Novel curing agent having ester group and amide group, method for preparing the same, and epoxy composition, cured product and article comprising the same

Abstract

Provided are a novel curing agent exhibiting excellent low dielectric loss characteristics and processability (specifically, desmear property) in an epoxy material, a method for preparing the same, an epoxy composition including the novel curing agent, a cured product of the epoxy composition, and an article including the epoxy composition.SOLUTION: A curing agent represented by the following chemical formula (1) is provided. Wherein A is hydrogen or an allyl group and B is an OH group or a group. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel curing agent having an ester group and an amide group, a method for producing the same, and an epoxy composition, cured product, and article containing the same. Specifically, the present invention relates to a novel curing agent having both an ester group and an amide group in a benzene unit, which exhibits excellent low dielectric loss properties (low dielectric dissipation factor or low Df) and processability, a method for producing the same, and an epoxy composition, cured product, and article containing the same. [Background technology]

[0002] With the development of semiconductor packaging technology, there is a demand for the development of technology that can transmit large volumes of data as quickly as possible without transmission loss.If the dielectric loss value of the epoxy material used as semiconductor packaging material is high, data transmission loss will be large and the quality of the transmitted signal will deteriorate.Therefore, the low dielectric loss (low dielectric dissipation factor or low Df) characteristic of semiconductor insulating materials is a very important characteristic for high-quality high-speed data transmission.

[0003] As disclosed in Korean Patent No. 2051374, the most representative method for reducing the dielectric loss of epoxy materials is to use an active ester compound as a curing agent. Conventionally, the use of an active ester curing agent has significantly improved the dielectric loss characteristics of epoxy insulating materials, but it has the problem of reducing processability, especially the desmearing ability of the epoxy film.

[0004] Therefore, in order to manufacture semiconductor components for ultra-high-speed semiconductor data transmission, it is necessary to develop an epoxy insulating material that can simultaneously satisfy the excellent dielectric loss (Df) (i.e., low Df) characteristics and processability of epoxy insulating materials. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent No. 2051374 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, there is a need for the development of a material that satisfies both low dielectric loss (Df) and processability, specifically desmearing properties, in cured epoxy products. The present inventors have discovered that a novel curing agent having both an ester group and an amide group in a benzene unit not only exhibits improved processability, specifically desmearing properties, in epoxy materials, but also exhibits excellent low dielectric loss (Df) properties in cured epoxy products, and the present invention is based on this discovery. Accordingly, the present invention provides a novel curing agent having both an ester group and an amide group in a benzene unit that exhibits excellent low dielectric loss properties (low dielectric dissipation factor or low Df) and processability, a method for producing the curing agent, and epoxy compositions, cured products, and articles containing the curing agent. [Means for solving the problem]

[0007] According to a first aspect of the present invention, there is provided a curing agent represented by the following chemical formula (1):

[0008] [ka] (wherein A is hydrogen or an allyl group, B is an OH group or [ka] (Et is an ethyl group.)

[0009] According to a second aspect of the present invention, A method for producing a curing agent in which B is an OH group in the following chemical formula (1), A first step of mixing isophthaloyl chloride with at least one of phenol and 2-allylphenol to form an ester group; and A method is provided which includes a second step of combining the reaction product of the first step with at least one of m-aminophenol, p-aminophenol, and o-aminophenol to form an amide functionality.

[0010] [ka] (wherein A is hydrogen or an allyl group, and B is an OH group.)

[0011] According to a third aspect of the present invention, In the following chemical formula (1), B is [ka] (Et is an ethyl group) group, A first step of mixing isophthaloyl chloride with at least one of phenol and 2-allylphenol to form an ester group; a second step of combining the reaction product of the first step with at least one of m-aminophenol, p-aminophenol, and o-aminophenol to form an amide functional group; and A method is provided which includes a third step of combining the reaction product of the second step with 3-(triethoxysilyl)propyl isocyanate to form an alkoxysilyl group.

[0012] [ka] (wherein A is hydrogen or an allyl group, and B is [ka] (Et is an ethyl group.)

[0013] According to a fourth aspect of the present invention, In the second or third aspect, in the first step, 0.6 to 1.4 equivalents of at least one of phenol and 2-allylphenol are mixed with 1 equivalent of isophthaloyl chloride; In the second step, the reaction product of the first step is mixed with at least one of m-aminophenol, p-aminophenol and o-aminophenol in an amount of 0.6 to 1.4 equivalents of at least one of m-aminophenol, p-aminophenol and o-aminophenol relative to 1 equivalent of isophthaloyl chloride used in the first step.

[0014] According to a fifth aspect of the present invention, there is provided a method according to the third aspect, characterized in that in the third step, 0.1 to 1.0 equivalent of 3-(triethoxysilyl)propyl isocyanate is mixed with 1 equivalent of hydroxy groups in the reaction product of the second step.

[0015] According to a sixth aspect of the present invention, (A) an epoxy resin and (B) a curing agent, As the (B) curing agent, (i) the curing agent represented by the chemical formula (1) of claim 1 is used alone, or (ii) an epoxy composition is provided in which the curing agent (a) represented by the chemical formula (1) of claim 1 is used in combination with at least one curing agent (b) selected from active ester-based curing agents and phenol-based curing agents.

[0016] According to a seventh aspect of the present invention, there is provided an epoxy composition in which, when the curing agent (a) represented by chemical formula (1) of the sixth aspect is used in combination with at least one curing agent (b) selected from active ester-based curing agents and phenol-based curing agents, the curing agents (a) and (b) are used in a molar ratio of curing agent (a):curing agent (b) of 0.5:9.5 to 9.5:0.5.

[0017] According to an eighth aspect of the present invention, there is provided a cured product of the epoxy composition according to the sixth or seventh aspect.

[0018] According to a ninth aspect of the present invention, there is provided an article comprising the epoxy composition according to the sixth or seventh aspect, or the cured product according to the eighth aspect.

[0019] According to a tenth aspect of the present invention, in the ninth aspect, the article is an insulating film, a semiconductor panel, An article is provided that is a packaging epoxy film, an adhesive film, a build-up film, a substrate film, or an epoxy encapsulant. [Effects of the Invention]

[0020] According to the present invention, a novel curing agent having both an ester group and an amide group in a benzene unit (hereinafter also referred to as "novel curing agent") is used as a curing agent for epoxy resins. Epoxy compositions containing such novel curing agents achieve low dielectric loss (Df) and improved processability (specifically, desmearing properties).

[0021] Due to these improved properties, the epoxy composition of the present invention containing the novel curing agent of the present invention is suitable for use as an insulating film, an epoxy film for semiconductor packaging, an adhesive film, a build-up film, a substrate film, an epoxy encapsulant for semiconductor packaging, etc. DETAILED DESCRIPTION OF THE INVENTION

[0022] According to the present invention, there are provided a novel curing agent that exhibits excellent low dielectric loss properties and processability (specifically, desmearing property) in epoxy materials, a method for producing the same, an epoxy composition containing the novel curing agent, a cured product of the epoxy composition, and an article containing the epoxy composition. These are described below.

[0023] A. A new curing agent that simultaneously has an ester group and an amide group in the benzene unit According to the present invention, there is provided a novel curing agent having both an ester group and an amide group in a benzene unit represented by the following chemical formula (1).

[0024] [ka]

[0025] In chemical formula (1), A is hydrogen or an allyl group, and B is an OH group or [ka] (Et is an ethyl group). The substitution position of B on the benzene ring is not specified, and it may be substituted at any of the ortho, meta, or para positions, preferably at the meta or para position. Here, the functional group linked to the ester group and amide group preferably has a benzene structure ((a) (a with a circle) benzene unit and (b) (b with a circle) benzene unit). For example, a naphthalene structure rather than a benzene structure is not preferred because it reduces solution dispersibility, and an alkyl group or alicyclic structure is not preferred because it reduces physical properties such as dielectric loss.

[0026] In the application of epoxy compositions and / or epoxy cured products containing the novel curing agents according to the present invention, Therefore, excellent low dielectric properties and processability (specifically, desmearing properties) are realized by the chemical structural characteristics of the novel curing agent according to the present invention. The ester and amide functional groups bonded to the meta position in the central benzene unit, and the structures of (a)(a to ◯) benzene and (b)(b to ◯) benzene, provide an optimal molecular architecture in terms of the balance between low dielectric properties and processability. From this perspective, it is not preferable for the ester and amide groups to be bonded to the para and ortho positions in the central benzene unit. That is, the structure of the central benzene unit in which the -CO- of the bonded ester and amide groups are linked is preferably an isophthaloyl unit structure, and a terephthaloyl unit structure (where the carbonyl group is -para to the benzene ring) and a phthaloyl unit structure (where the carbonyl group is -ortho to the benzene ring) are not preferred.

[0027] The novel curing agent of the above chemical formula (1) has a weight-average molecular weight (Mw) of 300 to 1,000 g / mol, more preferably 300 to 900 g / mol. The above-mentioned range of Mw is preferred from the viewpoints of physical properties and processability. An Mw of less than 300 g / mol is undesirable because the novel curing agent of the present invention cannot be synthesized, while an Mw of more than 1,000 g / mol is undesirable because it is difficult to simultaneously ensure dielectric properties and processability. Therefore, polymers having a repeating unit are not preferred. Here, the Mw of the novel curing agent is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0028] The novel curing agent of the above chemical formula (1) has a curing agent equivalent weight (the solid content mass of the curing agent divided by the number of functional groups capable of reacting with epoxy groups) of 80 to 300 g / Eq, preferably 90 to 250 g / Eq. A curing agent equivalent weight within this range is preferred from the viewpoint of ensuring physical properties and processability, while a curing agent equivalent weight of less than 80 g / Eq or more than 300 g / Eq is undesirable because it does not ensure dielectric properties and processability. During the curing reaction with an epoxy resin, the novel curing agent separates into phenol, aminophenol, and an isophthaloyl moiety, which then participate in the curing reaction.

[0029] The ester and amide groups bonded to the benzene unit of the novel curing agent of formula (1) according to the present invention can improve dielectric loss characteristics by suppressing and / or blocking the generation of secondary alcohols during the epoxy curing reaction. In addition, the simultaneous presence of the ester and amide groups improves the affinity of the curing agent to the solvent, thereby improving solubility and dispersibility of the epoxy composition, as well as desmearing and solution dispersibility.

[0030] Furthermore, the ester and amide groups bonded to the benzene units exhibit improved low dielectric loss and processability (specifically, desmearing properties) due to the harmonization of their molecular architecture.

[0031] When present, the alkoxysilyl group suppresses the generation of secondary alcohols, and therefore contributes not only to improving the dielectric loss of the epoxy cured product (i.e., low dielectric loss characteristics), but also to improving desmearing.

[0032] B. New method for producing hardener The novel curing agent according to the present invention is prepared by the following steps: (1) forming an ester group (first step); (2) forming an amide group (second step); and (3) optionally forming an alkoxysilyl group (third step).

[0033] As shown in Reaction Scheme 1 below, in the first step, benzene units are substituted by the reaction of isophthaloyl chloride with at least one of phenol and 2-allylphenol. A steric functional group is formed.

[0034] [Reaction Scheme 1: Reaction of isophthaloyl chloride with 2-allylphenol (Step 1)] [ka]

[0035] For example, but not limited to, the reaction of the reactants isophthaloyl chloride with at least one of phenol and 2-allylphenol (hereinafter also referred to as "phenols") may be carried out by contacting the isophthaloyl chloride with the phenol, such as by mixing the reactants. The mixing may be carried out by, but not limited to, stirring the reactants.

[0036] In the first step, isophthaloyl chloride and a phenol are reacted in an amount of 0.6 to 1.4 equivalents, preferably 1 to 1.4 equivalents, of the phenol relative to 1 equivalent of isophthaloyl chloride (here, 1 equivalent of isophthaloyl chloride corresponds to 2 equivalents based on the acyl chloride, which is the reactive functional group). If the amount of phenol is less than the lower limit, it is not preferable because sufficient ester groups cannot be formed, and if it is more than the upper limit, it is not preferable because it hinders the formation of amide groups in the subsequent second-step reaction.

[0037] Considering the solubility of the reactants and the reaction time, the first step can be carried out at a temperature of 0° C. to 80° C., preferably 25° C. to 60° C. Temperatures below 0° C. are not preferred because the reaction rate may be significantly slowed, while temperatures above 80° C. are not preferred because side reactions may occur.

[0038] The reaction time varies depending on the structure of the reactants, the degree of reaction, the solvent, and the amount of base, but is preferably 1 to 48 hours, more preferably 1 to 24 hours, from the viewpoint of reaction efficiency. A reaction time of less than 1 hour is undesirable because the reaction does not proceed sufficiently, and a reaction time of more than 48 hours is undesirable because an addition reaction may occur.

[0039] On the other hand, the reaction of isophthaloyl chloride with phenol and / or 2-allylphenol can be carried out in the presence of a base and / or any solvent, if necessary.

[0040] When a separate base is used, it is used to neutralize the acid generated during the reaction or to increase the reaction rate. Examples of bases that can be used include, but are not limited to, NaOH, KOH, K2CO3, Na2CO3, KHCO3, NaHCO3, triethylamine, and diisopropylethylamine. These bases can be used alone or in combination of two or more. When a base is used, it is recommended from the standpoint of reaction efficiency to use 2 to 10 equivalents, preferably 2 to 4 equivalents, per equivalent of isophthaloyl chloride (2 equivalents based on the acyl chloride). If the base content is less than 2 equivalents, neutralization of the acid generated during the reaction may be insufficient. Even if more than 10 equivalents are used, the effect of adding the base will not be further improved, so use of a larger amount is unnecessary.

[0041] A solvent can be used as needed. For example, in the first step of the reaction, However, if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without a separate solvent, a separate solvent may not be required. That is, if the viscosity of the reactants is low enough that mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, and this can be easily determined by those skilled in the art. If a solvent is used, any solvent may be used as long as it can dissolve the reactants well and can be easily removed after the reaction without adversely affecting the reaction. Examples of solvents that can be used include, but are not limited to, toluene, xylene, acetonitrile, THF (tetrahydrofuran), MEK (methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), chloroform (CHCl), and water (HO). These solvents can be used alone or in combination of two or more. The amount of solvent used is not particularly limited, and an appropriate amount can be used as long as it sufficiently dissolves the reactants and does not adversely affect the reaction. Those skilled in the art can select an appropriate amount taking this into consideration.

[0042] In the second step, an amide functional group is formed on the benzene unit by reaction of the reaction product of the first step with an aminophenol, as shown in Reaction Scheme 2 below.

[0043] [Reaction Scheme 2: Reaction of the reaction product of the first step with aminophenol (second step)] [ka]

[0044] In the second step, the reaction of the reaction product of the first step with an aminophenol (m-aminophenol, p-aminophenol, and / or o-aminophenol) can be carried out by contacting the reaction product of the first step with an aminophenol, for example, but not limited to, mixing the reaction product of the first step with the aminophenol. Mixing can be carried out by, but not limited to, stirring the reactants.

[0045] In the second reaction step, 0.6 to 1.4 equivalents of aminophenol, preferably 0.6 to 1 equivalent, can be used per equivalent of isophthaloyl chloride (2 equivalents based on acyl chloride) used as a reactant in the first reaction step. Less than 0.6 equivalents of aminophenol is undesirable because some of the isophthaloyl chloride remains unreacted, which may cause side reactions. More than 1.4 equivalents of aminophenol is undesirable because it increases the purification time and may contain by-products.

[0046] Considering the solubility of the reactants and the reaction time, the second step can be carried out at a temperature of 0° C. to 80° C., preferably 25° C. to 60° C. Temperatures below 0° C. are not preferred because the reaction rate may be significantly slowed, while temperatures above 80° C. are not preferred because side reactions may occur.

[0047] The reaction time varies depending on the structure of the reactants, the degree of reaction, the solvent, and the amount of base, but is preferably 1 to 48 hours, more preferably 1 to 24 hours, from the viewpoint of reaction efficiency. A reaction time of less than 1 hour is undesirable because the reaction does not proceed sufficiently, and a reaction time of more than 48 hours is undesirable because an addition reaction may occur.

[0048] On the other hand, the reaction of the reaction product of the first step with aminophenol may be carried out in the presence of a base and / or can be carried out in the presence of any solvent.

[0049] When a separate base is used, it is used to neutralize the acid generated during the reaction or to increase the reaction rate. Examples of bases that can be used include, but are not limited to, NaOH, KOH, K2CO3, Na2CO3, KHCO3, NaHCO3, triethylamine, and diisopropylethylamine. These bases can be used alone or in combination of two or more. When a base is used, it is best to use 2 to 10 equivalents, preferably 2 to 4 equivalents, per equivalent of isophthaloyl chloride (2 equivalents based on the acyl chloride) from the perspective of reaction efficiency. If the base content is less than 2 equivalents, the intended effect of adding the base may be insufficient. Using more than 10 equivalents is unnecessary because the effect of adding the base is not further improved.

[0050] In addition, a solvent can be used as needed. For example, in the second step of the reaction, if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without a separate solvent, a solvent may not be used. That is, if the viscosity of the reactants is low enough that mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required; this can be easily determined by those skilled in the art. When a solvent is used, any solvent may be used as long as it can dissolve the reactants well and can be easily removed after the reaction without adversely affecting the reaction. Examples of solvents that can be used include, but are not limited to, toluene, xylene, acetonitrile, THF (tetrahydrofuran), MEK (methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), chloroform (CHCl), and water (HO). These solvents can be used alone or in combination. The amount of solvent used is not particularly limited, and can be an appropriate amount within the range in which the reactants are sufficiently dissolved and the amount does not adversely affect the reaction, and a person skilled in the art can select an appropriate amount taking this into consideration.

[0051] Upon completion of the second stage reaction, a novel curing agent according to the present invention is obtained, in which A is hydrogen or an allyl group and B is an OH group in the chemical formula (1).

[0052] As is generally known in the chemical field, in a chemical reaction, not all reactants proceed 100% completely. The reaction product includes the final product (i.e., the novel curing agent represented by Chemical Formula (1)) as intended in this application, and is a mixture of starting materials, a product in which the reaction has progressed completely, a product in which the reaction has progressed partially, and the like, depending on various factors such as the reactivity of the reactants. The reaction product (hereinafter, for convenience, referred to as the "final product") in which such various substances are mixed can be used as the novel curing agent represented by Chemical Formula (1) in an epoxy composition.

[0053] Meanwhile, the amounts (i.e., equivalent ratio) of the phenols used in the first stage and the aminophenols used in the second stage can be adjusted to control the physical properties and / or processability (specifically, desmearing ability) exhibited by the novel curing agent in the final product obtained after completion of the second stage. For example, from the viewpoint of the balance between the solution dispersibility and physical properties (thermal properties, glass transition temperature, etc.) of the novel curing agent, it is preferable to adjust the amounts of the phenols used in the first stage and the aminophenols used in the second stage to an equivalent ratio (molar ratio) of phenols:aminophenols in the range of 7:3 to 3:7, more preferably 6:4 to 4:6, and most preferably 5:5. For example, to improve the dielectric properties (i.e., low dielectric loss properties) of an epoxy composition, the concentration of the phenols can be increased, and to further improve physical properties (thermal expansion resistance, etc.), the concentration of the aminophenol can be increased. If the aminophenol content is higher than the above range, the dielectric properties may be reduced due to the relatively low content of phenols, and if the aminophenol content is lower than the above range, the thermal properties may be reduced.

[0054] As shown in Reaction Scheme 3 below, in the third step, an alkoxysilyl group is formed by reacting the reaction product of the second step with an isocyanate silane coupling agent, 3-(triethoxysilyl)propyl isocyanate (i.e., OCN-(CH2)3-Si(OEt)3). However, the third step is an optional step that can be performed if alkoxysilyl groups are desired.

[0055] [Reaction Scheme 3: Reaction of the reaction product of the second step with 3-(triethoxysilyl)propyl isocyanate (third step)] [ka]

[0056] For example, but not limited to, in the third step, the reaction of the reaction product of the second step with 3-(triethoxysilyl)propyl isocyanate (i.e., OCN—(CH)—Si(OEt)) can be carried out by contacting, such as by mixing, the reaction product of the second step with 3-(triethoxysilyl)propyl isocyanate (i.e., OCN—(CH)—Si(OEt)). Mixing can be carried out, but not limited to, by stirring the reactants.

[0057] In the third stage, the OH groups of the reaction product of the second stage react with 3-(triethoxysilyl)propyl isocyanate, so from the viewpoint of the silylation ratio and reaction efficiency, 0.1 to 1.0 equivalents of 3-(triethoxysilyl)propyl isocyanate are added per equivalent of hydroxy groups of the reaction product of the second stage. If the amount of 3-(triethoxysilyl)propyl isocyanate is less than 0.1 equivalents, it may be insufficient for the silylation reaction, and adding more than 1.0 equivalent is unnecessary because the reaction has already progressed sufficiently.

[0058] The third-stage reaction can be carried out at a reaction temperature of 60°C to 150°C, preferably 80°C to 120°C. Considering the solubility of the reactants and the reaction time in the reaction process, the reaction temperature is 60°C to 150°C. Temperatures below 60°C are not preferred because unreacted reactants may remain, while temperatures above 150°C are not preferred because side reactions may occur due to the high reaction rate.

[0059] The reaction time for the third step is 1 hour to 72 hours, preferably 12 hours to 24 hours, and varies depending on the structure of the reactants, the degree of reaction, the amount of solvent, and the amount of base. If it is less than 1 hour, the reaction may not proceed sufficiently, and if it exceeds 72 hours, the reaction will not proceed further, which is undesirable.

[0060] The reaction of the third step can be carried out in the presence of any base and / or any solvent.

[0061] That is, the reaction in the third step can be carried out in the presence of a base, if necessary. The use of a base can increase the reaction rate. Examples of bases that can be used include, but are not limited to, triethylamine, diisopropylethylamine, and pyridine. These bases can be used alone or in combination of two or more. When a base is used, it is preferable to use 0.1 to 5 equivalents of the base per equivalent of the hydroxy group in the reaction product of the second step from the viewpoint of reaction efficiency. If the base content is less than 0.1 equivalents, the intended effect of adding the base may be insufficient, and even if more than 5 equivalents are used, the effect of adding the base will not be further improved and is therefore unnecessary.

[0062] In addition, a solvent may be used as needed. For example, in the third step, if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without a separate solvent, a separate solvent may not be used. That is, if the viscosity of the reactants is low enough that mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required; this can be easily determined by those skilled in the art. If a solvent is used, any solvent may be used as long as it can dissolve the reactants well and can be easily removed after the reaction without adversely affecting the reaction. Examples of solvents that can be used include, but are not limited to, toluene, xylene, acetonitrile, THF (tetrahydrofuran), MEK (methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), chloroform (CHCl), and water (HO). These solvents may be used alone or in combination. The amount of solvent used is not particularly limited, and can be an appropriate amount within the range in which the reactants are sufficiently dissolved and the amount does not adversely affect the reaction, and a person skilled in the art can select an appropriate amount taking this into consideration.

[0063] As is generally known in the field of chemistry, in a chemical reaction, not all reactants react 100% completely, and the reaction product is a mixture of starting materials, a completely reacted product, a partially reacted product, etc., depending on various factors such as the reactivity of the reactants, including the novel curing agent intended in the present application. Such a mixture of various substances can be used as a curing agent in an epoxy composition as is.

[0064] C. Epoxy composition In yet another embodiment of the present invention, there is provided an epoxy composition that not only exhibits improved low dielectric loss properties in an epoxy cured product but also exhibits excellent processability (specifically, desmearing ability), and the epoxy composition of the present invention includes (A) an epoxy resin and (B) a curing agent.

[0065] The epoxy composition of the present invention may further contain one or more of (C) an inorganic filler, (D) a thermoplastic resin, and (E) a curing catalyst, as necessary. Each of the components of the epoxy composition of the present invention will be described below.

[0066] (A) Epoxy resin The epoxy composition of the present invention contains an epoxy resin (A) as a base resin. The epoxy resin (A) may be any epoxy resin conventionally known in this technical field, and its type and / or physical properties are not limited. Since such matters relating to epoxy resins are generally known in this technical field, they will not be described in detail here.

[0067] Common epoxy resins include, but are not limited to, bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, triphenylmethane, 1,1,2,2-tetraphenylene, and the like. Examples of epoxy resins include glycidyl-based epoxy resins selected from the group consisting of tetraphenylethane, tetraphenylmethane, 4,4'-diaminodiphenylmethane, aminophenol, glycidyl ether-based epoxy resins having alicyclic, aliphatic, or novolak units, glycidyl amine-based epoxy resins, and glycidyl ester-based epoxy resins; and alicyclic epoxy resins. At least one selected from these epoxy resins may be used. The general epoxy resins include both liquid-phase and solid-phase epoxy resins. The general epoxy resins may also include epoxy resins having an alkoxysilyl group in addition to an epoxy group.

[0068] In this technical field, it is common to use various epoxy resins in combination, taking into consideration the epoxy composition, its cured product, and its application field, as well as physical properties such as processability, drying property, and viscosity in subsequent processes of processing the epoxy composition. Therefore, those skilled in the art can appropriately mix and use various common epoxy resins as needed, taking into consideration the physical properties required depending on the application field of the epoxy composition, and this will not be described in detail in this specification.

[0069] The epoxy equivalent of the epoxy resin is not particularly limited, and may be, for example, 70 g / Eq to 1000 g / Eq, preferably 80 g / Eq to 1000 g / Eq, more preferably 80 g / Eq to 800 g / Eq, and even more preferably 100 g / Eq to 500 g / Eq. By using an epoxy resin with an epoxy equivalent in the above range, the crosslink density of the cured product becomes sufficient, and it is possible to ensure the cured physical properties.

[0070] The weight-average molecular weight (Mw) of the epoxy resin is not particularly limited, but may be, for example, 300 to 8000 g / mol, preferably 300 to 5000 g / mol, and more preferably 300 to 4000 g / mol, from the viewpoints of processability and compatibility with inorganic fillers. Here, the weight-average molecular weight of the epoxy resin is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0071] (B) Hardener The epoxy composition of the present invention contains a curing agent (B), and the curing agent can be [1] the novel curing agent represented by the chemical formula (1) of the present invention described above, used alone, or [2] the novel compound represented by the chemical formula (1) of the present invention described above, used in combination with a conventional curing agent.

[0072] In the epoxy composition of the present invention, the novel curing agent represented by chemical formula (1) of the present invention is used, and therefore, the contents of the novel curing agent having both an ester group and an amide group in the benzene unit described in the above item (a) are all applicable.

[0073] Conventional curing agents that can be used together with the novel curing agent are active ester-based curing agents and / or phenol-based curing agents.

[0074] From the viewpoint of low dielectric properties of the cured product of the epoxy composition of the present invention, it is preferable to use the novel curing agent in combination with an existing curing agent. The cured product of the epoxy composition using the novel curing agent alone exhibits a dielectric loss of less than 0.007, preferably less than 0.006. The cured product of the epoxy composition using the novel curing agent in combination with an existing curing agent exhibits a dielectric loss of less than 0.005, preferably less than 0.003.

[0075] As the active ester curing agent, any active ester curing agent known to be used for existing epoxy resins can be used. For example, the active ester curing agent is preferably, but not limited to, a compound having two active ester groups in one molecule. An active ester obtained by reacting a carboxylic acid compound with a hydroxy compound. Preferred compounds are the carboxylic acid compounds used to generate the active ester curing agent. Here, preferred are isophthalic acid, terephthalic acid, etc., and preferred are phenol, naphthol, etc., as the hydroxy compound. The active ester curing agents can be used alone or in any combination of two or more.

[0076] The phenolic curing agent can be any phenolic novolac curing agent known for use in existing epoxy resins. Examples of phenolic curing agents include, but are not limited to, phenolic novolac resins, trifunctional phenolic novolac resins, cresol novolac resins, bisphenol A novolac resins, xylene novolac resins, triphenyl novolac resins, biphenyl novolac resins, dicyclopentadiene novolac resins, naphthalene novolac resins, phenolic p-xylene resins, phenolic 4,4'-dimethylbiphenylene resins, xylok (p-xylene-modified), and triazine compounds. Furthermore, the phenolic curing agent can further contain an alkoxysilyl group in addition to the phenol group. Therefore, the phenolic curing agent includes all phenolic curing agents having both a phenol group and an alkoxysilyl group. The phenolic curing agents can be used alone or in any combination of two or more.

[0077] The amount of curing agent in the epoxy composition is determined by the equivalent ratio to the epoxy resin. While not limited thereto, for example, the curing agent is used in a range of 0.7 to 1.4 equivalents, preferably 0.7 to 1.3 equivalents, per equivalent of epoxy resin. If the amount is less than 0.7 equivalents, sufficient dielectric loss characteristics may not be ensured, and if the amount exceeds 1.4 equivalents, the curing efficiency of the epoxy cured product may decrease.

[0078] The amount of the curing agent is the amount of the novel curing agent when the novel curing agent is used alone, and is the total amount of the novel curing agent and the conventional curing agent when the novel curing agent and the conventional curing agent are used together as curing agents.

[0079] Here, the equivalent weight of an epoxy resin is the solids mass of the epoxy resin divided by the number of epoxide functional groups, and the equivalent weight of a curing agent is the solids mass of the curing agent divided by the number of functional groups capable of reacting with epoxy groups. The equivalent weight of the curing agent is the sum of all curing agents used in the formulation. Therefore, when the novel curing agent is used alone, it is the equivalent weight of the novel curing agent. When the novel curing agent and a conventional curing agent are used together as curing agents, it is the equivalent weight of the combined amount of the novel curing agent and the conventional curing agent. Here, "solids mass" refers to the weight of the pure epoxy resin and curing agent, excluding incidental liquids and solvents that may be present in the epoxy resin and curing agent. Calculation of the equivalent weight of an epoxy resin and a curing agent is generally well known in the art.

[0080] On the other hand, when the novel curing agent (a) is used in combination with the existing curing agent (b) (i.e., an active ester-based curing agent and / or a phenol-based curing agent), the novel curing agent (a) and the existing curing agent (b) are preferably used in combination in a molar ratio of 0.5:9.5 to 9.5:0.5, preferably 9:1 to 1:9. That is, the novel curing agent (a) and the existing curing agent (b) are mixed in the above molar ratio, and the mixed curing agent can be used in a range of 0.7 to 1.4 equivalents, preferably 0.7 to 1.3 equivalents, per equivalent of the epoxy resin.

[0081] In the molar ratio of the novel curing agent (a) to the conventional curing agent (b), if the novel curing agent is used at a level below the lower limit, the intended physical properties cannot be fully secured by using the novel curing agent, which is undesirable. On the other hand, if the novel curing agent is used at a level above the upper limit, the effect of blending the novel curing agent no longer increases, which is undesirable.

[0082] When an active ester curing agent and a phenolic curing agent are used in combination as conventional curing agents, the mixing ratio thereof is not particularly limited, and the phenolic curing agent and the active ester curing agent can be mixed in any appropriate ratio taking into consideration the intended physical properties of the cured product. This is generally known in this technical field, so it will not be described in detail here.

[0083] (C) Inorganic filler The epoxy composition of the present invention may further contain an inorganic filler, if necessary. Inorganic fillers are components commonly used in this technical field to reinforce the physical properties of epoxy compositions.

[0084] For example, the inorganic filler may be any inorganic filler known in the art for reinforcing the physical properties of conventional epoxy resins. Examples of inorganic fillers include, but are not limited to, silica (including, for example, fused silica and crystalline silica), zirconia, titania, alumina, metal oxides such as magnesium oxide, aluminum nitride, silicon nitride, aluminum nitride, and silsesquioxane. The inorganic fillers may be used alone or in a mixture of two or more. The average particle size of the inorganic filler is not limited thereto. For example, the inorganic filler may be a spherical powder having a particle size (cut size) of 0.01 μm to 100 μm, preferably 0.02 μm to 70 μm, and more preferably 0.02 μm to 50 μm, from the viewpoints of dispersibility, processability, reliability, etc. If the average particle size of the inorganic filler is less than 0.01 μm, it is not only expensive but also may have problems with dispersion, and if it exceeds 100 μm, problems may arise with fine pattern formation and filling.

[0085] Inorganic fillers are generally known in the art and will not be described in detail here.

[0086] In the epoxy composition of the present invention, the inorganic filler content can be, for example, 93 wt% or less (e.g., 93 parts by weight or less per 100 parts by weight of the solid content of the epoxy composition) based on the total weight of the solid content of the epoxy composition, from the viewpoint of using an amount necessary to ensure the required physical properties of the epoxy composition. Since the inorganic filler can be added as needed, there is no particular lower limit to the amount added. However, when added, it can be added at least 10 wt% (e.g., 10 parts by weight per 100 parts by weight of the solid content of the epoxy composition) so that the effect of the addition can be realized. In consideration of ensuring the physical properties and dispersibility of the epoxy composition, the inorganic filler can be added in the above-mentioned amount, specifically, 10 wt% to 93 wt%, preferably 20 wt% to 90 wt%. A content of less than 10 wt% is undesirable because it is difficult to ensure the intended physical properties of the epoxy cured product by adding the filler, and a content of more than 93 wt% is undesirable because it is difficult to disperse the filler.

[0087] (D) Thermoplastic resin The epoxy composition of the present invention may further contain a thermoplastic resin, if necessary. For example, a thermoplastic resin may be further used when it is necessary to impart film properties and / or flexibility.

[0088] The thermoplastic resin may be any thermoplastic resin generally known to be used in this technical field, such as acrylic resin, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide-imide resin, polyether sulfone resin, or polysulfone resin. One or more types of thermoplastic resins can be used in combination, and there are no limitations on the structure, molecular weight, etc. Matters relating to thermoplastic resins are generally known in this technical field, so they will not be described in detail here.

[0089] When a thermoplastic resin is used, it may be used in an amount commonly used in this technical field and is not particularly limited. However, for example, the thermoplastic resin may be blended as an optional component in an amount of 7 wt% or less based on the total solids content of the epoxy composition (i.e., 7 parts by weight or less per 100 parts by weight of the total solids content of the epoxy composition). However, when blended, in order to achieve the intended effect, for example, taking into consideration the processability (film formability) and / or flexibility of the epoxy blend, it may be blended in an amount of 0.5 wt% to 7 wt% based on the total solids content of the epoxy composition (i.e., 0.5 to 7 parts by weight per 100 parts by weight of the total solids content of the epoxy composition). Addition of less than 0.5 wt% of the thermoplastic resin is undesirable because the physical properties intended by the thermoplastic resin, such as the processability and flexibility of the film, are insufficient. Addition of more than 7 wt% is undesirable because the physical properties of the epoxy material may be reduced.

[0090] (E) Curing catalyst The epoxy composition of the present invention may further contain a curing catalyst. By using the curing catalyst to rapidly cure the epoxy composition, the crosslinked structure in the cured product becomes uniform and the crosslink density becomes high.

[0091] The curing catalyst is not particularly limited, and any curing catalyst known in the art to be used as a curing catalyst for curing epoxy resins can be used. The curing catalysts may be used alone or in combination of two or more.

[0092] Examples of the curing catalyst include imidazole compounds, amine compounds, organic phosphine compounds, and organic phosphonium salt compounds.

[0093] Examples of the imidazole compounds include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trimethylimidazole ... Azine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2- Examples include methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole, 1,3,5-triazine-2,4-diamine 6-[2-(2-methyl-1H-imidazol-1-yl)ethyl] and 1,3,5-triazine-2,4,6(1H,3H,5H)-trione (1:1).

[0094] Examples of the amine compounds include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4-dimethylaminopyridine (DMAP), benzyl dimethyl amine (BDMA), trisdimethylamine, and the like. Examples include diaminomethylphenol (DMP-30), triethylenediamine, and diazabicycloundecene (DBU).

[0095] As the organic phosphine compounds and organic phosphonium salt compounds, TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, TPTP-SCN (trade names of Hokko Chemical Industry Co., Ltd.), etc. may be used alone or in combination of two or more.

[0096] The curing catalyst can be used in an amount commonly used in this technical field. While not limited thereto, the curing catalyst can be used in an amount of, for example, 0.1 to 10 parts by weight, e.g., 0.2 to 10 parts by weight, per 100 parts by weight of epoxy resin. If the amount of curing catalyst used is less than 0.1 part by weight, the effect of using the curing catalyst is insufficient, and even if it exceeds 10 parts by weight, no further improvement effect is obtained, which is undesirable. The curing catalyst is preferably used in the above amount from the viewpoint of accelerating the curing reaction and controlling the rate of the curing reaction. By using the curing catalyst in the above amount, rapid curing can be achieved, and improved throughput can be expected.

[0097] (F) Other additives The epoxy composition according to any aspect of the present invention may further contain, as needed, other additives commonly used in epoxy compositions in this technical field to adjust the physical properties of the epoxy composition, such as flame retardants, plasticizers, antibacterial agents, leveling agents, defoamers, colorants, stabilizers, coupling agents, viscosity modifiers, diluents, and molding agents, as long as the physical properties of the epoxy composition are not impaired. Furthermore, a solvent may be used to disperse the epoxy composition, if necessary, to facilitate dispersibility of the compound before curing. The type, composition, and amount of such other additives and / or solvents are generally known to those skilled in the art and will not be described in detail herein.

[0098] In the present invention, the "solids content of an epoxy composition" refers to the components of the epoxy composition that will be cured to form a final product (e.g., a cured product) excluding any liquid components, such as liquid components and solvents, that are removed during drying and / or curing when a liquid component is accidentally present in the epoxy composition and / or a solvent is used (even liquid components that constitute the final product are included in the solids content). For example, in the case of an epoxy composition containing (A) an epoxy resin, (B) a curing agent, and optionally containing (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing catalyst, and / or (F) other additives as described above, the "solids content" refers to the total weight of the components of the epoxy composition that will be cured to form a final product (e.g., a cured product) excluding any liquid components, such as solvents, that are removed during drying and / or curing in the epoxy composition (even liquid components that constitute the final product are included in the solids content).

[0099] Furthermore, in the above and below, the term "composition of the present invention" is understood to refer to an epoxy composition that essentially contains (A) an epoxy resin and (B) a curing agent, and optionally contains, as needed, (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing catalyst, and / or (F) other additives as described above.

[0100] For example, the epoxy composition of the present invention may contain (B) curing agent in the range of 0.7 to 1.4 equivalents based on 1 equivalent of epoxy resin, (C) inorganic filler in an amount of 93 wt% or less, preferably 10 to 93 wt%, based on the total weight of the epoxy composition, and (D) thermoplastic resin in an amount of 7 wt%, preferably 0.5 to 7 wt%, based on the total weight of the epoxy composition. The above epoxy composition may further contain (E) curing catalyst and, if necessary, (F) other additives in amounts commonly used in this technical field. In such an epoxy composition of the present invention, the remainder (e.g., the remainder of 100 wt%) may be epoxy resin.

[0101] The epoxy composition of the present invention contains these components in the above-mentioned blending ratio ranges so that the total sum is 100% by weight based on the solid content. When the composition of a component (e.g., component (C) and component (D)) whose blending ratio is expressed in weight % based on the total weight of the solid content of the epoxy composition does not amount to 100% by weight, the remainder is composed of other components (specifically, (A) epoxy resin, (B) curing agent, (E) curing catalyst, and / or (F) other additives) so that the remainder is 100% by weight.

[0102] D. Cured products of epoxy compositions and their uses According to another embodiment of the present invention, a cured product of the epoxy composition according to the present invention is provided. The cured product can be obtained by curing the epoxy composition, for example, by thermal curing. Those skilled in the art can curing the epoxy composition by appropriately selecting any curing method and curing conditions generally known in the art, and the curing method and / or curing conditions are not particularly limited.

[0103] Additionally, the curing method and curing conditions for the epoxy composition are generally known in the art and will not be described in detail here. The term "cured product" refers to both partially cured and fully cured epoxy cured products, and includes epoxy cured products without inorganic fillers (fillers) and epoxy composites containing fillers. As described above, the cured product formed from the epoxy composition of the present invention exhibits low dielectric loss properties as well as improved processability (specifically, desmearing properties).

[0104] For example, the cured epoxy composition containing the novel curing agent of the present invention exhibits a dielectric loss of less than 0.010, preferably less than 0.009, and more preferably less than 0.008. Furthermore, the cured epoxy composition containing the novel curing agent of the present invention has a glass transition temperature of 120°C or higher, preferably 130°C or higher.

[0105] Furthermore, according to another embodiment of the present invention, there is provided an article comprising an epoxy composition according to any aspect of the present invention and / or a cured product thereof.

[0106] As described above, the epoxy composition containing the novel curing agent of the present invention not only achieves low dielectric loss in the cured epoxy product but also excellent processability, i.e., desmearing properties, and is suitable for use in insulating films, epoxy films for semiconductor packaging, adhesive films, build-up films, substrate films, epoxy encapsulating materials, specifically, next-generation semiconductor packaging, for example, packaging for processing large amounts of data at ultra-high speeds (advanced semiconductor packaging).

[0107] The article may be an epoxy insulating film, specifically an insulating film for IC substrates, an epoxy film for semiconductor packaging, an adhesive film, a build-up film, a substrate film, or an epoxy sealing material, for example, an epoxy molding material for semiconductor packaging, an underfill, for example, a next-generation semiconductor packaging part, for example, a packaging part for processing large amounts of data at ultra-high speed, etc.

[0108] The epoxy insulating film using the epoxy composition of the present invention, for example, an insulating film for IC substrates, an epoxy film for semiconductor packaging, an adhesive film, a build-up film, a substrate film, or an epoxy sealing material, for example, an epoxy molding material for semiconductor packaging, an underfill, for example, a next-generation semiconductor packaging part, for example, a packaging part for processing large amounts of data at ultra-high speed, may be produced by any method known in this technical field, and will not be described in detail here.

[0109] For example, but not limited to, the film-form article can be produced by applying the epoxy composition of the present invention to a release film in a film-forming step, followed by drying and curing to form a film, or by extruding the epoxy composition, etc. As the film-forming step, various methods known in the art can be used, and examples thereof include, but are not limited to, various printing methods such as offset printing and screen printing, blade coating, dip coating, spin coating, bar coating, slit coating, inkjet printing, and die coating.

[0110] Example The present invention will be described in more detail with reference to the following examples, which are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

[0111] A. Synthesis example (1) Synthesis Example 1 15 g of isophthaloyl chloride and 150 g of chloroform were placed in a two-neck flask and stirred under nitrogen at room temperature (15°C to 25°C). 9.91 g of allylphenol and 9.55 g of N,N-diisopropylethylamine (DIPEA) were then added sequentially over 30 minutes, and the mixture was further stirred for 2 hours to synthesize a first-stage reaction product having an ester functional group.

[0112] To the reaction product obtained in the first step, 8.06 g of 3-aminophenol and 19.10 g of N,N-diisopropylethylamine (DIPEA) were added sequentially at room temperature for 30 minutes. The mixture was then stirred at room temperature for 10 hours to proceed with the second step. After the reaction was completed, the base and solvent were removed using a rotary evaporator, and the mixture was dried using a vacuum pump to synthesize a new curing agent with ester and amide groups bonded to benzene units (curing agent equivalent: 94 g / Eq, [ester group]:[amide group] = 5.0:5.0 by mol).

[0113] (2) Synthesis Example 2 A novel curing agent having an ester group and an amide group (curing agent equivalent: 103 g / Eq, [ester group]:[amide group]=7:3) was prepared in the same manner as in Synthesis Example 1 above, except that 9.73 g of phenol and 13.37 g of N,N-diisopropylethylamine (DIPEA) were used in the first reaction step, and 4.84 g of 3-aminophenol was used in the second reaction step. by mol) was synthesized.

[0114] (3) Synthesis Example 3 15 g of isophthaloyl chloride and 150 g of chloroform were placed in a two-neck flask and stirred at room temperature under nitrogen. 5.95 g of allylphenol and 5.73 g of N,N-diisopropylethylamine (DIPEA) were then added sequentially at room temperature over 30 minutes, followed by further mixing for 2 hours to synthesize the first-stage reaction product having an ester functional group.

[0115] To the reaction product obtained in the first step, 11.29g of 4-aminophenol and 19.10g of N,N-diisopropylethylamine (DIPEA) were added sequentially over 30 minutes. The second step of the reaction was carried out by mixing at room temperature for 10 hours. Then, 13.37g of N,N-diisopropylethylamine (DIPEA) and 25.60g of 3-(triethoxysilyl)propyl isocyanate were added and mixed at 90°C for an additional 12 hours to carry out the third step. After lowering the temperature to room temperature, the base catalyst and solvent were removed using a rotary evaporator, and the mixture was dried using a vacuum pump to obtain a novel curing agent having ester and amide groups (curing agent equivalent: 148g / Eq, [ester group]:[silylated amide group] = 3.0:7.0 by mol) was synthesized.

[0116] (4) Synthesis Example 4 In the reaction of the first stage, 6.95 g of phenol and 9.55 g of N,N - diisopropylethylamine (DIPEA) were used. In the reaction of the second stage, 8.06 g of 3 - aminophenol was used. In the reaction of the third stage, except that 9.55 g of N,N - diisopropylethylamine (DIPEA) and 18.28 g of 3 - (triethoxysilyl)propyl isocyanate were used, the reaction proceeded in the same manner as in Synthesis Example 3 above. The final compound obtained in the reaction was a novel curing agent having an ester group and an amide group (equivalent weight of the curing agent: 146 g / Eq, [ester group]:[silylated amide group] = 5.0:5.0 by mol).

[0117] B. Production and Physical Property Evaluation of Epoxy Cured Products (1) Dielectric Loss (D f ) and Production and Evaluation of CTE Samples <Production of Samples> An epoxy resin, a curing agent, a thermoplastic resin, and silica were dissolved in methyl ethyl ketone according to the composition shown in Table 1 below. This mixed solution was mixed at a speed of 1500 rpm for 30 minutes using a mixer. Then, a curing catalyst was added thereto and mixed to form a uniform solution, and then cast onto a release film so as to have a uniform thickness, and the solvent of the casting film was dried in a convection oven heated to 70°C. The above - dried film was cured under the curing conditions of 190°C for 90 minutes to prepare a sample.

[0118] <Evaluation of Dielectric Loss> The dielectric loss of the produced epoxy film was evaluated using an E5071C from Agilent Technologies at room temperature and under the condition of 5.125 GHz. The size of the sample for dielectric loss measurement was 60 mm×50 mm×0.1 mm.

[0119] <CTE Evaluation> The thermal expansion characteristics of the epoxy cured product, that is, the dimensional change due to temperature, were evaluated using a Thermo - mechanical Analyzer. The size of the sample for CTE measurement was 4 mm×40 mm×0.1 mm.

[0120] (2) Blister rating: Epoxy resin, curing agent, thermoplastic resin, and silica were dissolved in methyl ethyl ketone according to the composition shown in Table 1 below. This mixture was mixed at 1500 rpm for 30 minutes using a mixer. A curing catalyst was then added and mixed to form a uniform solution. The mixture was then cast onto a release film to a uniform thickness, and the solvent from the cast film was dried in a convection oven heated to 70°C. The dried film was laminated onto a copper foil substrate using a film bonding machine (GMP Co., Ltd., GHQ-320AUTO) and further cured in an oven. The curing conditions for the laminated film were 40 minutes at 120°C and 20 minutes at 180°C.

[0121] The cured epoxy film was immersed in a swelling solution (Atotech Japan, Swelling Dip Securigant P) at 80°C for 5 minutes, then immersed in a roughening solution (Atotech Japan, Concentrate Compact P) at 80°C for 20 minutes. Finally, it was immersed in a neutralizing solution (Atotech Japan, Reduction Solution Securigant P) at 50°C for 5 minutes, after which any remaining chemicals on the surface were washed off and desmeared.

[0122] The desmeared epoxy film was electrolessly copper plated and then heated at 150°C for 1 hour, then electrolytic copper plating was performed and heat treatment was carried out at 190°C for 2 hours, and the presence or absence of blistering was observed and evaluated as follows:

[0123] <Evaluation criteria> No blistering: O Blister occurrence: X

[0124] [Table 1] Note: The compounds used in Table 1 above are as follows: (1) Samhwa Paint Industry Co., Ltd., EEW 420g / Eq, SSE-B20H (2) Samhwa Paint Industries Co., Ltd., EEW 348g / Eq, Serapoxy SHE0002 (3) Samhwa Paint Industry Co., Ltd., EEW 438g / Eq, SSE-D30H (4) Sigma Aldrich, EEW 105g / Eq (5) DIC Corporation, EEW 205g / Eq, HP4770 (6) Sigma Aldrich, EEW 188.5 g / Eq, diglycidyl ether of bisphenol A (7) Mitsubishi Chemical Corporation, EEW 190, YX4000HK (8) DIC Corporation, 220g / Eq, Epicolon HPC 8000L (9) Meiwa Plastic Industries, 107g / Eq, HF-1M (10) Admatechs, SC2050-MTX (11)Sekisui Chemical Co., Ltd., BX-5 (12) Sigma Aldrich (13) Evonik, Imidazole, CUREZOL®

[0125] As can be seen from Table 1 above, the cured products of the epoxy compositions of Examples 1 to 5 containing the novel curing agent of the present invention exhibited excellent (1) low dielectric loss and (2) desmear properties. Specifically, the cured products of the epoxy compositions of Examples 1 to 5 containing the novel curing agent of the present invention exhibited significantly lower dielectric loss values ​​than the cured product using a conventional phenolic curing agent (Comparative Example 1). Furthermore, the films produced using the compositions of Examples 1 to 5 exhibited improved desmear properties and did not develop blisters during high-temperature heat treatment. However, the sample of Comparative Example 1 containing the phenolic curing agent underwent severe etching during desmear treatment, causing the epoxy film to peel off from the substrate, making it impossible to produce a copper foil film sample. Furthermore, the cured epoxy composition of Comparative Example 2 using a conventional active ester curing agent exhibited excellent dielectric loss (i.e., low Df value), but did not undergo satisfactory etching during desmear treatment, resulting in blisters during high-temperature heat treatment due to poor copper foil adhesion.

[0126] From this, it can be seen that the epoxy composition containing the novel curing agent of the present invention not only exhibits excellent low dielectric loss properties and processability (specifically, desmear property) compared to the epoxy composition containing only a conventional phenolic curing agent (Comparative Example 1), but also exhibits improved desmear property compared to the epoxy composition containing only a conventional ester-based curing agent (Comparative Example 2).

[0127] Thus, the novel curing agent of the present invention overcomes the problems of not only conventional phenolic curing agents but also ester curing agents.

[0128] Specifically, the problems of conventional phenolic curing agents and ester curing agents could be overcome not only by using the novel curing agent of the present invention alone, but also by using the novel curing agent of the present invention in combination with a phenolic curing agent and / or an ester curing agent. Specifically, Example 3, which used the novel curing agent in combination with a phenolic curing agent, showed significantly improved dielectric properties and desmear properties compared to the epoxy cured product (Comparative Example 1) which used a conventional phenolic curing agent alone.

[0129] Furthermore, in the cases of Examples 2 and 4 containing the novel curing agent of the present invention and an active ester curing agent, and Example 5 containing the novel curing agent of the present invention, an active ester curing agent, and a phenolic curing agent, not only did they exhibit excellent dielectric properties (i.e., low Df values) comparable to those of Comparative Example 2, but they also showed no blisters and excellent desmear properties.

[0130] In addition to the dielectric loss and processability mentioned above, thermal expansion characteristics are important characteristics that determine the reliability and processability of epoxy parts. In this regard, Examples 1 to 5 containing the novel curing agent of the present invention exhibited excellent dielectric properties (i.e., Not only did it exhibit low Df values ​​and no blisters, but it also exhibited improved thermal expansion properties (i.e., low CTE1 and CTE2 values) compared to Comparative Example 2.

Claims

1. A curing agent represented by the following chemical formula (1): 【Chemistry 1】 wherein A is hydrogen or an allyl group; B is an OH group or 【Chemistry 2】 (Et is an ethyl group)

2. A method for producing a curing agent in which B in the following chemical formula (1) is an OH group, A first step of mixing isophthaloyl chloride with at least one of phenol and 2-allylphenol to form an ester group; and The process includes a second step of combining the reaction product of the first step with at least one of m-aminophenol, p-aminophenol, and o-aminophenol to form an amide functionality. 【Transformation 3】 (wherein A is hydrogen or an allyl group, and B is an OH group.)

3. In the following chemical formula (1), B is 【Chemistry 4】 (Et is an ethyl group) group, A first step of mixing isophthaloyl chloride with at least one of phenol and 2-allylphenol to form an ester group; a second step of combining the reaction product of the first step with at least one of m-aminophenol, p-aminophenol, and o-aminophenol to form an amide functional group; and The method includes a third step of combining the reaction product of the second step with 3-(triethoxysilyl)propyl isocyanate to form an alkoxysilyl group. 【Transformation 5】 (wherein A is hydrogen or an allyl group, and B is 【Transformation 6】 (Et is an ethyl group)

4. In the first step, 1 equivalent of isophthaloyl chloride is mixed with 0.6 to 1.4 equivalents of at least one of phenol and 2-allylphenol; 4. The method according to claim 2 or 3, wherein in the second step, the reaction product of the first step is mixed with at least one of m-aminophenol, p-aminophenol and o-aminophenol in an amount of 0.6 to 1.4 equivalents of at least one of m-aminophenol, p-aminophenol and o-aminophenol per equivalent of isophthaloyl chloride used in the first step.

5. The method according to claim 3, wherein in the third step, 0.1 to 1.0 equivalent of 3-(triethoxysilyl)propyl isocyanate is mixed with 1 equivalent of hydroxy groups of the reaction product of the second step.

6. (A) an epoxy resin and (B) a curing agent, As the curing agent (B), (i) the curing agent represented by the chemical formula (1) of claim 1 is used alone, or (ii) 10. An epoxy composition comprising a curing agent (a) represented by the chemical formula (1) of claim 1 and at least one curing agent (b) selected from active ester curing agents and phenolic curing agents.

7. The epoxy composition according to claim 6, wherein when the curing agent (a) represented by chemical formula (1) according to claim 1 is used in combination with at least one curing agent (b) selected from active ester-based curing agents and phenol-based curing agents, the curing agent (a) and the curing agent (b) are used in a molar ratio of curing agent (a):curing agent (b) of 0.5:9.5 to 9.5:0.

5.

8. A cured product of the epoxy composition according to claim 6.

9. An article comprising the epoxy composition of claim 6.

10. The article according to claim 9 , wherein the article is an insulating film, an epoxy film for semiconductor packaging, an adhesive film, a build-up film, a substrate film, or an epoxy encapsulant.

Images