JP2017048388A - Epoxy resin, epoxy resin composition, cured product, and electric/electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tetramethylbiphenol type epoxy resin which has high crystallization speed and is excellent in productivity, and has a small amount of hydrolyzable chlorine and is excellent in electric characteristics; to provide an epoxy resin composition which contains the epoxy resin and has a low coefficient of elasticity and excellent heat resistance at high temperature and a cured product thereof; and to provide electric/electronic components including the epoxy resin composition.SOLUTION: An epoxy resin is represented by formula (1), and has a number average molecular weight (Mn) of 270-300 and/or a weight average molecular weight (Mw) of 370-610. In formula (1), n represents an integer of 0-10.SELECTED DRAWING: None

Description

  The present invention is a tetramethylbiphenol type epoxy resin having a high crystallization speed, excellent productivity, low hydrolyzable chlorine content and excellent electrical characteristics, and a low elastic modulus at high temperature and heat resistance, including this epoxy resin. The present invention relates to an excellent epoxy resin composition and a cured product. The present invention also relates to an electrical / electronic component comprising the epoxy resin composition.

  Epoxy resins are cured with various curing agents, and generally become cured products with excellent mechanical properties, heat resistance, electrical properties, etc., so a wide range of fields such as adhesives, paints, electrical and electronic materials, etc. It is used in. Particularly in the field of electrical and electronic materials, tetramethylbiphenol type epoxy resins are frequently used in semiconductor encapsulant applications because they can provide high added-value encapsulants.

  Patent Document 1 describes that a tetramethylbiphenol type epoxy resin was produced by a reaction of 4,4′-bishydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epichlorohydrin. There is no description about the number average molecular weight (Mn) and the weight average molecular weight (Mw), and these are all excluded from the present invention.

  Patent Document 2 describes a tetramethylbiphenol type epoxy resin having an epoxy equivalent of 190 g / eq or less and a hydrolyzable chlorine content of 500 ppm or less, specifically, an epoxy equivalent of 184 g / eq and a hydrolyzable chlorine content. Has been shown to produce a tetramethylbiphenol type epoxy resin having an epoxy equivalent of 182 g / eq and an amount of hydrolyzable chlorine of 230 ppm. Regarding the number average molecular weight (Mn) and the weight average molecular weight (Mw) There is no description.

Tetramethylbiphenol type epoxy resin has excellent heat resistance and moisture absorption resistance due to its rigid tetramethylbiphenyl skeleton, and its melt viscosity at 150 ° C is low, so it can be filled with a high filler as a semiconductor sealing material. While it is possible and effective in preventing wire flow during molding of a sealing material on a semiconductor, it has the following drawbacks.
That is, in crystallization important for the production of epoxy resins, conventional tetramethylbiphenol type epoxy resins cannot be said to be sufficient in productivity due to crystallization inhibition by tetramethyl groups, and have recently been demanded. In terms of low chlorination, the amount of hydrolyzable chlorine is not sufficient.

Patent Document 3 discloses a commercially available tetramethylbiphenol type epoxy resin (“jER YX4
000 ", epoxy equivalent 186, total organic halogen content 1180 ppm), in a mixed solvent of isobutyl ketone and dimethyl sulfoxide, by adding a KOH or NaOH / isopropanol solution and reacting at 70 ° C or 60 ° C, the epoxy equivalent Is 188 or 190, and an epoxy resin having a total organic chlorine content of 410 or 340 ppm is described, but the crystallization rate is not studied. Also, the total organic chlorine content is not sufficiently reduced. This Patent Document 3 also does not describe the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the epoxy resin, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) of jERYX4000 are those of the present invention. Out of range.

JP 58-039677 JP-A-10-147629 JP 2000-239346 A

  The object of the present invention is to provide a tetramethylbiphenol type epoxy resin having a high crystallization speed and excellent productivity, low hydrolyzable chlorine content and excellent electrical characteristics, and elasticity at high temperatures containing this epoxy resin. An object of the present invention is to provide an epoxy resin composition having a low rate and excellent heat resistance and a cured product thereof. Moreover, the subject of this invention is providing the electric / electronic component which consists of this epoxy resin composition.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, a tetramethylbiphenol type epoxy resin in which the molecular weight distribution and / or the epoxy equivalent is controlled within a specific range, and an epoxy resin composition containing this epoxy resin and a curing agent However, it has been found that the above problems can be solved, and the present invention has been completed.
That is, the gist of the present invention resides in the following [1] to [10].

[1] An epoxy resin represented by the following formula (1) and having a number average molecular weight (Mn) of 270 to 300.

(In the formula, n represents an integer of 0 to 10.)
[2] An epoxy resin represented by the following formula (1) and having a weight average molecular weight (Mw) of 370 to 610.

(In the formula, n represents an integer of 0 to 10.)
[3] An epoxy resin represented by the following formula (1), having a number average molecular weight (Mn) of 270 to 300 and a weight average molecular weight (Mw) of 370 to 610.

(In the formula, n represents an integer of 0 to 10.)
[4] The epoxy resin according to any one of [1] to [3], which has a melt viscosity at 150 ° C. of 0.3 Pa · s or less.
[5] The epoxy resin according to any one of [1] to [4], wherein the content of hydrolyzable chlorine is 90 ppm or less with respect to the epoxy resin.
[6] An epoxy resin composition containing 0.01 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy resin according to any one of [1] to [5].
[7] The epoxy resin composition according to [6], wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent.
[8] The epoxy resin composition according to [6] or [7], further comprising an epoxy resin different from the epoxy resin according to any one of [1] to [5].
[9] A cured product obtained by curing the epoxy resin composition according to any one of [6] to [8].
[10] An electrical / electronic component obtained by curing the epoxy resin composition according to any one of [6] to [8].

According to the present invention, a tetramethylbiphenol type epoxy resin having a high crystallization speed and excellent productivity, a low hydrolyzable chlorine content and excellent electrical characteristics, and the tetramethylbiphenol type epoxy resin are included. An epoxy resin composition and a cured product having a low elastic modulus at high temperature and excellent heat resistance are provided.
Since the epoxy resin composition of the present invention has the above-described effects, it can be applied particularly effectively to electrical / electronic components such as semiconductor encapsulants and laminates.

  Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless it exceeds the gist. Absent. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.

〔Epoxy resin〕
The epoxy resin of the present invention is a tetramethylbiphenol type epoxy resin represented by the following formula (1), has a high crystallization speed, excellent productivity, a small amount of hydrolyzable chlorine, and an appropriate melt viscosity. It is what you have.

(In the formula, n represents an integer of 0 to 10.)
Since the epoxy resin of the present invention has a high crystallization speed and excellent productivity, the production efficiency of the epoxy resin is good and the economy is good. In addition, since the amount of hydrolyzable chlorine is small, free chlorine when cured is reduced, thereby preventing wiring corrosion of electrical / electronic equipment and preventing troubles such as defective insulation. Furthermore, since it has an appropriate melt viscosity, it is excellent in handleability.

The number of epoxy groups in the tetramethylbiphenol type epoxy resin of the present invention represented by the formula (1) (hereinafter sometimes referred to as “epoxy resin (1)”) is shown as an epoxy equivalent described later.
Moreover, n in the said Formula (1) is an integer of 0-10, and an epoxy resin (1) is provided as a mixture of the several compound from which n differs in the range of n = 0-10.

[Weight average molecular weight (Mw)]
The epoxy resin (1) preferably has a Mw of 370 to 610 from the viewpoint of low hydrolyzable chlorine and excellent electrical properties, and more preferably 370 to 431 from the viewpoint of making the melt viscosity a good value. It is more preferable that it is 391-431 from a viewpoint of obtaining the more outstanding crystallization rate.
The mechanism by which the crystallization speed is improved by setting Mw within the above specific range is not clear, but when Mw is within the above range, it is represented by the formula (1) contained in the epoxy resin (1). It is considered that this is because crystallization is promoted by the oligomer component.
In addition, a weight average molecular weight (Mw) can be measured as a polystyrene conversion value by gel permeation chromatography.

[Number average molecular weight (Mn)]
The epoxy resin (1) preferably has a Mn of 270 to 300 from the viewpoint of low hydrolyzable chlorine and excellent electrical characteristics, more preferably 270 to 278 from the viewpoint of making the melt viscosity a good value, From the viewpoint of obtaining a more excellent crystallization rate, it is more preferably 271 to 278.

  Although the mechanism by which Mn is in the above specific range improves the crystallization rate is not clear, when Mn is in the above range, it is represented by the formula (1) contained in the epoxy resin (1). It is considered that this is because crystallization is promoted by the oligomer component.

In addition, a number average molecular weight (Mn) can be measured as a polystyrene conversion value by gel permeation chromatography.
It is known that Mw and Mn are calculated from the following equations.
Mw: Σ (Mi ^ 2 * Ni) / Σ (Mi * Ni) Mn: Σ (Mi * Ni) / Σ (Ni)
M is the molecular weight, N is the number of molecules, Mw is a weighted average using the molecular weight as a weight, and Mn is a simple arithmetic average. In general, low molecular weight epoxy resins are mainly composed of monomer components at the time of synthesis, and it is difficult to make a large difference in the values of Mw and Mn.
The difference between w and Mn increases.

[Preferred combination of Mn and Mw]
The epoxy resin (1) preferably has Mw of 370 to 610 and Mn of 270 to 300 from the viewpoint of low hydrolyzable chlorine and excellent electrical characteristics, and Mw of 370 from the viewpoint of improving the melt viscosity. ~ 431 and Mn are preferably 270 to 278, and Mw is more preferably 391 to 431 and Mn is more preferably 271 to 278 from the viewpoint of obtaining a better crystallization rate.
Although the mechanism by which Mn and Mw are within the above specific ranges and the crystallization speed is good is not clear, when Mn and Mw are within the above ranges, the above formula (1) contained in the epoxy resin (1) ( It is thought that crystallization is promoted by the oligomer component represented by 1).

[Epoxy equivalent]
The epoxy resin (1) preferably has an epoxy equivalent of 195 to 208 g / equivalent from the viewpoint of low hydrolyzable chlorine and excellent electrical characteristics, and 195 to 199 g / equivalent from the viewpoint of obtaining a good melt viscosity. More preferably, it is more preferably 196 to 199 g / equivalent from the viewpoint of obtaining a higher crystallization rate.
Although the mechanism by which the epoxide equivalent is in the above specific range makes the crystallization speed good is not clear, the epoxy equivalent (C) contained in the epoxy resin (1) is within the above range. It is considered that crystallization is promoted by the oligomer component represented by
In the present invention, “epoxy equivalent” is defined as “the mass of an epoxy resin containing one equivalent of an epoxy group” and can be measured according to JIS K7236.

[Preferred combination of Mn and epoxy equivalent]
From the viewpoint of epoxy resin (1) having low hydrolyzable chlorine and excellent electrical properties, the epoxy equivalent is preferably 195 to 208 g / equivalent, and Mn is preferably 270 to 300, from the viewpoint of improving the melt viscosity. The epoxy equivalent is preferably 195 to 199 g / equivalent, and the Mn is preferably 270 to 278. From the viewpoint of obtaining a better crystallization rate, the epoxy equivalent is 196 to 199 g / equivalent and the Mn is 271 to 278. Is more preferable.
Although the mechanism by which Mn and an epoxy equivalent make the said specific range the crystallization speed | rate is favorable is not clear, when Mn and an epoxy equivalent are in the said range, it is contained in an epoxy resin (1). It is considered that crystallization is promoted by the oligomer component represented by the formula (1).

[Preferred combination of Mw and epoxy equivalent]
From the viewpoint of epoxy resin (1) having low hydrolyzable chlorine and excellent electrical properties, the epoxy equivalent is preferably 195 to 208 g / equivalent, and Mw is preferably 370 to 610, from the viewpoint of improving the melt viscosity. The epoxy equivalent is preferably 195 to 199 g / equivalent, and the Mw is preferably 370 to 431. From the viewpoint of obtaining a better crystallization rate, the epoxy equivalent is 196 to 199 g / equivalent and the Mw is 391 to 431. Is more preferable.
The mechanism by which the crystallization speed is improved by setting the Mw and epoxy equivalent in the specific range is not clear, but if the Mw and epoxy equivalent are in the above range, the epoxy resin (1) contains the above. It is considered that crystallization is promoted by the oligomer component represented by the formula (1).

[Preferred combination of Mn, Mw and epoxy equivalent]
From the viewpoint of low hydrolyzable chlorine and excellent electrical properties, the epoxy resin (1) preferably has an epoxy equivalent of 195 to 208 g / equivalent, Mw of 3370 to 610, Mn of 270 to 300, and good melt viscosity. From the standpoint of making it, the epoxy equivalent is 195 to 199 g
/ Equivalent, Mw is preferably 370 to 431, and Mn is preferably 270 to 278. From the viewpoint of obtaining a better crystallization rate, it is 196 to 199 g / equivalent, Mw is 391 to 431, and Mn is 271 to 278. More preferably it is.
Although the mechanism by which Mn, Mw, and epoxy equivalent are within the above specific ranges to improve the crystallization rate is not clear, if Mn, Mw, and epoxy equivalent are within the above ranges, the epoxy resin (1) This is considered to be because crystallization is promoted by the oligomer component represented by the formula (1) contained in.

  In order to make the epoxy equivalent and Mw and Mn of the epoxy resin (1) within the above preferable ranges, in the production method of the epoxy resin (1) described later, in purification of the crude epoxy resin by reaction of the crude epoxy resin and strong alkali, What is necessary is just to control the usage-amount of strong alkali, reaction temperature, and reaction time. Further, the desired resin can be obtained by confirming each numerical value by a method of sampling over time and analyzing by GPC.

[Hydrolyzable chlorine content]
The epoxy resin (1) preferably has a hydrolyzable chlorine content (hereinafter sometimes referred to as “hydrolyzable chlorine content”) of 90 ppm or less.
The smaller the amount of hydrolyzable chlorine, the better in terms of the electrical reliability of the product obtained, and more preferably 90 ppm or less. The lower limit of the amount of hydrolyzable chlorine is 0 ppm, that is, “below the detection limit” in the following measurement of the amount of hydrolyzable chlorine. If the amount of hydrolyzable chlorine is excessively lowered, the epoxy equivalent, Mw and Mn are Usually, the lower limit of the amount of hydrolyzable chlorine is usually 10 ppm because it is difficult to make it in a suitable range.

As a method for measuring the amount of hydrolyzable chlorine, for example, about 0.5 g of epoxy resin is dissolved in 20 ml of dioxane, refluxed with 5 ml of 1N KOH / ethanol solution for 30 minutes, and then titrated with 0.01N silver nitrate solution. The method of quantifying by is mentioned.
In order to reduce the amount of hydrolyzable chlorine in the epoxy resin (1), the crude epoxy resin may be purified by a reaction between the crude epoxy resin and a strong alkali in the production method of the epoxy resin (1) described later.

[Melt viscosity]
The epoxy resin (1) preferably has a melt viscosity at 150 ° C. of 3.0 Pa · s or less from the viewpoint of handleability, and from the viewpoint of improving the handleability, the melt viscosity is preferably 0.00. It is 001 Pa · s or more and more preferably 1.4 Pa · s or less.
In the present invention, the “melt viscosity” is a viscosity measured at a rotational speed of 750 rpm by melting an epoxy resin on a hot plate of a cone plate viscometer (manufactured by Tokai Yagami Co., Ltd.) adjusted to 150 ° C. .

  In order to make the melt viscosity of the epoxy resin (1) within the above-mentioned preferable range, in the production method of the epoxy resin (1) described later, for example, in the case of the production method by a one-step method, use of epihalohydrin for the raw material polyvalent hydroxy compound The amount may be controlled, and the melt viscosity can be lowered by increasing the amount of epihalohydrin, and the melt viscosity can be increased by decreasing the amount.

[Production method of epoxy resin (1)]
The epoxy resin (1) of the present invention satisfying the above-mentioned preferable hydrolyzable chlorine content and melt viscosity is a tetramethylbiphenol type epoxy according to a conventional method. It can be produced by producing a resin (hereinafter sometimes referred to as “crude epoxy resin”) and then purifying it by reacting with a strong alkali.

[Production method of crude epoxy resin]
Although there is no restriction | limiting in particular about the manufacturing method of a crude epoxy resin, For example, the manufacturing method by the one-step method etc. which are demonstrated below are mentioned.

<Production method by one-step method>
In the production method by the one-step method, the following 4,4′-bishydroxy-3,3 ′, 5,5′-tetramethylbiphenyl (2) (hereinafter sometimes referred to as “tetramethylbiphenol (2)”). A crude epoxy resin is produced by reacting with epihalohydrin.

  In the case of producing a crude epoxy resin by a one-step method, at least tetramethylbiphenol (2) and epihalohydrin are used as raw materials, but a polyvalent hydroxy compound other than tetramethylbiphenol (2) (hereinafter “other polyvalent hydroxy compounds”). May be used as a mixture of the epoxy resin (1) and other epoxy resins. However, from the viewpoint of enhancing the effect of the present invention, the proportion of tetramethylbiphenol (2) is preferably 30 mol% or more, more preferably 50 mol% or more, and still more preferably, based on the total amount of the polyvalent hydroxy compound used as a raw material. It is 80 mol% or more. Moreover, the upper limit is 100 mol%, Most preferably, it is 100 mol%. The “polyhydric hydroxy compound” in the present invention is a general term for dihydric or higher phenol compounds and dihydric or higher alcohols.

Other polyhydroxy compounds include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcin, methylresorcin, biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin Various polyphenols such as resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, naphthol novolac resins, brominated bisphenol A, brominated phenol novolac resins (Excluding tetramethylbiphenol (2)) and various phenols Polyhydric phenol resins obtained by condensation reaction of aldehydes with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal, polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols, heavy oil Or various phenol resins such as co-condensation resins of pitches, phenols and formaldehyde, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3- Chain aliphatic diols such as pentanediol, 1,4-pentanediol, 1,5-pentanediol and 1,6-hexanediol; cycloaliphatic diols such as cyclohexanediol and cyclodecanediol; polyethylene ether glycol; Polio Trimethylene ether glycol, polyalkylene ether glycols such as polypropylene ether glycol, and the like. Among these, phenol novolak resin, phenol aralkyl resin, polyhydric phenol resin obtained by condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resin, naphthol aralkyl resin, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol,
Chain aliphatic diols such as 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclodecanediol, etc. And polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol.

  Tetramethylbiphenol (2) used as a raw material and other polyvalent hydroxy compounds used as necessary are usually 0.8 to 20 equivalents, preferably 1 to 20 equivalents per hydroxyl group of the total polyvalent hydroxy compound, which is the total of these. Is dissolved in an amount of epihalohydrin corresponding to 0.9 to 15 equivalents, more preferably 1.0 to 10 equivalents, to obtain a uniform solution. It is preferable that the amount of epihalohydrin is not less than the above lower limit because the high molecular weight reaction can be easily controlled and the resulting epoxy resin can have an appropriate melt viscosity. On the other hand, when the amount of epihalohydrin is less than or equal to the above upper limit, production efficiency tends to improve, which is preferable. In addition, as epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used.

  Next, while stirring the solution, it is usually 0.5 to 2.0 equivalents, preferably 0.7 to 1.8 equivalents, more preferably 0.9 per equivalent of hydroxyl groups of all polyvalent hydroxy compounds of the raw material. An amount of alkali metal hydroxide corresponding to ˜1.6 equivalents is added and reacted as a solid or an aqueous solution. It is preferable for the amount of the alkali metal hydroxide to be not less than the above lower limit because the unreacted hydroxyl group and the generated epoxy resin are difficult to react and the high molecular weight reaction can be easily controlled. Further, it is preferable that the amount of the alkali metal hydroxide is not more than the above upper limit value because impurities due to side reactions are hardly generated. As the alkali metal hydroxide used here, sodium hydroxide or potassium hydroxide is usually mentioned.

  This reaction can be performed under normal pressure or reduced pressure, and the reaction temperature is preferably 40 to 150 ° C, more preferably 60 to 100 ° C, and still more preferably 80 to 100 ° C. It is preferable for the reaction temperature to be equal to or higher than the above lower limit because the reaction can easily proceed and the reaction can be easily controlled. Further, it is preferable that the reaction temperature is not more than the above upper limit because the side reaction is unlikely to proceed, and in particular, chlorine impurities are easily reduced.

  In the reaction, the reaction liquid is azeotroped while maintaining a predetermined temperature as necessary, the condensed liquid obtained by cooling the vaporized vapor is separated into oil / water, and the oil component excluding moisture is returned to the reaction system. It is carried out while dehydrating by the method. In order to suppress a rapid reaction, the alkali metal hydroxide is preferably 0.1 to 8 hours, more preferably 0.1 to 7 hours, and still more preferably 0.5 to 6 hours. Or add continuously. When the addition time of the alkali metal hydroxide is not less than the above lower limit, it is possible to prevent the reaction from proceeding abruptly and to easily control the reaction temperature. It is preferable for the addition time to be less than or equal to the above upper limit because chlorine impurities are less likely to be generated, and from the viewpoint of economy. The total reaction time is usually 1 to 15 hours. After completion of the reaction, the insoluble by-product salt is removed by filtration or removed by washing with water, and then the unreacted epihalohydrin is distilled off under reduced pressure to obtain the desired crude epoxy resin.

  In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2-ethyl Catalysts such as imidazoles such as -4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used.

Furthermore, in this reaction, alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; aprotic such as dimethyl sulfoxide and dimethylformamide An inert organic solvent such as a polar solvent may be used.

[Purification of crude epoxy resin]
In the present invention, the crude epoxy resin produced as described above is purified by reacting with a strong alkali to improve solvent solubility and reduce the amount of hydrolyzable chlorine.
Moreover, Mw and Mn, and also an epoxy equivalent can be adjusted to the suitable range prescribed | regulated by this invention by reaction with this strong alkali.
That is, for example, Mw can be increased by increasing the temperature, the resin content relative to the solvent, and the alkali amount, and conversely, the Mw can be decreased by decreasing the temperature, the resin content relative to the solvent, and the alkali amount. be able to.

In addition, Mn can be increased by increasing the temperature, the resin content with respect to the solvent, and the alkali amount, and conversely, by decreasing the temperature, the resin content with respect to the solvent and the alkali amount, the Mn can be decreased. it can.
Moreover, the epoxy equivalent can be increased by increasing the temperature, the resin content relative to the solvent, and the alkali amount, and conversely, the epoxy equivalent can be decreased by decreasing the temperature, the resin content relative to the solvent, and the alkali amount. be able to.

About melt viscosity, melt viscosity can be made high by making temperature, the resin content with respect to a solvent, and the amount of alkalis high. Conversely, the melt viscosity can be lowered by lowering the temperature, the resin content relative to the solvent, and the alkali amount. About hydrolyzable chlorine, hydrolyzable chlorine can be made low by making temperature, the resin content with respect to a solvent, and the amount of alkalis high. Conversely, hydrolyzable chlorine can be increased by lowering the temperature, the resin content relative to the solvent, and the alkali amount.
The detailed conditions for producing the epoxy resin of the present invention will be described below, but depending on the conditions, the reaction time may be longer or shorter, so sampling is performed appropriately, and Mw and Mn as well as the epoxy equivalent are analyzed as described above. By doing so, a desired epoxy resin can be obtained.

  An organic solvent for dissolving the epoxy resin may be used for the reaction between the crude epoxy resin and the strong alkali. The organic solvent used in the reaction is not particularly limited. However, from the viewpoint of purification efficiency, handleability, workability, etc., an aprotic polar solvent and an inert organic solvent other than the aprotic polar solvent are used. A mixed solvent is preferred.

  Examples of the aprotic polar solvent include dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, dimethylformamide, dimethylacetamide, hexamethylphosphoramide and the like. These may be used alone or in combination of two or more. Among these aprotic polar solvents, dimethyl sulfoxide is preferable because it is easily available and has excellent effects.

  Examples of the organic solvent used together with the aprotic polar solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ethers such as dioxane and ethylene glycol dimethyl ether. Of these, aromatic hydrocarbon solvents or ketone solvents are preferable from the viewpoints of effects and ease of post-treatment, and toluene, xylene or methyl isobutyl ketone is particularly preferable. These may be used alone or in combination of two or more.

The aprotic polar solvent and the other organic solvent are preferably used so that the proportion of the aprotic polar solvent is 3 to 20% by weight based on the total of these.
The amount of the organic solvent used is such that the concentration of the crude epoxy resin is usually 3 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. is there.

  As the strong alkali, a solid or solution of an alkali metal hydroxide can be used, and examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide. The alkali metal hydroxide may be used after being dissolved in an organic solvent or water. The amount of the alkali metal hydroxide used is preferably 0.2 parts by weight or more and 1.1 parts by weight or less based on 100 parts by weight of the crude epoxy resin in terms of solid content of the alkali metal hydroxide. By making the usage-amount of an alkali metal hydroxide into this range, it becomes possible to adjust easily Mn and Mw of the epoxy resin (1) obtained, and also an epoxy equivalent within the above-mentioned suitable range.

The reaction temperature is preferably 30 to 120 ° C, more preferably 40 to 110 ° C, and the reaction time is preferably 0.1 to 15 hours, more preferably 0.3 to 12 hours.
After the reaction, excess alkali metal hydroxide and secondary salts are removed by a method such as washing with water, and the organic solvent is further removed by distillation under reduced pressure and / or steam distillation to obtain the epoxy resin (1) of the present invention. be able to.
It can be seen that the epoxy resin of the present invention belongs to the technical scope of the present invention by a method of sampling with time and analyzing by GPC.

[Epoxy resin composition]
The epoxy resin composition of this invention contains the epoxy resin (1) of this invention mentioned above and a hardening | curing agent at least. In addition, the epoxy resin composition of the present invention may be cured with an epoxy resin other than the epoxy resin (1) of the present invention (hereinafter, may be simply referred to as “other epoxy resin”), if necessary. An accelerator, an inorganic filler, a coupling agent and the like can be appropriately blended.

The epoxy resin composition of the present invention including the epoxy resin (1) of the present invention having excellent crystallization speed and low hydrolyzable chlorine content is excellent in cured product properties such as heat resistance and moisture absorption, and is required for various applications. It provides a cured product that sufficiently satisfies various physical properties.
That is, since the epoxy resin (1) has a rigid tetramethylbiphenyl skeleton, it gives a cured product excellent in heat resistance and moisture absorption resistance. Epoxy resin compositions and cured products with excellent heat resistance are less susceptible to thermal stress in the encapsulated resin when used as a semiconductor encapsulant, etc., passivation and chip damage, aluminum wiring slides, packages It is difficult to cause defects such as cracks, and a product with excellent reliability can be realized.

[Curing agent]
In this invention, a hardening | curing agent shows the substance which contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of an epoxy resin. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy resin, it is regarded as a curing agent. To do.

In the epoxy resin composition of the present invention, the content of the curing agent is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. Further, it is more preferably 500 parts by weight or less, and still more preferably 300 parts by weight or less. In the present invention, the “solid content” means a component excluding the solvent, and includes not only a solid epoxy resin but also a semi-solid or viscous liquid material. The “total epoxy resin component” corresponds to the amount of the epoxy resin contained in the epoxy resin composition of the present invention. When the epoxy resin composition of the present invention contains only the epoxy resin (1), the epoxy resin When the amount of (1) corresponds and includes epoxy resin (1) and other epoxy resins, it corresponds to the total of epoxy resin (1) and other epoxy resins.

There is no restriction | limiting in particular as a hardening | curing agent, Generally what is known as an epoxy resin hardening | curing agent can be used. For example, amine curing agents such as phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles, etc. Is mentioned.
Among these, the epoxy resin composition of the present invention can provide excellent heat resistance, stress resistance, moisture absorption resistance, flame resistance, etc. by including a phenolic curing agent. It is preferable that a system hardening agent is included. From the viewpoint of heat resistance and the like, it is preferable to include an acid anhydride curing agent and an amide curing agent. It is also preferable to use imidazoles from the viewpoint of sufficiently proceeding the curing reaction and improving heat resistance.

  A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more kinds of curing agents are used in combination, they may be used after mixing them in advance to prepare a mixed curing agent, and when mixing each component of the epoxy resin composition, each component of the curing agent may be used. They may be added separately and mixed at the same time.

<Phenolic curing agent>
Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac 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 novolak resin, brominated bisphenol A, brominated phenol novolak Various polyphenols such as resins, various phenols and benzalde , Polyhydric phenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols, heavy oil or Co-condensation resin of pitches, phenols and formaldehyde, phenol / benzaldehyde / xylylene dimethoxide polycondensate, phenol / benzaldehyde / xylylene dihalide polycondensate, phenol / benzaldehyde / 4,4'-dimethoxide biphenyl Various phenol resins such as polycondensate and phenol / benzaldehyde / 4,4′-dihalide biphenyl polycondensate are listed.
These phenolic curing agents may be used alone or in combination of two or more in any combination and blending ratio.

Among these, from the viewpoint of heat resistance after curing of the composition, curability and the like, among the phenolic curing agents, a phenol novolak resin (for example, a compound represented by the following formula (3)), a phenol aralkyl resin (for example, the following) A compound represented by the formula (4)), a biphenyl aralkyl resin (for example, a compound represented by the following formula (5)), a naphthol novolak resin (for example, a compound represented by the following formula (6)), a naphthol aralkyl resin (for example, A compound represented by the following formula (7)), a trisphenolmethane type resin (for example, a compound represented by the following formula (8)), a phenol / benzaldehyde / xylylene methoxide polycondensate (for example, the following formula (9)) Compound), phenol / benzaldehyde / xylylene dihalide polycondensate (for example, represented by the following formula (9)) Compound), phenol-benzaldehyde-4,4'-dimethoxide biphenyl polycondensate (for example, a compound represented by the following formula (10)), phenol-benzaldehyde-4,4'-dihalide biphenyl polycondensate (for example, Compounds represented by the following formula (10)) and the like are preferred, in particular phenol novolak resins (for example, compounds represented by the following formula (3)), phenol aralkyl resins (for example, compounds represented by the following formula (4)), Biphenyl aralkyl resin (for example, a compound represented by the following formula (5)), phenol / benzaldehyde / xylylene dimethoxide polycondensate (for example, a compound represented by the following formula (9)), phenol / benzaldehyde / xylylene dihalide heavy Condensates (for example, compounds represented by the following formula (9)), phenol / benzaldehyde 4,4'-dimethoxide biphenyl polycondensate (for example, a compound represented by the following formula (10)), phenol-benzaldehyde 4,4'-dihalide biphenyl polycondensate (for example, the following formula (10) Are preferred).

(However, in the above formulas (3) to (8), k1 to k6 each represents a number of 0 or more.)

(However, in the above formulas (9) and (10), k7, k8, l1, and l2 each represent a number of 1 or more.)
The blending amount of the phenolic curing agent is preferably 0.1 to 1000 parts by weight, more preferably 500 parts by weight or less, and still more preferably 300 parts by weight with respect to 100 parts by weight of all epoxy resin components in the epoxy resin composition. Part or less, particularly preferably 100 parts by weight or less, particularly preferably 60 parts by weight or less.

<Amine-based curing agent>
Examples of amine curing agents (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like are exemplified. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include 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, diaminodiethyl Examples thereof include dimethyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.

The amine curing agents mentioned above may be used alone or in combination of two or more in any combination and mixing ratio.
Said amine type hardening | curing agent is used so that it may become the range of 0.8-1.5 in the equivalent ratio of the functional group in a hardening | curing agent with respect to the epoxy group in all the epoxy resin components contained in an epoxy resin composition. preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .
The tertiary amines mentioned above may be used alone or in combination of two or more in any combination and blending ratio.
The tertiary amine is used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in all epoxy resin components contained in the epoxy resin composition is in the range of 0.8 to 1.5. preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

<Acid anhydride curing agent>
Examples of the acid anhydride curing agent include acid anhydrides and modified acid anhydrides.

  Examples of acid anhydrides include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyadipic acid anhydride, polyazelinic acid anhydride, polysebacic acid Anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methylhymic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bis trimellitate dianhydride, het acid anhydride, nadic acid anhydride, Methyl nadic acid Water, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4 -Tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc. are mentioned.

  Examples of modified acid anhydrides include those obtained by modifying the above acid anhydride with glycol. Here, examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and pothitetramethylene ether glycol. It is done. Furthermore, a copolymer polyether glycol of two or more kinds of these and / or polyether glycol can also be used.

  In the modified product of acid anhydride, it is preferable to modify with 0.4 mol or less of glycol with respect to 1 mol of acid anhydride. When the modification amount is not more than the above upper limit, the viscosity of the epoxy resin composition does not become too high, the workability tends to be good, and the rate of the curing reaction with the epoxy resin also tends to be good. .

The acid anhydride curing agents listed above may be used alone or in combination of two or more in any combination and blending amount.
When using an acid anhydride curing agent, use an equivalent ratio of functional groups in the curing agent to epoxy groups in all epoxy resin components in the epoxy resin composition in a range of 0.8 to 1.5. Is preferred. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

<Amide-based curing agent>
Examples of the amide-based curing agent include dicyandiamide and derivatives thereof, and polyamide resins. An amide type | system | group hardening | curing agent may be used only by 1 type, or may mix and use 2 or more types by arbitrary combinations and a ratio. When using an amide type | system | group hardening | curing agent, it is preferable to use it so that an amide type | system | group hardening | curing agent may be 0.1-20 weight% with respect to the sum total of all the epoxy resin components and amide type hardening | curing agents in an epoxy resin composition.

<Imidazoles>
Examples of imidazoles 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 trimellitate, 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'-methylimidazolyl- (1 ')]-ethyl-s-tri Azine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and an epoxy resin and the above imidazoles Examples include adducts. In addition, since imidazoles have catalytic ability, they can generally be classified as curing accelerators, but in the present invention, they are classified as curing agents.

The imidazoles listed above may be used alone or in combination of two or more in any combination and ratio.
When using imidazole, it is preferable to use it so that it may become 0.1-20 weight% with respect to the sum total of all the epoxy resin components and imidazoles in an epoxy resin composition.

<Other curing agents>
In the epoxy resin composition of the present invention, other curing agents can be used in addition to the curing agent. Other curing agents that can be used in the epoxy resin composition of the present invention are not particularly limited, and any of those generally known as curing agents for epoxy resins can be used. These other curing agents may be used alone or in combination of two or more.

[Other epoxy resins]
The epoxy resin composition of the present invention can further contain other epoxy resins in addition to the epoxy resin (1). By including other epoxy resins, the heat resistance, stress resistance, moisture absorption resistance, flame retardancy, and the like of the epoxy resin composition of the present invention can be improved.

Other epoxy resins that can be used in the epoxy resin composition of the present invention are all epoxy resins other than the epoxy resin (1), and specific examples thereof include bisphenol A type epoxy resins and trisphenol methane type epoxy. Resin, anthracene type epoxy resin, phenol modified xylene resin type epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diisopropylidene resorcin type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone Type epoxy resin, dibutylhydroquinone type epoxy resin, resorcinol type epoxy resin, methylresorcinol type epoxy resin, biphenol type epoxy resin, epoxy resin (1) Lamethylbiphenol type epoxy resin, tetramethylbisphenol F type epoxy resin, dihydroxydiphenyl ether type epoxy resin, epoxy resin derived from thiodiphenols, dihydroxynaphthalene type epoxy resin, dihydroxyanthracene type epoxy resin, dihydroxydihydroanthracene type epoxy resin , Dicyclopentadiene type epoxy resins, epoxy resins derived from dihydroxystilbenes, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol Aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, terpene phenol type Poxy resin, dicyclopentadiene phenolic epoxy resin, epoxy resin derived from phenol-hydroxybenzaldehyde condensate, epoxy resin derived from phenol-crotonaldehyde condensate, epoxy derived from phenol-glyoxal condensate Resin, heavy oil or epoxy resin derived from co-condensation resin of pitches and phenols and formaldehyde, epoxy resin derived from diaminodiphenylmethane, epoxy resin derived from aminophenol, derived from xylenediamine Examples thereof include an epoxy resin, an epoxy resin derived from methylhexahydrophthalic acid, an epoxy resin derived from dimer acid, and the like. These may be used alone, or two or more may be used in any combination and mixing ratio.

  Among these, from the viewpoints of the fluidity of the composition and the heat resistance, moisture absorption resistance, flame retardancy, etc. of the cured product, among the above epoxy resins, tetras other than bisphenol A type epoxy resins and epoxy resins (1). Methyl biphenol type epoxy resin and 4,4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin and dihydroxyanthracene type epoxy resin, dicyclopentadiene type epoxy resin, orthocresol novolac type epoxy resin, tris Phenolmethane type epoxy resin is particularly preferred.

  When the epoxy resin composition of the present invention contains the other epoxy resin, the content thereof is preferably 0.01 to 60 parts by weight with respect to 100 parts by weight of the total epoxy resin component in the composition, More preferably, it is 40 parts by weight or less, more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and more preferably 1 part by weight or more.

[Curing accelerator]
The epoxy resin composition of the present invention preferably contains a curing accelerator. By including a curing accelerator, the curing time can be shortened and the curing temperature can be lowered, and a desired cured product can be easily obtained.
The curing accelerator is not particularly limited, but specific examples include phosphorus compounds such as organic phosphines and phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, and boron halide amine complexes.

Examples of phosphorus compounds that can be used as curing accelerators 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) phosphine, trialkylphosphine, dialkyl Organic phosphines such as aryl phosphines and alkyldiaryl phosphines, complexes of these organic phosphines with organic borons, and 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 Examples include compounds formed by adding quinone compounds such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, and compounds such as diazophenylmethane.

Among the curing accelerators mentioned above, organic phosphines and phosphonium salts are preferable, and organic phosphines are most preferable. Moreover, only 1 type may be used for a hardening accelerator among the above-mentioned, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.
The curing accelerator is preferably used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of all epoxy resin components in the epoxy resin composition. More preferably, it is 0.5 parts by weight or more, further preferably 1 part by weight or more, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less. When the content of the curing accelerator is not less than the above lower limit value, a favorable curing accelerating effect can be obtained. On the other hand, it is preferable that the content is not more than the above upper limit value because desired cured properties are easily obtained.

[Inorganic filler]
An inorganic filler can be blended in the epoxy resin composition of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, calcium sulfate, talc, boron nitride and the like. These may be used alone or in combination of two or more in any combination and blending ratio. Among these, when used for semiconductor sealing, a crushing type and / or spherical, fused and / or crystalline silica powder filler is preferable.

  By using an inorganic filler, when the epoxy resin composition is used as a semiconductor encapsulant, the thermal expansion coefficient of the semiconductor encapsulant can be made closer to the internal silicon chip or lead frame, and the semiconductor encapsulant can be used. Since the moisture absorption amount of the entire stopper can be reduced, the solder crack resistance can be improved.

The average particle diameter of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, more preferably 2 to 30 μm. When the average particle size is not less than the above lower limit value, the melt viscosity is not excessively high and fluidity is not easily lowered, and when the average particle size is not more than the above upper limit value, a narrow gap in the mold is formed during molding. It is preferable because the filler is not easily clogged and the filling property of the material is easily improved.
When an inorganic filler is used in the epoxy resin composition of the present invention, the inorganic filler is preferably blended in the range of 60 to 95% by weight of the entire epoxy resin composition.

[Release agent]
A release agent can be blended in the epoxy resin composition of the present invention. Examples of the release agent include natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; higher fatty acids such as stearic acid and zinc stearate and metal salts thereof; and hydrocarbon release agents such as paraffin. it can. These may be used alone or in combination of two or more in any combination and blending ratio.

  When mix | blending a mold release agent with the epoxy resin composition of this invention, the compounding quantity of a mold release agent becomes like this. Preferably it is 0.1-5.0 with respect to 100 weight part of all the epoxy resin components in an epoxy resin composition. Part by weight, more preferably 0.5 to 3.0 parts by weight. It is preferable for the amount of the release agent to be within the above-mentioned range since good release properties can be expressed while maintaining the curing characteristics of the epoxy resin composition.

[Coupling agent]
A coupling agent is preferably blended in the epoxy resin composition of the present invention. The coupling agent is preferably used in combination with an inorganic filler, and the adhesiveness between the matrix epoxy resin and the inorganic filler can be improved by blending the coupling agent. Examples of coupling agents include silane coupling agents and titanate coupling agents.

  Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxy Aminosilane such as silane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

Any of these coupling agents may be used alone or in a combination of two or more in any combination and ratio.
When using a coupling agent for the epoxy resin composition of this invention, the compounding quantity becomes like this. Preferably it is 0.1-3.0 weight part with respect to 100 weight part of all the epoxy resin components. If the blending amount of the coupling agent is equal to or more than the above lower limit value, the effect of improving the adhesion between the epoxy resin as a matrix and the inorganic filler due to the blending of the coupling agent tends to be improved. When the blending amount of the agent is not more than the above upper limit value, the coupling agent is less likely to bleed out from the resulting cured product.

[Other ingredients]
In the epoxy resin composition of the present invention, components other than those described above (may be referred to as “other components” in the present invention) can be blended. Examples of other components include flame retardants, plasticizers, reactive diluents, pigments, and the like, which can be appropriately blended as necessary. However, the epoxy resin composition of the present invention does not prevent any compounding other than the components listed above.

  Examples of the flame retardant used in the epoxy resin composition of the present invention include halogenated flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, red phosphorus, phosphate esters, and phosphines. Examples include phosphorus-based flame retardants, nitrogen-based flame retardants such as melamine derivatives, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[Cured product]
The cured product of the present invention can be obtained by curing the epoxy resin composition of the present invention. The cured product of the present invention obtained by curing the epoxy resin composition of the present invention has excellent heat resistance.

  The method for curing the epoxy resin composition of the present invention is not particularly limited, but usually a cured product can be obtained by a thermosetting reaction by heating. During the thermosetting reaction, it is preferable to select a curing temperature as appropriate depending on the type of curing agent used. For example, when a phenolic curing agent is used, the curing temperature is usually 130 to 300 ° C. Further, the curing temperature can be lowered by adding a curing accelerator to these curing agents. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and further preferably 3 to 15 hours. It is preferable for the reaction time to be not less than the above lower limit value because the curing reaction tends to proceed sufficiently. On the other hand, when the reaction time is not more than the above upper limit value, it is preferable because deterioration due to heating and energy loss during heating are easily reduced.

The epoxy resin composition of the present invention is excellent in heat resistance and has a low elastic modulus at high temperatures, but it is 10 MPa or less. The lower the modulus of elasticity at high temperatures, the higher the glass transition temperature of the cured product, the less the thermal stress is applied to the resin encapsulated when used as a semiconductor encapsulant, etc., passivation and chip damage, aluminum wiring slides, packages This is preferable because defects such as cracks are less likely to occur.
Here, the elastic modulus at a high temperature is measured by the method described in the section of Examples described later.
It can be seen that the epoxy resin composition of the present invention belongs to the technical scope of the present invention by a method of sampling with time and analyzing by GPC.

[Use]
The epoxy resin (1) of the present invention has a small amount of hydrolyzable chlorine and excellent crystallization speed, and the epoxy resin composition of the present invention containing the epoxy resin (1) of the present invention is excellent in heat resistance and the like. Therefore, the epoxy resin and epoxy resin composition of the present invention can be effectively used for any application as long as these physical properties are required. For example, paint fields such as electrodeposition paints for automobiles, heavy-duty anti-corrosion paints for ships and bridges, paints for the inner surface of beverage cans; electrical and electronic fields such as laminates, semiconductor encapsulants, insulating powder paints, and coil impregnations ; Suitable for use in applications such as seismic reinforcement of bridges, concrete reinforcement, flooring of buildings, linings of water supply facilities, drainage / water-permeable pavement, civil engineering / architecture / adhesive fields of adhesives for vehicles and aircraft Can do. Among these, it is particularly useful for electrical / electronic applications such as semiconductor encapsulants and laminates.
The epoxy resin composition of the present invention may be used after curing for the application, or may be cured in the production process for the application.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Production and evaluation of epoxy resin]
[Production Example 1]
A 2 L four-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 137 g of tetramethylbiphenol (Mitsubishi Chemical Corporation), 627 g of epichlorohydrin, 244 g of isopropyl alcohol and 87 g of water, and the temperature was raised to 65 ° C Then, 108 g of 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 90 minutes. After completion of dropping, the reaction is completed by holding at 65 ° C. for 30 minutes. The reaction solution is transferred to a 3 L separatory funnel and allowed to stand at 65 ° C. for 1 hour, and then the aqueous layer is extracted from the separated oil layer and aqueous layer. Raw salt and excess sodium hydroxide were removed. Subsequently, excess epichlorohydrin and isopropyl alcohol were distilled off from the product under reduced pressure to obtain a crude epoxy resin.

  This crude epoxy resin was dissolved in 300 g of methyl isobutyl ketone, 4 g of a 48.5 wt% aqueous sodium hydroxide solution was added, and the mixture was reacted again at a temperature of 65 ° C. for 1 hour. Thereafter, 167 g of methyl isobutyl ketone was added, followed by washing with water 4 times using 500 g of water. Thereafter, methyl isobutyl ketone was completely removed under reduced pressure at 150 ° C. to obtain an epoxy resin having an epoxy equivalent of 185 g / eq.

[Example 1]
100 g of the epoxy resin obtained in Production Example 1, 120 g of methyl isobutyl ketone and 30 g of dimethyl sulfoxide were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the reaction temperature was raised to 65 ° C. After uniformly dissolving, 4.8 g of 8 wt% potassium hydroxide / isopropanol solution was added and reacted for 1 hour. Thereafter, 112 g of methyl isobutyl ketone was added, followed by washing with water 4 times using 200 g of water. Thereafter, methyl isobutyl ketone was completely removed under reduced pressure at 150 ° C. to obtain an epoxy resin.

[Example 2]
An epoxy resin was obtained in the same manner as in Example 1 except that the 8 wt% potassium hydroxide / isopropanol solution was changed to 7.1 g.

[Comparative Example 1]
The epoxy resin synthesized in Production Example 1 was used.

[Comparative Example 2]
An epoxy resin was obtained in the same manner as in Example 1 except that the addition amount of the 8 wt% potassium hydroxide / isopropanol solution was changed to 2.4 g.

[Comparative Example 3]
An epoxy resin was obtained in the same manner as in Example 1 except that the 8 wt% potassium hydroxide / isopropanol solution was changed to 9.7 g.
The epoxy equivalent of the epoxy resins obtained in Examples 1 and 2 and Comparative Examples 1 to 3, the amount of hydrolyzable chlorine, the melt viscosity at 150 ° C., the weight average molecular weight (Mw), and the number average molecular weight (Mn) are as described above. In addition to measurement by the method, the following crystallization test was conducted and the results are shown in Table 1.

[Crystallization test]
Weigh 20g of epoxy resin in a 50cc vial. Then, the epoxy resin was completely melted by heating at 150 ° C. and stored at 23 ° C. A product that was completely crystallized within 7 hours in a vial was rated “good” for crystallization speed, and a product that was not crystallized was rated “poor” for poor crystallization.

[Production and evaluation of epoxy resin composition]
[Examples 3 and 4 and Comparative Examples 4 and 5]
The epoxy resin and the curing agent were blended in the proportions shown in Table 2, heated to 100 ° C. and stirred until uniform. Then, it cooled to 80 degreeC, the hardening accelerator was added in the ratio shown in Table 2, and it stirred until it became uniform, and prepared the epoxy resin composition. In Table 2, “part” represents “part by weight”.

The used curing agents and curing accelerators are as follows.
Curing agent: phenol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH7800 (hydroxyl equivalent: 174 g / equivalent))
Curing accelerator: Triphenylphosphine (trade name, triphenylphosphine, manufactured by Tokyo Chemical Industry Co., Ltd.)

Two glass plates each having a release pet film laminated on one surface were prepared, and these glass plates were provided with the release pet film side as an inner surface, and a glass plate interval was adjusted to 4 mm to prepare a casting plate.
An epoxy resin composition was cast on this casting plate and cured by heating at 120 ° C. for 2 hours and then at 175 ° C. for 6 hours to obtain a cured product.
About the obtained hardened | cured material, glass transition temperature was measured with the following method as heat resistance evaluation, and the result was shown in Table 2.

[Elastic modulus at high temperature (measurement of 200 ° C (E ')]
The cured product was cut into a length of 5 cm, a width of 1 cm, and a thickness of 4 mm to obtain a test piece. Analysis was performed by a thermomechanical analyzer (DMS: EXSTAR6100 manufactured by Seiko Instruments Inc.) in the three-point bending mode by the following measurement method, and 200 ° C. (E ′) of 1 Hz was defined as an elastic modulus at a high temperature.
(Measuring method)
First temperature increase: 5 ° C / min, 30 ° C to 250 ° C

[Evaluation of results]
From Table 1, the epoxy resin of Example 1, 2 which manufactured the epoxy resin (1) of this invention whose epoxy equivalent, Mw, and Mn are in the prescription | regulation range of this invention, all are the epoxy resins of Comparative Examples 1-3. On the other hand, it can be seen that the crystallization rate is excellent.
Moreover, from Table 2, the epoxy resin hardened | cured material of Example 3, 4 using the epoxy resin (1) of this invention whose epoxy equivalent, Mw, and Mn are in the prescription | regulation range of this invention are the comparative examples 4 and 5. It turns out that it has a low elastic modulus superior to a cured epoxy resin.

Claims (10)

An epoxy resin represented by the following formula (1) and having a number average molecular weight (Mn) of 270 to 300.

(In the formula, n represents an integer of 0 to 10.) An epoxy resin represented by the following formula (1) and having a weight average molecular weight (Mw) of 370 to 610.

(In the formula, n represents an integer of 0 to 10.) An epoxy resin represented by the following formula (1), having a number average molecular weight (Mn) of 270 to 300 and a weight average molecular weight (Mw) of 370 to 610.

(In the formula, n represents an integer of 0 to 10.)   The epoxy resin according to any one of claims 1 to 3, wherein the melt viscosity at 150 ° C is 0.3 Pa · s or less.   The epoxy resin according to any one of claims 1 to 4, wherein the content of hydrolyzable chlorine is 90 ppm or less with respect to the epoxy resin.   The epoxy resin composition which contains 0.01-1000 weight part of hardening | curing agents with respect to 100 weight part of epoxy resins of any one of Claims 1-5.   The epoxy resin composition according to claim 6, wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent. The epoxy resin composition according to claim 6 or 7, further comprising an epoxy resin different from the epoxy resin according to any one of claims 1 to 5.   Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claim 6-8.   The electrical / electronic component formed by hardening | curing the epoxy resin composition of any one of Claims 6-8.