TW201839031A - Phosphinated active polyester, method for preparing the same, epoxy composition and cured object - Google Patents

Abstract

A phosphinated active polyester, a method for preparing the same, an epoxy composition and a cured object are provided. The phosphinated active polyester is represented by general formula (a): In general formula (1), R and Ar are the same as defined in the detailed description.

Description

Phosphorus-based reactive polyester, preparation method thereof, epoxy resin composition and cured product

The present invention relates to a reactive polyester, a method for preparing the same, an epoxy resin composition comprising the active polyester, and a cured product, and more particularly to a phosphorus-based reactive polyester and a method for preparing the same, comprising a phosphorus-based reactive polymer Epoxy resin composition and cured product.

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

The present invention provides a phosphorus-based reactive polyester which can be used as a curing agent to realize a cured epoxy resin having high processability, high heat resistance, good dielectric properties, and high toughness.

The present invention provides a method for producing a phosphorus-based reactive polyester, which can produce a cured epoxy resin having high processability, high heat resistance, good dielectric properties, and high toughness.

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 phosphorus-based reactive polyester of the present invention is represented by the following formula (1): (1) In the formula (1), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy, substituted or not Substituted phenyl or -CF ₃ ; n is an integer from 10 to 100; and Ar is an aromatic group.

In an embodiment of the invention, the 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, the above R may be hydrogen or a methyl group, and Ar may be a 1,4-phenylene group or a 1,3-phenylene group.

The method for producing the phosphorus-based reactive polyester represented by the following general formula (1) of the present invention is, for example, as described in the following procedure. (1) A phosphorus compound represented by the following formula (a) is provided: (a) reacting the above phosphorus compound with a dichloro chloro compound and a base catalyst. In the formula (1) and the formula (a), R is hydrogen, substituted or unsubstituted C ₁ To a C ₆ alkyl group, a substituted or unsubstituted C ₁ to C ₆ alkoxy group, a substituted or unsubstituted phenyl group or —CF ₃ ; n is an integer of 10 to 100; and Ar is an aromatic group. group.

In an embodiment of the invention, the 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, the dichloro chloro compound is, for example, at least one of the following structural formulae (b-1) to (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 an embodiment of the invention, the above base catalyst is, for example, CsF, KF, CsCl, KCl, K ₂ CO ₃ , Na ₂ CO ₃ , KOH, NaOH or a combination thereof.

In an embodiment of the invention, the molar ratio of the above-mentioned diterpene chlorine compound to the phosphorus compound is, for example, 0.7 to 1.3.

In an embodiment of the invention, the molar ratio of the alkali catalyst to the phosphorus compound is from 0.5 to 1.5.

The epoxy resin composition of the present invention includes an epoxy resin and a phosphorus-based reactive polyester represented by the following general formula (1). (1) In the formula (1), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy, substituted or not Substituted phenyl or -CF ₃ ; n is an integer from 10 to 100; and Ar is an aromatic group. In some embodiments, the ratio of the epoxy single amount of the epoxy resin to the ester equivalent number of the phosphorus-based reactive polyester is from 0.8 to 1.2. In another embodiment, the ratio of the epoxy single amount of the epoxy resin to the ester equivalent number of the phosphorus-based reactive polyester is 1.0.

In an embodiment of the invention, the epoxy resin is, for example, a bisphenol A-based epoxy, a phenol novolac-based epoxy, or a methyl phenolic epoxy resin. Cresol novolac-based epoxy), dicyclopentadiene-phenol based epoxy, epoxy resin containing a naphthalene ring structure, or a combination thereof.

In one embodiment of the present invention, 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 an embodiment of the invention, the amount of the above-mentioned curing accelerator is, for example, 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 phosphorus-based reactive polyester of the present invention can be used as a curing agent for an epoxy resin composition, and since the phosphorus-based reactive polyester has an active ester group, the phosphorus-based reactive polyester can be crosslinked with an epoxy resin. In addition, the hydroxyl groups generated during the reaction with the epoxy resin can be blocked, so that the dielectric constant and the 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 phosphorus-based reactive polyester ]

The present invention provides a phosphorus-based reactive polyester represented by the following general formula (1): (1) In the formula (1), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy, substituted or not Substituted phenyl or -CF ₃ ; n is an integer from 10 to 100; and Ar is an aromatic group.

In this embodiment, the above 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, R is hydrogen or methyl, and Ar is 1,4-phenylene or 1,3-phenylene. [ Preparation method of phosphorus-based reactive polyester ]

The phosphorus-based reactive polyester of the present invention is represented by the following formula (1): (1), wherein R and Ar are as defined above, and will not be described again.

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

First, a phosphorus compound is provided. The phosphorus compound is represented by the following formula (a): (a) In the formula (a), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy, substituted or not Substituted phenyl or -CF ₃ .

Next, the above phosphorus compound is mixed with a dichloro chloro compound and a base catalyst to obtain a phosphorus-based active polyester of the present invention. In some embodiments, the molar content of the dioxonium chloride compound is greater than or equal to the molar content of the phosphorus based compound. In the present embodiment, the molar ratio of the diterpene chlorine compound to the phosphorus compound (i.e., the dichloro chloro compound/phosphorus compound) is, for example, 0.7 to 1.3. In another embodiment, the molar ratio of the dioxonium compound to the phosphorus 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 phosphorus compound with the diterpene chlorine 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 phosphorus compound is from 0.5 to 1.5.

In the present embodiment, the ester equivalent of the phosphorus-based reactive polyester of the present invention is half the molecular weight of the repeating unit. For example, in the following Synthesis Example 1, the phosphorus-based reactive polyester 1 has a repeating unit molecular weight of 574, and its ester equivalent is 287 (i.e., 574/2 = 287).

Since the formed phosphorus-based reactive polyester of the present invention has an active ester group, if the phosphorus-based reactive polyester is used as a curing agent in the epoxy resin composition, the phosphorus-based reactive polyester can be crosslinked with the epoxy resin. In addition to the reaction, the hydroxyl groups generated during the reaction with the epoxy resin can 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. [ Epoxy Resin Composition ]

The epoxy resin composition of the present invention includes an epoxy resin and the above-mentioned phosphorus-based reactive polyester as a curing agent, and the description of the phosphorus-based reactive polyester is the same as that of the above embodiment, and will not be described herein.

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 phosphorus-based reactive polyester is from 0.8 to 1.2. In another embodiment, the ratio of the epoxy single amount of the epoxy resin to the ester equivalent number of the phosphorus-based reactive polyester is 1.0. When the epoxy resin and the phosphorus-based reactive polyester are blended in the above range, an epoxy resin cured product 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 a phosphorus-based reactive polyester represented by the general formula (1) as a curing agent for an epoxy resin composition, wherein the phosphorus-based reactive polyester has an active ester group, and thus the phosphorus-based reactive polyester can be produced in addition to an epoxy resin. In addition to the crosslinking reaction, the hydroxyl groups generated during the reaction with the epoxy resin can also be blocked, thereby effectively reducing the dielectric constant and the loss tangent of the cured epoxy resin and improving the heat resistance of the cured epoxy resin. .

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 phosphorus-based reactive polyester ]

Synthesis Example 1: Synthesis of Phosphorus-Based Reactive Polyester 1

[Reaction Flow Chart 1]

5.0 g (11.67 mmol) of the compound a-1 was added to 23.34 mL (23.34 mmol) of a 1 M aqueous sodium hydroxide solution to obtain a mixed aqueous solution. 2.3692 g (11.67 mmol) of p-benzoic acid chloride was added to 40 ml of dichloromethane to obtain a mixed solution of the oil phase. Next, the mixed solution of the aqueous phase was separately stirred for 30 minutes, and then 0.25 g of Benzyltriethylammonium chloride (BTEAC) was added to the mixed solution of the aqueous phase. Then, the mixed solution of the oil phase was slowly dropped into the mixed solution of the aqueous phase using a feed tube, and vigorously stirred under nitrogen and ice for 3 hours to obtain a white viscous body. Thereafter, the white viscous body was placed in hot water and stirred to obtain a white solid, which was then dissolved in dichloromethane and then added dropwise to methanol to give a white strip of phosphorus-based active polyester 1. ¹ H NMR spectrum (ppm, DMSO-D ₆ ) of phosphorus-based reactive polyester 1 : δ = 1.7 (3H, CH ₃ ), 7.0-8.4 (20H, Ar-H), and the integrated area ratio was in accordance with the structure.

Fig. 1 is a ¹ H NMR spectrum chart of a compound a-1 and a phosphorus-based reactive polyester 1. As shown in Fig. 1, in the ¹ H NMR spectrum of the phosphorus-based reactive polyester 1, the peak of 6.6 ppm (H of phenol group) originally appearing in the compound a-1 has disappeared, and there is a new one near 8.2 ppm. The peak formation (i.e., CO-ph-CO) showed that the phenolic group of compound a-1 had reacted completely with terephthalic acid.

Synthesis Example 2: Synthesis of phosphorus-based reactive polyester 2

[Reaction Flow Chart 2]

5.0 g (11.67 mmol) of the compound a-1 was added to 23.34 mL (23.34 mmol) of a 1 M aqueous sodium hydroxide solution to obtain a mixed aqueous solution. 2.3692 g (11.67 mmol) of m-xylylene chloride was added to 40 ml of dichloromethane to obtain a mixed solution of the oil phase. Next, the mixed solution of the aqueous phase was separately stirred for 30 minutes, and then 0.25 g of Benzyltriethylammonium chloride (BTEAC) was added to the mixed solution of the aqueous phase. Then, the mixed solution of the oil phase was slowly dropped into the mixed solution of the aqueous phase using a feed tube, and vigorously stirred under nitrogen and ice for 3 hours to obtain a white viscous body. Thereafter, the white viscous body was placed in hot water and stirred to obtain a white solid, which was then dissolved in dichloromethane, and then added dropwise to methanol to precipitate to obtain a white strip-like phosphorus-based reactive polyester 2. ¹ H NMR spectrum (ppm, DMSO-D ₆ ) of phosphorus-based reactive polyester 2: δ = 1.7 (3H, CH ₃ ), 7.0-8.4 (20H, Ar-H), and the integrated area ratio was in accordance with the structure. [ 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, a phosphorus-based reactive polyester 1 and a diglycidyl ether of bisphenol A (DGEBA) epoxy resin (epoxy equivalent weight: 188 g/eq) were dissolved in Dimethylacetamide (Dimethylacetamide, In the DMAc) solvent, both of the ester equivalents of the phosphorus-based reactive polyester 1 and the epoxy equivalent of the epoxy resin were adjusted to a ratio of 1:1 to obtain a mixed solution having a solid content of 40% 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.

Then, the above epoxy resin composition was coated on a glass substrate with a knife coater, and then the glass substrate coated with the epoxy resin composition was placed in a circulating oven and dried at 110 ^o C for 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. Example 2

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 epoxy resin HP7200 (epoxy equivalent weight 250 g/eq) was used in place of the DGEBA epoxy resin of Example 1. Example 3

Preparation of epoxy resin cured product 3

Epoxy Resin Composition 2 was prepared in a manner similar to that of Example 1, except that the epoxy resin CNE (epoxy equivalent weight 200 g/eq) was used in place of the DGEBA epoxy resin of Example 1. Example 4

Preparation of epoxy resin cured product 4

Epoxy Resin Composition 2 was prepared in a manner similar to that of Example 1, except that the phosphorus-based reactive polyester 2 prepared in Synthesis Example 2 was used instead of the phosphorus-based reactive polyester 1 of Example 1. Example 5

Preparation of epoxy resin cured product 5

Epoxy Resin Composition 2 was prepared in a manner similar to that of Example 1, except that the epoxy resin HP7200 and the phosphorus-based reactive polyester 2 prepared in Synthesis Example 2 were used in place of the DGEBA epoxy resin of Example 1 and Phosphorus-based reactive polyester 1. Example 6

Preparation of epoxy resin cured material 6

Epoxy Resin Composition 2 was prepared in a manner similar to that of Example 1, except that the epoxy-based CNE and the phosphorus-based reactive polyester 2 prepared in Synthesis Example 2 were used in place of the DGEBA epoxy resin of Example 1 and Phosphorus-based reactive polyester 1.

2 is an IR spectrum chart of a phosphorus-based reactive polyester 1, an epoxy resin cured product 1 to an epoxy resin cured product 3. Specifically, FIG. 2 is an IR spectrum chart of a carbon-oxygen double bond (C=O) portion of the phosphorus-based reactive polyester 1, the epoxy resin cured product 1 to the epoxy resin cured product 3. As shown in FIG. 2, the characteristic peak of the carbon-oxygen double bond of the phosphorus-based reactive polyester 1 is 1735 cm ^-1 , and the characteristic peak of the carbon-oxygen double bond of the epoxy resin cured product 1 to the epoxy resin cured product 3 is 1725 cm ^{- 1} . That is to say, the phosphorus-based reactive polyester 1 has a carbon-oxygen double bond characteristic peak shifted from 1735 cm ^-1 to 1725 cm ^-1 after being cured with an epoxy resin. This is because the oxygen of the benzene ring in the ester group of the original phosphorus-based reactive polyester 1 resonates with the benzene ring and relatively reduces the resonance of the carbon-oxygen double bond (C=O), so the carbon of the phosphorus-based reactive polyester 1 The oxygen double bond characteristic peak will be at a higher wave number. However, in the reaction between the phosphorus-based reactive polyester 1 and the epoxy resin, the oxygen of the benzene ring in the ester group of the phosphorus-based reactive polyester 1 reacts with the epoxy group, and thus cannot resonate with the benzene ring. It is a resonance with a carbon-oxygen double bond (C=O), which in turn reduces the wave number of the characteristic peak of the carbon-oxygen double bond.

3 is a photographic image of the cured epoxy resin 1 to the cured epoxy resin 6. As shown in FIG. 3, the epoxy resin cured product 1 to the epoxy resin cured product 6 prepared by the present invention have high flexibility and transparency with respect to the hard brittleness of the conventional epoxy resin cured product. [ Evaluation of thermal properties and dielectric properties of epoxy resin cured materials ]

The prepared epoxy resin cured product 1 to epoxy resin cured product 6 were evaluated for thermal properties and dielectric properties by the following methods. The results are listed in Table 1.

(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.

(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 1

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. However, as can be seen from Table 1, the glass transition temperatures of the cured epoxy resin 1 to the cured epoxy resin 6 of the present invention are 210 ° C, 217 ° C, 217 ° C, 210 ° C, 217 ° C, and 212, respectively. °C, the epoxy resin cured product prepared by the phosphorus-based reactive polyester as the curing agent of the present invention has a high glass transition temperature.

Please continue to refer to Table 2, in the TGA test, the 5% thermogravimetric loss temperature of the epoxy resin cured product 1 to the epoxy resin cured product 6 of the present invention is 405 ° C, 407 ° C, 407 ° C, 400, respectively. °C, 408 ° C and 408 ° C. Further, the coke residual ratios of the epoxy resin cured product 1 to the epoxy resin cured product 6 were 38%, 28%, 50%, 40%, 43%, and 43%, respectively, and showed a phosphorus system as a curing agent of the present invention. The cured epoxy resin prepared from the reactive polyester has good thermal stability (i.e., heat resistance).

Further, in the evaluation of the dielectric ability of the epoxy resin cured product, the dielectric constant of the epoxy resin cured product 1 to the epoxy resin cured material 6 of the present invention is between 2.8 U and 3.2 U, and the loss tangent is between From 5.7 mU to 9.7 mU, the loss tangent is significantly lower than that of the conventional phenol-based hardened epoxy resin.

In summary, the phosphorus-based reactive polyester prepared in the above examples can be used as a curing agent for the epoxy resin composition, and since the phosphorus-based reactive polyester has an active ester group, the phosphorus-based reactive polyester can be combined with an epoxy The resin can also form a cross-linking reaction, and can also block the hydroxyl groups generated during the reaction with the epoxy resin, thereby effectively reducing the dielectric constant and loss tangent of the cured epoxy resin and improving the heat resistance of the cured epoxy resin. . 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.

Fig. 1 is a ¹ H NMR spectrum chart of a compound a-1 and a phosphorus-based reactive polyester 1. 2 is an IR spectrum chart of a phosphorus-based reactive polyester 1, an epoxy resin cured product 1 to an epoxy resin cured product 3. 3 is a photographic image of the cured epoxy resin 1 to the cured epoxy resin 6.

Claims (16)

A phosphorus-based reactive polyester represented by the following general formula (1): (1) In the formula (1), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy, substituted or not substituted phenyl or -CF _3; n is an integer from 10 to 100; and Ar is an aromatic group. The phosphorus-based reactive polyester 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 phosphorus-based reactive polyester according to claim 1 or 2, wherein R is hydrogen or methyl, and Ar is 1,4-phenylene or 1,3-phenylene. A method for producing a phosphorus-based reactive polyester represented by the following general formula (1), (1), including: providing a phosphorus-based compound represented by the following general formula (a): (a) In the formula (1) and formula (a), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy a substituted or unsubstituted phenyl group or -CF ₃ ; n is an integer of 10 to 100; and Ar is an aromatic group; and the phosphorus compound is mixed with a diterpene chlorine compound and a base catalyst. reaction. A method for producing a phosphorus-based reactive polyester represented by the following general formula (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 -. A method for producing a phosphorus-based reactive polyester represented by the following general formula (1), wherein the diterpene chlorine compound comprises the following structural formula (b-1) to a structural formula, as described in claim 4 or 5; At least one of (b-4): Wherein X is a single bond, -CH ₂ -, -O-, C=O, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -. A method for producing a phosphorus-based reactive polyester represented by the following general formula (1), wherein the alkali catalyst comprises CsF, KF, CsCl, KCl, K ₂ CO ₃ , as described in claim 4 or 5 _{, Na 2 CO 3, KOH,} NaOH , or a combination thereof. The method for producing a phosphorus-based reactive polyester represented by the following general formula (1), wherein the molar ratio of the diterpene chlorine compound to the phosphorus compound is 0.7. To 1.3. The method for producing a phosphorus-based reactive polyester represented by the following general formula (1), wherein the molar ratio of the alkali catalyst to the phosphorus-based compound is 0.5 to 1.5. An epoxy resin composition comprising: an epoxy resin; and a phosphorus-based reactive polyester represented by the following general formula (1): (1) In the formula (1), R is hydrogen, substituted or unsubstituted C ₁ to C ₆ alkyl, substituted or unsubstituted C ₁ to C ₆ alkoxy, substituted or not Substituted phenyl or -CF ₃ ; n is an integer from 10 to 100; and Ar is an aromatic group, wherein the epoxy single amount of the epoxy resin and the ester equivalent number of the phosphorus-based reactive polyester The ratio is 0.8 to 1.2. The epoxy resin composition according to claim 10, 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 10 or 11, further comprising a curing accelerator. The epoxy resin composition according to claim 12, wherein the curing accelerator comprises 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 12, wherein 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. A cured product obtained by heat-curing an epoxy resin composition according to claim 10 or 11. The cured product according to claim 15, wherein the heat curing temperature is from 140 ° C to 240 ° C.