound prepared by the Mannich reaction of a phenolic compound, a primary amine and a formaldehyde compound. The reaction undergoes ring-opening polymerization under the action of heat or a catalyst to form a network structure similar to that of phenolic resin, which can also be referred to as a benzoxazine resin. In a preferred embodiment, the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a bisamine-type polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is at least one selected from the group consisting of bisphenol A 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.

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

In the diisocyanate compound described herein, the diisocyanate forms a bond with the polybenzoxazine compound and the anhydride of the toughening agent to achieve chemical modification. The cyanate compound can increase the reactive functional groups in the resin structure, thereby increasing the crosslinking density of the epoxy cured product and improving the heat resistance. For example, the cyanate compound can be a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, or a polyfunctional aromatic isocyanate compound, such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl diisocyanate, 1,3-butyl diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene diisocyanate, or the like. Cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, and the like. In a preferred embodiment, the modifier includes: isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (Methylene dicyclohexyl diisocyanate or hydrogenated MDI, HMDI) or hexamethylene diisocyanate (HEXAMETHYLENE DISOCYANATE, HDI).

In a preferred embodiment, the toughened modified compound of the present invention includes a polybenzoxazine compound selected from isophorone diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride toughened (IPDI/SEBS-g-MA/BZ), a polybenzoxazine compound modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride toughened (HMDI/SEBS-g-MA/BZ), a polybenzoxazine compound modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride toughened (HDI/SEBS-g-MA/BZ), a polybenzoxazine compound modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride toughened (IPDI/PP- g-MA/BZ), polybenzoxazine compounds modified by methylene dicyclohexyl diisocyanate and grafted with maleic anhydride to strengthen the toughness (HMDI/PP-g-MA/BZ), polybenzoxazine compounds modified by hexamethylene diisocyanate and grafted with maleic anhydride to strengthen the toughness (HDI/PP-g-MA/BZ), polybenzoxazine compounds modified by isophorone diisocyanate and grafted with maleic anhydride to strengthen the toughness (IPDI/PE-g-MA/BZ), polybenzoxazine compounds modified by methylene dicyclohexyl diisocyanate and grafted with maleic anhydride to strengthen the toughness (HMDI/PE-g-MA/BZ), and polybenzoxazine compounds modified by hexamethylene diisocyanate and grafted with maleic anhydride to strengthen the toughness (HDI/PE-g-MA/BZ).

In a preferred embodiment, in the toughened resin composition of the present invention, (A) the toughened modified compound is 30 to 50 parts by weight, such as 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 foregoing values; (B) the thermosetting polymer is 5 or 8 to 15 parts by weight, such as 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 foregoing values or 5 parts by weight.

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 may also be bismaleimide tris(III)

In a preferred embodiment, the thermosetting polymer of the present invention is a dimaleimide (BMI) resin, which has a carbonyl group, a nitrogen-containing epoxy resin, and is cured by the unsaturation of the terminal group during processing and molding, and the curing process does not produce volatile substances, which will facilitate the processing of composite materials.

The toughened resin composition of the present invention may further include: a filler, a toughening resin 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 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 foregoing values.

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.

In a preferred embodiment, the resin composition further includes: a toughening resin, such as a core-shell polymer and/or a polybutadiene resin. The core-shell polymer is, for example, a core-shell rubber (CSR). The polybutadiene resin is, for example, a polybutadiene homopolymer or a butadiene-styrene copolymer. In a preferred embodiment, the toughening resin is 10 to 15 parts by weight, such as but not limited to: 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight or between any two of the foregoing values.

The present invention not only chemically modifies the polyimide bond by reacting isocyanate with anhydride, but also modifies olefin polymers and polybenzoxazine compounds to achieve the effect of toughening and improving, so that the present invention has high toughness and excellent mechanical properties. Furthermore, if the present invention is blended with other materials, it can form a composite material with excellent properties.

Embodiment

The present invention will be further described below with detailed explanations and implementations. However, it should be understood that these implementations are only used to help make the present invention easier to understand and to illustrate various aspects of the present invention and the benefits achieved, rather than to limit the scope of the present invention.

Embodiment 1

According to the present invention, six toughened and modified compounds (Example Compounds A-F) were prepared. Then, Example Compounds A-F were used to prepare metal foil laminates.

Example Compound A

Please refer to the exemplary reaction formula of FIG. 1 , in which m, n, X, and Y are the same or different positive integers. 200 g of bisphenol A benzoxazine (BPA-BZ) 110 and 600 g of toluene are added to a 3-liter four-necked separable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and the temperature is raised to about 60° C. and stirred evenly. Under stirring, 20 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA) 120 is gradually added to the toluene solution within 20 minutes, and the temperature of the synthetic solution is raised to 90° C. to make it completely dissolved. Then, add about 5 grams of isophorone diisocyanate (IPDI) 130, heat and gradually increase the temperature of the synthetic solution to about 130°C, and react for 1 hour. Then stop heating and cool to room temperature to obtain Example Compound A, that is, toughened modified compound 100.

Example Compound B

200 grams of ODA-BZ and 600 grams of toluene were added to a 3-liter four-necked separable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and the temperature was raised to about 60°C and stirred evenly. While stirring, 20 grams of SEBS-g-MA were gradually added to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of IPDI was added, and the synthetic solution was heated and gradually heated 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

200 grams of BPA-BZ and 600 grams of toluene were added to a 3-liter four-necked separable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and the temperature was raised to about 60°C and stirred evenly. While stirring, 20 grams of PP-g-MA were gradually added to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of IPDI was added, and the synthetic solution was heated and gradually heated 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

200 grams of BPA-BZ and 600 grams of toluene were added to a 3-liter four-necked separable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and the temperature was raised to about 60°C and stirred evenly. While stirring, 20 grams of PE-g-MA were gradually added to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of IPDI was added, and the synthetic solution was heated and gradually heated 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

200 grams of BPA-BZ and 600 grams of toluene were added to a 3-liter four-necked separable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and the temperature was raised to about 60°C and stirred evenly. While stirring, 20 grams of SEBS-g-MA were gradually added to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of HMDI was added, and the synthetic solution was heated and gradually heated 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

200 grams of BPA-BZ and 600 grams of toluene were added to a 3-liter four-necked separable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and the temperature was raised to about 60°C and stirred evenly. While stirring, 20 grams of SEBS-g-MA were gradually added to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rose to 90°C, and it was completely dissolved. Then, about 5 grams of HDI was added, and the synthetic solution was heated and gradually heated 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.

Material

BPA-BZ and ODA-BZ are produced by Yuan Hong Company; SEBS-g-MA is produced by Taiwan's Lee Chang Rong Company; PP-g-MA is produced by ExxonMobil Chemical Company (ExxonMobil), product model Exxelor ^TM PO1015; PE-g-MA is produced by ExxonMobil Chemical Company, product model Exxelor ^TM PE1040.

Table 1 below shows the preparation ingredients and contents of Example compounds A-F.

Embodiment 2

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

Embodiment Laminated board 1

Preparation of resin composition: Take 30 grams of the above-mentioned Example Compound A solution, add 5 grams of thermosetting resin (BMI), 25 grams of CNE epoxy resin and 40 grams of solvent (methyl ethyl ketone, MEK), and mix them evenly with a homogenizer to dissolve the components. After they are completely dissolved, add 40 grams of silicon dioxide, continue to mix evenly with a homogenizer and disperse it in the solvent to prepare a varnish liquid resin composition.

Preparation of prepreg: Impregnate or coat the reinforcing fiberglass 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 180°C for 7 minutes to obtain a semi-cured (B-stage) prepreg.

Preparation of metal foil laminate: Four prepreg sheets are laminated, and a 0.5 ounce metal foil (copper foil) is laminated on each of the outermost layers on both sides, and then placed in a hot press for high-temperature hot pressing curing. The hot pressing conditions are: heating at a rate of 3.0℃/min to 200℃ to 220℃, and at this temperature, hot pressing is performed for 180 minutes at a full pressure of 15 kg/cm2 (initial pressure of 8 kg/cm2) to obtain a copper foil laminate.

Example 2-10

Embodiments of the stacking plates 2-10 are prepared according to a method similar to that of embodiment of the stacking plate 1, however, embodiment of the stacking plates 2-10 may differ in one or more aspects, the specific differences being shown in Table 2 below.

Table 2 shows the preparation components and contents of the laminates 1-10 of the embodiment, as well as the physical property measurement results such as strength, thermal expansion coefficient in the Z-axis direction, and heat resistance.

Comparison example laminate 1

Preparation of resin composition: Add 30g of unmodified BPA-BZ, 5g of thermosetting resin (BMI), 25g of epoxy resin, 2g of toughening resin and 40g of solvent (methyl ethyl ketone, MEK), and mix them evenly with a homogenizer to dissolve the ingredients. After they are completely dissolved, add 40g of silicon dioxide, continue to mix evenly with a homogenizer and disperse it in the solvent to make a varnish liquid resin composition.

Preparation of prepreg: Impregnate or coat the reinforcing fiberglass 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 180°C for 7 minutes to obtain a semi-cured (B-stage) prepreg.

Preparation of metal foil laminate: Four prepreg sheets are laminated, and a 0.5 ounce copper foil is laminated on each of the outermost layers on both sides, and then placed in a hot press for high-temperature hot pressing curing. The hot pressing conditions are: heating at a rate of 3.0℃/min to 200℃ to 220℃, and at this temperature, hot pressing is performed for 180 minutes at a full pressure of 15 kg/cm2 (initial pressure of 8 kg/cm2). Copper foil laminate is obtained.

Comparison example laminate 2-6

Comparative example laminates 2-6 are prepared according to a method similar to the method of comparative example laminate 1, however, comparative example laminates 2-6 may differ in one or more aspects, the specific differences are disclosed in Table 3 below.

Table 3 compares the preparation components and contents of example laminates 1-6, as well as the physical property measurement results such as strength, thermal expansion coefficient in the Z-axis direction, and heat resistance.

Material

BPA-BZ and ODA-BZ are produced by Yuan Hong Company; filler _SiO2 is 10um cut produced by Sibelco; thermosetting resin BMI (KI-70) is produced by Yamato Chemical Company; CNE epoxy resin is produced by Chang Chun Synthetic Resin Company; reinforcement material is E-Glass cloth 2116 produced by Taiwan Glass Company; toughening resin is CSR produced by Kaneka Company and Ricon 100 produced by Polyscope Company; copper foil is H1 0.5 OZ produced by Nan Ya Company.

Characteristic test

CTE test: According to IPC-TM-650 2.4.24.5 specification, a thermal mechanical analyzer (TMA) is used to measure the coefficient of thermal expansion (CTE) of the sample under test at a temperature below the glass transition temperature (Tg) in the Z-axis direction (total z-CTE). Z-CTE is measured in the temperature range of 50℃ to 260℃, and the unit is %.

Tear strength test: Tear strength refers to the adhesion of 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 of the adhesion is expressed by the amount of force required. The unit of tear strength is pound force/inch (lbf/in).

Heat resistance test: Soak the dried metal foil laminate in a solder bath at 288℃ and 300℃ for 100 seconds, and repeat the process 3 times. If the heat resistance is good, it is recorded as "○". If there are bubbling bulges on the surface, it means that the heat resistance is poor, and it is recorded as "×".

From the above results, it can be seen that compared with the comparative example laminates 1 to 6 containing the untoughened polybenzoxazine compound, the mechanical properties of the crosslinked hard and brittle are poor, and even adding a large amount of toughening agent or rubber cannot improve it. The embodiment laminates 1 to 10 contain the toughened resin composition of the present invention, showing good mechanical properties and heat resistance. Therefore, the present invention is more suitable for application in a wide range of fields such as composite materials and electronic circuit materials.

In summary, the present invention provides a toughened modified compound and a method for manufacturing the same, wherein an olefin polymer is used to toughen and modify a polybenzoxazine compound, and a diisocyanate compound is used to form a chemical bond with the compound, so that the compound of the present invention has good mechanical properties and heat resistance. Therefore, compared with the known polybenzoxazine compound having brittle mechanical properties after thermal ring-opening polymerization, the present invention is more suitable for application in composite materials and electronic circuit materials, etc., and the resin material using the toughened modified compound of the present invention can be used in a wide range of fields such as aerospace, electronic machinery, and automotive industries.

As used herein and not otherwise defined, the terms "substantially" and "approximately" are used to describe and describe small variations. When used in conjunction with an event or circumstance, the term may include the exact time at which the event or circumstance occurred, as well as the event or circumstance occurring to a close approximation. For example, when used in conjunction with a numerical value, the term may include a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%.

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

100: Toughened and modified compound

110: Bisphenol A type polybenzoxazine

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

130: Isophorone diisocyanate

Claims (9)

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; and (C) a CNE epoxy resin; wherein the diisocyanate in the toughened modified compound forms a bond with the polybenzoxazine compound and the anhydride grafted olefin polymer, respectively; wherein (A) the toughened modified compound is 30 to 50 parts by weight; and (B) the thermosetting polymer is 5 parts by weight. The resin composition as claimed in claim 1, wherein the thermosetting polymer is bismaleimide (BMI) resin, bismaleimide tris(III) resin,

polymer, cyanate ester polymer, benzocyclobutene polymer, or phenolic resin. The resin composition as described in claim 1, wherein the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a diamine-type polybenzoxazine. The resin composition as described in claim 1, wherein 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 polyimidized benzoxazine. The resin composition as described in claim 1, wherein the anhydride-grafted olefin polymer comprises: styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride, polypropylene grafted with maleic anhydride or polyethylene grafted with maleic anhydride. The resin composition as claimed in claim 1, wherein the diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl diisocyanate, 1,3-butyl diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, The group consisting of hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate. The resin composition as described in any one of claims 1 to 6 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, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene. The resin composition as described in claim 7, wherein the filler is 40 to 60 parts by weight. The resin composition as described in any one of claims 1 to 6 further comprises: 10 to 15 parts by weight of toughening resin.