TWI626272B - Epoxy composition and cured object thereof - Google Patents

Abstract

An epoxy resin composition and a cured product thereof. The epoxy resin composition includes an epoxy resin and an active polyester represented by the following general formula (1): (1) In the general formula (1), the definitions of Y, n1, n2, m, and Ar are the same as in the embodiment.

Description

Epoxy resin composition and cured product thereof

The present invention relates to a resin composition and a cured product thereof, and more particularly to an epoxy resin composition and a cured product thereof.

With the development of high-performance and networked signal communication equipment, in order to process a large number of signals for high-speed transmission, the operation signals are moving toward high speed and high frequency. Therefore, in order to achieve the above object, the material of the printed circuit board of the signal communication device needs to have good dielectric capability (low dielectric constant and low loss dissipation factor) to meet the needs of high frequency transmission of signals, and the need It has good heat resistance and machinability to meet the reliability of printed circuit boards.

Among the materials conventionally used for printed wiring boards, a cured epoxy resin prepared from an epoxy resin composition mainly composed of an epoxy resin and a curing agent is widely used as a material of a printed wiring board. However, if a general-purpose curing agent is used as a curing agent for the epoxy resin composition, a highly polar secondary alcohol is generated in the process of curing the epoxy resin, resulting in a higher loss tangent and a decrease in heat resistance of the substrate material. The use of active esters as epoxy hardeners now avoids the formation of highly polar secondary alcohols. For example, Republic of China Patent I579332 uses an active ester hardener (trade name EPICLON HPC-8000-65T) containing a Dicyclopentadiene (DCPD) structure copolymerized with an epoxy resin and a cyanate to give a dielectric loss of about 8 A cured product of mU.

The Republic of China Patent No. I565750 discloses a novel active ester resin which is excellent in solubility in various solvents, has a low dielectric constant and a loss tangent of a cured product, and is excellent in low hygroscopicity, and is used as a hardener. An epoxy resin composition, a cured product thereof, a semiconductor sealing material, a prepreg, a circuit board, and a laminated film. The above active ester resin has a molecular structure represented by the following structural formula, wherein X is a benzene ring or a naphthalene ring; R ^{1 is} each independently a methyl group or a hydrogen atom; k is 0 or 1; n is 1 or 2 ;l is 1 or 2; m is the average of repeating units, ie 0.25~1.5.

The Republic of China Patent I565750 uses an epoxy resin, a cyanate resin, an active ester, and a hardening accelerator to carry out a curing reaction to obtain a resin composition having a low dielectric tangent and excellent adhesion strength to a conductor after an accelerated environmental test. The active esters used are: EXB9460-65T (ie EPICLON HPC-8000-65T, DIC, active base equivalent 223), DC808 (novolak acetylated product, Japanese epoxy resin, active base equivalent 149), YLH1026 (Novolak benzamidine product, made of Japanese epoxy resin, active base equivalent of 200). The Republic of China Patent I532784 uses a dicyclopentadiene type benzoxazine resin, an epoxy resin and an active ester (HPC-8000-65T) to prepare a low dielectric tangent cured product.

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO or PPE for short) has low dielectric properties. In order to achieve high performance and high dimensional stability, the copper foil substrate resin requires thermosetting. However, due to the structural relationship of PPO itself, it is difficult to cross-link harden itself, which limits the development and application of PPO in the substrate. In 2006, Ishii et al. synthesized low molecular weight telechelic PPE macromonomers (PPE-M) and carried out the phenolic terminal group of the macromonomer and 4-chloromethylstyrene. The reaction is carried out to obtain a vinylated phenylated PPE macromonomer (VB-PPE-M) of a styrene-terminated PPO compound (see U.S. Patent No. 6,995,195 B2).

In 2007, Peters et al. copolymerized PPE-M with epoxy resins and cyanates to significantly improve the performance of the thermosetting products (EN Peters, AK, E. Delsman, H. Guo, A. Carrillo, G. Rocha In Society of Plastics Engineers Annual Technical Conference (ANTEC 2007): Plastics Encounter, Cincinnati, Ohio., 6-11 May, 2007; Curran Associates, Inc.; pp 2125-2128.).

In 2011, Peters et al. modified the terminal phenolic group of SABIC's PPE-M (or Noryl ^® SA90) to have an unsaturated double bond structure at its end. When introduced into the PPE-M-containing methacrylate (methacrylate) terminal group, the methacryloyl group of available PPE macromer (M-PPO-M), the trade name NORYL ^TM Resin SA 9000 (S. Fisher, HG, M. Jeevanath, E. Peters, SABIC Innovative Plastics In Polyphenylene Ether Macromonomer : X. Vinyl Terminated Telechelic Macromers , 69th Annual Technical Conference of the Society of Plastics Engineers 2011 (ANTEC 2011), Boston, Massachusetts, USA, 1 -5 May, 2011; pp 2819-2822.).

The Republic of China Patent No. TW I301842 discloses a polyester obtained by reacting a xylene ether oligomer with dioxonium chloride, which can be formed independently or by mixing with polystyrene, and a metal foil layer. Pressing to form a laminate. The dielectric constant (10 GHz) is between 2.47 and 2.72 U, and the dielectric loss (10 GHz) is between 3.8 and 5.9 mU. However, this patent does not mention the use of active esters and crosslinking reactions with epoxy resins. Patent No. 201510152403.2 of the People's Republic of China proposes an active ester containing a 2,6-dimethylether ether structure. The structure applied for is a double-ended polyfunctional active ester containing a PPO primary bond, and its structure is as follows:

When using 1,4 benzodiazepine or 1,3 benzodiazepine and PPO oligomers (Note: PPO oligomers are derived from the rearrangement of polymeric PPO), followed by functional phenol R ₂ When -OH is blocked, an oligomer of n3 = n4 = 1 can be obtained. When 1,3,5-benzenetrimethylphosphonium chloride and a PPO oligomer are reacted and then blocked with a functional phenol R ₂ -OH, an oligomer of n3 = n4 = 2 can be obtained. When 1,2,4,5 benzenetetramine chloride is reacted with a PPO oligomer, and further blocked with a functional phenol R ₂ -OH, an oligomer of n3 = n4 = 3 can be obtained. The active ester group of this patent is only located at the end of the molecular chain.

In 2012 ( Polym. Chem. , 2012, 3, 935-945), Lin et al. performed a hardening reaction with a main-chain type polybenzoxazine, and the obtained cured product was smaller than the small molecule. The cured product obtained from benzoxazine has a high glass transition temperature and good mechanical properties. In 2013 (Polymer 2013, 54, 1612), Lin et al. performed a hardening reaction with a polymeric phenolic hardener and an epoxy resin, and the obtained cured product has a cured product obtained by using a small molecular type hardener. High glass transfer temperature and good mechanical properties. It is known from the above examples that the polymer epoxy resin hardener has the potential to obtain a high-performance cured product.

Therefore, development of an epoxy resin cured product having high solvent property, high heat resistance, good dielectric property, and high toughness is an urgent task.

The present invention provides an epoxy resin composition capable of realizing an epoxy resin cured product having high processability, high heat resistance, good dielectric properties, and high toughness.

The present invention provides a cured product which has high processability, high heat resistance, good dielectric ability, and high toughness.

The epoxy resin composition of the present invention comprises an epoxy resin and an active polyester represented by the following general formula (1): (1) In the formula (1), Y is a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a carbonyl group, an oxygen atom or a sulfonyl group, n1 and n2 Each is independently a positive integer, and 4 < n1+n2 < 26, m is an integer from 2 to 50, and Ar is an aromatic group, wherein the ratio of the epoxy single amount of the epoxy resin to the ester equivalent number of the reactive polyester It is 0.8 to 1.2.

In an embodiment of the invention, Y may be a single bond, a methylene group, an isopropylene group, a carbonyl group, an oxygen atom or a sulfonyl group.

In an embodiment of the invention, Ar may be selected from the group consisting of the following structural formulas: Wherein X is a single bond, -CH ₂ -, -O-, C=O, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -.

In an embodiment of the invention, Y may be an isopropyl group and Ar may be a 1,4-phenylene group or a 1,3-phenylene group.

In an embodiment of the invention, the epoxy resin may include a bisphenol A type epoxy resin, a novolac epoxy resin, a methyl phenolic epoxy resin, a dicyclopentadiene-phenol epoxy resin, and a naphthalene ring structure. Epoxy resin or a combination thereof.

In an embodiment of the invention, the epoxy resin composition may further include a curing accelerator.

In an embodiment of the invention, the curing accelerator may include an imidazole curing accelerator, an amine curing accelerator, an organic phosphorus curing accelerator, or a combination thereof.

In an embodiment of the invention, the amount of the curing accelerator is from 0.1% by weight to 1.0% by weight based on the total weight of the epoxy resin.

The cured product of the present invention is obtained by heating and curing the above epoxy resin composition.

In an embodiment of the invention, the heat curing temperature is 140 ° C to 240 ° C.

Based on the above, the reactive polyester of the present invention can be used as a curing agent for the epoxy resin composition, and since the reactive polyester has an active ester group, the reactive polyester can be reacted with the epoxy resin in addition to the crosslinking reaction. The hydroxyl group generated during the reaction of the epoxy resin is blocked, so that the dielectric constant and loss tangent of the cured epoxy resin can be effectively reduced and the heat resistance of the cured epoxy resin can be improved. Further, the cured epoxy resin prepared by the epoxy resin composition of the present invention has high processability, high heat resistance, good dielectric ability, and high toughness.

The above described features and advantages of the invention will be apparent from the following description.

The invention is further illustrated by the following examples, which are intended to be illustrative only and not to limit the scope of the invention.

[ Structure of reactive polyester ]

The present invention provides a reactive polyester, in particular, an active polyester comprising a (2,6-dimethylphenyl ether) oligomer. The above reactive polyester is represented by the following general formula (1): (1) In the formula (1), Y is a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a carbonyl group, an oxygen atom or a sulfonyl group, n1 and n2 Each is independently a positive integer, and 4 < n1 + n2 < 26, m is an integer from 2 to 50, and Ar is an aromatic group.

In an embodiment of the invention, Y is, for example, a single bond, a methylene group, an isopropylene group, a carbonyl group, an oxygen atom or a sulfonyl group.

In an embodiment of the invention, Ar is selected from the group consisting of the following structural formulas: Wherein X is a single bond, -CH ₂ -, -O-, C=O, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -.

In an embodiment of the invention, Y is an isopropyl group and Ar is a 1,4-phenylene group or a 1,3-phenylene group.

[ Method for preparing phosphorus-based reactive polyester ]

The reactive polyester of the present invention is represented by the following formula (1): (1), wherein Y, n1, n2, m, and Ar are as defined above, and are not described herein again.

The above preparation method of the phosphorus-based reactive polyester includes the following steps.

First, a bisphenol compound containing a (2,6-dimethylphenyl ether) oligomer, which is represented by the following formula (a), is provided: (a) In the formula (a), Y is a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a carbonyl group, an oxygen atom or a sulfonyl group, n1 and n2 Each is independently a positive integer, and 4 < n1 + n2 < 26, m is an integer from 2 to 50.

In an embodiment of the present embodiment, the above Y is, for example, a single bond, a methylene group, an isopropylene group, a carbonyl group, an oxygen atom or a sulfonyl group. In another embodiment of the invention, the above Y is an isopropyl group.

Next, the above bisphenol compound is mixed with a dioxonium compound and a base catalyst to carry out a reaction to obtain the active polyester of the present invention. In the present embodiment, the molar ratio of the diterpene chlorine compound to the bisphenol compound (i.e., the dichloro chloro compound/bisphenol compound) is, for example, 0.7 to 1.3. In another embodiment, the molar ratio of the dioxonium compound to the bisphenol compound is 1.0.

In the present embodiment, the diterpene chlorine compound is, for example, an aromatic diterpene chlorine. In another embodiment, the diterpene chlorine compound may include at least one of the following structural formula (b-1) to structural formula (b-4): Wherein X is a single bond, -CH ₂ -, -O-, C=O, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -.

In the present embodiment, the reaction of the bisphenol compound with the dioxonium chloride compound is carried out in the presence of a base catalyst. The base catalyst is, for example, CsF, KF, CsCl, KCl, K ₂ CO ₃ , Na ₂ CO ₃ , KOH, NaOH or a combination thereof. The molar ratio of the base catalyst to the bisphenol compound is, for example, from 0.5 to 1.5.

In the present embodiment, the ester equivalent of the reactive polyester of the present invention is half the molecular weight of the repeating unit.

Since the reactive polyester of the present invention has an active ester group, if the active polyester is used as a curing agent in the epoxy resin composition, the reactive polyester can be reacted with the epoxy resin in addition to the epoxy resin. The hydroxyl group generated during the resin reaction is blocked, so that the dielectric constant and loss tangent of the formed epoxy resin cured product can be effectively reduced and the heat resistance of the cured epoxy resin can be improved.

[ Epoxy Resin Composition ]

The epoxy resin composition of the present invention comprises an epoxy resin and the above-mentioned reactive polyester represented by the general formula (1) as a curing agent, wherein the related description of the reactive polyester represented by the general formula (1) and the above examples The same, no longer repeat here.

In this embodiment, the epoxy resin is, for example, a bisphenol A type epoxy resin, a novolac epoxy resin, a methyl phenolic epoxy resin, a dicyclopentadiene-phenol epoxy resin, an epoxy resin having a naphthalene ring structure, or Combination thereof, but the invention is not limited thereto.

In the present embodiment, the ratio of the epoxy single amount of the epoxy resin to the ester equivalent number of the reactive polyester is from 0.8 to 1.2. In another embodiment, the ratio of the epoxy amount of the epoxy resin to the number of ester equivalents of the reactive polyester is 1.0. When the epoxy resin and the reactive polyester are blended in the above range, a cured epoxy resin having high processability, high heat resistance, good dielectric properties, and high toughness can be obtained.

In the present embodiment, the epoxy resin composition may further include a curing accelerator. The curing accelerator is, for example, an imidazole-based curing accelerator, an amine-based curing accelerator, an organic phosphorus-based curing accelerator, or a combination thereof. In the present embodiment, the imidazole-based curing accelerator is, for example, imidazole, 2-methylimidazole or 2-methyl-4-ethylimidazole. The organophosphorus curing accelerator is, for example, triphenylphosphine. The amine-based curing accelerator is, for example, 4-dimethylaminopyridine (DMAP).

When the above curing accelerator is used, the amount of the curing accelerator is, for example, 0.1% by weight to 1.0% by weight based on the total weight of the epoxy resin.

In the present embodiment, the epoxy composition of the present invention can be further heat-cured to obtain a cured epoxy resin having a crosslinked structure. The temperature at which the heat is cured is, for example, 140 ° C to 240 ° C.

The present invention uses the reactive polyester represented by the general formula (1) as a curing agent for the epoxy resin composition, wherein the reactive polyester has an active ester group, so that the reactive polyester can not only react with the epoxy resin but also react with the epoxy resin. The hydroxyl group generated during the reaction with the epoxy resin can be blocked, so that the dielectric constant of the cured epoxy resin and the loss tangent can be effectively reduced and the heat resistance of the cured epoxy resin can be improved.

The invention is further illustrated by the following examples, which are intended to be illustrative only and not to limit the scope of the invention.

[ Synthesis of reactive polyester ]

Synthesis Example 1: Synthesis of Reactive Polyester 1

[Reaction Flow Chart 1]

Take 5.0 g (3.125 mmol) of compound a-1 (SABIC commercial SA90, molecular weight 1600 g/mol), 0.634 g (3.125 mmol) of terephthalic acid chloride and 22 g (20 wt%) of o-dichlorobenzene (o-dichlorobenzene) was placed in a 100 ml three-necked reactor. A condensing tube was set up and connected to a ventilated bottle containing an aqueous solution of NaOH, and stirred and reacted for 12 hours with a magnet under a nitrogen atmosphere at 160 °C. After the reaction, it was precipitated with methanol, and the precipitate was washed with methanol and deionized water, and dried at 60 ° C to obtain an active polyester 1 of a brown solid, wherein the average value of n1 was 7, and the average value of n2 was 7, m. Between 8 and 32. ¹ H NMR spectrum of the reactive polyester 1 (ppm, CDCl ₃ ): δ = 1.7 (3H, H ³ ), 2.2 (21H, H ³ ), 6.5 (14H, H ⁴ ), 6.9 (2H, H ² ), 8.3 (4H, H ⁵ ), the integral area ratio is in accordance with its structure.

Synthesis Example 2: Synthesis of Reactive Polyester 2

[Reaction Flow Chart 2]

5.0 g (3.125 mmol) of compound a-1, 0.634 g (3.125 mmol) of m-benzoic acid chloride and 22 g (20 wt%) of o-dichlorobenzene were placed in a 100 ml three-neck reaction. In the device. A condensing tube was set up and connected to a ventilated bottle containing an aqueous solution of NaOH, and stirred and reacted for 12 hours with a magnet under a nitrogen atmosphere at 160 °C. After the reaction, it was precipitated with methanol, and the precipitate was washed with methanol and deionized water, and dried at 60 ° C to obtain a brown solid active polyester 2, wherein the average value of n1 was 7, and the average value of n2 was 7, m. Between 8 and 32. ¹ H NMR spectrum (ppm, CDCl ₃ ) data of the reactive polyester 2: δ = 1.7 (3H, H ³ ), 2.2 (21H, H ³ ), 6.5 (14H, H ⁴ ), 6.9 (2H, H ² ) , 7.7 (1H, H ⁷ ), 8.5 (2H, H ⁶ ), 9.1 (1H, H ⁵ ), the integral area ratio conforms to its structure.

Figure 1 is a ¹ H NMR spectrum of Compound a-1 and Reactive Polyester 2. As shown in Fig. 1, in the ¹ H NMR spectrum of the reactive polyester 1, the 4.3 ppm peak (the phenolic H) originally present in the compound a-1 disappeared, and was at 7.7 ppm, 8.5 ppm, and 9.1 ppm. There is a new peak formation nearby (i.e., CO-ph-CO), indicating that the phenolic group of compound a-1 has been completely reacted with isophthalic chloride.

[ Solubility test of reactive polyester]

5 mg of the above-prepared active polyester 1 and active polyester 2 were separately added to different solvents to test the solubility of the reactive polyester 1 and the reactive polyester in different solvents.

The results are shown in Table 1 below. The reactive polyester 1 and the reactive polyester 2 are soluble in most common solvents, that is, the reactive polyester 1 and the reactive polyester 2 have high solvent properties. The high solvent properties of the reactive polyester 1 and the reactive polyester 2 contribute to the application in the copper foil substrate process. [Table 1] <TABLE border="1"borderColor="#000000"width="85%"><TBODY><tr><td></td><td> Toluene </td><td> THF </td><td> DMAc </td><td> NMP </td><td> MEK </td><td>CHCl₃</td><td> DMSO </td ></tr><tr><td> Reactive Polyester 1 </td><td> + </td><td> + </td><td> + </td><td> + </td ><td> +h </td><td> + </td><td> + </td></tr><tr><td> Reactive Polyester 2 </td><td> + </ Td><td> + </td><td> + </td><td> + </td><td> +h </td><td> + </td><td> + </td ></tr></TBODY></TABLE>Toluene: toluene; THF: tetrahydrofuran; DMAc: dimethylacetamide; NMP: N-methylpyrrolidone; MEK: methyl ethyl ketone; CHCl ₃ : chloroform; dimethyl sulfoxide; +: dissolved at room temperature; + H: soluble heated at 50 ^o C

[ Preparation of epoxy resin cured product ]

The cured epoxy resin of the present invention can be formed, for example, by the procedure shown below.

Example 1

Preparation of epoxy resin cured product 1

First, the reactive polyester 1 and epoxy resin (HP7200, epoxy equivalent of 250 g/eq) synthesized in Synthesis Example 1 were dissolved in a solvent of Dimethylacetamide (DMAc) and activated poly The ester equivalent number of the ester 1 was adjusted in a ratio of 1:1 to the epoxy equivalent of the epoxy resin to obtain a mixed solution having a solid content of 20% by weight.

Next, 0.5% by weight of DMAP was added to the mixed solution in an amount of epoxy resin and completely dissolved to obtain an epoxy resin composition 1.

Then, the epoxy resin composition to a knife coater on a glass substrate, and then coated with the epoxy resin composition of the glass substrate 1 is placed in a circulating oven, and dried at 100 ^o C 12 hours to remove most of the solvent.

After again warming stage manner to sequentially raised to ^{180 o C, 200 o C,} 220 o C ( two hours each) for curing. Next, the glass substrate was subjected to release film in water to obtain a cured epoxy resin 1.

Preparation of epoxy resin cured product 2

Epoxy Resin Composition 2 was prepared in a manner similar to that of Example 1, except that the reactive polyester 2 synthesized in Synthesis Example 2 was used instead of the reactive polyester 1 of Example 1.

2 is an IR spectrum diagram of the reactive polyester 1, the epoxy resin composition 1 (before curing), and the epoxy resin cured product 1. As shown in FIG. 2, the characteristic peak of the carbon-oxygen double bond of the reactive polyester 1 was 1741 cm ^-1 , and the characteristic peak of the carbon-oxygen double bond of the cured epoxy resin 1 was 1725 cm ^-1 . That is to say, after the curing of the reactive polyester 1 with the epoxy resin, the characteristic peak of the carbon-oxygen double bond is shifted from the original 1741 cm ^-1 to 1725 cm ^-1 . This is because the oxygen of the benzene ring in the ester group of the original reactive polyester 1 resonates with the benzene ring and relatively reduces the resonance of the carbon-oxygen double bond (C=O), so the carbon-oxygen double bond characteristics of the active polyester 1 The summit is at a higher wave number. However, during the reaction of the reactive polyester 1 with the epoxy resin, the oxygen of the benzene ring in the ester group of the reactive polyester 1 reacts with the epoxy group, and thus cannot resonate with the benzene ring but with carbon and oxygen. The double bond (C=O) produces resonance, which in turn reduces the wave number of the characteristic peak of the carbon-oxygen double bond.

3 is an IR spectrum diagram of the reactive polyester 2, the epoxy resin composition 2 (before curing), and the epoxy resin cured product 2. The activated carbon 2 has a carbon-oxygen double bond characteristic peak shifted from 1745 cm-1 to 1725 cm-1 after curing with epoxy resin, which is similar to FIG.

[Evaluation of thermal properties and dielectric properties of epoxy resin cured materials]

The prepared epoxy resin cured product 1 and epoxy resin cured product 2 were evaluated for thermal properties and dielectric properties by the following methods. The results are listed in Table 2.

(1) Glass transition temperature (Tg)

The glass transition temperature was measured using thermo-mechanical analysis (TMA). The thermomechanical analysis was carried out under the conditions of measuring the glass transition temperature of the sample using a Dynamic Mechanical Analyzer (DMA) (Model: Perkin-Elmer Pyris Diamond) at a heating rate of 5 ° C /min. 4 is a dynamic mechanical analysis (DMA) chart of the epoxy resin cured product 1 and the epoxy resin cured product 2, the data of which is summarized in Table 2.

(2) 5% thermogravimetric loss temperature (T _d5% ) and coke residual rate

Thermo-gravimetric analysis (TGA) was used to measure the 5% thermogravimetric loss temperature of the sample and the Char yield of 800 °C. The thermogravimetric analysis was carried out under the condition that the weight change of the sample was measured using a thermogravimetric analyzer (Model: Thermo Cahn Versa Therm) under a nitrogen atmosphere at a heating rate of 20 ° C / min. The 5% thermogravimetric loss temperature refers to a temperature at which the weight loss of the sample reaches 5%, and the higher the 5% thermogravimetric loss temperature, the better the thermal stability of the sample. The coke residual ratio at 800 ° C refers to the residual weight ratio of the sample at a heating temperature of 800 ° C, wherein the higher the residual weight ratio at 800 ° C, the better the thermal stability of the sample.

(3) Dielectric constant and loss tangent

The dielectric constant and loss tangent of the sample were measured using an Agilent Wheel Dielectric Analyzer (E4991A) at 25 ° C, 1 G Hz.

[Table 2]  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Tg (^oC) </ Td><td> T_d5% (^oC) </td><td> coke residual rate (%) </td><td> dielectric constant ( U) </td><td> loss tangent (mU) </td></tr><tr><td> epoxy resin cured material 1 </td><td> 219 </td><td> 421 </td><td> 17 </td><td> 2.72±0.003 </td><td> 8.3±0.1 </td></tr><tr><td> Epoxy Resin Cured 2 </ Td><td> 214 </td><td> 419 </td><td> 18 </td><td> 2.68±0.002 </td><td> 7.8±0.2 </td></tr> </TBODY></TABLE>

According to the content of US Patent Publication No. 2014034216 A1, the glass transition temperature of the cured epoxy resin prepared by using the active polyester curing agent HPC-8000-65T and the epoxy resin HP7200 manufactured by DIC Corporation is 165 ° C; using DIC The glass transition temperature of the cured epoxy resin prepared by the reactive polyester curing agent HPC-8000-65T and epoxy resin N-6900 manufactured by Co., Ltd. was 160 °C. As can be seen from Table 2, the glass transition temperature of the epoxy resin cured product of the present invention and the epoxy resin cured product 2 was 219 ° C and 214 ° C, respectively, and was prepared by using the active polyester as a curing agent of the present invention. The epoxy resin cured product has a high glass transition temperature.

Referring to Table 2, in the TGA test, the 5% thermogravimetric loss temperatures of the epoxy resin cured product 1 and the epoxy resin cured product 2 of the present invention were 421 ° C and 419 ° C, respectively. Further, the coke residual ratios of the epoxy resin cured product 1 and the epoxy resin cured product 2 were 17% and 18%, respectively, and it was revealed that the cured epoxy resin prepared by the active polyester as the curing agent of the present invention has good properties. Thermal stability (ie heat resistance).

Further, in the evaluation of the dielectric ability of the cured epoxy resin, the dielectric constant of the cured epoxy resin 1 and the cured epoxy resin 2 of the present invention is between 2.68 U and 2.72 U, and the loss tangent is 7.8. From mU to 8.3 mU, the loss tangent is significantly lower than that of the conventional phenol-based hardened epoxy resin.

In summary, the reactive polyester prepared in the above examples can be used as a curing agent for the epoxy resin composition, and since the reactive polyester has an active ester group, the reactive polyester can be crosslinked with the epoxy resin. The hydroxyl group generated during the reaction with the epoxy resin can also be blocked, so that the dielectric constant and loss tangent of the cured epoxy resin can be effectively reduced and the heat resistance of the cured epoxy resin can be improved. Further, the cured epoxy resin prepared by the epoxy resin composition of the above examples has high processability, high heat resistance, good dielectric properties, and high toughness.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

no.

Figure 1 is a ¹ H NMR spectrum of Compound a-1 and Reactive Polyester 2. 2 is an IR spectrum chart of the reactive polyester 1, the epoxy resin composition 1, and the cured epoxy resin 1. 3 is an IR spectrum chart of the reactive polyester 2, the epoxy resin composition 2, and the epoxy resin cured product 2. 4 is a dynamic mechanical analysis (DMA) diagram of the epoxy resin cured product 1 and the epoxy resin cured product 2.

Claims (10)

An epoxy resin composition comprising: an epoxy resin; and an active polyester represented by the following general formula (1): (1) In the formula (1), Y is a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a carbonyl group, an oxygen atom or a sulfonyl group, and n1 and n2 are each Independently a positive integer, and 4 < n1+n2 < 26, m is an integer from 2 to 50, and Ar is an aromatic group, wherein the epoxy single amount of the epoxy resin and the ester equivalent of the reactive polyester The ratio of the numbers is 0.8 to 1.2. The epoxy resin composition according to claim 1, wherein Y is a single bond, a methylene group, an isopropylene group, a carbonyl group, an oxygen atom or a sulfonyl group. The epoxy resin composition according to claim 1, wherein Ar is selected from the group consisting of the following structural formulas: Wherein X is a single bond, -CH ₂ -, -O-, C=O, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -. The epoxy resin composition according to claim 1, wherein Y is an isopropyl group and Ar is a 1,4-phenylene group or a 1,3-phenylene group. The epoxy resin composition according to claim 1, wherein the epoxy resin comprises a bisphenol A type epoxy resin, a novolac epoxy resin, a methyl phenolic epoxy resin, a dicyclopentadiene-phenol ring An oxyresin, an epoxy resin containing a naphthalene ring structure, or a combination thereof. The epoxy resin composition according to claim 1, further comprising a curing accelerator. The epoxy resin composition according to claim 6, wherein the curing accelerator includes an imidazole-based curing accelerator, an amine-based curing accelerator, an organic phosphorus-based curing accelerator, or a combination thereof. The epoxy resin composition according to claim 6, wherein the curing accelerator is in an amount of from 0.1% by weight to 1.0% by weight based on the total weight of the epoxy resin. A cured product obtained by heat-curing an epoxy resin composition as described in claim 1 of the patent application. The cured product according to claim 9, wherein the heat curing temperature is from 140 ° C to 240 ° C.