TW202344606A - 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 containing an olefin polymer polymer toughened modified polybenzoxazine compound.

Polybenzoxazine is a type of thermosetting resin that contains nitrogen and has a structure similar to phenolic resin. Its performance is better than traditional phenolic resin. Benzoxazine compounds are generally composed of phenolic compounds, primary amines and formaldehyde compounds through Mannich ( Mannich) reaction, which undergoes ring-opening polymerization under the action of heat or a catalyst to form a network structure similar to phenolic resin, called benzoxazine resin.

Compared with traditional phenolic resins, benzoxazine resins have many excellent properties, such as: no small molecule by-products are released during the polymerization process, low volume shrinkage; low moisture absorption; heat resistance, mechanical properties, electrical properties, The flame retardant properties are all good. Therefore, benzoxazine resin is widely used in composite matrix resin, solvent-free impregnating paint, electronic packaging materials, flame retardant materials and electrical insulation materials.

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

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

The main purpose of the present invention is to provide a toughened resin composition, which includes: (A) a toughened modified compound, which includes a polybenzoxazine compound, an acid anhydride-grafted olefin polymer polymer, and A diisocyanate compound; and (B) a thermosetting polymer; wherein, in the toughened modified compound, the diisocyanate is formed by an olefin polymer polymer grafted with the polybenzoxazine compound and the acid anhydride respectively. bond.

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

In a preferred embodiment, the thermosetting polymer is bismaleimide (BMI) resin, bismaleimide trisulfide polymer, cyanate ester polymer, benzocyclobutene polymer, or phenolic resin.

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

In a preferred embodiment, the polybenzoxazine compound is selected from the group consisting of bisphenol A-type benzoxazine, bisphenol F-type benzoxazine, bisphenol S-type benzoxazine, and diaminodiphenylmethane. A group consisting of benzoxazines, diaminodiphenyl ether benzoxazines and polyimidized benzoxazines.

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 Maleic anhydride.

In a preferred embodiment, the diisocyanate compound is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 1,2-propylene diisocyanate. Isocyanates, 1,3-butylene diisocyanate, dodecylethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc., 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 A group consisting of diisocyanates and xylylene diisocyanates.

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, A group consisting of 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 uses an olefin polymer polymer to toughen and modify a polybenzoxazine compound, and uses a diisocyanate compound to form a bond with it. 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 composite materials. Therefore, the present invention has It has a wide range of applications in electronics, aerospace and other fields.

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. Elements, components, regions, layers and/or sections shall 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" used herein do not imply a sequence or order unless otherwise clearly indicated by the context.

Unless otherwise stated, "or" used herein means "and/or". Reference herein to "comprising" or "including" means not excluding the presence of or addition to the stated component, step, operation and/or element; similarly , "includes", "includes", "contains", "includes", and "has" mentioned in this article can be interchanged without limitation. "一" means that the grammatical object of the thing is one or more than one (that is, at least one). When used herein and in the claims, the singular forms "a", "an", "an" and "the" include plural references.

The invention is a toughened resin composition, which includes: (A) a toughened modified compound, which includes a polybenzoxazine compound, an acid anhydride-grafted olefin polymer polymer and a diisocyanate compound; and (B) thermosetting polymer; wherein, in the toughened and modified compound, the diisocyanate forms bonds with the polybenzoxazine compound and the acid anhydride-grafted olefin polymer polymer respectively.

The "polybenzoxazine compound (polybenzoxazine, also referred to as BZ in this article)" described in this article is a type of thermosetting resin that contains nitrogen and has a structure similar to phenolic resin. Benzoxazine compounds are composed of oxygen atoms and nitrogen atoms. The six-membered heterocyclic compound system is generally a compound prepared through the Mannich reaction of phenolic compounds, primary amines and formaldehyde compounds. This reaction undergoes ring-opening polymerization under the action of heating or a catalyst to generate a similar The network structure of phenolic resin can also be called benzoxazine resin. In a preferred embodiment, the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a diamine-type polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is selected from the group consisting of bisphenol A-type benzoxazine (BPA-BZ), bisphenol F-type benzoxazine (BPF-BZ), and bisphenol S-type benzoxazine. Benzoxazine (BPS-BZ), diaminodiphenylmethane-type benzoxazine (DDM-BZ), diaminodiphenyl ether-type benzoxazine (ODA-BZ) and polyimide benzene At least one member of the group consisting of polybenzoxazine with polyimide.

The anhydride-grafted olefin polymer polymer described herein has excellent electrical properties and good impact resistance. Preferably, the olefin polymer polymer of the toughener of the present invention is grafted with maleic anhydride. , has good compatibility with the base 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 maleic anhydride (SEBS-g-MA), polypropylene grafted maleic anhydride (PP(Poly Propylene)-g-MA) or polyethylene grafted maleic anhydride (PE(Poly Ethylene)-g-MA).

Among the diisocyanate compounds described herein, the diisocyanate forms bonds with the polybenzoxazine compound and the acid anhydride of the toughening agent respectively to achieve chemical modification. Cyanate ester compounds can increase the reactive functional groups in the resin structure, thereby increasing the cross-linking density of the epoxy cured product and improving the heat resistance. For example, the cyanate compound can be a multifunctional aliphatic isocyanate compound, a multifunctional alicyclic isocyanate compound, a multifunctional aromatic isocyanate compound, such as: trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecylethylene diisocyanate, 2,4,4-trimethyl Hexamethylene diisocyanate, etc., 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone Ketone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate Isocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diisocyanate Phenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, etc. In a preferred embodiment, the modifier 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 a polyethylene selected from isophorone diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride toughened. Benzoxazine compound (IPDI/SEBS-g-MA/BZ), methylene dicyclohexyl diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polystyrene Oxazine compound (HMDI/SEBS-g-MA/BZ), hexamethylene diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine Compound (HDI/SEBS-g-MA/BZ), isophorone diisocyanate modified polypropylene grafted with maleic anhydride toughened polybenzoxazine compound (IPDI/PP-g-MA/BZ), methylene Hexamethylene diisocyanate modified polypropylene grafted with maleic anhydride toughened polybenzoxazine compound (HMDI/PP-g-MA/BZ), hexamethylene diisocyanate modified polypropylene grafted with maleic anhydride Anhydride-toughened polybenzoxazine compound (HDI/PP-g-MA/BZ), isophorone diisocyanate-modified polyethylene grafted maleic anhydride-toughened polybenzoxazine compound (IPDI/PE- g-MA/BZ), methylene dicyclohexyl diisocyanate modified polyethylene grafted maleic anhydride toughened polybenzoxazine compound (HMDI/PE-g-MA/BZ) and hexamethylene diisocyanate A group consisting of isocyanate-modified polyethylene grafted with maleic anhydride-toughened polybenzoxazine compounds (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 Parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight or between any two of the aforementioned values; (B) Thermosetting polymerization 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 any two of the above between values.

The thermosetting polymer of the present invention can also be bismaleimide triamine. polymer, cyanate ester polymer, benzocyclobutene polymer, or phenolic resin. In a preferred embodiment, the thermosetting polymer of the present invention is bismaleimide (BMI) resin, which has a carbonyl group and a nitrogen-containing epoxy resin. It 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 the processing and molding of composite materials.

The toughened resin composition of the present invention may further include: a filler, a toughened 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, and 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, such as but not limited to: 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight or between any two of the aforementioned values.

In a preferred embodiment, the solvent is selected from the group consisting of toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, and N,N-dimethylmethane. The group consisting of amide, N,N-dimethylacetamide, N-methylpyrrolidone and combinations thereof.

In a preferred embodiment, the resin composition further includes: toughening resin, such as: a core-shell polymer and/or polybutadiene resin. Core shell polymers such as core shell rubber (CSR). The polybutadiene resin is, for example, polybutadiene homopolymer or butadiene-styrene copolymer. In a preferred embodiment, the toughening resin is 10 to 15 parts by weight, 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 between any two of the aforementioned values.

The present invention not only achieves the chemical modification of polyimide bonds through the reaction of isocyanate and acid anhydride, but also achieves the effect of toughening improvement through the modification of olefin polymer polymers and polybenzoxazine compounds, making the present invention have high toughness. with excellent mechanical properties. Furthermore, if the present invention is blended with other materials, composite materials with excellent properties can be formed. Example

In the following, the present invention will be further described with detailed descriptions and implementation examples. However, it should be understood that these implementation examples 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. It is not intended to limit the scope of the present invention. Example 1

Six toughened and modified compounds (example compounds AF) were prepared according to the present invention. Subsequently, Example Compound AF was used to prepare a metal foil laminate. Example Compound A

Please also refer to the exemplary reaction formula in Figure 1. In Figure 1, m, n, X, and Y are the same or different positive integers. Add 200 grams of bisphenol A-type benzoxazine (BPA-BZ) 110 and 600 grams of toluene into a 3-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube. , heat up to about 60°C, and stir evenly. While stirring, gradually add 20 grams of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA) 120 into the toluene solution within 20 minutes. At this time, the solution is synthesized. The temperature rises to 90°C to completely dissolve it. Then, add about 5 grams of isophorone diisocyanate (IPDI) 130, heat and gradually increase the temperature of the synthesis solution to about 130°C, and react for 1 hour. Then the heating was stopped and the temperature was cooled to room temperature to obtain Example Compound A, that is, the toughened modified compound 100. Example Compound B

Add 200 grams of ODA-BZ and 600 grams of toluene into a 3-liter, four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, raise the temperature to about 60°C, and stir evenly. While stirring, gradually add 20 grams of SEBS-g-MA to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rises to 90°C to completely dissolve it. Then, add about 5 grams of IPDI, heat and gradually increase the temperature of the synthetic solution to about 130°C, and react for 1 hour. Then, the heating was stopped and the temperature was cooled to room temperature to obtain Example Compound B. Example Compound C

Add 200 grams of BPA-BZ and 600 grams of toluene into a 3-liter, four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, raise the temperature to about 60°C, and stir evenly. While stirring, gradually add 20 grams of PP-g-MA into the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rises to 90°C to completely dissolve it. Then, add about 5 grams of IPDI, heat and gradually increase the temperature of the synthetic solution to about 130°C, and react for 1 hour. Then, the heating was stopped and the temperature was cooled to room temperature to obtain Example Compound C. Example Compound D

Add 200 grams of BPA-BZ and 600 grams of toluene into a 3-liter, four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, raise the temperature to about 60°C, and stir evenly. While stirring, gradually add 20 grams of PE-g-MA to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rises to 90°C to completely dissolve it. Then, add about 5 grams of IPDI, heat and gradually increase the temperature of the synthetic solution to about 130°C, and react for 1 hour. Then the heating was stopped and the temperature was cooled to room temperature to obtain the compound D of Example. Example Compound E

Add 200 grams of BPA-BZ and 600 grams of toluene into a 3-liter, four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, raise the temperature to about 60°C, and stir evenly. While stirring, gradually add 20 grams of SEBS-g-MA to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rises to 90°C to completely dissolve it. Then, add about 5 grams of HMDI, heat and gradually increase the temperature of the synthesis solution to about 130°C, and react for 1 hour. Then the heating was stopped and the temperature was cooled to room temperature to obtain the compound E of Example. Example Compound F

Add 200 grams of BPA-BZ and 600 grams of toluene into a 3-liter, four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, raise the temperature to about 60°C, and stir evenly. While stirring, gradually add 20 grams of SEBS-g-MA to the toluene solution within 20 minutes. At this time, the temperature of the synthetic solution rises to 90°C to completely dissolve it. Then, add about 5 grams of HDI, heat and gradually increase the temperature of the synthetic solution to about 130°C, and react for 1 hour. Subsequently, the heating was stopped and the temperature was cooled to room temperature to obtain Example Compound F. Material

BPA-BZ and ODA-BZ are produced by Yuanhong Company; SEBS-g-MA is produced by Taiwan Li Changrong 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.

Table 1 Example compounds A B C D E F Acid anhydride-grafted olefin polymer polymer SEBS-g-MA 20 20 20 20 PP-g-MA 20 PE-gMA 20 Polybenzoxazine compounds BPA-BZ 600 600 600 600 600 ODA-BZ 600 Solvent Toluene 600 600 600 600 600 600 Modifier IPDA 5 5 5 5 HMDI 5 HDI 5 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 the Example compounds were prepared according to methods similar to those disclosed below. . However, the specific methods for preparing Example Laminated Sheets 1-10 and Comparative Example Laminated Sheets 1-6 will generally differ from the methods disclosed below in one or more aspects. Example laminated board 1

Preparation of the resin composition: Take 30 grams of the compound A solution of the above example, add 5 grams of thermosetting resin (BMI), 25 grams of CNE epoxy resin and 40 grams of solvent (butanone, MEK), mix evenly with a homogenizer and mix The ingredients dissolve. After it is completely dissolved, add 40 grams of silica, continue to mix evenly with a homogenizer and disperse it in the solvent to prepare a varnish liquid resin composition.

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

Preparation of metal foil laminates: Laminate four prepreg sheets, and laminate a 0.5-ounce metal foil (copper foil) on each of the outermost layers on both sides, and then place them in a heat press for high-temperature hot-press curing. The hot pressing conditions are: heating up to 200°C to 220°C at a heating rate of 3.0°C/min, and at this temperature, using a full pressure of 15kg/cm2 (initial pressure of 8kg/cm2). Press for 180 minutes to prepare a copper foil laminated board. Example laminated board 2-10

Embodiment laminated board 2-10 is prepared according to a method similar to that of embodiment laminated board 1. However, embodiment laminated board 2-10 will be different in one or more aspects. The specific differences are shown in Table 2 below.

Table 2 shows the preparation ingredients and contents of the laminated boards 1-10 of Examples, as well as the measurement results of physical properties such as bonding strength, thermal expansion coefficient, thermal expansion coefficient in the Z-axis direction, and heat resistance.

Table 2 Example laminated board 1 2 3 4 5 6 7 8 9 10 Example compounds A 30 20 40 B 30 35 40 C 30 D 30 E 30 F 30 thermosetting resin BMI KI-70 5 5 5 5 5 5 5 5 5 5 Epoxy resin CNE epoxy 25 25 25 25 25 25 35 15 20 15 filler SiO ₂ 40 40 40 40 40 40 40 40 40 40 Solvent MEK 40 40 40 40 40 40 40 40 40 40 Reinforcement material Glass Cloth EG EG EG EG EG EG EG EG EG EG Measure physical properties Tg (TMA) ^o C 177 173 176 180 172 172 173 172 172 174 Z-CTE % 2.3% 2.5% 2.5% 2.1% 2.8% 2.1% 2.6% 2.8% 2.8% 2.9% Then strength lbf/in 4.7 4.4 4.9 4.2 4.9 4.4 4.2 4.2 4.7 4.6 Heat resistance 288 ^o C ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance 300 ^o C ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Note: EG in the table means E-Glass. The adding unit of each ingredient in the table is grams. Comparative Example Laminated Board 1

Preparation of resin composition: add 30 grams of BPA-BZ without toughening modification, 5 grams of thermosetting resin (BMI), 25 grams of epoxy resin, 2 grams of toughening resin and 40 grams of solvent (Methyl Ketone, MEK). Mix evenly with a homomixer and dissolve the ingredients. After it is completely dissolved, add 40 grams of silica, continue to mix evenly with a homogenizer and disperse it in the solvent to prepare a varnish liquid resin composition.

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

Preparation of metal foil laminates: Laminate four prepreg sheets, and laminate a 0.5-ounce copper foil on the outermost layers on both sides, and then place them in a hot press for high-temperature hot pressing and solidification. The hot pressing conditions are: heating up to 200°C to 220°C at a heating rate of 3.0°C/min, and at this temperature, using a full pressure of 15kg/cm2 (initial pressure of 8kg/cm2). Press for 180 minutes. A copper foil laminated board was produced. Comparative Example Laminated Board 2-6

Comparative Example laminated boards 2-6 were prepared according to a method similar to that of Comparative Example laminated board 1. However, Comparative Example laminated boards 2-6 will be different in one or more aspects, and the specific differences are disclosed in Table 3 below.

Table 3 shows the preparation ingredients and contents of the laminates 1-6 of Comparative Examples, as well as the measurement results of physical properties such as bonding strength, thermal expansion coefficient, thermal expansion coefficient in the Z-axis direction, and heat resistance.

table 3 Comparative Example Laminated Board 1 2 3 4 5 6 Unmodified BZ BPA-BZ 30 30 30 ODA-BZ 30 30 30 thermosetting resin BMI KI-70 5 5 5 5 5 5 Epoxy resin CNE epoxy 25 25 25 25 25 25 Toughened resin CSR 2 4 1.5 1 Ricon 100 2 1 filler SiO ₂ 40 40 40 40 40 40 Solvent MEK 40 40 40 40 40 40 Reinforcement material Glass Cloth EG EG EG EG EG EG Measure physical properties Tg (TMA) ^o C 169 167 158 162 168 167 Z-CTE % 3.4% 3.1% 4.1% 3.3% 3.5% 3.8% Then strength lbf/in 4.3 4.1 4.8 4.6 4.4 4.1 Heat resistance 288 ^o C ○ ○ ○ × × × Heat resistance 300 ^o C × × × × × × Note: The CSR in the table is the core-shell rubber body. Ricon 100 is a butadiene-styrene copolymer. EG stands for E-Glass. The adding unit of each ingredient in the table is grams. Material

BPA-BZ and ODA-BZ are produced by Yuanhong Company; the filler _SiO2 is 10 um cut produced by Sibelco Company; the thermosetting resin BMI (KI-70) is produced by Daiwa Chemical Company; CNE epoxy resin is produced by Produced by Changchun Artificial Resin Company; the reinforcing material is E-Glass glass cloth 2116 produced by Taiwan Glass Company; the toughening resin is CSR produced by Kaneka Company, and Ricon 100 produced by Polyscope Company; the copper foil is H1 0.5 OZ produced by Nanya Company. Feature testing

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

Adhesion strength test: Adhesion strength refers to the adhesion of the metal foil to the laminated prepreg sheet. In this test, a copper foil with a width of 1/8 inch is peeled vertically from the board surface and the required strength is used. The size expresses the strength of adhesion. Tear strength is measured in pounds of force per inch (lbf/in).

Heat resistance test: Soak the dried metal foil laminate in a soldering bath at 288°C and 300°C for 100 seconds. Repeat the process three times. It indicates excellent heat resistance and is recorded as "○"; when there is a bulge in the appearance When the bubbles are raised, it indicates poor heat resistance and is recorded as "×".

It can be seen from the above results that compared with the comparative example laminates 1 to 6, which contain polybenzoxazine compounds without toughening modification, their hard and brittle mechanical properties are poor after cross-linking, and even if a large amount of toughening agent is added externally, Or rubber cannot be improved. The laminates 1 to 10 of Examples include 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 manufacturing method thereof, which uses olefin polymer polymers to toughen and modify the polybenzoxazine compound, and uses a diisocyanate compound to form a chemical bond with it. The compound of the present invention has good mechanical properties and heat resistance. Therefore, compared with the mechanical properties of conventional polybenzoxazine compounds that are relatively brittle after thermal ring-opening polymerization, the present invention is more suitable for application in composite materials and electronic circuit materials. The toughened modified compound of the present invention is used. Resin materials can be used in a wide range of fields such as aerospace, electronics and motors, and the automotive industry.

As used herein and not otherwise defined, the terms "substantially" and "approximately" are used to describe and describe small changes. When used in connection with an event or situation, the term may include the precise moment at which the event or situation occurs, as well as the event or situation occurring to a close approximation. For example, when combined 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 components of several embodiments are summarized above so that those with ordinary skill in the technical field to which the present invention belongs can better understand the concepts of the embodiments of the present invention. It should be understood by those of ordinary skill in the technical field 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 purposes and/or achieve the same results as the embodiments introduced herein. benefits. Those with ordinary skill in the technical field 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 modifications can be made without departing from the spirit and scope of the present invention. Changes, Substitutions and Alternatives. Therefore, the protection scope of the present invention shall be determined by the appended patent application scope.

100: Toughened and modified compound 110: Bisphenol A polybenzoxazine 120: Styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride 130: Isophorone diisocyanate

The details of one or more embodiments 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 become apparent from the description, drawings and claims, among which:

Figure 1 is a schematic diagram of a reaction scheme of a preferred embodiment of the present invention.

100: Toughened and modified compound

110: Bisphenol A polybenzoxazine

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

130: Isophorone diisocyanate

Claims (10)

A toughened resin composition containing: (A) A toughened modified compound, which includes a polybenzoxazine compound, an anhydride-grafted olefin polymer polymer and a diisocyanate compound; and (B) Thermosetting polymers; Wherein, in the toughened and modified compound, the diisocyanate forms bonds with the polybenzoxazine compound and the acid anhydride-grafted olefin polymer polymer respectively. The resin composition according to claim 1, wherein (A) the toughened modified compound is 30 to 50 parts by weight; (B) the thermosetting polymer is 8 to 15 parts by weight. The resin composition according to claim 1, wherein the thermosetting polymer is bismaleimide (BMI) resin, bismaleimide tris polymer, cyanate ester polymer, benzocyclobutene polymer, or phenolic resin. The resin composition according to claim 1, wherein the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a diamine-type polybenzoxazine. The resin composition according to 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, bisphenol S-type benzoxazine, A group consisting of aminodiphenylmethane-type benzoxazines, diaminodiphenyl ether-type benzoxazines and polyimidized benzoxazines. The resin composition according to claim 1, wherein the anhydride-grafted olefin polymeric polymer includes: styrene-ethylene/butylene-styrene copolymer grafted with maleic anhydride, polypropylene grafted with maleic anhydride Or polyethylene grafted with maleic anhydride. The resin composition according to claim 1, wherein the diisocyanate compound is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2 -Propylene diisocyanate, 1,3-butylene diisocyanate, dodecylethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc., 1,3-cyclopentene diisocyanate Isocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenyl methylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, A group consisting of 1,5-naphthalene diisocyanate and xylylene diisocyanate. The resin composition according to any one of claims 1 to 7, further comprising: a filler selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, nitrogen 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 claim 8, wherein the filler is 40 to 60 parts by weight. The resin composition according to any one of claims 1 to 7, further includes: 10 to 15 parts by weight of toughening resin.