TWI636071B - Hardener for epoxy resin and the preparing method thereof - Google Patents

Abstract

The present invention relates to a curing agent for epoxy resin, and more particularly to a curing agent for epoxy resin. The cured product based on the curing agent of the present invention has high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength, and Low thermal expansion coefficient, while significantly improving electrical characteristics such as dielectric constant and dielectric loss, can be widely used in the field of electrical and electronics.

Description

   Curing agent for epoxy resin and preparation method thereof   

The present invention relates to a curing agent for epoxy resin and a preparation method thereof, and more specifically relates to a curing agent for epoxy resin. The cured product based on the curing agent of the present invention has a high glass transition temperature, low hygroscopicity, excellent adhesion, With high peel strength and low thermal expansion coefficient, electrical properties such as dielectric constant and dielectric loss can be significantly improved.

Recently, with the increase in the capacity and ultra-high speed of the semiconductor industry, the trend toward miniaturization has been achieved through the integration of dissimilar metals and components. In this integrated composite technology, packaging technology that inserts different materials and components into the device is the core. To this end, it is necessary to develop a low thermal expansion coefficient (Low CTE), low dielectric constant (Low Dk), and low dielectric loss (Low Df) and heat-resistant core raw materials.

As a next-generation integrated circuit (IC) substrate, printed circuit board (PCB), flexible display substrate, etc., as a method for high integration, miniaturization, and high performance, Generally, the integration degree used to process a multi-capacity semiconductor device increases in a short time, which means that the width and width of the device wiring are narrowed. By increasing the switching speed of the transistor, the device can be made faster.

As described above, various methods for reducing the wiring width of a device have recently been disclosed. However, in order to form a fine circuit pattern, in the conventional patterning method of copper etching, there is a limitation in reducing the circuit pattern interval. As a result, copper (Copper) circuit pattern formation by a chemical method can achieve 20/20 μm or less, but there is a disadvantage that the light intensity of the unpatterned surface is significantly reduced. Therefore, in order to achieve a narrow line width between wirings on a high-density wafer, a high-molecular substance having excellent electrical insulation characteristics with low dielectric constant and low dielectric loss and excellent adhesion is required.

High-molecular substances with the above effects and frequently used substances include epoxy resins that are widely used and have excellent electrical, mechanical, and adhesive properties, and active hydrogens such as amines that are often used as curing agents. (amine) compound, phenol (phenol) compound.

However, when the epoxy resin is cured with the above-mentioned curing agent with active hydrogen, the epoxy group and the active hydrogen react to generate a polar high hydroxyl group, so that the final cured product has high hygroscopicity, and has a dielectric constant and a dielectric loss. Isoelectric properties are lowered, and because the glass transition temperature of the cured product is low, heat resistance or peel strength is lowered. Therefore, the mechanical properties are lowered and the physical properties cannot be satisfied at the same time.

In addition, even if the final cured product has a better physical property, other physical properties decrease, especially as the electrical characteristics such as dielectric constant and dielectric loss decrease, there will be those that cannot simultaneously satisfy low hygroscopicity, high heat resistance, and excellent properties. Problems with mechanical properties and excellent electrical properties.

Korean Patent Application No. 2011-0105763 discloses an epoxy resin composition that can be used as a bonding and sealing material for electronic devices. However, in the case of containing a curing agent for the above composition, general amines cannot be used. The curing agent minimizes the dielectric constant and the dielectric loss, and because the cured product has high hygroscopicity, it cannot increase the adhesive force, and thus it cannot be used as a high-performance, highly integrated electrical and electronic material.

"Existing Technology Literature"

Patent document: Korean Patent Gazette: No. 2011-0105763.

The present invention is made to solve the above problems, and the problem to be solved by the present invention is to provide a curing agent for epoxy resin, so that the cured product has a high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength, low At the same time, the thermal expansion coefficient can significantly improve electrical characteristics such as dielectric constant and dielectric loss.

The second problem to be solved by the present invention is that the curing agent of the present invention can generate high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength and low thermal expansion coefficient, and at the same time significantly improve the dielectric constant and dielectric Electrical characteristics such as loss are provided as sealing materials for electrical and electronic applications or as laminated materials for electrical and electronic substrates.

The present invention has been made in view of the problems described above, and provides a compound represented by the following Chemical Formula 1 including a weight average molecular weight of 1,000 to 13,000:

In the above Chemical Formula 1, R ₁ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A ₁ , A ₂ and A ₃ are each independently a hydrogen atom, or , At least one of the above A ₁ , A ₂ and A ₃ is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A ₄ is a hydrogen atom, , Among them, R ₂ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, R ₃ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R ₄ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, and p is A rational number of 0.1 to 8, R ₅ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is Hydrogen atom, the other is methyl.

In addition, according to an embodiment of the present invention, the R ₁ , R ₂ , R ₃ , R _4, and R ₅ are each independently an alkyl group having 4 or less carbon atoms or a substituted or unsubstituted aryl group, and the aryl group It may include a group selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a pyrene group, a perylene group, (chrysene) group, cresol group and fluorene group.

Moreover, according to an embodiment of the present invention, the R ₁ , R ₂ , R ₃ , R _4, and R ₅ may be each independently an unsubstituted phenyl group, a naphthyl group, or a biphenyl group.

In addition, the present invention provides a curing agent for epoxy resin containing a copolymer copolymerized with monomers represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4, and the copolymer has a weight average molecular weight (Mw (molecular weight)) of 1,000 to 13000.

In the above Chemical Formula 2, a is a rational number of 0 to 8; if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is a hydrogen atom, the other is a methyl group.

In the above Chemical Formula 3, B is or or X ₁ is a halogen atom.

In the above Chemical Formula 4, X ₂ is a halogen atom, and R ₆ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

Furthermore, according to an embodiment of the present invention, the X ₁ and X ₂ are each independently one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, the R ₆ is a substituted or unsubstituted aryl group, and the aryl group May include a member selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, One of the group consisting of 2, cresol and fluorenyl.

In addition, according to an embodiment of the present invention, the R ₆ may be one selected from the group consisting of an unsubstituted phenyl group, a naphthyl group, and a biphenyl group.

In addition, according to an embodiment of the curing agent for epoxy resin according to the present invention, a monomer including the above-mentioned chemical formula 2, chemical formula 3, and chemical formula 4 having a molar ratio of 1: 0.1 to 1.5: 0.1 to 3 may be copolymerized. Copolymer.

In addition, the present invention provides a method for preparing a curing agent for epoxy resin. The method for preparing the curing agent for epoxy resin includes the following steps: 1. Introducing a chemical formula 2 with a molar ratio of 1: 0.1 to 1.5: 0.1 to 3 into a reaction tank. Monomers represented by Chemical Formula 3 and Chemical Formula 4; and Step 2, reacting the monomers introduced in Step 1 to prepare a copolymer represented by Chemical Formula 1 below.

In the above Chemical Formula 2, a is a rational number of 0 to 8; if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is a hydrogen atom, the other is a methyl group.

In the above Chemical Formula 3, B is or or X ₁ is a halogen atom.

In the above Chemical Formula 4, X ₂ is a halogen atom, and R ₆ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

In the above Chemical Formula 1, R ₁ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or , , A ₁ , A ₂ and A ₃ are each independently a hydrogen atom, or , At least one of the above A ₁ , A ₂ and A ₃ is not a hydrogen atom, n, m and k are each independently a rational number of 0-8, l is a rational number of 0.1-12, and A4 is a hydrogen atom, , The R ₂ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, the R ₃ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R ₄ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, p It is a rational number of 0.1 to 8. The above R ₅ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If the above R ₇ and R ₈ are both hydrogen atoms or R ₇ and R ₈ One is a hydrogen atom, and the other is a methyl group.

In addition, according to an embodiment of the present invention, the method may further include the steps of: after reacting the monomers, introducing water into the reaction tank to remove salts generated as reaction by-products, and then preparing the prepared epoxy resin The process of separation with a curing agent is performed more than once.

In addition, according to an embodiment of the present invention, in the above step 2, triethylamine, trimethylamine, tripropylamine, pyridine, and N-methylpyridine (N -methyl piperidine).

The present invention also provides an electrical and electronic sealing material containing the above-mentioned curing agent for epoxy resin and epoxy resin.

The present invention also provides an electrical and electronic substrate laminate material including the above-mentioned curing agent for epoxy resin and epoxy resin.

The present invention also provides an epoxy resin composition containing the above-mentioned curing agent for epoxy resin and epoxy resin.

The cured product of the curing agent for epoxy resins of the present invention exhibits excellent thermal stability by having a high glass transition temperature, and having a low hygroscopic force can minimize moisture absorption in semiconductors and the like, thereby preventing the soldering during soldering. Problems such as peeling or cracking inside the semiconductor during the manufacturing process. In addition, by having excellent adhesive force and high peel strength, the durability of the cured product is significantly increased, and the coefficient of thermal expansion is low, which can prevent the bending phenomenon of the package. Furthermore, by significantly improving the dielectric constant, dielectric loss, and the like, it is possible to significantly improve the high-density integration of semiconductors based on electrical insulation characteristics, and thus it can be widely used for electrical and electronic sealing materials, laminated materials, and the like.

FIG. 1 is an infrared (IR) spectrum of an embodiment of the present invention.

FIG. 2 is a gel permeation chromatography (GPC) curve diagram according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings so that those skilled in the art to which the present invention pertains can easily implement. The invention can be implemented in many different ways and is not limited to the embodiments described herein. In the drawings, in order to clearly explain the present invention, parts irrelevant to the description are omitted, and the same or similar structural elements are marked with the same drawing symbols throughout the specification.

As described above, the conventional curing agents for epoxy resins include commonly used curing agents such as amine compounds and phenol compounds having active hydrogen, but the curing agents having the above-mentioned active hydrogen are used to cure epoxy ( In the case of epoxy) resin, the reaction between the epoxy group and the active hydrogen generates a polar high hydroxyl group. Therefore, there is a problem that the hygroscopicity of the final cured product becomes high, and the electrical characteristics such as dielectric constant and dielectric loss are reduced.

In view of this, in the present invention, the above-mentioned problem is solved by providing a curing agent for an epoxy resin containing a compound represented by the following Chemical Formula 1 having a weight average molecular weight (molecular weight) of 1,000 to 13,000.

In the above Chemical Formula 1, R ₁ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A ₁ , A ₂ and A ₃ are each independently a hydrogen atom, or , At least one of the above A ₁ , A ₂ and A ₃ is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A ₄ is a hydrogen atom, , The R ₂ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, the R ₃ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R ₄ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, p It is a rational number of 0.1 to 8. The above R ₅ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If the above R ₇ and R ₈ are both hydrogen atoms or R ₇ and R ₈ One is a hydrogen atom, and the other is a methyl group.

As described above, the curing agent containing the present invention has a high glass transition temperature and excellent heat resistance. It improves the reliability of cured products based on low moisture absorption, excellent mechanical properties based on excellent adhesion and high peel strength, and low The reduction in the production of the cured product with a thermal expansion coefficient is reduced, and at the same time, the realization of the integrated circuit based on the improvement of the electrical characteristics, such as the dielectric constant and the dielectric loss, can be realized.

First, the compound represented by Chemical Formula 1 will be described. The curing agent for epoxy resins of the present invention includes a compound represented by the following Chemical Formula 1 having a weight average molecular weight (molecular weight) of 1,000 to 13,000.

In the above Chemical Formula 1, R ₁ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A ₁ , A ₂ and A ₃ are each independently a hydrogen atom, or (Hereinafter referred to as Chemical Formula X).

At this time, not only the above-mentioned A ₁ , A _2, and A ₃ are independent, but also one or more selected from the group consisting of A ₁ , A _2, and A ₃ are also independent. For example, in the above Chemical Formula 1, n is 4, m is 3, k is 2, the included A ₁ is 4, A ₂ is 3, A ₃ is 2, at this time, the respective A ₁ is independent of each other, each A ₂ is independent of each other, and each A ₃ is also independent of each other.

Further, in the above-mentioned A _1, A ₂ and A ₃ are not hydrogen. When the curing agent in which all of A ₁ , A ₂ and A ₃ are hydrogen is cured with an epoxy resin, a polar high hydroxyl group is generated by a reaction between an epoxy group and an active hydrogen, so that a final cured product may exist. The problem is that the hygroscopicity becomes high, and the electrical characteristics such as the dielectric constant (Dk) and the dielectric loss (Df) decrease.

Secondly, the above-mentioned n, m, and k are each independently a rational number of 0 to 8. In terms of glass transition temperature, heat resistance, and electrical characteristics of the cured product, more preferably, n, m, and k can be independently 1.5 to 1.5. Rational number of 6. In the case where one or more members selected from the group consisting of n, m, and k is greater than 8, when cured with epoxy, the surface of the cured product is uneven, and there may be a problem in the adhesive force. There is a problem that it is not suitable for use as a laminated material or a sealing material.

In addition, the above-mentioned l is a rational number of 0.1-12. In the case where l is less than 0.1, when curing with epoxy, there is a problem that the heat resistance of the cured product is lowered and the glass transition temperature is lowered. The heat resistance of the cured product is lowered and the glass transition temperature is lowered. Problems such as permittivity and dielectric loss factor that make it difficult to achieve the desired physical properties. In addition, when l is greater than 12, there is a possibility of forming a gel. When curing with epoxy, the surface of the cured product is uneven and causes problems in adhesion, which is not suitable for lamination. Problems with materials and sealing materials.

In the above chemical formula X, A ₄ is a hydrogen atom, , In this case, o is a rational number from 0 to 8, and p is a rational number from 0.1 to 8. More preferably, in terms of the glass transition temperature, heat resistance, and electrical characteristics of the cured product, o and p may be independently a rational number of 2 to 6, respectively. In the case where o and / or p is greater than 8, when curing with epoxy, the surface of the cured product is uneven, and there may be problems in adhesion, so there is a problem that it is not suitable for use as a laminate or sealing material. .

In the curing agent for epoxy resins of the present invention, the R ₁ , R ₂ , R ₃ , R _4, and R ₅ are independently substituted or unsubstituted aryl groups, and the aryl group may include a group selected from phenyl, Phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, A compound in the group consisting of 1, cresol group and fluorenyl group, more preferably, the above R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be each independently selected from unsubstituted phenyl and naphthalene One of the group consisting of phenyl and biphenyl. In the case where R ₁ , R ₂ , R ₃ , R _4, and R ₅ are each independently one selected from the group consisting of unsubstituted phenyl, naphthyl, and biphenyl, Among the physical properties of the copolymer represented by Chemical Formula 1, R ₆ is anthracenyl, phenanthryl, fluorenyl, fluorenyl, Compared with cured products obtained by curing copolymers of fluorene-based monomers, the dielectric constant and dielectric loss are significantly reduced, enabling high-density integration based on semiconductors with significantly improved electrical insulation characteristics to be widely used. For electrical and electronic sealing materials, laminated materials, etc.

On the other hand, the weight average molecular weight (molecular weight) of the compound represented by the above Chemical Formula 1 can only be 1000 to 13,000, because the compound represented by the Chemical Formula 1 of the present invention can have a wide range of molecular weights. Therefore, the effect of the object of the present invention can be expressed without being called a compound represented by Chemical Formula 1.

The reason why the compound represented by Chemical Formula 1 of the present invention can have a wide range of molecular weight distribution is specifically observed because the copolymer includes polymers whose molecular weight can be randomly determined (A ₁ , A _2, and A ₃ ) Grafted repeating unit. That is, when A ₁ is the above-mentioned chemical formula X, the polymer represented by the chemical formula X further includes one or more selected from the group consisting of A ₁ , A _2, and A ₃ , which can be represented by the chemical formula X. This is described below in the copolymerization of the monomer represented by Chemical Formula 3 and the monomer represented by Chemical Formula 2. The molecular weight of the polymer represented by Chemical Formula 2 can be very random according to the degree of polymerization of the polymer, except that In addition, the greater the degree of polymerization of the polymer represented by Chemical Formula 2, the more reaction sites that can react with the monomer represented by Chemical Formula 3, that is, the hydroxyl groups contained in the polymer represented by Chemical Formula 2 increase, and again for each hydroxyl group. Polymerization is performed by randomly reacting with the monomer of Chemical Formula 3, so the molecular weight is very random and it can have a very wide molecular weight distribution.

To sort this out, the compound represented by Chemical Formula 1 of the present invention may include A ₁ (A _1a , A _1b , A _1c , ...) and / or A ₂ (A _2a , A _2b , A _2c , ... ") and / or A ₃ (A _3a , A _3b , A _3c , ...), along with A _1a (and / or A _1b) , A _1c , ...) and / or, A _2a (and / or, A _2b , A _2c , ...) and / or A _3a (and / or A _3b , A _3c , The layer-by-layer grafting method can include A _1a (A _1a , A _1b , A _1c , ...), A _2a (A _2a , A _2b , _A2c , ...) and _A3a ( _A3a , _A3b , _A3c , ...) The compounds of Chemical Formula 1 may have a wide range of molecular weight distributions. However, even if it is simply The compound represented by the above Chemical Formula 1 does not express the desired physical properties of the present invention, and has the structural formula of the aforementioned Chemical Formula 1 and needs to satisfy a specific molecular weight in order to express the desired physical properties.

Therefore, the weight average molecular weight of the compound represented by the above-mentioned chemical formula 1 of the present invention satisfies 1,000 to 13,000, and thus a cured product cured by containing the curing agent for an epoxy resin of the present invention can have both excellent heat resistance and high heat resistance. Mechanical strength, excellent hygroscopicity and significantly improved electrical characteristics. In the case where the weight average molecular weight (molecular weight) of the compound represented by Chemical Formula 1 is less than 1,000, when curing with epoxy, there is a problem that the heat resistance of the cured product is lowered and the glass transition temperature is lowered, and there is a dielectric constant and a dielectric The electrical characteristics of the loss factor are also reduced. When the weight average molecular weight is greater than 13,000, there is a possibility of forming a gel. When curing with epoxy, the peel strength is reduced, and the surface of the cured product is uneven. In order to cause a problem in adhesion, there may be a problem that it is not suitable for use as a laminated material and a sealing material. According to a preferred embodiment of the present invention, in order to achieve more improved physical properties, the weight average molecular weight of the compound represented by Chemical Formula 1 may be 5,000 to 9,000.

In addition, the present invention provides a curing agent for an epoxy resin as a copolymer that copolymerizes monomers represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 including a copolymer having a weight average molecular weight (molecular weight) of 1,000 to 13,000.

In the above Chemical Formula 2, a is a rational number of 0 to 8; if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is a hydrogen atom, the other is a methyl group.

In the above Chemical Formula 3, B is or or X ₁ is a halogen atom.

In the above Chemical Formula 4, X ₂ is a halogen atom, and R ₆ is an aryl group having 5 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

First, the above-mentioned chemical formula 2 will be described. The monomer represented by the above Chemical Formula 2 and the monomer represented by the above Chemical Formula 3 form a copolymer, and a is a rational number of 0 to 8. Considering the heat resistance of the cured product and the glass transition temperature, the average value may not be zero. When the average value of a is larger than 8, curing of the epoxy resin causes unevenness in the surface of the cured product, which causes problems in adhesion. Therefore, it is not suitable for use as a laminated material and a sealing material.

According to the present invention, the monomers represented by the above Chemical Formula 2 and Chemical Formula 3 can be copolymerized at a molar ratio of 1: 0.1 to 1.5, and preferably 1: 0.5 to 1.2. The cured product using the curing agent of the present invention satisfies the above-mentioned range, thereby improving the heat resistance based on a high glass transition temperature, being excellent in electrical characteristics such as a dielectric constant, a dielectric loss factor, and having a high peel strength, so that there are mechanical properties. The advantages are improved.

When the monomers represented by the above Chemical Formulas 2 and 3 are copolymerized at a molar ratio of less than 1: 0.1, there is a possibility that a gel may be formed, and when cured together with epoxy, the peel strength is reduced. In addition, the surface of the cured product is not uniform, which causes problems in adhesion. Therefore, it may be unsuitable for use as a laminated material and a sealing material.

Next, the above-mentioned chemical formula 3 will be described. In the monomer represented by the above Chemical Formula 3, X1 is a halogen atom and may include one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and may preferably be a chlorine atom.

The monomer represented by the above Chemical Formula 3 is a monomer that forms a copolymer with the monomers represented by the aforementioned Chemical Formulas 2 and 4, and more preferably, the monomer represented by the aforementioned Chemical Formula 3 may be represented by the following Chemical Formula 3-1 monomer.

In the above Chemical Formula 3-1, X ₁ is a halogen atom.

In the above Chemical Formula 3-1, the two functional groups (-COX ₁ ) combined with the benzene ring have a meta orientation, so that the two functional groups are ortho or para aligned with the two functional groups. Compared to the case, it is possible to achieve both improved heat resistance and excellent electrical characteristics, and it is possible to achieve internal hygroscopicity and a low coefficient of thermal expansion. Specifically, in the case of the cured product based on the following examples, it can be confirmed that the glass transition temperature is high, and the dielectric constant, the dielectric loss factor, the moisture absorption rate, the coefficient of thermal expansion (CTE) (a1, ppm), and the coefficient of thermal expansion (a2) (Ppm) value decreases.

In addition, it is preferable that the monomer represented by the chemical formula 3 includes only the monomer represented by the chemical formula 3-1, and includes a part of the monomer represented by the chemical formula 3-1, and is aligned in the ortho or para position. The remaining monomers have the problems of low glass transition temperature and high dielectric constant and dielectric loss.

Further, in the case of the aforementioned Chemical Formula 3-1, X ₁ as a halogen atom is included. In the case where X ₁ is a halogen atom, at a low temperature (for example, 60 ° C. or lower), the halogen atom can be easily removed by HX gas through a catalyst, and the reaction time can be significantly reduced. Under low temperature conditions, it is easy to perform in a short time, the risk of performing the steps is reduced, and productivity can be improved.

Next, the above-mentioned chemical formula 4 will be described. The monomer represented by the aforementioned Chemical Formula 4 is a monomer contained as a terminal chelating agent in the copolymerization reaction of the monomers represented by the aforementioned Chemical Formulas 2 and 3.

The physical properties of the cured product cured by the copolymer including the copolymer may vary depending on the types of X ₂ and R ₆ of the monomer represented by the aforementioned Chemical Formula 4.

According to the present invention, the X ₂ contains one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and the R _{6 is} a substituted or unsubstituted aryl group or a substituted or unsubstituted C ₁ ~ C ₄ alkyl, the aryl may include a group selected from phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, One of the group consisting of 2, cresol and fluorenyl. More preferably, the aforementioned R ₆ may be an unsubstituted phenyl group, a biphenyl group, or a naphthyl group.

In the case where R _{6 is an} unsubstituted phenyl, biphenyl, or naphthyl group, the physical properties of the copolymer represented by the above Chemical Formula 1 are different from those in which R ₆ is selected from anthracenyl, phenanthryl, and fluorene. Base, base, Compared with a cured product in which a copolymer of one monomer in the group consisting of cresol group and fluorenyl group is cured, the dielectric constant and the dielectric loss value are reduced, so that a cured product having significantly improved electrical characteristics can be obtained.

According to a preferred embodiment of the present invention, the monomers represented by the above Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 may be copolymerized with a molar ratio of 1: 0.1 to 1.5: 0.1 to 3, preferably 1: 0.5 ~ 1.2: 1.6 ~ 2.8.

The monomers represented by the above Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 can be copolymerized at a Mohr ratio of 1: 0.1 to 1.5: 0.1 to 3, respectively. By satisfying the above range, heat resistance can be improved, and the dielectric constant can be improved. It is excellent in electrical characteristics such as dielectric loss factor, and it has the advantage that the peel strength is increased to improve mechanical properties.

When the monomers represented by Chemical Formula 2 and Chemical Formula 3 are copolymerized at a molar ratio of less than 1: 0.1, there may be problems that the glass transition temperature of the cured product is low, and the electrical characteristics such as the dielectric constant and the dielectric loss factor are reduced. In the case of copolymerization at a molar ratio of more than 1: 1.5, there is a possibility of forming a gel. When curing with epoxy, the peel strength is reduced, and the surface of the cured product is uneven. Since a problem arises in the adhesive force, there is a problem that it is not suitable for use as a laminated material and a sealing material.

Next, the present invention provides a method for preparing a curing agent for epoxy resin. The method for preparing the above-mentioned curing agent for epoxy resin includes the following steps: Step 1. Introduce a molar ratio of 1: 0.1 to 1.5: 0.1 to 3 into the reaction tank from the following: Monomers represented by Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4; and Step 2, a copolymer represented by the following Chemical Formula 1 is prepared by reacting the monomer introduced in Step 1 described above.

In the above Chemical Formula 2, a is a rational number of 0 to 8; if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is a hydrogen atom, the other is a methyl group.

In the above Chemical Formula 3, B is or or X ₁ is a halogen atom.

In the above Chemical Formula 4, X ₂ is a halogen atom, and R ₆ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

In the above Chemical Formula 1, R ₁ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A ₁ , A ₂ and A ₃ are each independently a hydrogen atom, or , At least one of the above A ₁ , A ₂ and A ₃ is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A ₄ is a hydrogen atom, , The R ₂ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, the R ₃ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R ₄ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, p It is a rational number of 0.1 to 8. The above R ₅ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If the above R ₇ and R ₈ are both hydrogen atoms or R ₇ and R ₈ One is a hydrogen atom, and the other is a methyl group.

Hereinafter, the preparation method of the present invention will be described in detail according to the steps.

In the method for preparing a curing agent for epoxy resins of the present invention, in step 1 above, an organic solvent is charged into a reaction tank to which a nitrogen input pipe, a thermometer, and a circulation cooler are attached, and the ratio is 1: 0.1 to 1.5: 0.1 to A monomer represented by the above Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 is introduced at 3, and more preferably, it is introduced and dissolved at a molar ratio of 1: 0.5 to 1.2: 1.6 to 2.8, so that it is dissolved in a later step. The chemical formula 1 having a structure in which the monomers represented by the chemical formula 2, chemical formula 3, and chemical formula 4 are repeatedly copolymerized can be prepared.

When the monomers represented by Chemical Formula 2 and Chemical Formula 3 are copolymerized at a molar ratio of less than 1: 0.1, there may be problems that the glass transition temperature of the cured product is low, and the electrical characteristics such as dielectric constant and dielectric loss factor are reduced. In the case of copolymerization at a molar ratio of more than 1: 1.5, there is a possibility of forming a gel. When curing with epoxy, the peeling strength of the cured product is reduced, and the surface of the cured product is uneven. In order to cause a problem in adhesion, there may be a problem that it is not suitable for use as a laminated material and a sealing material.

At this time, when the above-mentioned organic solvent is an organic solvent contained in the preparation of the curing agent for epoxy resin, it can be used without limitation. As a non-limiting example, two or more kinds can be used independently or in combination. Organic solvents including one or more of the group consisting of methyl ethyl ketone and methyl isobutyl ketone.

In the method for preparing a curing agent for an epoxy resin of the present invention, in the above step 2, the monomer introduced in the above step 1 is completely dissolved at 20 to 40 ° C. under a nitrogen atmosphere, and the catalyst is dropped uniformly. After 1 to 3 hours, a maturation step of 1 to 3 hours is performed to prepare a copolymer represented by the above Chemical Formula 1. At this time, heat generation occurs during the dropping and aging steps, and therefore it is necessary to perform the reaction at a reaction temperature of 50 ° C or lower.

The above-mentioned catalyst functions as a catalyst for the reaction and an HCl gas generated in the ester process. A catalyst and an acid trapping agent that can be used in the copolymerization step of a general curing agent can be used. One or more of the group consisting of triethylamine, trimethylamine, tripropylamine, pyridine, and N-methyl piperidine, more preferably, use Triethylamine. These catalysts can be used alone or in combination with one or more catalysts.

The method for preparing a curing agent for epoxy resins of the present invention further includes the steps of: after reacting the monomers, introducing water into the reaction tank to remove salts generated as reaction by-products, and then The separation process of the prepared epoxy resin curing agent is preferably performed the above steps more than once.

The copolymer and the salt produced as an additive are precipitated by the reaction in Step 2 described above. In order to remove the salt produced as an additive, a solvent such as water can be added to carry out desalting. In the above desalting step, specifically, after dissolving the salt formed as an additional reaction, liquid separation can be performed to separate the copolymerized compound, and then the separated copolymerized compound is vacuum degassed at a temperature of 150 to 200 ° C. .

Furthermore, the present invention provides an encapsulant for electric and electronics, which comprises the curing agent for epoxy resin and epoxy resin of the present invention.

In addition, the present invention provides a laminated material for a substrate for electric and electronics, which comprises the curing agent for epoxy resin and epoxy resin according to the present invention.

The present invention also provides an epoxy resin composition comprising the curing agent for an epoxy resin of the present invention and an epoxy resin.

As the above-mentioned epoxy resin, a known epoxy resin may be used within a range that does not impair the effects of the present invention. As a non-limiting example, two or more types of divalent phenol-based epoxy resins may be used independently or in combination. Compounds such as bisphenol A, bisphenol F, bisphenol S, bisphenol hydrazone, 2,2'-biphenol, 3, 3 ', 5, 5'-tetramethyl-4, 4'-dihydroxyl Phenol, resorcinol, naphthalene glycols, etc .; epoxides of phenols above 3, such as tri- (4-hydroxyphenyl) methane, 1, 1, 2, 2-tetrakis (4-hydroxybenzene) Group) ethane, phenolic, o-cresol, etc .; epoxides of copolymerized resins of dicyclopentadiene and phenols; biphenylaralkyl phenol resins synthesized from phenols and dichloromethylbiphenyl Epoxides, naphthol aralkyl resins synthesized from naphthols and p-xylene dichloride, etc.

However, according to a preferred embodiment of the present invention, in order to express excellent electrical characteristics, internal hygroscopicity, improved peel strength, and heat resistance, the epoxy resin may include a material selected from the group consisting of o-phenylphenol novolac epoxy (Ortho Phenylphenol Novolac Epoxy), epoxy resin type of copolymer resin of dicyclopentadiene and phenols, and oxide type of biphenylaralkyl phenol resin synthesized from dichloromethyl biphenyl More than one of the group, the sealing material or laminated material cured at this time can have a dielectric constant (Dk) of 3.0 or less and a dielectric loss of 0.01 or less at a frequency of 1 GHz. In circuit boards, printed circuit boards, etc., it is possible to realize the advantage of high speed of a device that is highly integrated through semiconductors.

In addition, in order to improve the physical properties of the cured product, an inorganic filler may be blended in addition to the epoxy resin and the curing agent of the present invention. When an inorganic filler is blended, physical properties such as internal hygroscopicity can be improved, and when an inorganic filler is included, it can be suitably used for sealing. As the above-mentioned inorganic filler, an ordinary sealing material for electrics and electronics or an inorganic charging material for laminated materials for electric and electronic substrates can be used without limitation. As a non-limiting example, silicon dioxide, alumina, and zirconium can be used. Stone, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, mullite, titanium dioxide, etc. In the above, it is preferable to use fused silicon dioxide as a main component, and the shape thereof may be, for example, a crushed shape or a spherical shape. Generally, as the silica, a combination of silicas having several particle diameter distributions is used. Preferably, the average particle diameter of the silicon dioxide that can be combined ranges from 0.5 to 100 μmm. In the case of blending an inorganic filler, the content rate is preferably 83% by weight or more, and more preferably, it may be 83 to 90% by weight. If it is less than 83% by weight, the content rate of the organic component will be high, and the moisture resistance and low linear expansion property may not be sufficiently exhibited.

In addition, oligomers or polymer compounds such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, and phenoxy resin can be appropriately blended as required, and pigments can be blended. , Flame retardant, thixotropy imparting agent, coupling agent, fluidity improving agent and other additives.

Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicones, castor oils, fatty ammonium waxes, oxidized polyethylene waxes, and organic bentonite. In addition, curing accelerators such as amines, imidazoles, organic phosphines, and Lewis acids can also be added as required. The compounding amount of the curing accelerator is usually preferably 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

In addition, release agents such as carnauba wax, OP wax, etc .; coupling agents, such as γ-glycidoxypropyltrimethoxysilane, etc .; colorants, such as carbon black, etc .; , Such as antimony trioxide; low stress agents, such as petroleum, lubricants, such as calcium stearate.

The sealing material composition of the curing agent for epoxy resins of the present invention can be cured by molding methods such as injection molding, compression molding, and transfer molding to obtain a sealing material based on a preferred embodiment of the present invention. Preferably, it can be obtained by transfer molding. Generally, the temperature at which a cured product is generated may be 120 to 220 ° C.

Hereinafter, the present invention will be described more specifically with reference to the following examples. At this time, the following embodiments are only provided for easy understanding, and do not limit the scope of the present invention.

"Example"     Example 1. Preparation of curing agent for epoxy resin    

Step 1: Introduce 1,450 g of toluene as an organic solvent, 306 g of a monomer (0.45 mol) represented by the following chemical formula 2-1, and 81.2 g of the following into a reaction tank to which a nitrogen input pipe, a thermometer, and a circulation cooler are attached. A monomer (0.4 mole) represented by Chemical Formula 3-2 and 168.68 g of a monomer (1.2 mole) represented by the following Chemical Formula 4-1.

Step 2: Under the conditions of introducing nitrogen and 30 ° C temperature, completely dissolve the monomers represented by the following Chemical Formula 2-1, Chemical Formula 3-2, and Chemical Formula 4-1 introduced in the above Step 1, and 202.38 g of triethyl After the amine (2 moles) was added dropwise for 2 hours, a ripening step was performed for 2 hours. When the dropping and ripening steps were performed, the reaction temperature did not exceed 50 ° C.

At this time, in order to remove the salt produced as an additive, 350 g of water was added to carry out desalting, and in order to remove the remaining salt that separated the curing agent compound, the desalting step was performed again as described above, and then Liquid separation. Then, the separated curing agent compound was vacuum degassed at a temperature of 180 ° C. to obtain 435 g of a brown solid having a weight average molecular weight (molecular weight) of 5450 as the curing agent for epoxy resin as shown in Table 1 below.

The above b is 2.

    Example 2. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. 306 g (0.45 mol), 97.45 g (0.48 mol), and 146.19 g (1.04 mol) were respectively prepared from the above chemical formula 2-1, chemical formula 3-2, and chemical formula 4- The monomer represented by 1 was used to obtain 440 g of a brown solid solid having a weight average molecular weight (molecular weight) of 7180 as the curing agent for epoxy resins shown in Table 1 below.

    Example 3. Preparation of curing agent for epoxy resin    

Preparation was carried out in the same manner as in Example 1. 306 g (0.45 mol), 107.6 g (0.53 mol), and 132.13 g (0.94 mol) were prepared from the above chemical formulas 2-1, 3-2, and 4- The monomer represented by 1 was used to obtain 438 g of a brown solid solid having a weight average molecular weight (molecular weight) of 8737 as the curing agent for epoxy resins shown in Table 1 below.

    Example 4. Preparation of curing agent for epoxy resin    

The preparation was carried out in the same manner as in Example 1, and instead of the monomer represented by the above Chemical Formula 3-2, a monomer represented by the following Chemical Formula 3-3 was added to obtain 428 g of a brown solid having a weight average molecular weight (molecular weight) of 5670 as follows Table 1 is a curing agent for epoxy resin.

    Example 5. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 3-2, a monomer represented by the following Chemical Formula 3-4 was added to obtain 420 g of a brown solid having a weight average molecular weight (molecular weight) of 5530 as follows Table 1 is a curing agent for epoxy resin.

    Example 6. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of 81.2 g (0.4 mole) of the monomer represented by the above chemical formula 3-2, 40.6 g (0.2 mole) of the monomer represented by the following chemical formula 3-2 and 40.6 were prepared. g (0.2 mol) of the monomer represented by the following Chemical Formula 3-4 to obtain 410 g of a brown solid having a weight average molecular weight (molecular weight) of 5510 as a curing agent for an epoxy resin as shown in Table 1 below.

    Example 7. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mole) of the monomer represented by the above chemical formula 4-1, 228.756 g (1.2 mole) of the monomer represented by the following chemical formula 6 was added to obtain 455 g. The brown solid solid having a weight average molecular weight (molecular weight) of 7557 is a curing agent for epoxy resins as shown in Table 1 below.

    Example 8. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 228.756 g (1.2 mol) of the monomer represented by the following chemical formula 6-1 was used. 467 g of a brown solid having a weight average molecular weight (molecular weight) of 7323 was obtained as the curing agent for epoxy resins in Table 1 below.

    Example 9. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 94.188 g (1.2 mol) of the monomer represented by the following chemical formula 8 was added to obtain 360 g. The brown solid solid having a weight average molecular weight (molecular weight) of 4395 is a curing agent for epoxy resins as shown in Table 1 below.

    Example 10. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 111.024 g (1.2 mol) of the monomer represented by the following chemical formula 8-1 was used. 378 g of a brown solid having a weight average molecular weight (molecular weight) of 4620 was obtained as the curing agent for epoxy resins in Table 1 below.

    Example 11. Preparation of curing agent for epoxy resin    

The preparation was carried out in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 3-2, 111.648 g (0.4 mol) of the monomer represented by the following Chemical Formula 3-5 was added to obtain a weight average molecular weight (molecular weight) of 451 g. ) Is a brown solid of 7710 which is the curing agent for epoxy resins shown in Table 1 below.

    Comparative Example 1. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1, and 306 g (0.45 mole), 4.06 g (0.02 mole), and 275.517 g (1.96 mole) of the above-mentioned chemical formula 2-1, chemical formula 3-2, and chemical formula 4- The monomer represented by 1 was used to obtain 467 g of a brown solid solid having a weight average molecular weight (molecular weight) of 750 as the curing agent for epoxy resins shown in Table 1 below.

    Comparative Example 2. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. 306 g (0.45 mole), 182.718 g (0.9 mole), and 28.114 g (0.2 mole) were prepared from the above chemical formula 2-1, chemical formula 3-2, and chemical formula 4-. The monomer represented by 1 was used to obtain 402 g of a brown solid with a weight average molecular weight (molecular weight) of 15951 as the curing agent for epoxy resins in Table 1 below.

    Comparative Example 3. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 2-1, 206 g (0.677 mol) of the monomer represented by the following Chemical Formula 9 was added to obtain 339 g of a brown having a weight average molecular weight (molecular weight) of 2057. The solid state is as shown in Table 1 below.

At this time, the above-mentioned n is 1.

    Comparative Example 4. Preparation of curing agent for epoxy resin    

It was prepared in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 2-1, 228.29 g (1.0 mole) of the monomer represented by the following Chemical Formula 10 was added to obtain 347 g of a weight average molecular weight (molecular weight) of 1035. The brown solid is the curing agent for epoxy resin shown in Table 1 below.

    Experimental example    

Epoxy resin (Ortho Phenylphenol-Novolac Epoxy Resin), SE-5000, 250g / eq per epoxy, Xinya T & C, and the above-mentioned Examples 1 to 11 were respectively mixed in an equivalent ratio. 1. After the curing agent of Comparative Examples 1 to 4 and the curing agent based on Table 2 below, compound them as shown in Tables 3 to 5 and C11Z (curing accelerator, 2-undecylimidazole). To make varnish. Thereafter, a solidified product was produced by using BUEHLER's stamping equipment (SimpliMet1000 Automatic Mounting Press equipment) dosage form molding operation, and the following physical properties were measured to show the results in Tables 3 to 5.

As the above-mentioned molding operation, curing was performed at 180 ° C. and a pressure of 80 bar for 20 minutes, and after cooling with water for 10 minutes, post-curing was performed at 180 ° C. for 2 hours.

    "Physical Evaluation"         1. Dielectric Constant and Dissipation Factor    

Measured by the JIS-C-6481 method using an Agilent E4991A RF Impedance / Material analyzer. The lower the resin, the better the electrical characteristics of the cured product.

    2. Glass transition temperature (Tg) and quality reduction temperature (5% Weight Loss Temperature, Td)    

A differential scanning calorimeter (DSC) was used to measure the glass transition temperature and the 5% mass reduction temperature (Td) of the cured product. As a 5% mass reduction temperature of the cured product, the temperature was increased by a thermogravimetric analyzer (TGA) every minute. After 10 degrees, the temperature at which the weight loss of the cured product was 5% was measured.

    3． Moisture absorption (Water Absorption, weight percentage)    

The cured product was left as a moisture absorption rate in boiling water at 100 ° C. for 2 hours, and then measured at a weight increase rate (weight percentage). The lower the moisture absorption, the better the physical properties of the cured product.

    4． Peel Strength (1/2 oz copper Peel Strength)    

The peel strength was measured by the gIS C-6417 method. The greater the peel strength, the better the mechanical strength.

    5． Coefficient of Thermal Expansion (CTE, ppm / ℃)    

As the coefficient of thermal expansion (CTE, ppm / ° C), the coefficients of thermal expansion before and after the glass transition temperature were measured using a TMA (Mettler Toredo) device in accordance with the ASTM E831 method, and are shown as a1 and a2, respectively. The smaller the thermal expansion coefficient value, the less warpage of the semiconductor package occurs.

Specifically, as can be confirmed in the above Table 3, it can be confirmed that in the case of the cured product (cured product 1 to cured product 3) of Example 1 to Example 3, and the cured product of Example 4 to Example 5 (Cured product 4 to cured product 5), the glass transition temperature is higher, the dielectric constant, dielectric loss factor, moisture absorption, thermal expansion coefficient (a1, ppm), thermal expansion coefficient (a2, ppm) values are significantly lower.

In addition, it was confirmed that, compared with the cured product 6 based on Example 6, the cured products 1 to 3 based on Examples 1 to 3 had lower dielectric constants and dielectric losses, and a higher moisture absorption rate and thermal expansion coefficient (a1). , Ppm) and low coefficient of thermal expansion (a2, ppm). In addition, it was confirmed that the glass transition temperature was high.

In addition, it was confirmed that the cured products based on Examples 1 to 3 have lower dielectric constants and dielectric losses than the cured products based on Examples 7 to 8. On the contrary, it was confirmed that the glass transition temperature of the cured products based on Examples 1 to 3 was low, and the values of the coefficient of thermal expansion (a1, ppm) and the coefficient of thermal expansion (a2, ppm) were high.

In addition, it was confirmed that the cured products based on Examples 9 to 10 have the same dielectric constant and dielectric loss as the cured products based on Examples 1 to 3, but the glass transition temperature is low and the thermal expansion coefficient (a1 , Ppm) and the coefficient of thermal expansion (a2, ppm) are high.

In addition, it was confirmed that the cured product according to Example 11 has a lower dielectric loss loss than the cured product according to Examples 1 to 3, but has a higher dielectric constant.

In addition, as can be confirmed in the above Tables 3 to 5, it was confirmed that by using curing agents 1 to 7 such as phenol novolac (curing agent 1) and curing agents of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 Compared with the cured product cured by the curing agent based on the embodiment, the cured product to be cured has a significantly higher dielectric constant, dielectric loss, and moisture absorption rate, and some of the comparative compounds (comparative cured product 4, comparative cured product 5, comparative The glass transition temperature of the cured product 8) was also significantly low.

In addition, when the cured product 4, cured product 5, and cured product 9 were compared, the peel strength was also significantly low, and it was confirmed that the mechanical properties were not good.

Claims (13)

A curing agent for epoxy resin, which includes a compound represented by the following Chemical Formula 1, and the compound has a weight average molecular weight of 1,000 to 13,000:

In Chemical Formula 1, R ₁ is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is

or

or

, A ₁ , A ₂ and A ₃ are each independently a hydrogen atom,

or

At least one of A ₁ , A ₂ and A ₃ is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A ₄ is a hydrogen atom,

,

R ₂ is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms; R ₃ is a substituted or unsubstituted aryl group or carbon number having 6 to 24 carbon atoms Is 4 or less alkyl groups, i is a rational number of 0 to 8, j is a rational number of 0.1 to 8, R ₄ is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or having 4 or less carbon atoms Alkyl, o is a rational number from 0 to 8, p is a rational number from 0.1 to 8, R ₅ is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and if R ₇ and R ₈ are each a hydrogen atom or one of R ₇ and R ₈ is a hydrogen atom, and the other is a methyl group. The curing agent for epoxy resins according to item 1 of the scope of patent application, wherein the R ₁ , R ₂ , R ₃ , R _4, and R ₅ are each independently an alkyl group having 4 or less carbon atoms or substituted. Or an unsubstituted aryl group selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl,

One of the group consisting of a methyl group, a cresol group and a fluorenyl group. The curing agent for epoxy resins according to item 2 of the scope of patent application, wherein the R ₁ , R ₂ , R ₃ , R _4, and R ₅ are each independently an unsubstituted phenyl, naphthyl, or biphenyl base. A curing agent for epoxy resin, comprising a copolymer copolymerized by the monomers represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4, and the weight average molecular weight of the copolymer is 1000-13000:

In Chemical Formula 2, a is a rational number from 0 to 8, if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is a hydrogen atom, the other is methyl;

In Chemical Formula 3, B is

or

or

X ₁ is a halogen atom;

In Chemical Formula 4, X ₂ is a halogen atom, and R ₆ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. The curing agent for epoxy resins according to item 4 of the scope of the patent application, wherein X ₁ and X ₂ are each independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the R ₆ is an aryl group The aryl group is selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl,

One of the group consisting of a methyl group, a cresol group and a fluorenyl group. The curing agent for epoxy resins according to item 5 of the scope of patent application, wherein R _{6 is one of an} unsubstituted phenyl group, a naphthyl group, or a biphenyl group. The curing agent for epoxy resins as described in item 4 of the scope of patent application, wherein the single system represented by Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 is copolymerized at a molar ratio of 1: 0.1 to 1.5: 0.1 to 3. A method for preparing a curing agent for epoxy resin, comprising: step 1, introducing a monomer represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 into a reaction tank, and having a molar ratio of 1: 0.1 to 1.5: 0.1 to 3; And step 2, the monomer introduced in step 1 is reacted to prepare a copolymer represented by the following chemical formula 1:

In Chemical Formula 2, a is a rational number from 0 to 8, if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is a hydrogen atom, the other is methyl;

In Chemical Formula 3, B is

or

or

X ₁ is a halogen atom;

In Chemical Formula 4, X ₂ is a halogen atom, and R ₆ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms; and

In Chemical Formula 1, R ₁ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is

or

or

, A ₁ , A ₂ and A ₃ are each independently a hydrogen atom,

or

At least one of A ₁ , A ₂ and A ₃ is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A ₄ is a hydrogen atom,

,

R ₂ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, R ₃ is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, and i is Rational number from 0 to 8, j is a rational number from 0.1 to 8, R ₄ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, and p is 0.1 to A rational number of 8, R ₅ is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and if R ₇ and R ₈ are both hydrogen atoms or one of R ₇ and R ₈ is hydrogen Atom, the other is methyl. The method for preparing a curing agent for epoxy resins according to item 8 of the scope of patent application, further comprising: after reacting the monomers, introducing water into the reaction tank to remove salts generated as reaction by-products, The prepared curing agent for epoxy resin is separated, and the separation process is performed more than once. The method for preparing a curing agent for epoxy resins according to item 8 of the scope of patent application, wherein, in step 2, a material selected from the group consisting of triethylamine, trimethylamine, tripropylamine, pyridine and N-methylpyridine A group of more than one catalyst. An electrical and electronic sealing material, comprising: the curing agent for epoxy resin as described in any one of claims 1 to 7 of the scope of patent application; and epoxy resin. A laminate material for electric and electronic substrates, comprising: the curing agent for epoxy resins as described in any one of items 1 to 7 of the scope of patent application; and epoxy resins. An epoxy resin composition, comprising: the curing agent for epoxy resin as described in any one of items 1 to 7 of the scope of patent application; and epoxy resin.