TW202140603A - Thermosetting resin composition - Google Patents

Abstract

A thermosetting resin composition is provided, including an epoxy resin, a cyanate resin, a phenolphthalein type benzoxazine resin, a styrene maleic anhydride resin, and a phosphorus-containing flame retardant. The equivalent ratio of the phenolphthalein type benzoxazine resin to the styrene maleic anhydride resin is 1:1 to 1:5.

Description

Thermosetting resin composition

The present invention relates to a resin composition, and particularly relates to a thermosetting resin composition.

In order to cope with the rapid development of information transmission technology in recent years, application equipment is required to be lighter, thinner, shorter, smaller, and more dense. The increase in information transmission capacity and the increase in transmission processing speed are also very important. The physical and electrical properties of circuit boards are required. Achieve high heat resistance, low moisture absorption, low dielectric loss and low dielectric constant.

Because epoxy resin has good heat resistance, chemical resistance, insulation and dielectric properties, it is widely used in various electronic insulation materials. Its commonly used curing agents include amines, acid anhydrides, phenolics, especially copper foil In substrate (CCL) applications, dicyandiamide and phenolic resin are commonly used as epoxy curing agents, which have good processing performance, heat resistance, chemical resistance and insulation, but their dielectric constant and dielectric loss are high and cannot be satisfied. The need for high-frequency signal transmission integrity; and using styrene-maleic anhydride copolymer (SMA) as an epoxy resin curing agent can improve the higher dielectric constant and dielectric loss of the above-mentioned amine and phenolic curing agents. Problems, but the use of styrene-maleic anhydride copolymer and epoxy resin after crosslinking has a lower glass transition temperature (Tg), poor heat resistance and poor processability.

Based on the above, the development of a resin composition that has good dielectric constant and low dielectric loss, and can reach a high glass transition temperature of at least 200° C., is an urgent development goal for those skilled in the art.

The invention provides a thermosetting resin composition, which has good dielectric constant and low dielectric loss, and can reach a high glass transition temperature of at least 200°C.

The thermosetting resin composition of the present invention includes epoxy resin, cyanate ester resin, phenolphthalein benzoxazine resin, styrene maleic anhydride resin and phosphorus-containing flame retardant. The equivalent ratio of phenolphthalein benzoxazine resin to styrene maleic anhydride resin is 1:1 to 1:5.

In an embodiment of the present invention, based on the solid content ratio, the thermosetting resin composition includes 15 wt% to 40 wt% epoxy resin, 10 wt% to 50 wt% cyanate resin, and 1 wt% To 20 wt% of phenolphthalein type benzoxazine resin, 15 to 50 wt% of styrene maleic anhydride resin, and 5 to 30 wt% of phosphorus-containing flame retardant.

In an embodiment of the present invention, the epoxy resin includes a multifunctional novolac epoxy resin.

。In an embodiment of the present invention, the multifunctional novolac epoxy resin includes a trifunctional novolac epoxy resin, which is represented by the following chemical structural formula:

.

In an embodiment of the present invention, the epoxy resin includes a combination of a bifunctional epoxy resin and a trifunctional novolac epoxy resin, and the weight ratio of the bifunctional epoxy resin and the trifunctional novolac epoxy resin is 5:1 to 25:1.

In an embodiment of the present invention, the bifunctional epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, or dicyclopentadiene epoxy resin.

In an embodiment of the present invention, the cyanate ester resin includes bisphenol A type cyanate ester resin, dicyclopentadiene type (DCPD) cyanate ester resin, bisphenol F type cyanate ester resin, and novolac cyanate ester resin. Resin or a combination thereof.

In an embodiment of the present invention, the molecular weight of the styrene maleic anhydride resin is 3000 to 10000, and the molar ratio of styrene to maleic anhydride is 1:1 to 8:1.

。In an embodiment of the present invention, the phenolphthalein benzoxazine resin is represented by the following chemical structural formula:

.

In an embodiment of the present invention, the phosphorus-containing flame retardant includes a phosphazene compound, a phosphoric acid ester compound, a phosphorus-containing epoxy resin, a phosphorus-containing phenol resin, or a phosphorus-containing cyanate resin.

In an embodiment of the present invention, the thermosetting resin composition further includes a filler and a curing accelerator.

Based on the above, in the thermosetting resin composition of the present invention, the equivalent ratio of phenolphthalein benzoxazine resin to styrene maleic anhydride resin is 1:1 to 1:5, so a good dielectric constant can be achieved . In addition, in the thermosetting resin composition of the present invention, a multifunctional novolac epoxy resin is used in combination with a phenolphthalein benzoxazine resin, so that a higher glass transition temperature can be achieved.

Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative, and the present disclosure is not limited thereto.

In this article, the range represented by "a value to another value" is a general way to avoid listing all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range defined by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are written in the description in the description. The value range is the same.

The present invention provides a thermosetting resin composition including epoxy resin, cyanate ester resin, phenolphthalein benzoxazine resin, styrene maleic anhydride resin and phosphorus-containing flame retardant. Hereinafter, the above-mentioned various components will be described in detail. > Epoxy resin >

。圖1為由以上化學結構式表示之三官能酚醛型環氧樹脂的IR光譜圖，圖2為由以上化學結構式表示之三官能酚醛型環氧樹脂的凝膠滲透層析法（Gel Permeation Chromatography，GPC）圖。此外，本發明的環氧樹脂較佳例如是雙官能環氧樹脂及三官能酚醛型環氧樹脂的組合，雙官能環氧樹脂及三官能酚醛型環氧樹脂的重量比例例如是5：1至25：1，雙官能環氧樹脂可包括雙酚A型環氧樹脂、雙酚F型環氧樹脂或雙環戊二烯環氧樹脂。除了以上所提到的較佳實施例，環氧樹脂也可包括酚醛環氧樹脂、雙酚型環氧樹脂、含磷環氧樹脂、鄰甲酚醛環氧樹脂、雙酚A酚醛環氧樹脂、苯酚酚醛環氧樹脂、三官能酚型環氧樹脂、萘環型環氧樹脂、聯苯型環氧樹脂、含三嗪結構環氧樹脂（triazine）、含茀結構環氧樹脂(fluorene）或其組合。以固成分比例計算，熱固型樹脂組成物可包括15 wt%至40 wt%的環氧樹脂。> 氰酸酯樹脂 > The epoxy resin of the present invention may include a multifunctional novolac epoxy resin. When the multifunctional novolac epoxy resin is used in combination with a phenolphthalein benzoxazine resin, a higher glass transition temperature (above 200°C) can be achieved. In more detail, the multifunctional novolac epoxy resin used in the present invention is preferably, for example, a trifunctional novolac epoxy resin, which is represented by the following chemical structural formula:

. Figure 1 is the IR spectrum of the trifunctional novolac epoxy resin represented by the above chemical structural formula, and Figure 2 is the gel permeation chromatography (Gel Permeation Chromatography) of the trifunctional novolac epoxy resin represented by the chemical structural formula above. , GPC) graph. In addition, the epoxy resin of the present invention is preferably, for example, a combination of a bifunctional epoxy resin and a trifunctional novolac epoxy resin, and the weight ratio of the bifunctional epoxy resin and trifunctional novolac epoxy resin is, for example, 5:1 to 25:1, the bifunctional epoxy resin may include bisphenol A epoxy resin, bisphenol F epoxy resin or dicyclopentadiene epoxy resin. In addition to the preferred embodiments mentioned above, epoxy resins may also include novolac epoxy resins, bisphenol epoxy resins, phosphorus-containing epoxy resins, o-cresol novolac epoxy resins, bisphenol A novolac epoxy resins, Phenolic novolac epoxy resin, trifunctional phenol epoxy resin, naphthalene ring epoxy resin, biphenyl epoxy resin, triazine structure epoxy resin (triazine), fluorene structure epoxy resin (fluorene) or its combination. Based on the solid content ratio, the thermosetting resin composition may include 15 wt% to 40 wt% of epoxy resin. > Cyanate resin >

The cyanate ester resin of the present invention may include bisphenol A type cyanate ester resin, dicyclopentadiene type (DCPD) cyanate ester resin, bisphenol F type cyanate ester resin, novolac type cyanate ester resin, or a combination thereof. Based on the solid content ratio, the thermosetting resin composition may include 10 wt% to 50 wt% of the cyanate ester resin. When the content of the cyanate ester resin is within this range (especially if the content is greater than 10 wt%), lower dielectric loss can be achieved. > Phenolphthalein type benzoxazine resin >

。 圖3為由以上化學結構式表示之酚酞型苯并噁嗪樹脂的IR光譜圖。以固成分比例計算，熱固型樹脂組成物可包括1 wt%至20 wt%的酚酞型苯并噁嗪樹脂。> 苯乙烯馬來酸酐樹脂 > In the present invention, the phenolphthalein type benzoxazine resin is preferably represented by the following chemical structural formula, for example:

. Figure 3 is the IR spectrum of the phenolphthalein benzoxazine resin represented by the above chemical structural formula. Based on the solid content ratio, the thermosetting resin composition may include 1 wt% to 20 wt% of the phenolphthalein type benzoxazine resin. > Styrene maleic anhydride resin >

The molecular weight of the styrene maleic anhydride resin of the present invention is, for example, 3000 to 10,000, and the molar ratio of styrene to maleic anhydride is, for example, 1:1 to 8:1. In more detail, the equivalent ratio of the phenolphthalein type benzoxazine resin to the styrene maleic anhydride resin is, for example, 1:1 to 1:5. When the equivalent ratio of the phenolphthalein type benzoxazine resin to the styrene maleic anhydride resin is within this range, the thermosetting resin composition can achieve a good dielectric constant. Based on the solid content ratio, the thermosetting resin composition may include 15 wt% to 50 wt% of styrene maleic anhydride resin. > Phosphorus-containing flame retardant >

The phosphorus-containing flame retardant of the present invention may include a phosphazene compound, a phosphate ester compound, a phosphorus-containing epoxy resin, a phosphorus-containing phenol resin, or a phosphorus-containing cyanate resin. Based on the solid content ratio, the thermosetting resin composition may include 5 wt% to 30 wt% of the phosphorus-containing flame retardant. > Other additives >

The thermosetting resin composition of the present invention may optionally further include a filler and a curing accelerator. The curing accelerator may be selected from organic transition metal salts, triphenylphosphine compounds and imidazole compounds or a combination thereof, preferably imidazole compounds .

In this embodiment, the filler may include silicon dioxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, silicon carbide, carbonic acid Sodium, titanium dioxide, zinc oxide, zirconia, quartz, diamond, diamond-like, graphite, calcined kaolin, bailing clay, mica, hydrotalcite, hollow silica, polytetrafluoroethylene (PTFE) powder, glass beads, Carbon nanotubes, nano-grade inorganic powders or combinations thereof. Based on the solid content ratio, the thermosetting resin composition may include 0 wt% to 50 wt% filler and 0 to 20 PHR curing accelerator.

Hereinafter, the thermosetting resin composition proposed by the present invention will be explained in detail through experimental examples. However, the following experimental examples are not intended to limit the present invention. Experimental example

In order to prove that the thermosetting resin composition proposed by the present invention has a good dielectric constant, a relatively high glass transition temperature (above 200° C.) and a relatively low dielectric loss, this experimental example is specially made as follows. Preparation of resin composition and evaluation of properties

According to the composition ratios listed in Table 1 and Table 2 below, the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared. Mix the resin component and the solvent (solvent contains methyl ethyl ketone, cyclohexanone, propylene glycol methyl ether) uniformly to form a resin glue, use 2116 glass fiber cloth to impregnate the colloid, and bake it at a temperature of 171°C for 4 minutes to make the film form a prepreg. Take four prepregs and stack them in a hot press for high-temperature curing. The curing conditions are curing at a temperature of 210° C. for more than 3 hours, and a curing pressure of about 200 psi. After that, test the electrothermal properties of the test piece (the test methods are all measured in accordance with the IPC-TM-650 specification), and the test results are listed in Table 1 and Table 2 below.

。苯乙烯馬來酸酐樹脂為SMA EF30、SMA EF40。氰酸酯樹脂為雙酚A型氰酸酯樹脂、雙環戊二烯型（DCPD）氰酸酯樹脂。含磷阻燃劑為磷腈化合物SPB-100。酚酞型苯并噁嗪樹脂為成都科宜CB2系列。填料為二氧化矽RCS525、G2C。表 1   實例1 實例2 實例3 實例4 比較例1 比較例2 雙官能環氧樹脂 19.7 18.3 19.7 12.2 19.5 20.6 三官能酚醛型環氧樹脂 4.4 3.6 4.5 2.8 4.4 4.3 氰酸酯樹脂 11.5 14.2 14.8 20.6 7.4 8.1 苯乙烯馬來酸酐樹脂 26.3 24.6 22 17.1 26.2 28.1 酚酞型苯并噁嗪樹脂 5.4 7 3.8 12 7.6 3.2 含磷阻燃劑 13 12.3 13.2 12.5 13.1 14 填料 19.7 20 22 22.8 21.8 21.7 固化促進劑 0.06 0.05 0.035 0.005 0.04 0.07 酚酞型苯并噁嗪樹脂與苯乙烯馬來酸酐樹脂的當量比 1:4 1:3 1:4 1:1 1:2 1:8 Tg(DMA) 221 231 224 227 222 208 Td(5%熱重損失) 365 363 360 350 364 368 5GHZ@Dk 3.86 3.82 3.60 3.69 3.77 4.08 5GHZ@Df 0.0086 0.00837 0.00857 0.00789 0.009 0.00934 （固化促進劑以外的組分單位：wt%，以固成分比例計算） （固化促進劑單位：PHR）表 2   實例5 比較例3 雙官能環氧樹脂 19.7 1203 雙官能有鹵環氧樹脂   13.6 三官能酚醛型環氧樹脂 4.4   氰酸酯樹脂 11.5 8.8 苯乙烯馬來酸酐樹脂 26.3 10.2 酚酞型苯并噁嗪樹脂 5.4 23.2 四溴雙酚A阻燃劑   10.3 含磷阻燃劑 13   填料 19.7 21.6 固化促進劑 0.06 0.03 酚酞型苯并噁嗪樹脂與苯乙烯馬來酸酐樹脂的當量比 1:4 1:3 Tg(DSC) 213 171 Td(5%熱種損失) 365 314 （固化促進劑以外的組分單位：wt%，以固成分比例計算） （固化促進劑單位：PHR）In the following Table 1 and Table 2, the bifunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, and dicyclopentadiene epoxy resin. The trifunctional novolac epoxy resin is represented by the following chemical structural formula:

. Styrene maleic anhydride resin is SMA EF30 and SMA EF40. The cyanate ester resins are bisphenol A type cyanate ester resins and dicyclopentadiene type (DCPD) cyanate ester resins. Phosphorus-containing flame retardant is phosphazene compound SPB-100. Phenolphthalein type benzoxazine resin is Chengdu Keyi CB2 series. The filler is silica RCS525, G2C. Table 1 Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Bifunctional epoxy resin 19.7 18.3 19.7 12.2 19.5 20.6 Trifunctional phenolic epoxy resin 4.4 3.6 4.5 2.8 4.4 4.3 Cyanate resin 11.5 14.2 14.8 20.6 7.4 8.1 Styrene maleic anhydride resin 26.3 24.6 twenty two 17.1 26.2 28.1 Phenolphthalein type benzoxazine resin 5.4 7 3.8 12 7.6 3.2 Phosphorus flame retardant 13 12.3 13.2 12.5 13.1 14 filler 19.7 20 twenty two 22.8 21.8 21.7 Curing accelerator 0.06 0.05 0.035 0.005 0.04 0.07 The equivalent ratio of phenolphthalein benzoxazine resin to styrene maleic anhydride resin 1:4 1:3 1:4 1:1 1:2 1:8 Tg(DMA) 221 231 224 227 222 208 Td (5% thermogravimetric loss) 365 363 360 350 364 368 5GHZ@Dk 3.86 3.82 3.60 3.69 3.77 4.08 5GHZ@Df 0.0086 0.00837 0.00857 0.00789 0.009 0.00934 (Unit of components other than curing accelerator: wt%, calculated based on the proportion of solid content) (Unit of curing accelerator: PHR) Table 2 Example 5 Comparative example 3 Bifunctional epoxy resin 19.7 1203 Bifunctional halogenated epoxy resin 13.6 Trifunctional phenolic epoxy resin 4.4 Cyanate resin 11.5 8.8 Styrene maleic anhydride resin 26.3 10.2 Phenolphthalein type benzoxazine resin 5.4 23.2 Tetrabromobisphenol A flame retardant 10.3 Phosphorus flame retardant 13 filler 19.7 21.6 Curing accelerator 0.06 0.03 The equivalent ratio of phenolphthalein benzoxazine resin to styrene maleic anhydride resin 1:4 1:3 Tg(DSC) 213 171 Td (5% heat loss) 365 314 (Unit of components other than curing accelerator: wt%, calculated based on the proportion of solid content) (Unit of curing accelerator: PHR)

As shown in Table 1, when the cyanate ester resin content in the thermosetting resin composition is less than 10 wt%, the 5GHZ@Df of Comparative Example 1 is 0.009, and the 5GHZ@Df of Comparative Example 2 is 0.00934, indicating poor electrothermal properties . In Comparative Example 2, the equivalent ratio of the phenolphthalein benzoxazine resin to the styrene maleic anhydride resin is 1:8, therefore, 5GHZ@Dk is 4.08, and the electrothermal properties are poor. In contrast, Examples 1 to 4 are thermosetting resin compositions of the present invention, using trifunctional phenolic epoxy resin and phenolphthalein benzoxazine resin to match, therefore, a higher glass transition can be achieved Temperature (above 200℃). In addition, in Examples 1 to 4, the equivalent ratio of the phenolphthalein benzoxazine resin to the styrene maleic anhydride resin is 1:1 to 1:5, and therefore, a good dielectric constant can be achieved. On the other hand, based on the solid content ratio, the thermosetting resin compositions of Examples 1 to 4 include 10% to 50% by weight of cyanate ester resin, and therefore, lower dielectric loss can be achieved.

As shown in Table 2, since Comparative Example 3 did not use trifunctional phenolic epoxy resin and phenolphthalein benzoxazine resin to match, the glass transition temperature was as low as 171°C, which could not reach the higher glass transition temperature (200 ℃ above).

In summary, in the thermosetting resin composition of the present invention, the equivalent ratio of phenolphthalein benzoxazine resin to styrene maleic anhydride resin is 1:1 to 1:5, and therefore, a good medium can be achieved. Electric constant. In addition, in the thermosetting resin composition of the present invention, a multifunctional novolac epoxy resin is used in combination with a phenolphthalein benzoxazine resin, so that a higher glass transition temperature (above 200° C.) can be achieved. On the other hand, based on the solid content ratio, the thermosetting resin composition of the present invention includes 10 wt% to 50 wt% of cyanate ester resin, and therefore, lower dielectric loss can be achieved.

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Figure 1 is the IR spectrum of the trifunctional novolac epoxy resin. Figure 2 is a gel permeation chromatography (Gel Permeation Chromatography, GPC) diagram of trifunctional novolac epoxy resin. Figure 3 is the IR spectrum of the phenolphthalein benzoxazine resin.

Claims (11)

A thermosetting resin composition, including: Epoxy resin Cyanate resin Phenolphthalein type benzoxazine resin; Styrene maleic anhydride resin; and Phosphorus flame retardant, Wherein, the equivalent ratio of the phenolphthalein benzoxazine resin to the styrene maleic anhydride resin is 1:1 to 1:5. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition includes 15 wt% to 40 wt% of the epoxy resin, 10 wt% to 50 wt%, and calculated based on the solid content ratio. % Of the cyanate ester resin, 1 wt% to 20 wt% of the phenolphthalein benzoxazine resin, 15 wt% to 50 wt% of the styrene maleic anhydride resin, and 5 wt% to 30 wt% % Of the phosphorus-containing flame retardant. The thermosetting resin composition according to claim 1, wherein the epoxy resin includes a multifunctional novolac epoxy resin. The thermosetting resin composition according to claim 3, wherein the multifunctional novolac epoxy resin includes a trifunctional novolac epoxy resin, which is represented by the following chemical structural formula:

. The thermosetting resin composition according to claim 1, wherein the epoxy resin includes a combination of a bifunctional epoxy resin and a trifunctional novolac epoxy resin, the bifunctional epoxy resin and the trifunctional novolac epoxy resin The weight ratio of type epoxy resin is 5:1 to 25:1. The thermosetting resin composition according to claim 5, wherein the bifunctional epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, or dicyclopentadiene epoxy resin, and novolac epoxy resin. Resin, bisphenol type epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, naphthalene ring type epoxy resin, biphenyl type epoxy resin, Triazine-containing epoxy resin (triazine), fluorene-containing epoxy resin (fluorene), or a combination thereof. The thermosetting resin composition according to claim 1, wherein the cyanate resin includes bisphenol A type cyanate resin, dicyclopentadiene type (DCPD) cyanate resin, and bisphenol F type cyanate resin. Ester resin, phenolic cyanate ester resin, or a combination thereof. The thermosetting resin composition according to claim 1, wherein the styrene maleic anhydride resin has a molecular weight of 3000 to 10000, and the molar ratio of styrene to maleic anhydride is 1:1 to 8:1. The thermosetting resin composition according to claim 1, wherein the phenolphthalein type benzoxazine resin is represented by the following chemical structural formula:

. The thermosetting resin composition according to claim 1, wherein the phosphorus-containing flame retardant includes a phosphazene compound, a phosphate ester compound, a phosphorus-containing epoxy resin, a phosphorus-containing phenol resin, or a phosphorus-containing cyanate resin. The thermosetting resin composition according to claim 1 further includes a filler and a curing accelerator.

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