KR101355979B1 - Poly epoxy resin having excellent electrical properities, composition of that and preparing method thereof - Google Patents

Abstract

The present invention relates to a polyepoxy resin with excellent electrical properties, a composition used in manufacture thereof and a manufacturing method thereof. More specifically, the present invention relates to a manufacture of the polyepoxy resin exhibiting low dielectric constant, low dielectric loss, excellent adhesive and thermal properties with a high yield.

Description

Poly epoxy resin having excellent electrical properities, Composition of that and Preparing method

The present invention relates to a poly epoxy resin having excellent electrical properties, a composition and a manufacturing method thereof, and more particularly, to a poly epoxy resin having a low dielectric constant, dielectric loss, excellent adhesion and thermal properties, a composition thereof, and the same. A method for producing a poly epoxy resin.

Recently, the semiconductor industry has developed into a trend of miniaturization through the convergence of heterogeneous technologies and components with high capacity and ultra high speed. The core technology of such convergence technology is packaging technology in which dissimilar materials and components are inserted into a single device, and for this purpose, low Dk (low dielectric constant), Low Df (low dielectric loss), excellent adhesion and heat resistance Core material development is essential.

Increasing the integration of semiconductor devices in order to process a large amount of capacity in a short time for high integration, finer, and high performance, such as next-generation IC substrate, PCB, flexible display substrate, etc. This means that the width becomes narrower, and as a result, the switching speed of the transistor is increased, thereby speeding up the device. Recently, various methods for reducing the wiring width of the device have been proposed, but for the formation of a fine circuit pattern, conventional pattern formation through copper etching is limited in reducing the circuit pattern spacing. Due to this, copper circuit pattern formation through a chemical method can be implemented up to 20/20 μm or less, but has a disadvantage in that adhesive strength is remarkably decreased due to the inability of roughness of the surface of the formed pattern. In other words, the speed of the high density chip depends on the narrow line width between the wirings on the high density chip rather than the switching speed. In this case, low Dk (low dielectric constant), low Df (low dielectric loss), and high adhesion that have excellent electrical insulation properties are required. .

The development of materials with low dielectric constant is slower than the reduction of wiring width. Among them, organic materials include epoxy resin, Teflon (PTFE), cyanate resin, polyphenylene ether (PPE) or thermosetting PPE. Among them, Teflon material is known as a material showing the best dielectric properties among the organic material.

However, Teflon, which is an organic material having low dielectric constant, has a disadvantage in that the adhesion properties required in IC substrates, PCBs, and flexible display substrates are remarkably inferior, and its use is limited. In the case of cyanate resins, low dielectric constant Although it realizes the characteristics, when the curing temperature is higher than 230 ° C., high energy is required, and gelation is easily performed on alcoholic hydroxy such as moisture, which limits its use.

In addition, in the case of polyphenylene ether (PPE) or thermosetting PPE, it is simply added in a non-responsive manner to reduce the adhesive properties on the curing matrix of the adhesive layer, such as IC substrate, PCB, flexible display substrate, etc., uneven surface of the adhesive layer Cause. Due to these various problems, the use of epoxy resins having high adhesive properties, low dielectric constant, dielectric loss characteristics, and ease of use are increasing.

In general, a method for implementing adhesion properties to an epoxy resin may be implemented by reacting a bisphenol compound with a bisphenol-type epoxy, which may be obtained through the formation of a secondary alcohol through the addition reaction of the bisphenol-type epoxy and bisphenol A. . Specifically, Reaction Scheme 1 below shows an addition reaction between a conventional bisphenol A and a bisphenol A series epoxy compound (Kukdo Chemical, YD128).

[Reaction Scheme 1]

Provided that n is 0.1 to 12.

As can be seen in Scheme 1, when the addition reaction of the bisphenol compound to the bisphenol-type epoxy to give the adhesive properties of the epoxy inevitably produced secondary alcohol during the epoxy ring opening process. As a result, the properties of the adhesion of the epoxy compound subjected to the final addition reaction can be realized, but due to the hydrophilicity of the secondary alcohol produced by the addition reaction, the hygroscopicity, dielectric constant and dielectric loss of the final cured product are remarkably degraded. Occurred.

On the other hand, in the prior art of imparting the adhesive properties and heat resistance properties to the epoxy resin is a polyepoxy compound having a high glass transition temperature while excellent in adhesive properties through the formation of oxazolidone ring in the epoxy termination by reacting isocyanate with the epoxy resin To prepare. In this case, an oxazolidone ring is formed at the end of the epoxy by reacting an epoxy group with an isocyanate under an imidazole-based catalyst to improve the adhesion ability of the cured product and a cured product having a relatively high glass transition temperature through a curing reaction with an epoxy curing agent. Although there have been developments in the manufacturing process, electrical properties such as dielectric constant and dielectric loss are required to be improved.

The present invention has been made to solve the above problems, an object of the present invention is to use an epoxy resin, which has excellent adhesion properties and heat resistance properties, significantly improved electrical properties such as dielectric constant, dielectric loss, etc. It is to provide a composition and a method of producing the same.

In order to solve the above problems, the present invention relates to a composition used for producing a poly epoxy resin, comprising: a polyoxazolidone-containing epoxy compound containing a compound represented by the following general formula (3); And a compound represented by Formula 4 below.

 (3)

[Chemical Formula 4]

In Formula 3, n is a free number of 0 to 2, R ₅ is -H, OH or C _{1 ~ 10} alkyl group,

이며, D의 R₀는 -H, OH기 또는 C_{1 ~10}의 알킬기이며, D의 n은 0 ~ 0.2의 유리수이며, x는 0 또는 1이고, A는

,

,

,

,

,

, 또는

이며, A의 R₁, R'₁, R₂, R₃ 및 R₄ 은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, A의 n은 독립적으로 0 ~ 4의 유리수이다.D is

And, R ₀ of D is -H, an alkyl group of the OH group or a C _{1 ~ 10,} and the D n is a rational number of 0 ~ 0.2, x is 0 or 1, A is

,

,

,

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} Are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} the A n are independently a rational number of 0 to 4.

이고, R₆ 및/또는 E의 R₇은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이고, E의 n은 0 ~ 2의 유리수며, q 는 0 ~ 4의 유리수이다.In Formula 4, E is

And R ₆ And / or R ₇ in E are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} n of said E is a rational number from 0 to 2, q is a rational number of 0 to 4.

,

,

,

,

,

, 또는

이며, F의 R₁, R₂, R₃ 및 R₄ 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, F의 n은 독립적으로 0 ~ 4의 유리수이다.And F of E

,

,

,

,

,

, or

R ₁ , R ₂ , R ₃ and R _{4 of} F Are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} n of F is independently a rational number of 0 to 4.

,

,

, 또는

이며, F의 R₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H 또는 C_{1 ~3}의 알킬기이며, F의 n은 각각 독립적으로 0 ~ 2의 유리수인 것을 특징으로 할 수 있다.As a preferred embodiment of the present invention, in the poly epoxy resin composition of the present invention, n of Formula 3 is a free number of 0 to 3, R _{0 of} D And and / or an alkyl group of formula (3) in R ₅ is independently -H or C _{1 ~ 5} alkyl group and the formula (4) of the R ₆ and / or R ₇ in E are each independently -H or C _{1 ~ 3,} N in E is a rational number from 0 to 1, q is a rational number from 0 to 4, F is

,

,

, or

R ₁ , R ₂ , R ₃ and R ₄ of F are each independently -H or an alkyl group of _{1 to 3} , and each of n of F may be independently a free number of 0 to 2.

As another preferred embodiment of the present invention, the poly epoxy resin composition of the present invention comprises from 10 to 90 parts by weight of the compound represented by the formula (4) based on 100 parts by weight of the polyoxazolidone-containing epoxy compound Can be.

As a preferred embodiment of the present invention, the poly epoxy resin composition of the present invention is 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-Ethyl-4-Methyl Imidazole, 1 At least one selected from 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole and 2-undecyl immidazole. Containing imidazole compounds; Trialkyl compounds containing at least one selected from triphenylphosphate and Triphenylphosphate Iodide; And 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2,5-diamino pyridine, 2,6-diamino It may further comprise a catalyst containing at least one selected from pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine. have.

As another preferred embodiment of the present invention, the poly epoxy resin composition of the present invention may be characterized in that the epoxy equivalent of the polyoxazolidone-containing epoxy compound is 200 ~ 550 g / eq.

Another aspect of the present invention relates to a poly epoxy resin, it may be characterized by comprising a poly epoxy compound represented by the following formula (5).

 [Chemical Formula 5]

이고, G의 r은 0 ~ 3의 유리수이며, G의 R₀ 및 R₆은 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이고, x는 0 또는 1이며, 상기 E는

이며, E의 R₇은 -H, OH 또는 C_{1 ~10}의 알킬기이고, E의 n은 0 ~ 2의 유리수며, E의 q 는 0 ~ 4의 유리수이다. 그리고, E의 F는

,

,

,

,

,

, 또는

이며, F의 R₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H, OH 또는 C_{1 ~10}의 알킬기이며, F의 n은 각각 독립적으로 0 ~ 4의 유리수이다.In Chemical Formula 5, n in Chemical Formula 5 is a rational number of 0 to 2, and R ₅ is an alkyl group of -H, OH group or a C _{1 ~ 10.} Then, G

R is a rational number of 0 to 3, and R _{0 of} G And R ₆ is independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} x is 0 or 1, said E is

And, R ₇ of E is -H, OH, or an alkyl group of C _{1 ~ 10,} n of said E is a rational number from 0 to 2, and q is a rational number of 0 to 4 for E. And F of E

,

,

,

,

,

, or

And, of _{F R 1, R 2, R} 3 and R ₄ are each independently -H, OH, or an alkyl group of C _{1 ~ 10,} the F n are each independently a rational number of 0 to 4.

이고, 화학식 4의 R₆ 및/또는 E의 R₇은 각각 독립적으로 -H 또는 C_{1 ~3}의 알킬기이고, E의 n은 0 ~ 1의 유리수며, q 는 0 ~ 4의 유리수이고, A는

,

,

, 또는

이며, A의 R₁, R'₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H 또는 C_{1 ~3}의 알킬기이며, As a preferred embodiment of the present invention, n in Chemical Formula 5 is 0 to 1 free radical, R _{0 of} G And / or 5 of the formula R ₅ is independently H or an alkyl group of C _{1 ~ 5,} E in the formula (4) is

R ₆ of Formula 4 And / or R ₇ of E are each independently -H or an alkyl group of _{1 to 3} , n of E is a rational number of 0 to 1, q is a rational number of 0 to 4, and A is

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} are Each independently -H or alkyl group of C _{1 ~ 3,}

,

,

, 또는

이며, F의 R₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H 또는 C_{1 ~3}의 알킬기이고, A 및 F의 n은 각각 독립적으로 0 ~ 2의 유리수인 것을 특징으로 할 수 있다.F is

,

,

, or

R ₁ , R ₂ , R ₃ and R ₄ of F are Each is independently -H or alkyl group of C _{1 ~ 3,} n of A and F may be characterized in that each independently a rational number of 0 to 2.

In addition, as a preferred embodiment of the present invention, the poly epoxy resin of the present invention may be characterized in that the epoxy equivalent of 300 ~ 850 g / eq.

In addition, as a preferred embodiment of the present invention, the poly epoxy resin of the present invention has a dielectric constant (GHz) of 2.80 to 3.20 and a loss ratio (GHz) of 0.010 to 0.020 when measured according to the JIS-C-6481 method. It can be characterized.

Another aspect of the present invention relates to a method for preparing a poly epoxy resin described above, by polymerizing an isocyanate compound and a epoxy compound represented by the formula (1) comprising a compound represented by the formula (2) to Preparing a polyoxazolidone-containing epoxy compound comprising the compound represented; And polymerizing the polyoxazolidone-containing epoxy compound and the compound represented by Chemical Formula 4 to prepare a poly epoxy compound comprising the compound represented by Chemical Formula 5; and may be prepared through a process.

[Formula 1]

In formula (1), R ₀ is -H, OH group or C _{1 ~ 10} alkyl group, n in formula (1) is a free number from 0 to 0.2, x is 0 or 1,

,

,

,

,

,

또는

이며, A의 R₁, R'₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, A의 n은 각각 독립적으로 0 ~ 4의 유리수이다.A is

,

,

,

,

,

or

And, the R _1, R 'an alkyl group of _1, R _2, R ₃ and R ₄ are independently -H, OH group or a C _{1 ~ 10,} each of the A, the A n are each independently a rational number of 0 to 4 .

 (2)

R ₅ of formula (II) is -H, an alkyl group of the OH group or a C _{1 ~ 10,} n is a rational number of 0 to 2.

 (3)

이며, D의 n은 0 ~ 0.2이고, 화학식 3의 R₅ 및/또는 D의 R₀ 는 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, x는 0 또는 1이고, D의 A는

,

,

,

,

,

, 또는

이며, A의 R₁, R'₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, A의 n은 각각 독립적으로 0 ~ 4의 유리수이고,In Chemical Formula 3, m is a rational number of 0 to 3, n is a rational number of 0 to 2, wherein D is

And n of D is 0 to 0.2, and R ₅ of Chemical Formula 3 And / or R _{0 of} D Are independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} x is 0 or 1, A is of the D

,

,

,

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} are Are each independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} the A n are independently a rational number of 0 to 4 respectively,

[Chemical Formula 4]

이고, 화학식 4의 R₆ 및/또는 E의 R₇은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이고, n은 0 ~ 2의 유리수이며, q 는 0 ~ 4의 유리수이고,In Formula 4 E is

R ₆ of Formula 4 A and / or R ₇ in E are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} n is a rational number from 0 to 2, q is a rational number of 0 to 4,

,

,

,

,

,

, 또는

이며, F의 R₁, R₂, R₃ 및 R₄은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, F의 n은 각각 독립적으로 0 ~ 4의 유리수이고,F is

,

,

,

,

,

, or

R ₁ , R ₂ , R ₃ and R ₄ of F are It is each independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} n F is a rational number of 0 to 4 independently,

[Chemical Formula 5]

In Chemical Formula 5, n in Chemical Formula 5 is a rational number of 0 to 2, and R ₅ is -H, an alkyl group of the OH group or a C _{1 ~ 10,}

이고, G의 r은 0 ~ 3의 유리수이며, G의 R₀ 및/또는 R₆은 독립적으로 -H, OH기 또는 C_1~10의 알킬기이고, x는 0 또는 1이며,G is

R is a rational number of 0 to 3, and R _{0 of} G And / or R ₆ is independently —H, OH group or C _1-10 alkyl group, x is 0 or 1,

이고, E의 R₇은 -H, OH 또는 C_{1 ~10}의 알킬기이고, E의 n은 0 ~ 2의 유리수이며, E의 q 는 0 ~ 4의 유리수이고, G의 A는

,

,

,

,

,

또는

이며, A의 R₁, R'₁, R₂, R₃ 및 R₄는 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, E의 F는

,

,

,

,

,

또는

이며, F의 R₁ ~ R₄은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이며, A의 n 및 F의 n은 각각 독립적으로 0 ~ 4의 유리수인 것을 특징으로 할 수 있다.E is

And, wherein R ₇ is -H, OH, or an alkyl group of C _{1 ~ 10} for E, and E n is a rational number of from 0 to 2, q is a rational number of 0 to 4 for E, G A is the

,

,

,

,

,

or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} are Each independently selected from -H, an alkyl group of the OH group or a C _{1 ~ 10,} F is the E

,

,

,

,

,

or

R ₁ to R ₄ of F are each independently a -H, an OH group or a C _{1 to 10} alkyl group, and n of A and n of F may each independently be a free number of 0 to 4. .

In a preferred embodiment of the present invention, in the method for producing a poly epoxy resin of the present invention, the polymerization of the step of preparing the polyoxazolidone-containing epoxy compound is 2-methyl imidazole, 2-ethyl-4-methyl imi An imidazole compound containing at least one selected from dozol, 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole and 2-undecyl imidazole; Trialkyl compounds containing at least one selected from triphenylphosphate and ETPPI; And 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2,5-diamino pyridine, 2,6-diamino pyridine, 2-amino- It may be characterized by performing under a catalyst containing at least one selected from 6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine.

In addition, as a preferred embodiment of the present invention, in the method for producing a poly epoxy resin of the present invention, the polymerization of the step of preparing the poly epoxy compound is 2-methyl imidazole, 2-ethyl-4-methyl imidazole, Imidazole compounds containing at least one selected from 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole and 2-undecyl imidazole; Trialkyl compounds containing at least one selected from triphenylphosphate and ETPPI; And 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2,5-diamino pyridine, 2,6-diamino pyridine, 2-amino- It can be characterized in that it is carried out under an imidazole-based catalyst containing at least one selected from 6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine. have.

The polyepoxy resin having excellent electrical characteristics of various forms of the present invention described above may be manufactured from a cured material such as an encapsulant, an IC substrate, a PCB, a flexible display substrate, and the like.

The poly epoxy resin produced by the method of the present invention using the poly epoxy resin composition of the present invention has a low dielectric constant, dielectric loss, excellent adhesion and thermal properties, the next generation IC substrate (IC substrate), PCB It is suitable for use in semiconductor materials that require high integration, high resolution, and high performance, such as flexible display substrates.

Hereinafter, the present invention will be described in more detail.

"C _{1 - 10"} in the terms used in the present invention to mean a group having a carbon number of 1 to 10 carbon atoms.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a poly epoxy resin having excellent electrical characteristics, and more particularly, to a poly epoxy resin having a low dielectric constant and a low dielectric loss.

The poly epoxy resin of the present invention having such characteristics may include a poly epoxy compound represented by the following formula (5).

 [Chemical Formula 5]

이다. 여기서, G의 r은 0 ~ 3의 유리수이며, 바람직하게는 r은 0 ~ 2의 유리수인데, 이때, r이 3을 초과하면 전기적 특성이 좋아질 수 있으나, 상기 에폭시 경화물의 유리전이 온도가 낮아지는 단점을 가질 수 있어 상기 값을 갖는 것이 좋다. 그리고, G의 x는 0 또는 1이다.In Chemical Formula 5, G is

to be. Here, r of G is a rational number of 0 to 3, preferably r is a rational number of 0 to 2, wherein when r exceeds 3, the electrical properties may be improved, but the glass transition temperature of the epoxy cured product is lowered. It may be disadvantageous to have the above value. And x of G is 0 or 1.

And, in the formula (5) R _{5 ,} G _{0 ,} and R ₆ of G is independently -H, alkyl groups of OH group or a C _{1 ~ 10,} preferably of formula (5) R _{5 ,} G _{0 ,} and R ₆ of G is independently -H or alkyl group of C _{1 ~ 5,} and more preferably -H or a C _1-4 alkyl group.

이고, E의 R₇은 -H, OH 또는 C_{1 ~10}의 알킬기이고, 바람직하게는 -H 또는 C_{1 ~3}의 알킬기이며, 더욱 바람직하게는 -H 또는 메틸기이다. 또한, E의 n은 0 ~ 2의 유리수며, 바람직하게는 0 ~ 1의 유리수다. 그리고, E의 q 는 0 ~ 4의 유리수이고, 바람직하게는 q 는 1 ~ 2의 유리수이다. In addition, E of G is

And, R ₇ of E is -H, and OH, or an alkyl group of C _{1 ~ 10,} preferably an alkyl group of -H or a C _{1 ~ 3,} more preferably -H or methyl. In addition, n of E is a rational number of 0-2, Preferably it is a rational number of 0-1. And q of E is a rational number of 0-4, Preferably q is a rational number of 1-2.

,

,

,

,

,

, 또는

이며, 바람직하게는

,

,

또는

이다. 그리고, 상기 A의 R₁, R'₁, R₂, R₃ 및 R₄ 각각 독립적으로 -H, -OH 또는 C_{1 ~10}의 알킬기이며, 바람직하게는 -H 또는 C_{1 ~3}의 알킬기이며, 더욱 바람직하게는 -H 또는 메틸기이다. 또한, A의 n은 각각 독립적으로 0 ~ 4의 유리수, 바람직하게는 0 ~ 2의 유리수이다.And A of G is

,

,

,

,

,

, or

, And preferably

,

,

or

to be. And, A ₁ R ₁ , R ' ₁ , R ₂ , R ₃ And R ₄ Each independently -H, -OH or an alkyl group of C _{1 ~ 10,} preferably an alkyl group of -H or a C _{1 ~ 3,} more preferably -H or methyl. In addition, n of A is respectively independently rational number of 0-4, Preferably it is rational number of 0-2.

,

,

,

,

,

, 또는

이며, 바람직하게는

,

,

또는

이다. 그리고, 상기 F의 R₁, R₂, R₃ 및 R₄ 각각 독립적으로 -H, OH 또는 C_{1 ~10}의 알킬기이며, 바람직하게는 -H 또는 C_{1 ~ 3} 의 알킬기이며, 더욱 바람직하게는 H 또는 메틸기이다. 또한, F의 n은 각각 독립적으로 0 ~ 4의 유리수, 바람직하게는 0 ~ 2의 유리수다.And F of E

,

,

,

,

,

, or

, And preferably

,

,

or

to be. And, R ₁ , R ₂ , R ₃ And R _{4 Of} The F Each independently selected from -H, an alkyl group of OH or C _{1 ~ 10,} preferably an alkyl group of -H or a C _{1 ~ 3,} more preferably H or methyl. In addition, n of F is respectively independently rational number of 0-4, Preferably it is rational number of 0-2.

In addition, n in the formula (5) is a rational number of 0 to 2, preferably n in the formula (5) is a rational number of 0 to 1.

In addition, the poly epoxy resin of the present invention may be characterized in that the epoxy equivalent of 300 ~ 850 g / eq, preferably 310 ~ 840 g / eq.

Further, the cured product of the polyepoxy resin of the present invention has a dielectric constant (1 GHz) of 2.80 to 3.20, preferably 3.00 to 3.20, loss ratio (1 GHz) of 0.010 to 0.020, measured according to the JIS-C-6481 method. Preferably, it may be characterized by having a low dielectric constant and a low loss rate of 0.012 to 0.020. More specifically, the dielectric constant before absorption is 2.80 to 3.20, preferably 3.00 to 3.20, the dielectric constant after absorption is 2.90 to 3.30, and preferably 3.00 to 3.25. And the loss ratio before the moisture absorption is 0.010 ~ 0.020, preferably 0.012 ~ 0.020, the loss ratio after the moisture absorption is 0.015 ~ 0.030, preferably 0.015 ~ 0.025.

In addition, after leaving the cured product specimen of the poly epoxy resin of the present invention in water at 100 ° C. for 2 hours, the moisture absorption rate measured by the weight increase rate (wt%) is 0.35% to 0.62%, preferably 0.40% to 0.60%. It may be characterized by.

In addition, after absorbing the cured product specimen in the same manner as described above, when measured according to the JIS-C-6481 method, the dielectric constant (GHz) is 3.00 to 3.30, preferably 3.05 to 3.25, and the loss ratio (GHz) is 0.015 to 3. 0.025, preferably 0.016 to 0.024.

In addition, the glass transition temperature (Tg) of the poly epoxy resin of the present invention was measured by increasing the temperature by 20 ℃ per minute using a differential thermal analyzer (DSC) and the glass transition temperature is 130 ~ 170 ℃, preferably 135 ℃ ~ 165 It may be characterized by being ℃.

In addition, the 5% heat loss temperature (Td) of the cured product of the polyepoxy resin of the present invention is heated by 10 ℃ per minute using a TGA equipment to measure when the weight loss of the cured product is 5%, 385 ℃ ~ 405 ° C, preferably 390 ° C to 400 ° C.

Such a polyepoxy resin of the present invention having a low dielectric constant and a low loss rate can be prepared using the following composition.

The poly epoxy resin composition of the present invention is a polyoxazolidone-containing epoxy compound containing a compound represented by the following formula (3); And a compound represented by Chemical Formula 4 below.

 (3)

In Chemical Formula 3, n is a rational number of 0 to 2, preferably 0 to 1 rational number. And, R ₅ of formula 3 is -H, an alkyl group of the OH group or a C _{1 ~ 10} alkyl group, preferably -H or a C _{1 ~ 3} of, more preferably -H or methyl.

이며, D의 R₀은 -H, OH기 또는 C_{1 ~10}의 알킬기이고, 바람직하게는 -H 또는 C_{1 ~5}의 알킬기이며, 더욱 바람직하게는 H 또는 C_{1 ~4}의 알킬기이다. 그리고, D의 n은 0 ~ 0.2의 유리수, 바람직하게는 0 ~ 0.13의 유리수이며, 화학식 1의 n이 0.13을 초과하면 알콜성 OH으로 인하여 전기적 특성이 떨어지는 위험이 있으므로 상기 범위 내의 n값을 갖는 것이 좋다. 그리고, D의 x는 0 또는 1이다.And D is

And, R ₀ of D is -H, an alkyl group of the OH group or a C _{1 ~ 10,} preferably an alkyl group of -H or C _{1 ~ 5,} and more preferably H or an alkyl group of C _{1 ~ 4.} In addition, n of D is a ratio of 0 to 0.2, preferably 0 to 0.13, and when n of Formula 1 is more than 0.13, there is a risk of falling electrical properties due to alcoholic OH. It is good. And x of D is 0 or 1;

,

,

,

,

,

, 또는

이며, 바람직하게는

,

,

또는

이다. 그리고, 상기 A의 R₁, R'₁, R₂, R₃ 및 R₄ 각각 독립적으로 -H, -OH 또는 C_{1 ~10}의 알킬기이며, 바람직하게는 -H 또는 C_{1 ~3}의 알킬기이며, 더욱 바람직하게는 -H 또는 메틸기이다. 또한, A의 n은 0 ~ 4의 유리수, 바람직하게는 0 ~ 2의 유리수다.And A of D

,

,

,

,

,

, or

, And preferably

,

,

or

to be. And, A ₁ R ₁ , R ' ₁ , R ₂ , R ₃ And R ₄ Each independently -H, -OH or an alkyl group of C _{1 ~ 10,} preferably an alkyl group of -H or a C _{1 ~ 3,} more preferably -H or methyl. In addition, n of A is rational number of 0-4, Preferably it is rational number of 0-2.

[Chemical Formula 4]

이고, R₆ 및 E의 R₇은 각각 독립적으로 -H, OH기 또는 C_{1 ~10}의 알킬기이고, 바람직하게는 -H 또는 C_{1 ~3}의 알킬기이며, 더욱 바람직하게는 -H 또는 메틸기이다. 그리고, E의 n은 0 ~ 2의 유리수, 바람직하게는 n은 0 ~ 1의 유리수다. 그리고, q 는 0 ~ 4의 유리수, 바람직하게는 q 는 1 ~ 2의 유리수이다.In Chemical Formula 4, E is

And R ₆ And R ₇ of E are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} preferably an alkyl group of -H or a C _{1 ~ 3,} more preferably -H or methyl. And n of E is a rational number of 0-2, Preferably n is a rational number of 0-1. And q is rational number of 0-4, Preferably q is rational number of 1-2.

,

,

,

,

,

, 또는

이며, 바람직하게는

,

,

또는

이다. 그리고, 상기 F의 R₁, R₂, R₃ 및 R₄ 각각 독립적으로 H, -OH 또는 C_{1 ~10}의 알킬기이며, 바람직하게는 H 또는 C_{1 ~ 3} 의 알킬기이며, 더욱 바람직하게는 H 또는 메틸기이다. 또한, F의 n은 각각 독립적으로 0 ~ 4의 유리수, 바람직하게는 0 ~ 2의 유리수다.
In Formula 4, F of E is

,

,

,

,

,

, or

, And preferably

,

,

or

to be. And, R ₁ , R ₂ , R ₃ And R _{4 Of} The F Each independently is an alkyl group of H, -OH, or C _{1 to 10} , preferably an alkyl group of H or C _{1 to 3} , more preferably an H or methyl group. In addition, n of F is respectively independently rational number of 0-4, Preferably it is rational number of 0-2.

The poly epoxy resin composition of the present invention may include 10 to 90 parts by weight, preferably 10 to 50 parts by weight of the compound represented by Formula 4 with respect to 100 parts by weight of the polyoxazolidone-containing epoxy compound, wherein If the compound represented by Formula 4 is less than 10 parts by weight, there may be a problem that the electrical properties in the cured product is lowered and the adhesion is lowered. If the compound represented by Formula 4 is more than 90 parts by weight, it may have a dielectric constant, dielectric loss, excellent adhesion and thermal properties. It may be a problem to have a limit point to increase the glass transition temperature of the cured product is preferably used within the above range.

In addition, the poly epoxy resin composition of the present invention is 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1-benzyl-2-methyl imide. An imidazole compound containing at least one selected from 1 -Benzyl-2-Methyl Imidazole, 2-heptadecyl Imidazole and 2-Undecyl Imidazole; Trialkyl compounds containing at least one selected from triphenylphosphate and Triphenylphosphate Iodide; And 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2,5-diamino pyridine, 2,6-diamino It may further comprise a catalyst containing at least one selected from pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine. There is .

 In the poly epoxy resin composition of the present invention, the epoxy equivalent of the polyoxazolidone-containing epoxy compound is 200 to 550 g / eq, preferably the epoxy equivalent is 220 to 520 g / eq. However, when the epoxy equivalent of the polyoxazolidone-containing epoxy compound is less than 200 g / eq, there is a problem that the adhesiveness of the cured product is significantly lowered because the modification rate of the isocyanate is low, and when it exceeds 550 g / eq, the modification rate of the isocyanate is increased. Additionally, when the compound represented by Chemical Formula 4 is polymerized, there is a possibility of gelation, and therefore, it is preferable to have an epoxy equivalent within the above range.

The poly epoxy resin of the present invention may be prepared by the following method using the composition described above, that is, a polyoxazolidone-containing epoxy compound comprising the compound represented by the formula (3) and represented by the formula (4) Polymerizing the compound to prepare a poly epoxy compound comprising the compound represented by the formula (5); can be prepared through a process comprising a.

Here, Formula 3, Formula 4 and Formula 5 are the same as described above.

In addition, the polyoxazolidone-containing epoxy compound may be prepared through the following steps.

An isocyanate compound including at least one selected from compounds represented by Formula 2; And polymerizing an epoxy compound represented by Formula 1; preparing a polyoxazolidone-containing epoxy compound including at least one selected from the compounds represented by Formula 3.

[Formula 1]

In the formula 1, R ₀ is independently -H, a OH group or a C _{1 ~ 10} alkyl group, preferably -H or a C _{1 ~ 5} alkyl group, more preferably -H or C _{1 ~ 4} Alkyl group. In addition, n in Formula 1 is a free number of 0 to 0.2, preferably 0 to 0.13, and when n of Formula 1 exceeds 0.13, the isocyanate of Formula 2 and / or Formula 2 reacts with the epoxy of Formula 1 Since there is a risk of molecular weight increase or gelation due to the heavy side reaction, it is preferable to have an n value within the above range.

,

,

,

,

,

, 또는

이며, 바람직하게는

,

,

또는

이다. 또한, A의 R₁, R'₁, R₂, R₃ 및 R₄ 각각은 독립적으로 -H, -OH 또는 C_{1 ~10}의 알킬기이며, 바람직하게는 -H 또는 C_{1 ~3}의 알킬기이고, 더욱 바람직하게는 -H 또는 메틸기이다. 그리고, A의 n은 독립적으로 0 ~ 4의 유리수이고, 바람직하게는 0 ~ 2의 유리수이다.And A is

,

,

,

,

,

, or

, And preferably

,

,

or

to be. In addition, R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} Each independently represent -H, -OH or an alkyl group of C _{1 ~ 10,} preferably an alkyl group of -H or a C _{1 ~ 3,} more preferably -H or methyl. And n of A is independently a rational number of 0-4, Preferably it is a rational number of 0-2.

(2)

N in the general formula (2) is a rational number of 0 to 2, preferably n is a rational number of 0 to 1. And, R ₅ of the formula (2) is -H, OH group or C _{1 ~ 10} alkyl group, preferably -H or C _{1 ~ 3} alkyl group, more preferably -H or methyl group.

As described above, the poly epoxy resin of the present invention not only has low dielectric constant and dielectric loss, but also has excellent adhesion and thermal properties, and thus high integration of next-generation IC substrates, PCBs, flexible display substrates, etc. It is suitable for use in semiconductor materials requiring high fineness and high performance.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[ Example ]

Preparation Example  1: Preparation of the compound represented by the formula (4-1)

In order to perform ester substitution reaction of the hydroxy group of the bisphenol a compound, 653.5 g of methyl ethyl ketone, 228 g (1 mole) of bisphenol a, and 212.1 g (2.1 mole) of triethylamine were added to a reaction tank at 25 ° C. under nitrogen gas injection. Bisphenol A was completely dissolved.

Next, 280.7 g (2 mole) of benzoyl chloride (Benzoyl Chloride) was added dropwise evenly for 1 hour, and then aged for 4 hours. At this time, the salt produced by the ester-substituted bisphenol A compound and the adduct produced by the above reaction was precipitated. Thereafter, 280 g of water was added to remove the salt formed as the reaction adduct, and the salt produced by the addition reaction was dissolved, followed by a filtering process to separate the ester-substituted bisphenol A compound, followed by drying at 120 ° C. 392.1 g (yield 90%) of final ester substituted bisphenol A compound represented by Formula 4-1 was obtained.

(FTIR Chart: 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group

Tm = 160)

[Formula 4-1]

이고, R₆ 은 -H이고, E의 R₇은 -H이며, E의 n은 1이고. q 는 1이며, E의 F는

이고, F의 R₁은 메틸기이다.
In Formula 4-1, E is

And R ₆ Is -H, R ₇ of E is -H, n of E is 1. q is 1, F of E

And R ₁ of F is a methyl group.

Example  One

(1) 800 g of bisphenol A epoxy (product name YD-128, 186 g / eq, Kukdo Chemical Co., Ltd.) were added to a reaction tank and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reaction tank. It was added to Tg (Toluene Diisocyanate, Kumho Mitsui Chemicals) at a T = 160 ℃ ~ 170 ℃ dropwise for 2 hours to carry out the reaction containing an oxazolidone represented by the following formula 3-1 having an epoxy equivalent of 282.1 g / eq Polyepoxy compound was obtained.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Formula 3-1]

In Chemical Formula 3-1, n is 1 and R ₅ is a methyl group.

이며, R₀ 은 -H이고, x는 1이며, D의 A는

이며, n은 0.11 ~ 0.13이고, R₁ 및 R'₁은 메틸기이다.
And D is

R ₀ Is -H, x is 1, and A in D is

And n is 0.11 to 0.13, and R ₁ and R ' ₁ are methyl groups.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-1 having an epoxy equivalent of 362.5 g / eq (hereinafter, epoxy). Defined as 1).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1, 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-1]

이고, G의 x는 1이며, G 의 A는

이고, R₁ 및 R'₁은 메틸기이며, r은 0.1 ~ 0.2이고 상기 G의 R₀는 -H이고 R₆은 -H이고 상기 G의 E는

이고, E의 R₇은 -H이고. 또한, E의 n은 4이며, E의 q는 1이다. In Chemical Formula 5-1, n is 1 and R ₅ is a methyl group. And G is

, X of G is 1, A of G is

R ₁ and R ′ ₁ are a methyl group, r is 0.1 to 0.2, R ₀ of G is -H, R ₆ is -H, and E of G is

And R ₇ of E is -H. In addition, n of E is 4, and q of E is 1.

이고 R₁ 은 메틸기이며, A의 R₁은 메틸기이다.
And F of E

And R ₁ is a methyl group, R ₁ in A is a methyl group.

Example  2

(1) 800 g of bisphenol F epoxy (product name YDF-170, 170 g / eq, Kukdo Chemical Co., Ltd.) were added to a reactor and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added thereto. The reaction mixture was added dropwise to 100 g of TDI (Kumho Mitsui Chemicals) at T = 160 ° C. to 170 ° C. for 2 hours to carry out the reaction. An epoxy compound was obtained.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

[Formula 3-2]

In Chemical Formula 3-1, n is 1 and R ₅ is a methyl group.

이며, R₀ 은 -H이고, x는 1이며, D의 A는

이며, D의 n은 0.11 ~ 0.13이고, R₁ 및 R'₁은 -H이다.
D is

R ₀ Is -H, x is 1, and A in D is

And n of D is 0.11 to 0.13, and R ₁ and R ' ₁ are -H.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added thereto, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-2 having an epoxy equivalent of 318.3 g / eq (hereinafter, epoxy). Defined as 2).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1, 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

 [Formula 5-2]

이고, G의 x는 1이며, G의 A는

이고, A의 R₁ 및 R'₁은 -H이고 상기 G의 r은 0.1 ~ 0.2이다.In Chemical Formula 5-2, n is 1 and R ₅ is a methyl group. G is

, X of G is 1, A of G is

R ₁ and R ′ _{1 of A} are —H and r of G is 0.1 to 0.2.

이고, E의 R₇은 -H이고, 또한, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고, R₁은 메틸기이다.
And R _{0 of} G Is -H and R ₆ is -H and E of G is

R ₇ of E is -H, n of E is 4, and q of E is 1. And F of E

And R ₁ is a methyl group.

Example  3

(1) 800 g of bisphenol jet epoxy (product name SEZ-250, 203 g / eq, Shin Art & C) was added to a reaction tank and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reaction tank. The oxazolidone-containing polyepoxy compound represented by the following formula (3-3) having an epoxy equivalent weight of 318.0 g / eq was added thereto while the reaction was carried out while dropping 100 g of TDI (Kumho Mitsui Chemicals) at T = 160 ° C to 170 ° C for 2 hours. Obtained.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Formula 3-3]

이며, R₀ 은 -H이고, D의 x는 1이며, D의 n은 0.11 ~ 0.13이며, D의 A는

이고, A의 R₄은 -H이다.
In Chemical Formula 3-3, n is 1 and R ₅ is a methyl group. D is

R ₀ Is -H, x of D is 1, n of D is from 0.11 to 0.13, and A of D is

And R ₄ in A is -H.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added thereto, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-3 having an epoxy equivalent weight of 420.9 g / eq. Defined as 3).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1, 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-3]

이고, G의 x는 1이며, G의 A는

이고, A의 R₄는 -H이고, r은 0.1 ~ 0.2이고, 상기 G의 R₀는 -H이고, R₆은 -H이고, 상기 G의 E는

이고, E의 R₇은 -H이다. 또한, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고 R₁은 메틸기이다.
In Chemical Formula 5-3, n is 1 and R ₅ is a methyl group. G is

, X of G is 1, A of G is

R ₄ of A is -H, r is 0.1 to 0.2, R ₀ of G is -H, R ₆ is -H, and E of G is

And R ₇ of E is -H. In addition, n of E is 4, and q of E is 1. And F of E

And R ₁ is a methyl group.

Example  4

(1) 800 g of TMP B-type epoxy (product name SE-400H, 180 g / eq, Shin Art & C) was added to a reactor and heated, followed by 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ). Was added to the reactor and the reaction was carried out while dropping 100 g of TDI (Kumho Mitsui Chemicals) at T = 160 ° C. to 170 ° C. for 2 hours to give an epoxy equivalent of 241.94 g / eq. An epoxy compound was obtained.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Chemical Formula 3-4]

이며, 이고 R₀은 메틸기이며, D의 x는 0이며, n은 0.11 ~ 0.13이다.
In Chemical Formula 3-4, n is 1, R ₅ is a methyl group, and D is

R ₀ is a methyl group, x of D is 0, and n is 0.11 to 0.13.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added thereto, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-4 having an epoxy equivalent of 347.3 g / eq (hereinafter, epoxy). Defined as 4).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1 , 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-4]

이고, G의 x는 0이며, G의 r은 0.1 ~ 0.2이고, 상기 G의 R₀는 메틸기이고, R₆ 은 -H이고, 상기 G의 E는

이고, E의 R₇은 -H이고, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고, R₁은 메틸기이다.
In Chemical Formula 5-4, n is 1 and R ₅ is a methyl group. G is

X of G is 0, G of r is 0.1-0.2, G of R ₀ is a methyl group, and R ₆ Is -H and E of G is

R ₇ of E is -H, n of E is 4 and q of E is 1. And F of E

And R ₁ is a methyl group.

Example  5

(1) 800 g of SE-0125 (epoxy equivalent 288 g / eq, Shin Art & C) was added to the reactor and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reactor and T 100 g of TDI (Kumho Mitsui Chemicals) was added dropwise at 160 ° C to 170 ° C for 2 hours to obtain an oxazolidone-containing polyepoxy compound represented by the following Chemical Formula 3-5 having an epoxy equivalent of 540.0 g / eq.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Formula 3-5]

이며, D의 x는 1이며, D에서의 A는

이며, D의 R₀는 -C₃H₉이고 n은 0.11 ~ 0.13이고, A에서 R₁은 -CH₃이며, R'₁은 -H이다.
In Chemical Formula 3-5, n is 1, R ₅ is a methyl group, and D is

Where x of D is 1 and A in D

R ₀ of D is -C ₃ H ₉ , n is 0.11 ~ 0.13, in A R ₁ is -CH ₃ , R ' ₁ is -H.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added thereto, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-5 having an epoxy equivalent weight of 825.0 g / eq (hereinafter, epoxy). Defined as 5).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1, 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-5]

이고, G의 x는 1이며, G의 A는

이며, R₁은 -CH₃, R'₁은 -H이고, r은 0.1 ~ 0.2이며, 상기 G의 R₀는 -C₃H₉이고, R₆은 -H이며, 상기 G의 E는

이고, E의 R₇은 -H이고. 또한, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고, R₁은 메틸기이다. In Chemical Formula 5-5, n is 1, R ₅ is a methyl group, and G is

, X of G is 1, A of G is

R ₁ is -CH ₃ , R ' ₁ is -H, r is from 0.1 to 0.2, R ₀ of G is -C ₃ H ₉ , R ₆ is -H, E of G is

And R ₇ of E is -H. In addition, n of E is 4, and q of E is 1. And F of E

And R ₁ is a methyl group.

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1, 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

Example  6

(1) 800 g of SE-0225 (epoxy equivalent 229.5 g / eq, Shin Art & C) was added to the reactor and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reactor. 100 g of TDI (Kumho Mitsui Chemicals) was dripped at T = 165 degreeC for 2 hours, and the oxazolidone containing polyepoxy compound represented by following formula (3-6) with an epoxy equivalent of 378.9 g / eq was obtained.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Chemical Formula 3-6]

이며, x는 1이며, R₀ 은 -H이고, D의 n은 0.11 ~ 0.13이며, D의 A는

이고, A의 R₄ 은 -CH₃이며, n은 3이다.
In Chemical Formula 3-6, n is 1, R ₅ is a methyl group, and D is

, X is 1, R ₀ Is -H, n of D is from 0.11 to 0.13, and A of D is

And R _{4 of} A Is -CH ₃ and n is 3.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-6 having an epoxy equivalent weight of 520.6 g / eq (hereinafter, epoxy). Defined as 6).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1 , 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-6]

이고, G의 x는 1이며, G의 A는

이고, A의 n은 3이며, R₄는 -CH₃이고, r은 0.1 ~ 0.2이고, 상기 G의 R₀는 -H이고, R₆ 은 -H이고, 상기 G 의 E는

이고, E의 R₇은 -H이다. 또한, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고 R₁은 메틸기이다.
In Chemical Formula 5-6, n is 1, R ₅ is a methyl group, and G is

, X of G is 1, A of G is

And n of A is 3, R ₄ is -CH ₃ , r is 0.1 to 0.2, R ₀ of G is -H, and R ₆ Is -H and E of G is

And R ₇ of E is -H. In addition, n of E is 4, and q of E is 1. And F of E

And R ₁ is a methyl group.

Example  7

(1) 800 g of SE-0325 (epoxy equivalent 288 g / eq, Shin Art & C) was added to the reactor and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reactor and T 100 g of TDI (Kumho Mitsui Chemicals) was added dropwise at = 165 ° C. for 2 hours to obtain an oxazolidone-containing polyepoxy compound represented by Chemical Formula 3-7 having an epoxy equivalent of 357.3 g / eq.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Chemical Formula 3-7]

이며, D의 x는 1이며, R₀ 은 -H이고, D의 n은 0.11 ~ 0.13이며, D의 A는

이고, A의 n은 1이고 R₃은 -H이다.
In Chemical Formula 3-7, n is 1, R ₅ is a methyl group, and D is

Where x is 1 and R ₀ Is -H, n of D is from 0.11 to 0.13, and A of D is

N is 1 and R ₃ is -H.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared according to Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-7 having an epoxy equivalent of 484.4 g / eq (hereinafter, epoxy). Defined as 7).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1, 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-7]

이고, G의 x는 1이며, G의 A는

이고, A의 n은 1이며, R₃는 -H이고, r은 0.1 ~ 0.2이며, 상기 G의 R₀ 는 -H이고, R₆ 은 -H이며, 상기 G의 E는

이고, E의 R₇은 -H이다. 또한, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고 R₁은 메틸기이다.
In Chemical Formula 5-7, n is 1, R ₅ is a methyl group, and G is

, X of G is 1, A of G is

N is 1, R ₃ is -H, r is 0.1-0.2, and R _{0 of} G is Is -H and R ₆ Is -H, and E of G is

And R ₇ of E is -H. In addition, n of E is 4, and q of E is 1. And F of E

And R ₁ is a methyl group.

Example  8

(1) 860 g of bisphenol A epoxy (product name YD-128, 186 g / eq, Kukdo Chemical Co., Ltd.) were added to a reactor and heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reactor. Oxazolidone-containing polyepoxy represented by the following Chemical Formula 3-8 having an epoxy equivalent weight of 277.07 g / eq, and the reaction was carried out while dropping 140 g of TDI (Kumho Mitsui Chemicals) at T = 160 ° C to 170 ° C for 2 hours. The compound was obtained.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

 [Chemical Formula 3-8]

이며, D의 x는 1이며, D의 A는

이며, R₁ 및 R'₁은 메틸기이고, R₀ 은 -H이며, n은 0.11 ~ 0.13이며 R₁ 은 메틸기이다.
In Chemical Formula 3-8, n is 1, R ₅ is a methyl group, and D is

Where x of D is 1 and A of D

R ₁ and R ' ₁ are Methyl group, R ₀ Is -H, n is from 0.11 to 0.13 and R ₁ Is a methyl group.

(2) Next, 100 g of the ester-substituted bisphenol A compound prepared in Preparation Example 1 was added to the reactor, and the temperature was raised to 110 ° C to completely dissolve the ester-substituted bisphenol A.

Next, 0.3 g of ETPPI (Ethyl Triphenyl Phosphonium Iodide) was added thereto, followed by bulk polymerization at a reaction temperature of 150 ° C. for 5 hours, followed by a poly epoxy resin represented by the following Chemical Formula 5-8 having an epoxy equivalent of 420.8 g / eq (hereinafter, epoxy). Defined as 8).

(FTIR Chart: oxazolidone (C = O); 1755 cm ^-1 , 3300 cm ^-1 OH Peak not detected, 1700 cm ^-1 C = O (Carbonyl Group, 915 cm ^-1 Epoxy Group)

[Formula 5-8]

이고, G의 x는 1이며, G 의 A는

이고, R₁ 및 R'₁은 메틸기이며, r은 0.1 ~ 0.2이고, 상기 G의 R₀는 -H이고 R₆ 은 -H이고 상기 G의 E는

이고, E의 R₇은 -H이고. 또한, E의 n은 4이며, E의 q는 1이다. 그리고, 상기 E의 F는

이고, R₁은 메틸기이다.
In Chemical Formula 5-8, n is 1, R ₅ is a methyl group, and G is

, X of G is 1, A of G is

And R ₁ and R ' ₁ are M is a methyl group, r is 0.1-0.2, R ₀ of G is -H and R ₆ Is -H and E of G is

And R ₇ of E is -H. In addition, n of E is 4, and q of E is 1. And F of E

And R ₁ is a methyl group.

Comparative Example  One

800 g of bisphenol A epoxy (product name YD-128, 186 g / eq, Kukdo Chemical Co., Ltd.) were added to the reactor, heated, and then 0.18 g of catalyst 2-ethyl-4-methylimidazole (2E4MZ) was added to the reactor. 100 g of M-100 (polymeric MDI, Kumho Mitsui Chemicals) was added dropwise at T = 165 ° C. for 2 hours to obtain an epoxy compound of Comparative Example 1 having an epoxy equivalent of 251.64 g / eq.

(FT-IR result: oxazolidone (C = O); 1755 cm ^-1 )

Comparative Example  2 to Comparative Example  8

An epoxy compound was obtained in the same manner as in Comparative Example 1, except that bisphenol A epoxy was used to prepare epoxy compounds using different types of epoxy as shown in Table 1 below.

division Epoxy class usage Epoxy equivalent of the obtained epoxy compound Comparative Example 1 Bisphenol A epoxy
(Product Name YD-128, 186 g / eq, Kukdo Chemical Co., Ltd.) 800 g 282.1 g / eq Comparative Example 2 Bisphenol F epoxy
(Product name YDF-170, 170 g / eq, Kukdo Chemical Co., Ltd.) 800 g 250.3 g / eq Comparative Example 3 Bisphenol Jet Epoxy
(Product name SEZ-250, 203 g / eq, Shin Art & C) 800 g 318.0 g / eq Comparative Example 4 TMP epoxy
(Product name SE-400H, 180 g / eq, Shin Art & C) 800 g 270.0 g / eq Comparative Example 5 SE-0125
(Epoxy equivalent 288g / eq, Shin Art & C) 800 g 540.0 g / eq Comparative Example 6 Bisphenol TMC Epoxy
(SE-0225, Epoxy Equivalent 229.5g / eq, Shin Art & C) 800 g 378.9 g / eq Comparative Example 7 Bisphenol Api Epoxy
(SE-0325, Epoxy Equivalent 288g / eq, Shin Art & C) 800 g 357.3 g / eq Comparative Example 8 Bisphenol A epoxy
(Product Name YD-128, 186 g / eq, Kukdo Chemical Co., Ltd.) 860 g 325.9 g / eq

Manufacturing example  1 to 8 and Comparative Manufacturing Example  1 to 15: epoxy resin curing agent Cured product  Produce

The epoxy resins prepared in Examples 1 to 8 and Comparative Examples 1 to 8 were each blended in the usual ratios in the mixing ratios as shown in Tables 2 to 3 to produce a cured epoxy resin curing agent, and Comparative Examples 1 to 8 were prepared. Production Examples 1-8 were carried out, respectively.

In addition, a cured product was prepared using an epoxy resin so as to have a compounding ratio as shown in Table 4, and Comparative Production Examples 9 to 15 were performed.

Specifically, the resins of Examples 1 to 8, Comparative Examples 1 to 8, and the epoxy resins shown in Table 4 were each blended in the following compounding ratios as in Tables 2 to 4 to produce varnishes, and then BUEHLER's SimpliMet 1000 was Automatic Mounting. Molding was performed using the press equipment to produce a specimen. The molding operation was cured for 20 minutes at a pressure of 80 bar at 180 ° C and then cooled for 10 minutes using water and then post-cured at 180 ° C for 2 hours.

division Mixing ratio Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Example
Suzy 100 100 100 100 100 100 100 KPN-2110 28.18 32.35 24.47 29.65 12.48 19.80 12.84 24.47 C11Z One One One One One One One One

division Mixing ratio Comparative Preparation Example 1 Comparative Production Example 2 Comparative Production Example 3 Comparative Production Example 4 Comparative Preparation Example 5 Comparative Preparation Example 6 Comparative Preparation Example 7 Comparative Preparation Example 8 Comparative Example
Suzy 100 100 100 100 100 100 100 100 KPN-2110 40.93 45.55 36.80 42.57 31.86 31.68 34.19 37.17 C11Z One One One One One One One One

division Mixing ratio Comparative Production Example 9
(YD-128) Comparative Production Example 10
(YDF-170) Comparative Production Example 11
(SEZ-250) Comparative Production Example 12
(SE-400H) Comparative Production Example 13
(SE-0125) Comparative Production Example 14
(SE-0225) Comparative Production Example 15
(SE-0325) Epoxy
Suzy 100 100 100 100 100 100 100 KPN-2110 55.37 60.58 50.73 57.22 35.76 44.88 46.73 C11Z One One One One One One One

In Tables 2 to 4, KPN-2110 is a phenol novolak curing agent OH equivalent 103 g / eq (Gangnam Chemical), and C11Z is 2-undecylimidazole as a curing accelerator.

And, each of the epoxy compounds used in Comparative Examples 9-15

① YD-128 is Bisphenol A epoxy (Kukdo Chemical Co., Ltd.) and epoxy equivalent is 186 g / eq.

② YDF-170 is Bisphenol F (Kukdo Chemical Co., Ltd.) and its epoxy equivalent is 170 g / eq.

③ SEZ-250 is Bisphenol Z epoxy (Shin Art & C) and epoxy equivalent is 203 g / eq.

④ SE-400H is Tetramethylbiphenol epoxy (Shin Art & C) and epoxy equivalent 180 g / eq.

SE-0125 is Ethyllidene bis (4,6-tert butylphenol) epoxy and epoxy equivalent is 288g / eq.

⑥ SE-0225 is Bisphenol TMC epoxy (Shin Art & C) and epoxy equivalent 229.5 g / eq.

⑦ SE-0325 is Bisphenol AP Epoxy (Shin Art & C) and Epoxy equivalent is 215.5 g / eq.

Experimental Example  Epoxy resin Cured product  Physical property measurement experiment

Physical properties of the cured epoxy resin curing agent prepared in Preparation Examples 1 to 8 and Comparative Preparation Examples 1 to 15 were measured as follows, and the results are shown in Tables 5 to 7 below.

(1) Dielectric constant and dissipation factor were measured using an Agilent E4991A RF Impedance / Material analyzer by the JIS-C-6481 method.

(2) Glass transition temperature measurement experiment was performed using differential thermal analyzer (DSC). (20 ° C / min)

(3) Water Absorption (% by weight) was measured by weight increase rate (% by weight) after the specimen was left for 2 hours in the water cutting the specimen at 100 ℃.

(4) 5% Weight Loss Temperature (T _d ) of the cured epoxy resin was measured by increasing the temperature by 10 ° C. per minute using a TGA equipment, when the weight loss of the cured product was 5%.

(5) Lead heat resistance visually evaluated the state of the hardened | cured material of the epoxy resin immersed for 120 second in the 300 degree lead bath by JIS-C-6481 method. O when expansion and equality were not observed visually, X was shown when observed.

(6) Peel strength (1/2 oz copper Peel Strength) was measured by GIS C-6417 method.

division Manufacturing example One 2 3 4 5 6 7 8 Permittivity [GHz] 3.18 3.19 3.16 3.17 3.04 3.05 3.10 3.20 Loss Rate [GHz] 0.014 0.015 0.014 0.013 0.018 0.019 0.016 0.014 Permittivity after moisture absorption [GHz] 3.20 3.22 3.19 3.20 3.09 3.09 3.14 3.22 Loss rate after moisture absorption [GHz] 0.020 0.022 0.017 0.017 0.020 0.024 0.019 0.022 Hygroscopicity [wt%] 0.40 0.45 0.41 0.45 0.37 0.39 0.55 0.48 Tg [℃] 135.41 133.25 136.15 143.5 151.4 159.74 154.1 137.25 Td [℃] 391.14 392.1 393.4 394.1 393.6 390.1 395.4 391.7 Heat resistance O O O O O O O O 1/2 oz copper Peel
Strength [Kgf / cm] 2.2 2.2 2.3 2.2 1.9 2.2 2.0 2.3

division Comparative Manufacturing Example One 2 3 4 5 6 7 8 Permittivity [GHz] 3.30 3.32 3.26 3.27 3.15 3.21 3.22 3.31 Loss Rate [GHz] 0.019 0.020 0.017 0.016 0.020 0.022 0.020 0.020 Permittivity after moisture absorption [GHz] 3.39 3.40 3.31 3.33 3.20 3.36 3.36 3.40 Loss rate after moisture absorption [GHz] 0.028 0.030 0.021 0.022 0.025 0.028 0.027 0.029 Hygroscopicity [wt%] 0.63 0.65 0.67 0.65 0.60 0.79 0.69 0.67 Tg [℃] 157.25 156.34 168.74 163.58 169.47 177.64 169.75 159.98 Td [℃] 391.4 389.7 395.4 391.15 394.57 396.45 394.84 394.15 Heat resistance O O O O O O O O 1/2 oz copper Peel
Strength [Kgf / cm] 2.0 2.0 2.2 2.1 1.8 2.1 1.9 2.2

division Comparative Manufacturing Example 9 10 11 12 13 14 15 Permittivity [GHz] 3.25 3.26 3.18 3.22 3.05 3.17 3.19 Loss Rate [GHz] 0.023 0.024 0.019 0.018 0.016 0.023 0.019 Permittivity after moisture absorption [GHz] 3.31 3.32 3.25 3.30 3.15 3.24 3.25 Loss rate after moisture absorption [GHz] 0.028 0.030 0.024 0.024 0.022 0.027 0.028 Hygroscopicity [wt%] 0.41 0.45 0.43 0.45 0.40 0.51 0.46 Tg [℃] 140.456 139.41 166.51 176.14 161.25 177.12 170.12 Td [℃] 395.45 394.36 392.39 391.54 390.47 395.35 396.16 Heat resistance O O O O O O O 1/2 oz copper Peel
Strength [Kgf / cm] 1.7 1.7 2.0 1.9 1.8 1.8 1.7

As can be seen from Tables 6 to 7 Comparative Example 9 The physical properties of Comparative Preparation Example 1 isocyanate-modified to the epoxy compound, the adhesion strength was significantly increased, but the electrical properties such as dielectric constant and loss rate were significantly decreased, the moisture absorption rate and the dielectric constant after moisture absorption And it can be confirmed that there are physical properties such as the loss rate is significantly higher.

However, the epoxy cured product of Preparation Example 1 prepared by further reacting the ester-substituted bisphenol A compound of Preparation Example 1 with excellent electrical properties such as remarkably high adhesive strength, low dielectric constant and loss rate compared with these. It was confirmed that can be obtained.

In addition, it can be seen that this trend shows the same trend as in Preparation Example 1 when comparing each of Comparative Preparation Examples 10 to 15, Comparative Preparation Examples 2 to 8 and Preparation Examples 2 to 8, respectively.

Through the above Examples and Experimental Examples it was confirmed that the cured product made of the epoxy resin of the present invention not only has a low dielectric constant and dielectric loss, but also has excellent adhesion and thermal properties.

Claims (13)

Polyoxazolidone containing epoxy compound represented by following General formula (3); And a compound represented by the following Chemical Formula 4; a poly epoxy resin composition having excellent electrical characteristics, including;
(3)

In Formula 3, n is a free number of 0 to 2, R ₅ is -H, OH group or C _{1 ~ 10} alkyl group,
D is

And, R ₀ of D is a group of -H, OH group or a C _{1 ~ 10,} the D n is a rational number of 0 ~ 0.2, x is 0 or 1,
A is

,

,

,

,

,

, or

_{And, R 1, R '1,} R 2, R 3 and R ₄ in A are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} and the A n are independently a rational number of 0 to 4,
[Chemical Formula 4]

In Formula 4 E is

And R ₆ And R ₇ of E are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} wherein n of said E is a rational number from 0 to 2, q is a rational number of 0 to 4,
E F

,

,

,

,

,

, or

_{And, R 1, R 2, R} 3 and R ₄ of F are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} n of F is independently a rational number of 0 to 4.
The polyepoxy resin composition having excellent electrical properties according to claim 1, comprising 10 to 90 parts by weight of the compound represented by Formula 4 with respect to 100 parts by weight of the polyoxazolidone-containing epoxy compound.
2. 2-Methyl Imidazole, 2-Ethyl-4-Methyl Imidazole, 1-benzyl-2-methyl imidazole An imidazole compound containing at least one selected from Benzyl-2-Methyl Imidazole), 2-Heptadecyl Imidazole and 2-Undecyl Imidazole;
Trialkyl compounds containing at least one selected from triphenylphosphate and Triphenylphosphate Iodide; And
4-Dimethylamino Pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2,5-diamino pyridine, 2,6-diamino pyridine Pyridine compounds containing at least one selected from 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine;
Poly epoxy resin composition excellent in electrical properties, characterized in that it comprises one or more selected from.
The method of claim 1,
N in Chemical Formula 3 is a rational number of 0 to 3, R _{0 of} D And R ₅ of Formula 3 is independently —H or an alkyl group having _{1 to 5} carbon atoms,
R ₆ of Formula 4 And R ₇ of E are each independently H or an alkyl group of _{1 to 3} , n of E is a free number of 0 to 1, q is a free number of 0 to 4, and F is

,

,

, or

R ₁ , R ₂ , R ₃ and R _{4 of} F Are each independently -H or an alkyl group of C _{1 to 3} , and n of F is each independently a free number of 0 to 2, wherein the poly epoxy resin composition having excellent electrical characteristics is excellent.
The polyepoxy resin composition having excellent electrical properties according to claim 1, wherein the epoxy equivalent of the polyoxazolidone-containing epoxy compound is 200 to 550 g / eq.
Poly epoxy resin having excellent electrical properties, characterized in that it comprises a poly epoxy compound represented by the formula (5);
[Chemical Formula 5]

In Formula 5, n is a free number of 0 to 2, R ₅ is -H, OH or C _{1 ~ 10} alkyl group,
G is

R is a rational number of 0 to 3, R _{0 of} G _, and R ₆ is independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} x is 0 or 1,
E is

And, R ₇ is an alkyl group of E of -H, OH group or a C _{1 ~ 10,} n of said E is a rational number of 0 to 2, q is a rational number of 0 to 4 for E,
G A

,

,

,

,

,

or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} The Each independently selected from -H, an alkyl group of the OH group or a C _{1 ~ 10,} F is the E

,

,

,

,

,

or

And R ₁ to R ₄ of F are each independently -H, OH group or C _{1 to 10} alkyl group, and n of A and n of F are each independently 0 to 4 free numbers.
The compound of claim 6, wherein n in Formula 5 is a rational number of 0 to 1, R _{0 of} G And R ₅ of formula (5) is independently an alkyl group of -H or C _{1 ~ 5,}
E of Chemical Formula 4 is

R ₆ of Formula 4 And R ₇ of E are each independently H or an alkyl group of C _{1 ~ 3,} wherein n of said E is a rational number of 0 ~ 1, q is a rational number of 0 ~ 4, A is

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} silver Each independently -H or alkyl group of C _{1 ~ 3,}
F is

,

,

, or

R ₁ , R ₂ , R ₃ and R ₄ of F are A polyepoxy resin having excellent electrical properties, wherein each of -H or C _{1 to 3} is independently an alkyl group, and n of A and F are each independently 0 to 2 free numbers.
The poly epoxy resin having excellent electrical properties according to claim 6 or 7, wherein the poly epoxy resin has an epoxy equivalent of 300 to 850 g / eq.
The cured product of the poly epoxy resin according to claim 6 or 7, wherein the dielectric constant (GHz) is 2.80 to 3.20, and the loss ratio (GHz) is 0.010 to 0.020 when measured according to the JIS-C-6481 method. Poly epoxy resin with excellent electrical characteristics.
Preparing a polyoxazolidone-containing epoxy compound comprising a compound represented by Formula 3 by polymerizing an isocyanate compound including the compound represented by Formula 2, and the epoxy compound represented by Formula 1;
Preparing a poly epoxy compound comprising a compound represented by Formula 5 by polymerizing the polyoxazolidone-containing epoxy compound and a compound represented by Formula 4 below;
Method for producing a poly epoxy resin excellent in electrical properties, characterized in that it comprises:
[Chemical Formula 1]

In formula (1), R ₀ is -H, OH group or C _{1 ~ 10} alkyl group, n in formula (1) is a free number from 0 to 0.2, x is 0 or 1,
A is

,

,

,

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} Are each independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} the A n independently is a 0-4 glass effort,
(2)

R ₅ of Formula 2 is -H, OH group or C _{1 ~ 10} alkyl group, n is a free number of 0 to 2
(3)

In Chemical Formula 3, n is a rational number of 0 to 2, wherein D is

, N of D is a rational number of 0 to 0.2, x is 0 or 1, and R ₅ of the formula (3) And R ₀ of D is independently -H, alkyl groups of OH group or a C _{1 ~ 10,} D A is the

,

,

,

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} are Are each independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} the A n are independently a rational number of 0 to 4 respectively,
[Chemical Formula 4]

In Formula 4 E is

R ₆ of Formula 4 And R ₇ of E are each independently -H, alkyl groups of OH group or a C _{1 ~ 10,} n is a rational number from 0 to 2, q is a rational number of 0 to 4,
F is

,

,

,

,

,

, or

R ₁ , R ₂ , R ₃ and R ₄ of F are Each independently selected from -H, an alkyl group of the OH group or a C _{1 ~ 10,} n of F are each independently a 0-4 glass effort,
[Chemical Formula 5]

In Chemical Formula 5, n in Chemical Formula 5 is a rational number of 0 to 2, and R ₅ is -H, an alkyl group of the OH group or a C _{1 ~ 10,}
G is

R is a rational number of 0 to 3, R _{0 of} G _, and R ₆ is independently -H, an alkyl group of the OH group or a C _{1 ~ 10,} x is 0 or 1,
E is

And, wherein R ₇ is -H, OH, or an alkyl group of C _{1 ~ 10} of the E, and q is a rational number of 0 to 4 for E,
G A

,

,

,

,

,

, or

R ₁ , R ' ₁ , R ₂ , R ₃ and R _{4 of A} are Each independently selected from -H, an alkyl group of OH or C _{1 ~ 10,} F is the E

,

,

,

,

,

, or

Is, R _{1 of} F ~ R ₄ is Each independently selected from -H, an alkyl group of OH or C _{1 ~ 10,} n of A and F are each independently a rational number of 0 to 4.
The method of claim 10, wherein the polymerization of the step of preparing the polyoxazolidone-containing epoxy compound and the polymerization of the step of preparing the poly epoxy compound are independently
Imidazole compounds containing at least one selected from 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole, and 2-undecyl imidazole ;
Trialkyl compounds containing at least one selected from triphenylphosphate and ETPPI; And
4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2,5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6 Poly with excellent electrical properties, characterized in that it is carried out under a catalyst containing at least one selected from -methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine. Method for producing an epoxy resin.
Hardened | cured material containing the poly epoxy resin of Claim 6 or 7.
The method of claim 12, wherein the cured product comprises at least one selected from various composite materials such as encapsulants, insulating plates, adhesives, coating agents, paints, IC substrate PCBs, and flexible display substrates. freight.