KR20230171848A - Tetramethylbiphenol epoxy resin and method for preparing the same - Google Patents

Abstract

The present invention relates to a tetramethylbiphenol-type epoxy resin and a manufacturing method thereof. More specifically, the present invention relates to a tetramethylbiphenol-type epoxy resin manufacturing process by adding a purification process using carboxylic acid to the tetramethylbiphenol-type epoxy resin. The content of metal cations contained in the epoxy resin can be reduced, and thus the purity of the tetramethylbiphenol-type epoxy resin can be improved.

Description

Tetramethylbiphenol type epoxy resin and method for manufacturing same {TETRAMETHYLBIPHENOL EPOXY RESIN AND METHOD FOR PREPARING THE SAME}

The present invention relates to a high-purity tetramethylbiphenol-type epoxy resin and a method for producing the same.

Epoxy resins are used for various purposes due to their excellent curing properties and ease of handling. In particular, when the epoxy resin is cured, a cured product with excellent mechanical properties, heat resistance, or electrical properties can be formed, and is used in a wide range of fields such as adhesives, paints, and electrical and electronic materials.

Materials used in the field of electrical and electronic materials require low dielectric constant and electrical insulation properties. In the field of semiconductor sealing materials among the electrical and electronic materials fields, tetramethylbiphenol-type epoxy resin is attracting attention as a sealing material with high added value.

The tetramethylbiphenol-type epoxy resin has excellent heat resistance and moisture absorption resistance due to its rigid tetramethylbiphenyl skeleton. In addition, since the tetramethylbiphenol-type epoxy resin has a low melt viscosity at 150°C, a semiconductor filler with a high filling rate can be implemented.

As epoxy resins are widely used in various fields, a higher level of quality is required for epoxy resins.

As one of the ways to improve the quality of epoxy resin, various research is being conducted on technology to increase the purity of epoxy resin by reducing the content of impurities.

Japanese Patent Laid-Open No. 1998-147629 discloses an epoxy resin with improved reliability by reducing the amount of hydrolyzable chlorine formed from a catalyst used in producing an epoxy resin. However, the possibility that various metal cations other than hydrolyzable chlorine may be detected in the epoxy resin cannot be ruled out, and when epoxy resins containing the metal cations are applied to the field of electrical and electronic materials, including semiconductor fillers, performance deterioration may occur. It may be possible.

Therefore, there is a need to develop technology that can reduce the content of metal cations that can be generated from catalysts or basic substances used in the epoxy resin manufacturing process.

Japanese Patent Publication No. 1998-147629

The present inventors conducted various studies to solve the above problems, and as a result, when a purification process using carboxylic acid was performed after producing tetramethylbiphenol-type epoxy resin, the final manufactured tetramethylbiphenol-type epoxy resin It was confirmed that the content of metal cations contained in the resin was significantly reduced, and a high-purity tetramethylbiphenol-type epoxy resin was produced.

Therefore, the purpose of the present invention is to provide a high-purity tetramethylbiphenol-type epoxy resin and a method for producing the same.

In addition, another object of the present invention is to provide an epoxy resin composition containing the high purity tetramethylbiphenol type epoxy resin.

The present invention is a tetramethylbiphenol-type epoxy resin represented by the following formula (1), wherein the content of metal cations contained in the tetramethylbiphenol-type epoxy resin is 2,000 ppb or less, and the metals include calcium, iron, sodium, and magnesium. It provides a tetramethylbiphenol-type epoxy resin containing at least one member selected from the group consisting of potassium, manganese, aluminum ammonium, and lithium:

<Formula 1>

In Formula 1, n is an integer from 0 to 5.

The present invention also relates to (S1) reacting 1.6 to 20 moles of epichlorohydrin, represented by Formula 3, with respect to 1 mole of tetramethylphenol, represented by Formula 2 below, to obtain Formula 4 below: forming the indicated halohydrin resin,

<Formula 2>

,

<Formula 3>

,

<Formula 4>

In Formula 4, n is an integer from 0 to 5;

(S2) reacting the halohydrin resin prepared in step (S1) with an alkali metal hydroxide to synthesize a tetramethylbiphenol-type epoxy resin represented by the following formula (1),

<Formula 1>

.

In Formula 1, n is an integer from 0 to 5; and

(S3) purifying the tetramethylbiphenol-type epoxy resin synthesized in step (S2) with an aqueous carboxylic acid solution to remove metal cations; providing a method for producing a tetramethylbiphenol-type epoxy resin comprising: do.

The present invention also provides an epoxy resin composition containing the tetramethylbiphenol-type epoxy resin and a curing agent.

The present invention also provides a cured product containing the above epoxy resin composition.

According to the present invention, the content of metal cations in a high-purity tetramethylbiphenol-type epoxy resin is significantly reduced, thereby lowering the dielectric constant, and thus the electrical insulation properties can be improved. Accordingly, it can exhibit excellent performance when applied in the field of electrical and electronic materials that require low dielectric constant and electrical insulation properties, especially in the field of semiconductor encapsulation materials.

Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

Terms or words used in this specification and claims should not be construed as limited to their ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.

Tetramethylbiphenol type epoxy resin

The present invention relates to a high-purity tetramethylbiphenol-type epoxy resin with a reduced content of metal cations.

The tetramethylbiphenol type epoxy resin is represented by the following formula (1):

<Formula 1>

In Formula 1, n is an integer from 0 to 5.

In general, metal cations may remain in the tetramethylbiphenol-type epoxy resin due to raw materials such as catalysts used in the synthesis process. The metal cation acts as an impurity and may cause performance degradation when applied to the electrical/electronic materials field, etc., so it is desirable to minimize the content of the metal cation.

The content of metal cations contained in the high-purity tetramethylbiphenol-type epoxy resin according to the present invention may be 2,000 ppb or less. The smaller the content of the metal cation is within the above range, the higher the purity. If it exceeds 2,000 ppb, the purity may decrease and the electrical conductivity may increase, making it difficult to use it in electrical and electronic devices. Specifically, the content of the metal cation may be 2,000 ppb or less, 1,700 ppb or less, 1,500 ppb or less, and 1,000 ppb or less. The lower limit of the metal cation content is not particularly limited and may be 0 ppb or more, 5 ppb or more, or 10 ppb or more. The content of the metal cation may be measured by inductively coupled plasma mass spectrometry (ICP-MS).

The metal may include one or more selected from the group consisting of calcium, iron, sodium, magnesium, potassium, manganese, aluminum ammonium, and lithium. In particular, the tetramethylbiphenol epoxy resin may include sodium as the metal, and the content of the sodium cation in the tetramethylphenol type epoxy resin may be 1,000 ppb or less. The smaller the sodium cation content within the above range, the higher the purity, and when the sodium cation content exceeds the 1,000 ppb range, when applied to the field of electrical and electronic materials including semiconductor encapsulants, dielectric properties are reduced. It can cause problems. Specifically, the content of the sodium cation may be 1,000 ppb or less, 900 ppb or less, 700 ppb or less, 500 ppb or less, or 300 ppb or less. The lower limit of the sodium cation content is not particularly limited and may be 0 ppb or more, 5 ppb or more, or 10 ppb or more. The content of sodium cations may be measured by inductively coupled plasma mass spectrometry (ICP-MS).

In the present invention, the epoxy equivalent weight of the tetramethylbiphenol-type epoxy resin may be 178 g/eq to 255 g/eq, and specifically, the epoxy equivalent weight is 178 g/eq or more, 180 g/eq or more, 183 g/eq or more. It may be more than g/eq or more than 185 g/eq, less than 200 g/eq, less than 220 g/eq, less than 240 g/eq, or less than 255 g/eq. The epoxy equivalent may be set in consideration of ease of handling when the tetramethylbiphenol-type epoxy resin is used for a semiconductor encapsulation material, and handling may be easiest within the epoxy equivalent range.

Manufacturing method of tetramethylbiphenol type epoxy resin

The present invention also relates to a method for producing the above tetramethylbiphenol type epoxy resin, (S1) tetramethylphenol (4,4'-bishydroxy-3,3',5) represented by the following formula (2) For 1 mole of 5'-tetramethylbiphenyl), 1.6 to 20 moles of epichlorohydrin represented by the following formula 3 are reacted to form a halohydrin resin represented by the following formula 4. steps to do,

<Formula 2>

,

<Formula 3>

,

<Formula 4>

In Formula 4, n is an integer from 0 to 5;

(S2) reacting the halohydrin resin prepared in step (S1) with an alkali metal hydroxide to synthesize a tetramethylbiphenol-type epoxy resin represented by the following formula (1),

<Formula 1>

In Formula 1, n is an integer from 0 to 5; and

(S3) purifying the tetramethylbiphenol-type epoxy resin synthesized in step (S2) by reacting it with an aqueous carboxylic acid solution to remove metal cations.

The tetramethylbiphenol-type epoxy resin of the present invention can be prepared by preparing the halohydrin resin represented by the above formula (4) according to a conventional production method and then reacting it with an alkali metal hydroxide, which is a strong alkali, and carboxyl By going through a purification process using acid, the content of specific metal cations can be reduced to produce high-purity tetramethylbiphenol-type epoxy resin.

Hereinafter, the method for producing tetramethylbiphenol-type epoxy resin according to the present invention will be described in more detail at each step.

In the present invention, in the step (S1), 1.6 to 20 moles of epichlorohydrin represented by Formula 3 are reacted with 1 mole of tetramethylphenol represented by Formula 2, A halohydrin resin represented by Chemical Formula 4 can be formed. Specifically, the amount of epichlorohydrin used may be 1.6 mol or more, 1.8 mol or more, 2.0 mol or more, 2.5 mol or more, 3.0 mol or more, 3.5 mol or more, 4.0 mol or more, 4.5 mol or more, or 5.0 mol or more, 10 It may be a mole or less, 12 moles or less, 14 moles or less, 16 moles or less, 18 moles or less, or 20 moles or less. If the amount of epichlorohydrin used is less than 1.6 mole, the halohydrin resin may not be sufficiently formed, and if it is more than 20 mole, the remaining epichlorohydrin may increase and production efficiency may decrease. That is, when the amount of epichlorohydrin used is within the above range, it is easy to control the reaction and improve production efficiency.

Specifically, the reaction may be carried out under a catalyst after mixing the tetramethylphenol and epichlorohydrin with an organic solvent.

The catalyst may be a quaternary ammonium salt including tetramethylammonium chloride and/or tetraethylammonium bromide; tertiary amines including benzyldimethylamine and/or 2,4,6-tris(dimethylaminomethyl)phenol; imidazoles including 2-ethyl-4-methylimidazole and/or 2-phenylimidazole; Phosphonium salts including ethyltriphenylphosphonium iodide; and phosphines including triphenylphosphine; and may include one or more types selected from the group consisting of.

Additionally, the organic solvent may include alcohols including ethanol and/or isopropanol; Ketones including acetone and/or methyl ethyl ketone; ethers including dioxane and/or ethylene glycol dimethyl; Glycol ethers including methoxypropanol; and an aprotic polar solvent including dimethyl sulfoxide and/or dimethyl formamide; it may contain one or more organic solvents selected from the group consisting of, and may especially contain an inert organic solvent.

Additionally, in order to promote the reaction, a water-soluble solvent such as water may be mixed together.

In addition, the reaction temperature at which the reaction is performed may be 50°C to 150°C. Specifically, the reaction temperature may be 50°C or higher, 55°C or higher, or 60°C or higher, and 80°C or lower, 100°C or lower, or 120°C or lower. Or it may be 150°C or lower. If the reaction temperature is less than 50°C, the reaction does not proceed smoothly, and if it exceeds 150°C, a high molecular weight is generated and the desired epoxy equivalent may not be obtained.

In the present invention, in the step (S2), the halohydrin resin synthesized in the step (S1) is reacted with an alkali metal hydroxide to form a tetramethylbiphenol-type epoxy resin represented by Formula 1.

The alkali metal hydroxide may be a strong alkali, for example, sodium hydroxide, calcium hydroxide, or potassium hydroxide, and may be used in the reaction in the form of an aqueous solution.

1.0 mole to 4.0 mole of the alkali metal hydroxide may be reacted per 1.0 mole of the halohydrin resin. Specifically, the alkali metal hydroxide may be 1.0 mole or more, 1.2 mole or more, or 1.5 mole or more, 2.5 mole or less, 3.0 mole or more. It may be less than or equal to 3.5 moles or less than or equal to 4.0 moles. If the alkali metal hydroxide is less than 1.0 mol, it is difficult to produce an epoxy resin produced by combining hydroxyl and chlorine functional groups, and the reaction time may take a long time, which may reduce productivity. If the alkali metal hydroxide is more than 4.0 mol, impurities, that is, high molecular weight, are generated due to side reactions. It may be difficult to manufacture the tetramethylbiphenol-type epoxy resin represented by Chemical Formula 1, and the use of water during the washing process to remove alkali metals may increase, which may cause problems with economic feasibility.

During the reaction, the reaction temperature may be 40°C to 150°C. Specifically, the reaction temperature may be 40°C or higher, 50°C or higher, 60°C or higher, or 70°C or higher, 90°C or lower, 100°C or lower, 110°C or higher. It may be below ℃, below 130℃ or below 150℃. If the reaction temperature is less than 40°C, the reaction may not proceed or the reaction time may be prolonged and process efficiency may be reduced, and if the reaction temperature is above 150°C, a side reaction may proceed.

Additionally, the reaction may be performed under normal pressure or reduced pressure.

In addition, the reaction may be carried out while maintaining the reaction temperature as necessary, azeotroping the reaction solution, cooling the volatilizing vapor, separating the obtained condensate into oil/water, and dehydrating the oil excluding water by returning it to the reaction system. It may be possible.

In order to suppress rapid reaction, the alkali metal hydroxide may be added for 0.1 to 8 hours to proceed with the reaction. Specifically, the reaction time may be 0.1 hour or more, 0.5 hour or more, or 1.0 hour or more, and 2 hours or less. , may be 4 hours or less, 6 hours or less, or 8 hours or less. If the reaction time is less than 0.1 hours, the reaction progresses rapidly and it is difficult to control the reaction temperature, so side reactions may occur. If the reaction time is more than 8 hours, the reaction time may become too long and process efficiency may decrease.

After the reaction is completed, by-products, unreacted products, or impurities are removed by washing with water and removing the water layer, thereby producing the tetramethylbiphenol-type epoxy resin represented by Formula 1. Alternatively, by-products, unreacted substances, or impurities may be removed by filtration or fractionation or reduced-pressure distillation.

In the present invention, in the step (S3), the tetramethylbiphenol-type epoxy resin synthesized in the step (S2) can be purified by reacting it with an aqueous carboxylic acid solution to remove metal cations.

As described above in step (S2), the prepared tetramethylbiphenol-type epoxy resin is washed with water, filtered, fractionated, or distilled under reduced pressure to remove by-product salts, unreacted products, or impurities, and then further purified with an aqueous carboxylic acid solution. Metal cations can be removed.

Most of the metal cations may originate from catalysts or alkali metal hydroxides used in the manufacturing process of the tetramethylbiphenol-type epoxy resin. When washing the tetramethylphenol-type epoxy resin with the aqueous carboxylic acid solution, the carboxylic acid combines with the metal cation to form a salt, and after the salt containing the metal cation moves to the water layer, the water layer By removing, a purification process in which metal cations contained in the water layer are removed can be performed.

In this way, if the purification process using the aqueous carboxylic acid solution is repeated several times, the content of metal cations contained in the tetramethylbiphenol-type epoxy resin can be reduced, thereby producing a high-purity tetramethylbiphenol-type epoxy resin.

The carboxylic acids include oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adolfgan, azela, sebacic acid, succinic acid, malic acid, glataric acid, malonic acid, and pimelic acid. , and suberic acid. Among the carboxylic acids, oxalic acid with a large amount of carboxylic acid in the molecule may be preferable.

In addition, the concentration of the carboxylic acid aqueous solution may be 1% to 50%, and specifically, the concentration of the carboxylic acid aqueous solution may be 1% or more, 5% or more, or 10% or more, and 20% or less, 30% or less. , may be 40% or less or 50% or less. If the concentration of the carboxylic acid aqueous solution is less than 1%, the number of cleaning processes increases, resulting in increased wastewater generation, which reduces economic efficiency and may cause environmental problems. If it exceeds 50%, the epoxy resin may precipitate or carboxylic acid may be formed. It is difficult for salts of acids and metal cations to move smoothly into the water layer, which may reduce purification efficiency.

Tetramethylbiphenol type epoxy resin composition

The present invention also relates to a tetramethylbiphenol-type epoxy resin composition comprising the tetramethylbiphenol-type epoxy resin and a curing agent. In addition, the tetramethylbiphenol-type epoxy resin composition may further include at least one selected from the group consisting of an additional epoxy resin, a curing accelerator, and an inorganic filler, and the additional epoxy resin is a tetramethylbiphenol-type epoxy resin and may be a different epoxy resin.

As described above, the tetramethylbiphenol-type epoxy resin composition according to the present invention contains a high-purity tetramethylbiphenol-type epoxy resin with a reduced content of metal cations, and therefore has not only heat resistance and moisture absorption resistance, but also low electrical conductivity and low dielectric constant. It can be applied to electrical and electronic materials, especially semiconductor encapsulation materials that require insulating properties.

The tetramethylbiphenol-type epoxy resin composition can be prepared by mixing the raw materials.

Tetramethylbiphenol type epoxy resin

In the present invention, the tetramethylbiphenol-type epoxy resin may be a high-purity tetramethylbiphenol-type epoxy resin represented by Chemical Formula 1 as described above.

The tetramethylbiphenol-type epoxy resin may be included in an amount of 10% to 30% by weight based on the total weight of the composition. Specifically, the content of the tetramethylbiphenol-type epoxy resin is 10% by weight or more and 12% by weight. It may be more than or equal to 14% by weight, and may be less than or equal to 16% by weight, less than or equal to 18% by weight, or less than or equal to 20% by weight. If the content of the tetramethylbiphenol type epoxy resin is less than 10% by weight, the electrical properties, heat resistance, and moisture absorption resistance of the composition and the cured product as described later may be reduced, and if it is more than 20% by weight, other components in the composition, such as curing agent, etc. Because the content is relatively low, problems such as difficulty in forming a cured product may occur.

hardener

In the present invention, the curing agent may contribute to the crosslinking reaction and/or chain length extension reaction between epoxy groups of the tetramethylbiphenol-type epoxy resin, thereby enabling the formation of a cured product.

The curing agent may be included in an amount of 5% to 20% by weight based on the total weight of the composition. Specifically, the content of the curing agent may be 5% by weight or more, 8% by weight or more, or 10% by weight or more, and 15% by weight. It may be 18% by weight or less or 20% by weight or less. If the content of the curing agent is less than 5% by weight, it may be difficult to form a cured product because the crosslinking reaction and/or chain length extension reaction between epoxy groups is not sufficient, and if it is more than 20% by weight, excessive curing may occur, resulting in loss of electrical properties, heat resistance, or Physical properties such as moisture absorption resistance may actually worsen.

The curing agent is not particularly limited, and any curing agent generally known as an epoxy resin can be used. For example, the curing agent may include one or more selected from the group consisting of phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and imidazoles. The amine-based curing agent may include one or more selected from the group consisting of a curing agent, aliphatic amine, polyether amine, alicyclic amine, aromatic amine, and tertiary amine.

Among these, by including a phenol-based curing agent, the epoxy resin composition of the present invention can obtain excellent heat resistance, stress resistance, moisture absorption resistance, flame retardancy, etc., so it is preferable to include a phenol-based curing agent as the curing agent. Additionally, from the viewpoint of heat resistance and the like, it is preferable to include an acid anhydride-based curing agent or an amide-based curing agent. Additionally, the use of imidazoles is also preferable from the viewpoint of sufficiently advancing the curing reaction and improving heat resistance.

Specific examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, and tea. Odiphenols, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, trisphenol methane type Resin, naphthol novolac resin, brominated bisphenol A, brominated phenol novolak resin, etc., various polyhydric phenols, various phenols, and various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal. Polyhydric phenol resins obtained, polyhydric phenol resins obtained by condensation reaction of xylene resins and phenols, cocondensation resins of heavy oils or pitches, phenols, and formaldehydes, phenol·benzaldehyde·xylylenedimethoxide polycondensate, phenol·benzaldehyde · Various phenol resins such as xylylene dihalide polycondensate, phenol·benzaldehyde·4,4'-dimethoxide biphenyl polycondensate, and phenol·benzaldehyde·4,4'-dihalide biphenyl polycondensate. You can. These phenol-based curing agents may be used alone or two or more types may be used in combination in any combination and mixing ratio.

Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Examples of aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, and iminobispropylamine. , bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, etc. can be used, and polyetheramines include , triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamine, etc., and alicyclic amines include isophorone diamine, methenediamine, and N-amino. Ethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro (5,5)Undecane, norbornediamine, etc. can be used, and finally, as aromatic amines, tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o -Phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4, 4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α '-bis(4-aminophenyl)-p-diisopropylbenzene, etc. can be used. The amine-based curing agents mentioned above may be used alone, or two or more types may be used in combination in any combination and mixing ratio. The above-mentioned amine-based curing agent is preferably used so that the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all epoxy resin components contained in the epoxy resin composition is in the range of 0.8 to 1.5. If it is within this range, it is preferable because it becomes difficult for unreacted epoxy groups or functional groups of the curing agent to remain.

As tertiary amines, 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. can be used. You can. Tertiary amines may be used alone or two or more types may be used in any combination and mixing ratio. The above-mentioned tertiary amine is preferably used so that the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all epoxy resin components contained in the epoxy resin composition is in the range of 0.8 to 1.5. If it is within this range, it is preferable because it becomes difficult for unreacted epoxy groups or functional groups of the curing agent to remain.

Examples of acid anhydride-based curing agents include acid anhydrides and modified products of acid anhydrides. Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, and poly(ethyl). Octadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic acid anhydride, trialkyltetrahydrophthalic anhydride, methyl Cyclohexenedicarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, hetic acid anhydride, nadic acid anhydride, methylnadic acid anhydride, 5-(2,5-dioxotetrahydro) -3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride , 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, etc.

Examples of amide-based curing agents include dicyandiamide and its derivatives, polyamide resins, and the like.

Examples of imidazole include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimelli Tate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2 ,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methyl Midazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazolisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole, epoxy resins, and adducts of the imidazoles.

additional epoxy resin

In the present invention, the additional epoxy resin may mean an epoxy resin different from the tetramethylbiphenol-type epoxy resin. By including such an additional epoxy resin, the heat resistance, stress resistance, moisture absorption resistance, flame retardancy, etc. of the tetramethylbiphenol type epoxy resin composition can be further improved.

The additional epoxy resin may be included in an amount of 5% to 20% by weight based on the total weight of the composition. Specifically, the content of the additional epoxy resin may be 5% by weight or more, 6% by weight or more, or 7% by weight or more. , may be 10% by weight or less, 15% by weight or less, or 20% by weight or less. If the content of the additional epoxy resin is less than 5% by weight, the effect of additionally improving heat resistance, stress resistance, moisture absorption resistance, or flame retardancy may be minimal, and if it exceeds 20% by weight, the content of other components may be relatively reduced, so the above range It can be used in appropriate amounts.

For example, the additional epoxy resin is bisphenol A type epoxy resin, biphenyl epoxy resin, trisphenolmethane type epoxy resin, anthracene type epoxy resin, phenol modified xylene resin type epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diiso Propylidene resorcin type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcin type epoxy resin, methylresorcin. New epoxy resins, biphenol-type epoxy resins, tetramethylbiphenol-type epoxy resins other than the tetramethylbiphenol-type epoxy resin represented by the above formula (1), tetramethylbisphenol F-type epoxy resins, and dihydroxydiphenyl ether-type epoxy resins. , epoxy resins derived from thiodiphenols, dihydroxynaphthalene type epoxy resins, dihydroxyanthracene type epoxy resins, dihydroxydihydroanthracene type epoxy resins, dicyclopentadiene type epoxy resins, and dihydroxystilbenes. Derivatized epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type Epoxy resin, terpene phenol type epoxy resin, dicyclopentadiene phenol type epoxy resin, epoxy resin derived from a condensate of phenol and hydroxybenzaldehyde, epoxy resin derived from a condensate of phenol and crotonaldehyde, phenol and glyoxal. Epoxy resins derived from condensates, epoxy resins derived from cocondensation resins of heavy oils or pitches with phenols and formaldehydes, epoxy resins derived from diaminodiphenylmethane, epoxy resins derived from aminophenols, xylenediamine Examples include epoxy resins derived from methylhexahydrophthalic acid, epoxy resins derived from dimer acid, and the like. These may be used alone or two or more types may be used in any combination and mixing ratio.

cure accelerator

In the present invention, the curing accelerator shortens the curing time and lowers the curing temperature, making it easier to obtain a desired cured product.

The curing accelerator may be included in an amount of 0.01% by weight to 1% by weight based on the total weight of the composition. Specifically, the content of the curing accelerator may be 0.01% by weight or more, 0.03% by weight or more, or 0.05% by weight or more, and 0.5% by weight or more. It may be less than 0.8% by weight or less than 1% by weight. If the content of the curing accelerator is less than 0.01% by weight, the curing accelerator effect may be minimal, and if it is more than 20% by weight, excessive curing may occur and the physical properties of the composition may be reduced, so an appropriate amount can be used within the above range.

The curing accelerator is not particularly limited, and specific examples include organic phosphines, phosphorus-based compounds such as phosphonium salts, tetraphenyl boron salts, organic acid dihydrazide, boron amine complexes, and the like.

Examples of phosphorus-based compounds that can be used as a curing accelerator include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl·alkoxyphenyl)phosphine, Tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl) ) Organic phosphines such as phosphine, trialkyl phosphine, dialkylaryl phosphine, and alkyl diaryl phosphine, or complexes of these organic phosphines and organic boron, or these organic phosphines and maleic anhydride, 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzo Examples include quinone compounds such as quinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, and compounds obtained by adding compounds such as diazophenylmethane.

Among the above curing accelerators, organic phosphines and phosphonium salts are preferable, and organic phosphines are most preferable. In addition, the curing accelerator may be used alone among those listed above, or two or more types may be mixed and used in any combination and ratio.

inorganic filler

In the present invention, the inorganic filler has the function of preventing cracks by making the thermal expansion coefficient closer to that of the internal silicon chip or lead frame when applying the composition as a semiconductor encapsulating material and reducing the amount of moisture absorption of the entire semiconductor encapsulating material. can do.

The content of the inorganic filler may be 50% to 70% by weight based on the weight of the composition, considering its utility as a semiconductor encapsulation material. Specifically, the content of the inorganic filler may be 50% by weight or more, 55% by weight. It may be more than 60% by weight or more than 60% by weight, and less than 65% by weight, less than 68% by weight, or less than 70% by weight.

Additionally, the inorganic filler is not particularly limited as long as it is one commonly used in the art. For example, the inorganic filler may include crystalline silica.

Coupling agent

In the present invention, the coupling agent can improve the adhesion between the matrix tetramethylbiphenol-type epoxy resin and the inorganic filler, and thus the coupling agent can be used in combination with the inorganic filler.

Considering the effect of improving the adhesion of the inorganic filler, the coupling agent may be used in an amount of 1% to 10% by weight based on the total weight of the composition. Specifically, the content of the coupling agent is 1% by weight or more, 3% by weight. It may be more than % or more than 5% by weight, and it may be less than 8% by weight or less than 10% by weight.

Examples of the coupling agent include silane coupling agent and titanate coupling agent.

Silane coupling agents include, for example, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, Amino silanes such as γ-ureidopropyltriethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, and vinyltris (β-methoxysilane). Vinyl silanes such as ethoxy) silane, vinyl trimethoxy silane, vinyl triethoxy silane, and γ-methacryloxypropyl trimethoxy silane, as well as epoxy-based, amino-based, and vinyl-based polymer-type silanes. You can.

As titanate coupling agents, for example, isopropyltriisostearoyl titanate, isopropyltri(N-aminoethyl·aminoethyl)titanate, isopropylbis(dioctylphosphate)titanate, and tetraisopropylbis(di). Octylphosphite)titanate, tetraoctylbis(ditridecylphosphite)titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctyl) Pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, etc. are mentioned. These coupling agents may be used alone, or two or more types may be mixed and used in any combination and ratio. When a coupling agent is used in the epoxy resin composition of the present invention, the compounding amount is preferably 0.1 to 3.0 parts by weight based on 100 parts by weight of all epoxy resin components. If the compounding amount of the coupling agent is less than the above range, the effect of improving the adhesion between the epoxy resin as a matrix and the inorganic filler by blending the coupling agent decreases. On the other hand, if the compounding amount of the coupling agent is more than the above range, the effect of improving the adhesion between the inorganic filler and the epoxy resin that is the matrix is reduced. It is unsuitable as there is a high possibility that the ring material will bleed out.

other ingredients

Components other than those mentioned above can be added to the tetramethylbiphenol type epoxy resin composition of the present invention. Other components include, for example, flame retardants, plasticizers, mold release agents, reactive diluents, pigments, etc., and can be blended appropriately as needed. In order to improve the properties required for the cured product, the properties of the cured product can be secured by adding appropriate materials.

hardened material

The present invention also relates to a cured product manufactured by curing a composition containing the tetramethylbiphenol type epoxy resin, wherein the cured product is excellent in heat resistance, moisture absorption resistance, heat resistance, especially low dielectric constant and electrical insulation properties. It has characteristics.

There are no particular limitations on the method for curing the tetramethylbiphenol-type epoxy resin composition of the present invention, but usually a cured product can be obtained through a thermosetting reaction by heating. During the thermal curing reaction, it is desirable to appropriately select the curing temperature depending on the type of curing agent used. For example, the curing temperature may typically be 130°C to 180°C. Additionally, the reaction time may be 0.1 to 20 hours, specifically 0.1 hour or more, 0.5 hour or more, or 1 hour or more, and may be 10 hours or less, 15 hours or less, or 20 hours or less. If the reaction time is below the above range, it is difficult for the curing reaction to proceed sufficiently, making it difficult to secure desirable physical properties. If the reaction time is above the above range, problems may occur due to deterioration due to heating and increased energy loss during heating.

Preferred examples are presented below to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is clear to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that changes and modifications fall within the scope of the attached patent claims.

In the following examples and comparative examples, when synthesizing tetramethylbiphenol-type epoxy resin, a purification process was performed using carboxylic acid or water as shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Refining process carboxylic acid 10% oxalic acid aqueous solution 15% oxalic acid aqueous solution 20% oxalic acid aqueous solution - water

In addition, in the following Examples and Comparative Examples, when manufacturing the tetramethylbiphenol-type epoxy resin composition, the manufacturing process was performed according to the composition as shown in Table 2 below.

Unit: weight% Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tetramethylbiphenol type
epoxy resin 15 15 15 15 15 addition
epoxy resin Bisphenol A type epoxy resin 7 7 - 7 - Biphenyl Epoxy Resin - - 7 - 7 hardener Phenol novolak 12.9 12.9 12.9 12.9 12.9 Hardening accelerator Triphenylphosphine 0.1 0.1 0.1 0.1 0.1 inorganic filler crystalline silica 65 65 65 65 65 Sum 100 100 100 100 100

Example 1

1-1. Synthesis of tetramethylbiphenol type epoxy resin

300 g of tetramethyl biphenol, 1386 g of epichlorohydrin, 554 g of isopropyl alcohol, and 191 g of water were added to a 3L four-necked flask, heated to 65°C to dissolve, and then 240g of a 50% aqueous sodium hydroxide solution was added dropwise over 180 minutes. . After completion of the dropwise addition, the reaction was completed by maturing at 65°C for 1 hour, water was added, allowed to stand, and by-product salts and excess sodium hydroxide were removed from the separated aqueous layer. Afterwards, the temperature was raised under reduced pressure, the remaining epichlorohydrin and isopropyl alcohol were distilled off, and an epoxy resin was synthesized.

The epoxy resin was dissolved in 600 g of methyl isobutyl ketone (MIBK), and 15 g of 50% potassium hydroxide aqueous solution was added and reacted for 1.5 hours at a temperature of 80°C. Afterwards, water was added and washed until pH reached 7, and the water layer was removed to synthesize tetramethylbiphenol-type epoxy resin.

As described in Table 1, the tetramethylbiphenol-type epoxy resin was washed three times using the same amount of 10% oxalic acid aqueous solution as the synthesized tetramethylbiphenol-type epoxy resin to remove metal cations. Afterwards, the pressure was reduced to 40 torr or less at a temperature of 150°C to completely remove residual methyl isobutyl ketone, and a purification process was performed.

1-2. Manufacturing of tetramethylbiphenol type epoxy resin composition

According to the composition as shown in Table 2, prepare a tetramethylbiphenol-type epoxy resin composition by mixing the tetramethylbiphenol-type epoxy resin synthesized in 1-1, additional epoxy resin, curing agent, curing accelerator, and inorganic filler. did.

1-3. Hardened product manufacturing

A cured product was prepared by molding and curing the tetramethylbiphenol-type epoxy resin composition prepared in 1-2 above.

The molding and curing process was performed using press equipment (BUEHLER, SimpliMet 1000 Automatic Mounting Press equipment). Specifically, the molding process was performed at a temperature of 180°C and a pressure of 80 bar. After that, it was cured for 20 minutes, cooled with water for 10 minutes, and then post-cured at 180°C for 2 hours to perform the curing process.

Example 2

Tetramethylbiphenol-type epoxy resin, tetramethylbiphenol-type epoxy resin composition, and cured product were prepared in the same manner as in Example 1, except that the product was washed twice with a 15% aqueous oxane solution.

Example 3

Tetramethylbiphenol-type epoxy resin, tetramethylbiphenol-type epoxy resin composition, and cured product were prepared in the same manner as in Example 1, except that they were washed twice with a 20% aqueous oxane solution.

Comparative Example 1

Tetramethylbiphenol-type epoxy resin, tetramethylbiphenol-type epoxy resin composition, and cured product were prepared in the same manner as in Example 1, except that the purification process of washing with 10% aqueous oxalic acid was not performed.

Comparative Example 2

A tetramethylbiphenol-type epoxy resin, a tetramethylbiphenol-type epoxy resin composition, and a cured product were prepared in the same manner as in Example 1, except that the product was washed three times with water instead of a 10% aqueous oxalic acid solution.

Experimental Example 1: Physical property evaluation

In order to evaluate the physical properties of the tetramethylbiphenol-type epoxy resin prepared in Examples 1 to 3 and Comparative Examples 1 to 2 and the cured product prepared using the same, the dielectric constant, dielectric loss, glass transition temperature, Moisture absorption rate and total ion amount were measured.

(1) Dielectric Constant (D _k ) and Dielectric Loss (Dissipation Factor, D _f )

Dielectric constant and dielectric loss were measured by the JIS-C-6481 method. Measurements were made using an Agilent E4991A RF Impedance/Material analyzer.

The lower the measured dielectric constant and dielectric loss values, the better the electrical properties of the cured product were evaluated.

(2) Glass transition temperature (Tg) measurement

Glass transition temperature (Tg) was measured using differential scanning calorimetry (DSC) (measurement conditions: temperature rise of 10°C per minute, range of 30 to 250°C).

The higher the measured glass transition temperature, the higher the heat resistance of the cured product was evaluated.

(3) Measurement of moisture absorption (W/A, wt%)

The moisture absorption rate was obtained by leaving the cured product in boiling water at 100°C for 2 hours and then calculating the weight increase rate (wt%).

The lower the measured moisture absorption rate, the better the physical properties such as moisture absorption resistance of the cured product were evaluated.

(4) Quantification of sodium ion amount and total metal ion amount (ppb)

The amount of metal cations in the tetramethylbiphenol-type epoxy resin synthesized in Examples 1 to 3 and Comparative Examples 1 to 2 was quantified using inductively coupled plasma mass spectrometry (ICP-MS). The metals include calcium, iron, sodium, magnesium, potassium, manganese, aluminum ammonium, and lithium, and the sum of these metal cations was quantified and expressed as the total amount of metal ions.

The lower the quantified total ion amount, the higher the purity of the tetramethylbiphenol-type epoxy resin was evaluated.

Evaluation items Example 1 Example 2 Example 3 Comparative Example 1 Comparative example 2 Dielectric constant (D _k ) 3.25 3.21 3.19 3.45 3.38 Dielectric loss (D _f ) 0.012 0.010 0.009 0.031 0.027 Glass transition temperature (Tg, ℃) 179.3 178.4 178.9 165.7 167.3 Moisture absorption rate (W/A, wt%) 0.25 0.24 0.26 0.37 0.31 Sodium ion amount (ppb) 900 200 50 3,500 2,000 Total metal ion amount (ppb) 1000 900 700 6,300 5,400

As a result, as shown in Table 3, Examples 1 to 3 have relatively excellent electrical properties because the measured dielectric constant (D _k ) and dielectric loss (D _f ) of the cured product are lower than those of Comparative Examples 1 to 2. It can be seen. In addition, Examples 1 to 3 have a higher glass transition temperature and good heat resistance characteristics compared to Comparative Examples 1 to 2, have a low moisture absorption rate and thus have good moisture absorption resistance, and have high purity due to the small sodium ion content and total metal ion amount. You can see that

From this, when synthesizing the tetramethylbiphenol-type epoxy resin and performing a purification process using carboxylic acid, a high-purity tetramethylbiphenol-type epoxy resin could be obtained. In addition, the cured product manufactured using the high-purity tetramethylbiphenol-type epoxy resin exhibits excellent electrical properties, heat resistance, and moisture absorption resistance, and is used in the field of electrical and electronic materials that require low dielectric constant and electrical insulation properties, especially in the field of semiconductor encapsulation materials. It can be seen that it will be applicable to .

Although the present invention has been described above with limited examples and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following description will be provided by those skilled in the art in the technical field to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equivalence of the patent claims.

Claims (9)

A tetramethylbiphenol-type epoxy resin represented by the following formula (1):
<Formula 1>

(In Formula 1, n is an integer from 0 to 5)
The content of metal cations contained in the tetramethylbiphenol-type epoxy resin is 2,000 ppb or less,
The metals include calcium, iron, sodium, magnesium, potassium, manganese, aluminum ammonium and lithium,
The content of sodium cations contained in the tetramethylbiphenol-type epoxy resin is 1,000 ppb or less,
The tetramethylbiphenol-type epoxy resin is manufactured by a manufacturing method comprising the following steps (S1) to (S3):
(S1) For 1 mole of tetramethylphenol represented by the following formula 2, 1.6 to 20 moles of epichlorohydrin represented by the following formula 3 are reacted at 50°C to 150°C to obtain the following formula 4 Forming a halohydrin resin represented by,
<Formula 2>
,
<Formula 3>
,
<Formula 4>

(In Formula 4, n is an integer from 0 to 5);
(S2) The halohydrin resin prepared in the step (S1) is reacted with an alkali metal hydroxide, and 1.0 to 4.0 moles of the alkali metal hydroxide are reacted per 1.0 mole of the halohydrin resin to obtain the product represented by Formula 1. Synthesizing tetramethylbiphenol-type epoxy resin; and
(S3) Purifying the tetramethylbiphenol-type epoxy resin synthesized in step (S2) by reacting it with an aqueous carboxylic acid solution to remove metal cations. According to paragraph 1,
The tetramethylbiphenol-type epoxy resin has an epoxy equivalent weight of 178 g/eq to 255 g/eq. (S1) For 1 mole of tetramethylphenol represented by the following formula 2, 1.6 to 20 moles of epichlorohydrin represented by the following formula 3 are reacted at 50°C to 150°C to obtain the following formula 4 Forming a halohydrin resin represented by,
<Formula 2>
,
<Formula 3>
,
<Formula 4>

In Formula 4, n is an integer from 0 to 5;
(S2) reacting the halohydrin resin prepared in step (S1) with an alkali metal hydroxide to synthesize a tetramethylbiphenol-type epoxy resin represented by the following formula (1),
<Formula 1>

In Formula 1, n is an integer from 0 to 5; and
(S3) purifying the tetramethylbiphenol-type epoxy resin synthesized in step (S2) with an aqueous carboxylic acid solution to remove metal cations, but comprising: Manufacturing method. According to paragraph 3,
The carboxylic acids include oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, malic acid, glataric acid, malonic acid, A method for producing a tetramethylbiphenol-type epoxy resin, comprising at least one selected from the group consisting of pimelic acid and suberic acid. A tetramethylbiphenol-type epoxy resin composition comprising the tetramethylbiphenol-type epoxy resin of claim 1 or 2 and a curing agent. According to clause 5,
A tetramethylbiphenol-type epoxy resin composition, wherein the tetramethylbiphenol-type epoxy resin is contained in an amount of 10 to 30% by weight based on the total weight of the composition. According to clause 5,
A tetramethylbiphenol-type epoxy resin composition wherein the curing agent includes at least one selected from the group consisting of phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and imidazoles. According to clause 5,
The epoxy resin composition further includes at least one selected from the group consisting of additional epoxy resins, curing accelerators, and inorganic fillers,
A tetramethylbiphenol-type epoxy resin composition, wherein the additional epoxy resin is an epoxy resin different from the tetramethylbiphenol-type epoxy resin. A cured product containing the tetramethylbiphenol-type epoxy resin composition according to claim 5.