TWI550023B - Resin formulations and resin compositions and composite materials comprising the resin compositions - Google Patents

Description

Resin formulation and composition and composite material containing the same

This invention relates to a resin formulation, and more particularly to a high heat resistant resin formulation.

In the composition of the halogen-free material, the phosphide is generally selected as a flame retardant, replacing the existing halogen compound, or with aluminum hydroxide to achieve the UL-94 V0 flame resistance requirement. In addition to the Bismaleimide Triazine (BT) resin, there are epoxy resin-based heat-resistant materials for thermo-mechanical analyzers (Thermal). Mechanical Analyzer, TMA) The measured Tg is around 180 °C, and it needs to be matched with flame-resistant inorganic powder or flame-resistant resin to achieve good flame resistance. Therefore, there is a need in the industry for a resin that is environmentally friendly, has high heat resistance (Tg over 180 ° C), and low dielectric to meet the needs of components.

One embodiment of the present disclosure provides a resin formulation comprising: a carboxy anhydride derivative having 5 to 100 parts by weight; a diisocyanate having 30 to 150 parts by weight; styrene maleic anhydride (styrene) A maleic anhydride (SMA) derivative having 5 to 70 parts by weight; and a bismaleimide (BMI) derivative having 60 to 400 parts by weight.

One embodiment of the present disclosure provides a resin prepolymer having the following chemical formula (I) or (II):

(II)

Wherein R ₁ is -(CH ₂ ) ₂ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₁₂ -, -CH ₂ -C(CH ₃ ) ₂ -CH ₂ - CH(CH ₃ )-CH ₂ -CH ₂ -, , A is a benzene ring or cyclohexane, R is -H, -CH ₃ or -COOH, q is 0-8, z is 1~2,000, x is 1~1,000, y is 1~1,000, m is 1~ 7, n is 2~15.

One embodiment of the present disclosure provides a resin composition prepared by heating the above-mentioned resin prepolymer.

An embodiment of the present disclosure provides a composite material comprising: a substrate; and a resin composition as described above formed on the substrate.

The above described objects, features and advantages of the present invention will become more apparent and understood.

An embodiment of the present invention provides a resin formulation comprising: a carboxy anhydride derivative having 5 to 100 parts by weight, for example 10 to 80 parts by weight; diisocyanate having 30 to 150 parts by weight, for example 40 to 120 parts by weight; styrene maleic anhydride (SMA) derivative having 5 to 70 parts by weight, for example 10 ~60 parts by weight; and a bismaleimide (BMI) derivative having 60 to 400 parts by weight, for example, 100 to 300 parts by weight.

The above carboxylic anhydride derivative may have the following chemical formula:

In the formula, A may be a benzene ring or a cyclohexane, R may be -H, -CH ₃ or -COOH, and q may be 0-8. The carboxylic anhydride derivative is, for example, trimellitic anhydride (TMA), c-TMA (Cyclohexane-1, 2,4-tricarboxylic acid-1, 2-anhydride) or a combination thereof.

The above diisocyanate may include methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), or a combination thereof.

The above styrene maleic anhydride (SMA) derivative may have the following chemical formula:

In the chemical formula, m can be from 1 to 7, and n can be from 2 to 15.

The above bismaleimide (BMI) derivative may have the following chemical formula:

In the formula, R ₁ may be -(CH ₂ ) ₂ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₁₂ -, -CH ₂ -C(CH ₃ ) ₂ - CH ₂ -CH(CH ₃ )-CH ₂ -CH ₂ -,

The solvent of the resin formulation may be appropriately selected according to the diisocyanate and bismaleimide (BMI) used, including but not limited to acetone, methyl ethyl ketone, and propylene glycol. 1-methoxy-2-propanol, 1,2-Propanediol monomethyl ether acetate, toluene, xylene, dimethyl formamide (DMF) , N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO) or a combination thereof.

In one embodiment, the above carboxylic anhydride, diisocyanate, styrene maleic anhydride (SMA), bismaleimide (BMI) and solvent are mixed and heated. To carry out a prepolymerization reaction, a prepolymer is formed, the reaction temperature is about 80 ° C to 140 ° C, for example, about 90 ° C to 130 ° C; and the reaction time is about 0.5 to 6 hours, for example, about 1 to 3.5 hours.

One embodiment of the present invention provides a resin prepolymer having the following chemical formula (I) or (II):

(II)

In the formulae (I) and (II), R ₁ may be -(CH ₂ ) ₂ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₁₂ -, -CH ₂ - C(CH ₃ ) ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -CH ₂ -, A may be a benzene ring or a cyclohexane, R may be -H, -CH ₃ or -COOH, q may be 0 to 8, z may be 1 to 2,000, x may be 1 to 1,000, and y may be 1 to 1,000. m can be 1~7, and n can be 2~15.

According to an embodiment of the present invention, there is provided a resin composition prepared by heating the above-mentioned resin prepolymer.

An embodiment of the present invention provides a composite material comprising: a substrate; and a resin composition as described above formed on the substrate.

The above substrate may comprise fibers or metals.

The high heat resistant resin prepolymer can be used for various applications according to actual needs. In one embodiment, the high heat resistant resin prepolymer solution can be used to prepare a high heat resistant resin composite material, the method comprising: applying the present high heat resistant resin prepolymer solution to a metal foil, such as a copper foil, about 175 ~225 ° C, for example, about 185 to 215 ° C, heat and pressure for about 1 to 4.5 hours, for example, about 1.5 to 3.5 hours, to obtain a high heat resistant resin composite material, which can be used as a high heat resistant substrate material.

In another embodiment, the high heat resistant resin prepolymer solution may be used in combination with the fiber to prepare a high heat resistant resin composite material, the method comprising: The fiber is impregnated with the high heat resistant resin prepolymer solution of the present disclosure, and is laminated and heated and pressurized. In an embodiment, the fibers in the high heat resistant resin composite may include glass fiber cloth or polyamide fiber. The heat hardening step is carried out at about 175 to 225 ° C, for example, about 185 to 215 ° C, for about 1 to 4.5 hours, for example, about 1.5 to 3.5 hours, to obtain a high heat resistant resin composite.

The resin composite material obtained by the above preparation method does not contain a halogen-based or phosphorus-based flame retardant, and can pass the UL94V-0 flame resistance test without adding an inorganic flame retardant powder such as aluminum hydroxide, and the dielectric constant (Dk) range thereof. It is between about 3.9 and 5.4, for example between about 4.1 and 4.3, and has a glass transition temperature (Tg) greater than about 180 ° C, such as between about 180 and 250 ° C.

[Examples] [Example 1] Preparation of composite materials (1)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 57.5 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 100g bismaleimide (KI Chemical Co.) and 376.3g DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes After the reaction is completed, the temperature is lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good storage properties (at room temperature) The glue viscosity is about 600 cps, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Example 2] Preparation of composite materials (2)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 57.5 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 150.9 g of bismaleimide (KI Chemical Co.) and 452.8 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C 180 In the minute, after the reaction is completed, the temperature is lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good water storage properties (the viscosity of the glue is about 600 cps at room temperature, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Example 3] Preparation of composite materials (3)

Using a 1000 ml, 3-port glass reactor, 2 impeller stir bars, 57.5 g TMA (trimellitic anhydride, Fu-Pao Chemical) Co.), 79.1 g MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4 g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g of bismaleimide (KI Chemical Co.) And 552.6 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes, and after the reaction was completed, the temperature was lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good water storage properties (the viscosity of the glue is about 600 cps at room temperature, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Embodiment 4] Preparation of composite materials (4)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 57.5 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 300g bismaleimide (KI Chemical Co.) and 676.3g DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes After the reaction is completed, the temperature is lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good storage properties (at room temperature) The glue viscosity is about 600 cps, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Embodiment 5] Preparation of composite materials (5)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 14.4 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 57.5 g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g of bismaleimide (KI Chemical Co.) and 552.6 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C 180 In the minute, after the reaction is completed, the temperature is lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good water storage properties (the viscosity of the glue is about 600 cps at room temperature, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Embodiment 6] Preparation of composite materials (6)

Using a 1000 ml, 3-port glass reactor, 2 impeller stir bars, 14.4 g TMA (trimellitic anhydride, Fu-Pao Chemical) Co.), 79.1 g MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4 g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g of bismaleimide (KI Chemical Co.) And 488.2 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes, and after the reaction was completed, the temperature was lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good water storage properties (the viscosity of the glue is about 600 cps at room temperature, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Embodiment 7] Preparation of composite materials (7)

Using a 1000 ml, 3-port glass reactor, 2 impeller stir bars, 77 g TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4 were added. g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g of bismaleimide (KI Chemical Co.) and 581.9 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes After the reaction is completed, the temperature is lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good storage properties (at room temperature) The glue viscosity is about 600 cps, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Embodiment 8] Preparation of composite materials (8)

Using a 1000 ml, 3-port glass reactor, 2 impeller stir bars, 57.5 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 40 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4 were added. g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g of bismaleimide (KI Chemical Co.) and 494 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes. After the end of the reaction, the temperature was lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good water storage properties (the viscosity of the glue is about 600 cps at room temperature, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Embodiment 9] Preparation of composite materials (9)

Using a 1000 ml, 3-port glass reactor, 2 impeller stir bars, 57.5 g TMA (trimellitic anhydride, Fu-Pao Chemical) Co.), 120 g MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4 g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g of bismaleimide (KI Chemical Co.) and 614 g of DMF (dimethylformamide, C-ECHO Co.) was stirred at 105 ° C for 180 minutes, and after the reaction was completed, the temperature was lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formula glue is impregnated into the glass fiber cloth, and the laminate is heated and pressed at 200 ° C for 3 hours to obtain a high heat-resistant composite material. This formula has good water storage properties (the viscosity of the glue is about 600 cps at room temperature, and the viscosity of the glue can be maintained within 600±50 cps for more than one month; the viscosity change is less than or equal to 10%). The composition and physical properties of this composite are shown in Table 1.

[Comparative Example 1] Preparation of composite materials (1)

Using a 1000 ml, 3-port glass reactor, 2 impeller stir bars, 79.1 g MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4 g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g bismaleimide (KI Chemical Co.) and 467 g DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes, after the reaction is completed, the temperature is lowered to room temperature, that is, high heat resistance is obtained. Formulated with varnish. Finally, the formulation glue was impregnated into the glass fiber cloth, and the substrate material was obtained by heating and pressing at 200 ° C for 3 hours. This formula has poor storage properties (cannot be stored for more than 1 month at room temperature). The composition and physical properties of this composite are shown in Table 1.

[Comparative Example 2] Preparation of composite materials (2)

Using a 1000 ml, 3-port glass reactor, two impeller stir bars, 14.4 g SMA3000F (styrene maleic anhydride, Cray Valley Co.), 217.5 g bismaleimide (KI Chemical Co.) and 348 g of DMF (dimethylformamide, C-ECHO Co.) was stirred at 105 ° C for 180 minutes, and after the reaction was completed, the temperature was lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formulation glue was impregnated into the glass fiber cloth, and the substrate material was obtained by heating and pressing at 200 ° C for 3 hours. This formula has poor storage properties (cannot be stored for more than 1 month at room temperature). The composition and physical properties of this composite are shown in Table 1.

[Comparative Example 3] Preparation of composite materials (3)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 79.1 g MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 217.5 g of bismaleimide (KI Chemical Co.) was added. And 445 g of DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes, and after the reaction was completed, the temperature was lowered to room temperature to obtain a high heat resistant formula varnish. Finally, the formulation glue was impregnated into the glass fiber cloth, and the substrate material was obtained by heating and pressing at 200 ° C for 3 hours. This formula has good storage properties (can be stored at room temperature for greater than or equal to 1 month). The composition and physical properties of this composite are shown in Table 1.

[Comparative Example 4] Preparation of composite materials (4)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 57.5 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 217.5 g of bismaleimide (KI Chemical Co.) and 532 g of DMF (dimethylformamide, C-ECHO Co.) were stirred at 105 ° C for 180 minutes, and after the reaction was completed, the temperature was lowered to room temperature, which was high. Heat resistant formula varnish. Finally, the formulation glue was impregnated into the glass fiber cloth, and the substrate material was obtained by heating and pressing at 200 ° C for 3 hours. This formula has good storage properties (can be stored at room temperature for greater than or equal to 1 month). The composition and physical properties of this composite are shown in Table 1.

[Comparative Example 5] Preparation of composite materials (5)

Using a 1000 ml, 3-neck glass reactor, two impeller stir bars, 57.5 g of TMA (trimellitic anhydride, Fu-Pao Chemical Co.), 79.1 g of MDI (methylene diphenyl isocyanate, Fu-Pao Chemical Co.), 14.4g SMA3000F (styrene maleic anhydride, Cray Valley Co.) and 227g DMF (dimethylformamide, C-ECHO Co.), stirred at 105 ° C for 180 minutes, after the reaction is completed, the temperature is lowered to room temperature, that is, high heat-resistant formula glue is obtained. (varnish). Finally, the formula is glued, impregnated with glass fiber cloth, and laminated and heated at 200 ° C for 3 hours. The substrate material is then obtained. This formula has poor storage properties (cannot be stored for more than 1 month at room temperature). The composition and physical properties of this composite are shown in Table 1.

TMA: trimellitic anhydride

MDI: methylene diphenyl diisocyanate

SMA: styrene maleic anhydride

BMI: bismaleimide

Dk: dielectric constant (dielectric constant)

Df: Dissipation factor

Tg: glass transition temperature

Td _5% : decomposition temperature

It can be seen from Table 1 that Examples 1 to 9 all have good flame resistance characteristics, which is obviously superior to the comparative examples.

The resin composite material provided by the above embodiments has the characteristics of environmental protection and high heat resistance, the Tg exceeds 180 ° C, and its low dielectric property makes it suitable for the high-temperature lead-free material process, which can provide benefits for the future high-temperature lead-free demand. Its chemical composition and physical properties can be combined with and matched with electronic component systems. It has the mechanical properties of environmentally friendly green materials and is an excellent high heat resistant composite material.

In the above embodiment, the solvent is about 10 to 2,000 parts by weight or 200 to 1,000 parts by weight.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the invention may be modified and retouched without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

Claims (5)

A resin formulation substantially derived from a carboxylic anhydride derivative, a diisocyanate, a styrene maleic anhydride (SMA) derivative, and a bismaleimide (BMI) derivative. a composition in which the carboxylic anhydride derivative has 14.4 to 77 parts by weight, the diisocyanate has 40 to 120 parts by weight, the styrene maleic anhydride derivative has 14.4 to 57.5 parts by weight, and the bismaleide The derivative has 100 to 300 parts by weight, wherein the carboxylic anhydride derivative has a chemical formula: Wherein A is a benzene ring or cyclohexane, R is -H, -CH ₃ or -COOH, q is 0-8, and the styrene maleic anhydride derivative has the chemical formula: , wherein m is 1 to 7, n is 2 to 15, and the bimaleimide derivative is a free chemical formula versus a group consisting of wherein R ₁ is -(CH ₂ ) ₂ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₁₂ -, -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -CH ₂ -, The resin formulation according to claim 1, wherein the diisocyanate comprises methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), diisocyanate Isophorone diisocyanate (IPDI) or a combination thereof. A resin composition prepared by heating a resin formulation as described in claim 1 of the patent application. A composite material comprising: a substrate; and a resin composition as described in claim 3, formed on the substrate. The composite of claim 4, wherein the substrate comprises fibers or metals.