JP6520582B2 - Epoxy resin, epoxy resin composition, cured product and electric / electronic component - Google Patents

Description

  The present invention is excellent in castability, blocking resistance, heat resistance, heat stress resistance, water absorption resistance, and epoxy resin excellent in electrical characteristics with low melt viscosity and low hydrolyzable chlorine, and this epoxy resin. The present invention relates to an epoxy resin composition and a cured product. The present invention also relates to an electric / electronic component comprising the epoxy resin composition.

Epoxy resins are cured with various curing agents, and they generally become cured products with excellent mechanical properties, heat resistance, electrical properties, etc., so they can be used in a wide range of fields such as adhesives, paints, electrical and electronic materials, etc. It is used by In particular, in the field of electric and electronic materials, epoxy resins are excellent in handling properties, insulating properties, heat resistance, hygroscopicity, and adhesiveness.
In recent years, with the miniaturization and thinning of electronic parts, the required characteristics required for materials are increasing. The epoxy resin alone includes a low melt viscosity for casting in a thin mold, and a low hydrolyzable chlorine for enhancing the electrical reliability. Also, the epoxy resin composition has a blocking resistance to prevent adhesion with other materials, a cured product has high heat resistance so that the electronic device can be used even in a more severe environment, and heat resistance to prevent cracking of the semiconductor element. It has stress resistance, water absorption resistance, etc.

Patent Document 1 describes a diglycidyl ether of 4,4′-butylidenebis- (6-t-butyl-3-methylphenol) as a coating material instead of bisphenol A.
Patent Document 2 describes a composition of a polymerized product of a diglycidyl ether of 4,4'-butylidene bis- (6-t-butyl-3-methylphenol) and a halogenated material, There is a disclosure of diglycidyl ethers of 4,4'-butylidenebis- (6-t-butyl-3-methylphenol).

Patent Document 3 discloses diglycidyl ether of 4,4'-butylidenebis- (6-t-butyl-3-methylphenol) as part of the novolak component of 2-t-butyl-5-methylphenol. ing.
However, in any case, only epoxy equivalents lower than the present invention are disclosed.
Patent document 4 discloses diglycidyl ether of 4,4'-butylidene bis (2-t-butyl-5-methylphenol), which is a metal-based coating for food or beverage containers It is a material, and nothing is disclosed about epoxy equivalent.

Japanese Patent Application Laid-Open No. 6-056963 JP-A-6-106676 JP-A-8-104739 JP-A-2014-510162

A first object of the present invention is to provide an epoxy resin excellent in the balance between hydrolyzable chlorine and melt viscosity, low in melt viscosity, and low in hydrolyzable chlorine and excellent in electrical characteristics. Those having such characteristics are excellent in electrical characteristics.
The second object of the present invention is to provide an epoxy resin composition excellent in castability, blocking resistance, heat resistance, heat stress resistance and water absorption resistance and a cured product thereof. Such an epoxy resin composition and its cured product are suitably used for electric and electronic parts.

As a result of intensive studies to solve the above problems by the present inventor, diglycidyl ether of 4,4'-butylidenebis- (6-t-butyl-3-methylphenol) whose epoxy equivalent and n number are controlled in a specific range Moreover, it also discovered that the epoxy resin composition containing this epoxy resin and a hardening agent can solve the said subject, and came to completion of this invention.
That is, the gist of the present invention resides in the following [1] to [9] .
[1] An epoxy resin represented by the following formula (1) and having an epoxy equivalent of 332 to 664 .

(In the formula, n takes an average value and is 0.1 to 9.23.)
[2] The epoxy resin according to [1], which has a softening point of 50 to 92 ° C.
[3] The epoxy resin according to [1] or [2], which has a melt viscosity at 150 ° C. of 5.4 Pa · s or less.
[4] The epoxy resin according to any one of [1] to [3], wherein the content of hydrolyzable chlorine is 190 ppm or less based on the epoxy resin.
[5] An epoxy resin composition comprising 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 [4].
[6] The epoxy resin composition according to [5], wherein the curing agent is at least one selected from the group consisting of phenolic curing agents, amine curing agents, acid anhydride curing agents, and amide curing agents.
[7] The epoxy resin composition according to [5] or [6], further comprising an epoxy resin different from the epoxy resin according to any one of [1] to [4].
[8] A cured product obtained by curing the epoxy resin composition according to any one of [5] to [7].
[9] An electric / electronic component obtained by curing the epoxy resin composition according to any one of [5] to [8].

According to the present invention, an epoxy resin having a low melt viscosity and a low hydrolyzable chlorine and excellent in electric characteristics, and castability, blocking resistance, heat resistance, heat stress resistance, water absorption resistance containing this epoxy resin The epoxy resin composition and the cured product are provided.
Since the epoxy resin composition of the present invention has the above-mentioned effects, it can be applied particularly effectively to electric / electronic parts such as semiconductor sealing materials and laminates.

  The embodiment of the present invention will be described in detail below, but the following description is an example of the embodiment of the present invention, and the present invention is not limited to the following contents unless the gist is exceeded. Absent. In addition, when using the expression "-" in this specification, it shall use as an expression containing the numerical value or physical-property value before and behind that.

〔Epoxy resin〕
The epoxy resin of the present invention is an epoxy resin represented by the following formula (1), and is excellent in the electrical characteristics, which has a low melt viscosity and a low hydrolyzable chlorine.

( Wherein n is the average number of repeating units shown in the above parenthesis;
It is a value determined from the formula weight of the structural formula of formula (1) . )
Since the epoxy resin of the present invention has a low melt viscosity, the epoxy resin composition of the present invention is electrically
Even when highly filled with a filler excellent in mechanical and heat resistance, the viscosity is low, so injection molding can be performed on large or thin articles. In the case of a high viscosity material, when it is injection molded into a large size or thin shape, the problem of being unfilled remains.

In addition, since the amount of hydrolyzable chlorine is small, free chlorine when used as a cured product is reduced, thereby preventing corrosion of wiring of electric and electronic devices and preventing troubles such as insulation failure.
Furthermore, since it has a moderate softening point, it becomes excellent in handleability.
The number of epoxy groups in the epoxy resin of the present invention represented by the above formula (1) (hereinafter sometimes referred to as "epoxy resin (1)") is shown as the epoxy equivalent described later.
Moreover, n in said Formula (1) which shows an epoxy resin (1) is shown in the said parenthesis
The average number of repeating units, which is determined from the epoxy equivalent and the formula weight of the structural formula of the above formula (1)
It is a value .

[Average value of n number]
The epoxy resin (1) preferably has an average value of n of 0.1 to 9.23 from the viewpoint of balance between low viscosity and handling property at the softening point, and from the viewpoint of making the softening point a good value, 0.15 It is more preferable that it is -9.23, and it is further more preferable that it is 0.15-2.21 from a viewpoint of making melt viscosity into a favorable value. From the viewpoint of setting the melt viscosity to a better value, it is particularly preferably 0.15 to 0.58.
In addition, the average value of n number can be calculated from the area ratio by calculating each component ratio as n = 0, 1, 2, 3 ... as a polystyrene conversion value by gel permeation chromatography.

[Epoxy equivalent]
The epoxy resin (1) preferably has an epoxy equivalent of 261 to 1463 g / equivalent from the viewpoint of balance between low viscosity and handling property at the softening point, and from 265 to 1463 g / equivalent from the viewpoint of making the softening point a good value. Is more preferable, and from the viewpoint of achieving a better melt viscosity, it is more preferably 265 to 664 g / equivalent. More preferably, it is 265 to 332 g / equivalent from the viewpoint of making the melt viscosity a good value.

By setting the epoxy equivalent to the above-mentioned specific range, the viscosity of the oligomer decreases because n or more oligomer components decrease. On the other hand, when the amount of the oligomer component is extremely reduced, the softening point is too low, which causes a problem in handling.
In the epoxy resin other than the epoxy resin represented by the formula (1) of the present invention, the effect of the present invention is hardly obtained even when the epoxy equivalent is in the same range as the above.

In the present invention, "epoxy equivalent" is defined as "mass of epoxy resin containing one equivalent of epoxy group" and can be measured according to JIS K7236.
In order to make the epoxy equivalent higher than 261 g / equivalent, the amount of epichlorohydrin at the time of epoxidation reaction can be lowered or the amount of alkali catalyst can be increased, and the desired epoxy equivalent can be confirmed by sampling. . In order to set the epoxy equivalent to 1463 g / equivalent or less, the operation can be carried out by increasing the amount of epichlorohydrin or decreasing the amount of alkaline catalyst and confirming the desired epoxy equivalent by sampling.

[Hydrolyzable chlorine content]
The epoxy resin (1) preferably has a hydrolyzable chlorine content (hereinafter sometimes referred to as "hydrolyzable chlorine amount") of 190 ppm or less.
The smaller the amount of hydrolyzable chlorine, the better in terms of the electrical reliability of the resulting product, etc., and more preferably 190 ppm or less. The lower limit of the amount of hydrolyzable chlorine is 0 ppm, that is, "below the detection limit" in the measurement of the amount of hydrolyzable chlorine below, but when the amount of hydrolyzable chlorine is excessively low, the epoxy equivalent, Mw and Mn Usually, the lower limit of the amount of hydrolyzable chlorine is usually 10 ppm because it is difficult to set it in a suitable range.
As a method of measuring the amount of hydrolyzable chlorine, for example, about 0.5 g of an epoxy resin is dissolved in 20 ml of dioxane, refluxed for 30 minutes with 5 ml of 1 N KOH / ethanol solution, and then titrated with 0.01 N silver nitrate solution The method of quantifying by is mentioned.

Melt viscosity
The melt viscosity of the epoxy resin of the present invention is preferably 5.4 Pa · s or less at 150 ° C. from the viewpoint of handleability, and from the viewpoint of making the handleability more favorable, the melt viscosity is 1. It is particularly preferable that the pressure is 5 Pa · s or less and 0.5 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 (made by Tokai Yagami Co., Ltd.) adjusted to 150 ° C. .

  In order to make melt viscosity of epoxy resin (1) into the above-mentioned suitable range, use of epihalohydrin with respect to raw material polyvalent hydroxy compound in the manufacturing method of below-mentioned epoxy resin (1), for example, in the case of manufacturing method by one-step method The amount may be controlled, and by increasing the amount of epihalohydrin, the melt viscosity can be increased by decreasing and decreasing the melt viscosity.

[Softening point]
The epoxy resin of the present invention preferably has a softening point of 92 to 50 ° C. from the viewpoint of handleability, and has a softening point of 77 to 50 ° C. from the viewpoint of lowering the melt viscosity and making the handling property good. It is particularly preferable that the temperature is 63 to 50 ° C. or less. On the other hand, the temperature is preferably 50 ° C. or higher from the viewpoint of blocking resistance. In the present invention, the term "softening point" means JIS.
It can measure according to K7234.

[Method of producing epoxy resin (1)]
The method for producing the epoxy resin (1) of the present invention, in which the n number and the epoxy equivalent are within the above-mentioned preferred ranges and further satisfies the above-mentioned preferable hydrolyzable chlorine amount, melt viscosity and softening point, is shown below.

[Method of producing epoxy resin]
Although there is no restriction | limiting in particular about the manufacturing method of the epoxy resin of this invention, For example, the manufacturing method by the 1 step | paragraph method demonstrated below, the manufacturing method via the allylation reaction, etc. are mentioned. These methods are described in detail below.

<Manufacturing method by one-step method>
In the production method by the one-step method, the following phenol resin (2) (hereinafter referred to as "phenol resin (2)
Sometimes referred to as ) And epihalohydrin to produce the epoxy resin of the present invention.

  In addition, when manufacturing an epoxy resin by a one-step method, although at least phenol resin (2) and epihalohydrin are used as raw materials, polyvalent hydroxy compounds other than phenol resin (2) (hereinafter referred to as "other polyvalent hydroxy compounds" In some cases, it may be manufactured as a mixture of epoxy resin (1) and other epoxy resin. However, from the viewpoint of enhancing the effect of the present invention, the proportion of the phenol resin (2) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 80 mol% with respect to the total amount of polyhydroxy compound used as a raw material. It is mol% or more. Moreover, the upper limit is 100 mol%, Especially preferably, it is 100 mol%. In the present invention, the "polyhydroxy compound" is a generic term for a dihydric or higher phenolic compound and a dihydric or higher alcohol.

  Other polyvalent hydroxy compounds include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AD, hydroquinone, resorcinol, methyl resorcinol, biphenol, tetramethyl biphenol, dihydroxy naphthalene, dihydroxy diphenyl ether, thiodiphenols, phenol novolac Resin, cresol novolac resin, phenol aralkyl resin, biphenylaralkyl resin, naphtholaralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolac resin, naphthol novolac resin, brominated bisphenol A, brominated phenol novolac resin, etc. Of polyhydric phenols (but excluding phenolic resin (2)), Polyphenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde and glyoxal, and polyphenol resins obtained by condensation reaction of xylene resin and phenols Various phenolic resins such as heavy oils or co-condensed resins of pitches, phenols and formaldehydes, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Linear aliphatic diols such as 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol; and cycloaliphatic diols such as cyclohexanediol and cyclodecanediol; Polyethylene Ether Guri Lumpur, polyoxytrimethylene ether glycols, polyalkylene ether glycols such as polypropylene ether glycol, and the like. Among them, preferred are 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, Linear aliphatic diols such as 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, Cycloaliphatic diols such as cyclohexanediol and cyclodecanediol, Polyalkylene ether glycos, such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol Le, and the like can be mentioned.

The phenol resin (2) and other polyvalent hydroxy compounds which are optionally used as raw materials are generally 0.8 to 20 equivalents, preferably preferably 1 to 20, per equivalent of the total polyvalent hydroxy compounds which is the total of them. It is dissolved in epihalohydrin in an amount corresponding to 0.9 to 15 equivalents, more preferably 1.0 to 10 equivalents, to form a homogeneous solution. It is preferable that the amount of epihalohydrin is equal to or more than the above lower limit because the polymerization reaction can be easily controlled and the resulting epoxy resin can have an appropriate melt viscosity. On the other hand, if the amount of epihalohydrin is less than the above upper limit, production efficiency tends to be improved, which is preferable. Epichlorohydrin or epibromohydrin is usually used as the epihalohydrin in this reaction.

  Then, while the solution is being stirred, the amount 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 equivalent to ̃1.6 equivalents is added and reacted in solid or aqueous solution. It is preferable that the amount of the alkali metal hydroxide is equal to or more than the above lower limit because the unreacted hydroxyl group and the generated epoxy resin are difficult to react with each other and the polymerization reaction can be easily controlled. In addition, it is preferable that the amount of the alkali metal hydroxide is less than or equal to the above upper limit value because impurities due to side reactions are less likely to be generated. As an alkali metal hydroxide used here, sodium hydroxide or potassium hydroxide is mentioned normally.

  This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is preferably 40 to 150 ° C., more preferably 60 to 100 ° C., still more preferably 80 to 100 ° C. It is preferable that the reaction temperature is equal to or higher than the above lower limit, because the reaction can easily proceed and the reaction can be easily controlled. Moreover, since a side reaction does not advance easily that reaction temperature is below the said upper limit and it is easy to reduce especially a chlorine impurity, it is preferable.

  In the reaction, if necessary, the reaction solution is azeotroped while maintaining a predetermined temperature, and the condensate obtained by cooling the volatilized vapor is separated into oil / water, and the oil free of water is returned to the reaction system It is done while dewatering by the method. The alkali metal hydroxide is preferably intermittently added in small portions over preferably 0.1 to 8 hours, more preferably 0.1 to 7 hours, still more preferably 0.5 to 6 hours, in order to suppress a rapid reaction. Or add continuously. If the addition time of the alkali metal hydroxide is more than the above lower limit, rapid progress of the reaction can be prevented, and control of the reaction temperature becomes easy, which is preferable. It is preferable that the addition time is less than or equal to the above upper limit because chlorine impurities are less likely to be generated, and it is also preferable 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 unreacted epihalohydrin is removed by evaporation under reduced pressure to obtain the target epoxy resin.

In this reaction, quaternary ammonium salts such as tetramethyl ammonium chloride and tetraethyl ammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2-ethyl Imidazoles such as -4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; and 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.

<Production Method via Allylation Reaction>
The epoxy resin can also be produced by a production method via an allylation reaction. In this case, there is a method of obtaining a crude epoxy resin by introducing an allyl group to the phenol resin (2) by an allylation reaction to obtain an allyl compound, and further causing an oxidation reaction to the allyl group.
The production method via the allylation reaction is, for example, as described in JP-A-2011-225711, JP-A-2012-092247, JP-A-2012-111858, etc., except that phenol resin (2) is used as a raw material. It can be implemented according to the method described.

[Purification of epoxy resin]
Although the method for purifying the epoxy resin of the present invention is described below, depending on the conditions, the reaction time may vary depending on the conditions. Therefore, sampling is appropriately performed, and the epoxy equivalents and n number are analyzed as described above. Epoxy resin can be obtained.
An organic solvent for dissolving the epoxy resin may be used for the reaction between the epoxy resin and the strong alkali. The organic solvent used for the reaction is not particularly limited, but from the viewpoint of purification efficiency, handleability, workability, etc., an aprotic polar solvent and an inert organic solvent other than the aprotic polar solvent It is preferable that it is a mixed solvent.

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

  Examples of the organic solvent to be 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, ethers such as dioxane and ethylene glycol dimethyl ether Among these, aromatic hydrocarbon solvents or ketone solvents are preferable, and toluene, xylene or methyl isobutyl ketone is particularly preferable, in view of effects and easiness of post-treatment. One of these may be used alone, or two or more may be mixed and used.

It is preferable to use said aprotic polar solvent and other organic solvents so that the ratio of an aprotic polar solvent may become 3 to 20 weight% with respect to these sum totals.
The amount of the organic solvent used is such that the concentration of the epoxy resin is usually 3 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight .

As a strong alkali, a solid or a solution of an alkali metal hydroxide can be used. As the alkali metal hydroxide, potassium hydroxide, sodium hydroxide and the like can be mentioned. The alkali metal hydroxide may be used by dissolving it in an organic solvent or water. The amount of the alkali metal hydroxide to be used is preferably 0.01 parts by weight or more and 1.5 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.
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 can be removed by washing with water, and the organic solvent can be further removed by distillation under reduced pressure and / or steam distillation.

[Epoxy resin composition]
The epoxy resin composition of the present invention contains at least the above-mentioned epoxy resin (1) of the present invention and a curing agent. Further, in the epoxy resin composition of the present invention, as needed, an epoxy resin other than the epoxy resin (1) of the present invention (hereinafter sometimes referred to simply as "other epoxy resin"), cured. An accelerator, an inorganic filler, a coupling agent, etc. can be mix | blended suitably.
The epoxy resin composition of the present invention containing the epoxy resin (1) of the present invention having a low melt viscosity and a small amount of hydrolyzable chlorine is excellent in handling properties such as castability and blocking resistance, and the cured product is heat resistant It is excellent in cured product properties such as heat resistance, heat stress resistance, moisture absorption resistance and the like, and sufficiently satisfies various physical properties required for various uses.

[Hardener]
In the present invention, the curing agent refers to a substance that contributes to the crosslinking reaction and / or the chain extension reaction between epoxy groups of the epoxy resin. In the present invention, even if it is a substance called "curing accelerator", it is regarded as a curing agent if it is a substance that contributes to the crosslinking reaction and / or the chain extension reaction between epoxy groups of the epoxy resin. 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, still more preferably 300 parts by weight or less. In the present invention, "solid content" means a component excluding a solvent and includes not only solid epoxy resin but also semi-solid and viscous liquid materials. The term "all epoxy resin component" corresponds to the amount of epoxy resin contained in the epoxy resin composition of the present invention, and 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 the epoxy resin (1) and the other epoxy resin are included, it corresponds to the total of the epoxy resin (1) and the other epoxy resin.

The curing agent is not particularly limited, and any of those generally known as epoxy resin curing agents can be used. For example, amine-based curing agents such as phenol-based curing agents, aliphatic amines, polyether amines, alicyclic amines and aromatic amines, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazoles, etc. Can be mentioned.
Among these, since the epoxy resin composition of the present invention can obtain excellent heat resistance, stress resistance, moisture absorption resistance, flame resistance and the like by containing a phenol-based curing agent, phenol as a curing agent can be obtained. It is preferable to contain a system curing agent. Moreover, it is preferable to contain an acid anhydride type curing agent and an amide type curing agent from the viewpoint of heat resistance and the like. The use of imidazoles is also preferable from the viewpoint of sufficiently advancing the curing reaction and improving the heat resistance.

  The curing agent may be used alone or in combination of two or more. When 2 or more types of curing agents are used in combination, these may be mixed in advance to prepare a mixed curing agent before use, or each component of the curing agent may be used when mixing each component of the epoxy resin composition. Each may be added separately and mixed simultaneously.

<Phenolic curing agent>
Specific examples of the phenol-based curing agent include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, Cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolac resin, trisphenol methane resin, naphthol novolac resin, brominated bisphenol A, brominated phenol novolak Resin and various polyhydric phenols, various phenols and benzalde Polyphenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal, polyphenol resins obtained by condensation reaction of xylene resin and phenols, heavy oil or Co-condensation resin of pitches, phenols and formaldehydes, polycondensate of phenol, benzaldehyde, xylylene dimethoxide, phenol, benzaldehyde, xylylene dihalide polycondensate, phenol, benzaldehyde, 4,4'-dimethoxide biphenyl Various phenolic resins such as polycondensates, phenol / benzaldehyde / 4,4'-dihalide biphenyl polycondensates, etc. may be mentioned.

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, etc., among the above-mentioned phenolic curing agents, phenol novolac resin (for example, a compound represented by the following formula (3)), phenol aralkyl resin (for example A compound represented by Formula (4), a biphenyl aralkyl resin (for example, a compound represented by the following Formula (5)), a naphthol novolac resin (for example, a compound represented by the following Formula (6)), a naphthol aralkyl resin (for example, Compounds represented by the following formula (7), trisphenol methane type resins (for example, compounds represented by the following formula (8)), phenol / benzaldehyde / xylylene methoxide polycondensates (for example, following formula (9) A compound represented by the formula), a phenol / benzaldehyde / xylylene halide polycondensate (eg, 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 preferable, and 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 methoxide polycondensate (for example, a compound represented by the following formula (9)), phenol / benzaldehyde / xylylene halide Condensation products (for example, compounds represented by the following formula (9)), phenol / benzaldehyde De, 4'-dimethoxide biphenyl polycondensate (for example, a compound represented by the following formula (10)), phenol benzaldehyde, 4,4'-dihalide biphenyl polycondensate (for example, following formula (10) The compound represented by is preferable.

(However, in the above formulas (3) to (8), k _{1 to} k ₆ each represent a number of 0 or more.)

(However, in the above formulas (9) and (10), k ₇ , k ₈ , l ₁ and l ₂ each represent a number of 1 or more.)
The compounding amount of the phenolic curing agent is preferably 0.1 to 1000 parts by weight, more preferably 500 parts by weight or less, still more preferably 300 parts by weight with respect to 100 parts by weight of all epoxy resin components in the epoxy resin composition. Parts by weight or less, particularly preferably 100 parts by weight or less.

<Amine curing agent>
Examples of the amine curing agent (but excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. As aliphatic amines, ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Examples include hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine and polyoxypropylene triamines. Alicyclic amines such as isophorone diamine, metacene diamine, N-aminoethyl piperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino Examples include propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornene diamine and the like. 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-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, alpha- (m-aminophenyl) ethylamine, alpha- (p-aminophenyl) Ethylamine, diaminodiethyl Examples include dimethyl diphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene and the like.

The amine-based curing agents listed above may be used alone or in combination of two or more in any combination and blending ratio.
The above-mentioned amine-based curing agent may be 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. It is preferable for the content to be in this range because unreacted epoxy groups and functional groups of the curing agent hardly remain.

Examples of tertiary amines include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like. .
The tertiary amines listed above may be used alone or in combination of two or more in any combination and blending ratio.
The above tertiary amine may be used in an equivalent ratio of 0.8 to 1.5 in 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 preferable. It is preferable for the content to be in this range because unreacted epoxy groups and functional groups of the curing agent hardly remain.

<Acid anhydride curing agent>
As the acid anhydride curing agent, an acid anhydride, a modified product of an acid anhydride, and the like can be mentioned.
As the acid anhydride, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic 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, hetic acid anhydride, nadic acid anhydride, Methyl nadic acid Hydrate, 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.

  As a modified product of the acid anhydride, for example, one obtained by modifying the above-mentioned acid anhydride with glycol and the like can be mentioned. Here, as an example of glycol which can be used for modification, alkylene glycols such as ethylene glycol, propylene glycol, neopentyl glycol etc .; polyether glycols such as polyethylene glycol, polypropylene glycol, potty tetramethylene ether glycol etc. are mentioned. Be Furthermore, copolymerized polyether glycols of two or more of these glycols and / or polyether glycols can also be used.

In the modified product of the acid anhydride, it is preferable to modify with 0.4 mol or less of glycol per 1 mol of the acid anhydride. If the modification amount is less 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 speed of the curing reaction with the epoxy resin also tends to be good. .
The acid anhydride curing agents mentioned above may be used alone or in combination of two or more in any combination and amount.

When using an acid anhydride-based curing agent, use it so that the equivalent ratio of the functional group in the curing agent to the epoxy group in all epoxy resin components in the epoxy resin composition is in the range of 0.8 to 1.5. Is preferred. It is preferable for the content to be in this range because unreacted epoxy groups and functional groups of the curing agent hardly remain.

<Amide curing agent>
Examples of the amide curing agent include dicyandiamide and derivatives thereof, and polyamide resins.
The amide-based curing agent may be used alone or in combination of two or more in any combination and ratio.
When an amide-based curing agent is used, it is preferable to use an amide-based curing agent in an amount of 0.1 to 20% by weight based on the total of all epoxy resin components in the epoxy resin composition and the amide-based curing agent.

<Imidazoles>
As imidazoles, 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 Azin isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and epoxy resin with the above imidazoles An adduct etc. are illustrated. Imidazoles can be generally classified as curing accelerators because they have catalytic ability, 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 imidazoles, it is preferable to use so that an imidazole may be 0.1 to 20 weight% with respect to the sum total of all the epoxy resin components in an epoxy resin composition, and imidazoles.

<Other curing agent>
In the epoxy resin composition of the present invention, other curing agents can be used besides the above-mentioned curing agent. There are no particular limitations on the other curing agents that can be used in the epoxy resin composition of the present invention, 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 resin]
The epoxy resin composition of the present invention can further contain another epoxy resin in addition to the epoxy resin (1). By containing other epoxy resin, the heat resistance, stress resistance, moisture absorption resistance, flame retardance, etc. of the epoxy resin composition of the present invention can be improved.
The other epoxy resins that can be used in the epoxy resin composition of the present invention correspond to all epoxy resins other than the above epoxy resin (1), and specific examples thereof include bisphenol A epoxy resin, trisphenol methane epoxy Resin, anthracene type epoxy resin, phenol modified xylene resin type epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diisopropylideneresorcinol type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone Type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcinol type epoxy resin, methyl resorcinol type epoxy resin, biphenol type epoxy resin, tetramethyl biphenol type Epoxy resin, tetramethyl bisphenol F type epoxy resin, dihydroxydiphenyl ether type epoxy resin, epoxy resin derived from thiodiphenols, dihydroxy naphthalene type epoxy resin, dihydroxy anthracene type epoxy resin, dihydroxy dihydro anthracene type epoxy resin, dicyclopentadiene Type epoxy resin, epoxy resin derived from dihydroxystilbene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin Biphenylaralkyl epoxy resin Terpenephenol epoxy resin Dicyclope Tadiene phenol type epoxy resin, epoxy resin derived from condensation product of phenol and hydroxybenzaldehyde, epoxy resin derived from condensation product of phenol and crotonaldehyde, epoxy resin derived from condensation product of phenol and glyoxal, heavy material Epoxy resin derived from co-condensed resin of oil or pitch, phenol and formaldehyde, epoxy resin derived from diaminodiphenylmethane, epoxy resin derived from aminophenol, epoxy resin derived from xylene diamine, methyl The epoxy resin derived from hexahydrophthalic acid, the epoxy resin derived from dimer acid, etc. are mentioned. These may be used alone or in any combination and proportion of two or more.

Among these epoxy resins, bisphenol A epoxy resin, tetramethyl biphenol epoxy resin, and 4 from the viewpoints of fluidity of the composition, heat resistance of cured product, moisture resistance, flame resistance, etc. , 4'-biphenol type epoxy resin, biphenylaralkyl type epoxy resin, phenolaralkyl type epoxy resin and dihydroxyanthracene type epoxy resin, dicyclopentadiene type epoxy resin, ortho cresol novolac type epoxy resin, trisphenolmethane type epoxy resin preferable.
When the epoxy resin composition of the present invention contains the other epoxy resin described above, its content 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, still more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and on the other hand, more preferably 1 part by weight or more.

[Hardening accelerator]
The epoxy resin composition of the present invention preferably contains a curing accelerator. By including the 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, and specific examples thereof include phosphorus compounds such as organic phosphines and phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes and the like.

As a phosphorus compound which can be used as a curing accelerator, 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 alkyl diaryl phosphines or 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 thereof include quinone compounds such as -benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds formed by addition of compounds such as diazophenylmethane.

Among the curing accelerators mentioned above, organic phosphines and phosphonium salts are preferable, and organic phosphines are most preferable. Moreover, a hardening accelerator may be used by only 1 type in what was mentioned above, and 2 or more types may be mixed and used by arbitrary combinations and a ratio.
The curing accelerator is preferably used in an amount of 0.1 parts by weight or more and 20 parts by weight or less based on 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, and on the other hand, more preferably, 15 parts by weight or less, 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 acceleration effect can be obtained, while when it is not more than the above upper limit value, a desired cured physical property is easily obtained, which is preferable.

[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, crushed and / or spherical, fused and / or crystalline silica powder fillers are preferred when used for semiconductor encapsulation applications.

By using the inorganic filler, when the epoxy resin composition is used as a semiconductor sealing material, the thermal expansion coefficient of the semiconductor sealing material can be made closer to the internal silicon chip or lead frame, and the semiconductor sealing material can be used. Since the amount of moisture absorption of the entire stopper can be reduced, the solder crack resistance can be improved.
The average particle size of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, and more preferably 2 to 30 μm. Melt viscosity does not become high too much that average particle diameter is more than the above-mentioned lower limit, and it is hard to reduce flowability, and it is preferable, and when average particle diameter is below the above-mentioned upper limit, It is preferable because the filler is less likely to be clogged and the filling property of the material is likely to be improved.
When using an inorganic filler for the epoxy resin composition of this invention, it is preferable to mix | blend an inorganic filler in 60 to 95 weight% of the epoxy resin composition whole.

[Release agent]
A mold release agent can be blended into the epoxy resin composition of the present invention. As the mold release agent, for example, 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; hydrocarbon type mold release agents such as paraffin and the like it can. These may be used alone or in combination of two or more in any combination and blending ratio.

  When the mold release agent is compounded into the epoxy resin composition of the present invention, the compounding amount of the mold release agent is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of all epoxy resin components in the epoxy resin composition. It is a part by weight, more preferably 0.5 to 3.0 parts by weight. When the compounding amount of the release agent is in the above range, it is preferable because good releasability can be exhibited while maintaining the curing characteristics of the epoxy resin composition.

[Coupling agent]
It is preferable to mix | blend a coupling agent with the epoxy resin composition of this invention. The coupling agent is preferably used in combination with the inorganic filler, and by blending the coupling agent, the adhesion between the epoxy resin as the matrix and the inorganic filler can be improved. As a coupling agent, a silane coupling agent, a titanate coupling agent, etc. are mentioned.

  As a silane coupling agent, for example, epoxysilane 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 Aminosilanes such as silane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilalas And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and further, epoxy type, amino type and vinyl type polymer type silanes, and the like.

  As a titanate coupling agent, for example, 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, etc. Be

Any of these coupling agents may be used alone, or two or more may be mixed and used in any combination and ratio.
When using a coupling agent for the epoxy resin composition of this invention, the compounding quantity is preferably 0.1-3.0 weight part with respect to 100 weight part of all the epoxy resin components. If the compounding amount of the coupling agent is not less than the above lower limit value, the effect of improving the adhesion between the epoxy resin which is the matrix and the inorganic filler by compounding the coupling agent tends to be improved, while the coupling It is preferable in order that it becomes difficult to bleed out a coupling agent from the hardened | cured material obtained as the compounding quantity of an agent is below the said upper limit.

[Other ingredients]
In the epoxy resin composition of the present invention, components other than those described above (sometimes referred to as "other components" in the present invention) can be blended. Examples of the other components include flame retardants, plasticizers, reactive diluents, pigments and the like, which can be appropriately blended as required. However, the epoxy resin composition of the present invention does not prevent the blending of components other than the components listed above.
Examples of flame retardants used in the epoxy resin composition of the present invention include halogen-based flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, red phosphorus, phosphoric esters, and phosphines. Examples thereof include phosphorus flame retardants, nitrogen 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, which is obtained by curing the epoxy resin composition of the present invention, has excellent properties in thermal decomposition resistance, thermal stress resistance, and moisture absorption resistance.
Although it does not specifically limit about the method to harden the epoxy resin composition of this invention, Usually, a hardened | cured material can be obtained by the thermosetting reaction by heating. At the time of heat curing reaction, it is preferable to appropriately select the curing temperature depending on the type of curing agent used. For example, when a phenol-based curing agent is used, the curing temperature is usually 130 to 300 ° C. It is also possible to lower the curing temperature 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 still more preferably 3 to 15 hours. If the reaction time is equal to or more than the above lower limit value, the curing reaction tends to be sufficiently facilitated, which is preferable. On the other hand, it is preferable for the reaction time to be equal to or less than the above upper limit because deterioration due to heating and energy loss at the time of heating can be easily reduced.

The epoxy resin composition of the present invention is excellent in thermal decomposition resistance, and can preferably give a cured product having a 5% weight loss temperature of 377 ° C. or higher. The higher the 5% weight loss temperature of the cured product, the smaller the thermal degradation in a high temperature environment, and the more preferable it is to be able to use the child electric parts in a more severe environment.
Here, the 5% weight loss temperature is measured by the method described in the section of Examples described later.

The epoxy resin composition of the present invention is excellent in thermal stress resistance, and can preferably give a cured product having an elastic modulus of 250 ° C. of 12 MPa or less. The lower the elastic modulus at 250 ° C. of the cured product is, the smaller the thermal stress at high temperature is, and the less cracking occurs under high temperature environment, so it is preferable because electronic electronic parts can be used under more severe environment.
Here, the elastic modulus at 250 ° C. is measured by the method described in the section of Examples described later.

The epoxy resin composition of the present invention is excellent in moisture absorption resistance, and preferably gives a cured product having a water absorption of 168 hours at 0.86% or less in a test specimen of 3 cm square and 5 mm thickness under an environment of 85 ° C. and humidity 85%. It can. As the moisture absorption rate of the cured product is lower, thermal stress due to the expansion of water absorbed at high temperatures is less likely to occur, and cracking at high temperatures is less likely to occur, so electronic electronic components can be used in more severe environments. preferable.
Here, the moisture absorption resistance is measured by the method described in the section of Examples described later.

[Use]
The epoxy resin (1) of the present invention has a small amount of hydrolyzable chlorine and is excellent in solvent solubility, 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 the epoxy resin composition of the present invention can be effectively used in any application as long as these physical properties are required. For example, paint fields such as electrodeposition paints for automobiles, heavy anticorrosion paints for ships and bridges, and paints for inner surface coating of cans for beverages; electric and electronics fields such as laminates, semiconductor sealing materials, insulating powder paints, and coil impregnation ; Suitable for applications such as seismic reinforcement of bridges, concrete reinforcement, floor coverings of buildings, lining of water supply facilities, drainage / water permeable pavement, civil engineering / building / adhesives field of adhesives for vehicles and aircraft, etc. Can. Among these, it is particularly useful for electric and electronic applications such as semiconductor encapsulants and laminates.

  The epoxy resin composition of the present invention may be used after curing for the application, and may be cured in the production process of the application.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited at all by the following examples. The values of various manufacturing conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit described above The range defined by the values of the following examples or the combination of the values of the examples may be used.

[Production and evaluation of epoxy resin]
Example 1
77 g of 4,4'-Butylidenebis- (6-t-butyl-3-methylphenol) (Mitsubishi Chemical Corp.) and 243 g of epichlorohydrin in a 2 L four-necked flask equipped with a thermometer, stirrer, and condenser After 236 g of methoxypropanol and 48 g of water were charged and the temperature was raised to 40 ° C. to dissolve uniformly, 39 g of a 48.5 wt% sodium hydroxide aqueous solution was added dropwise while raising the temperature to 65 ° C. over 90 minutes. After completion of the addition, the reaction is maintained at 65 ° C. for 30 minutes to complete the reaction, and after adding 58 g of water, the reaction liquid is transferred to a 3 L separatory funnel and left at 65 ° C. for 1 hour. The aqueous layer was removed from the solution to remove by-product salts and excess sodium hydroxide. Subsequently, excess epichlorohydrin and isopropyl alcohol were distilled off from the product under reduced pressure to obtain a crude epoxy resin. The crude epoxy resin was dissolved in 150 g of methyl isobutyl ketone, 2 g of a 48.5 wt% aqueous solution of sodium hydroxide was added, and the mixture was reacted again at a temperature of 65 ° C. for 1 hour. Thereafter, 83 g of methyl isobutyl ketone was added, and then water washing was performed four times using 500 g of water. Thereafter, methyl isobutyl ketone was completely removed under reduced pressure of 150 ° C. to obtain an epoxy resin.

Example 2
An epoxy resin was obtained in the same manner as in Example 1 except that 111 g of epichlorohydrin and 73 g of methoxypropanol were changed to isopropyl alcohol.
[Example 3]
An epoxy resin was obtained in the same manner as in Example 1 except that 60 g of epichlorohydrin and 34 g of methoxypropanol were changed to isopropyl alcohol.

Comparative Example 1
An epoxy resin was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin was changed to 729 g and the step of removing the oligomer component was finally performed by column purification. This epoxy resin is at the same level as the epoxy equivalent described in JP-A-2014-510162, and it is considered that an equivalent epoxy resin is obtained.

Comparative Example 2
An epoxy resin was obtained according to the method described in Synthesis Example 1 of JP-A-6-56963. That is,
114.6 g (0.6 OH moleq, OH equivalent 191 g / eq.) Of 1,1-bis (4-hydroxy-5-t-butyl-2-methylphenyl) butane, 388.5 g (4. 1) of epichlorohydrin. (2 mol), 195.3 g of dimethyl sulfoxide is charged in a 1-liter four-necked flat-bottomed flask equipped with a thermometer, a stirrer, and a condenser equipped with a separating tube, and 49.38 g of 48.6% sodium hydroxide aqueous solution under the conditions of Add 0.6 mol) dropwise over 4 hours. During this time, while maintaining the temperature at 48 ° C., the azeotropic epichlorohydrin and water were cooled and liquefied, and the organic layer was allowed to react back into the reaction system.
After completion of the reaction, unreacted epichlorohydrin was removed by vacuum concentration, an epoxidized product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone, and by-product salt and dimethyl sulfoxide were removed by hot water washing. By removing the solvent under reduced pressure, 143.1 g of an epoxy compound was obtained.

Comparative Example 3
An epoxy resin was obtained in the same manner as in Example 1 except that 30 g of epichlorohydrin and 34 g of methoxypropanol were changed to isopropyl alcohol.
The epoxy equivalent weight, n number, hydrolyzable chlorine content, softening point, melt viscosity of 150 ° C. of the epoxy resins obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the above-mentioned method, and the results are shown in Table 1 It was shown to.

[Production and Evaluation of Epoxy Resin Composition]
[Examples 4 to 6 and Comparative Examples 4 to 6]
The epoxy resin and the curing agent were compounded at the ratio shown in Table 2, and the mixture was 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 the epoxy resin composition was prepared. In Table 2, "parts" represents "parts by weight".

The curing agents and curing accelerators used are as follows.
Hardening agent: Phenol novolak resin (manufactured by Gunei Chemical Co., Ltd., trade name: PSM 4261 (hydroxy group equivalent: 103 g / equivalent))
Hardening accelerator: triphenyl phosphine (made by Tokyo Chemical Industry Co., Ltd. trade name: triphenyl phosphine)
The following evaluation was carried out on the preparation of a cured product of the epoxy resin composition, and the results are shown in Table 2.

[Castability]
Two glass plates having a release pet film laminated on one side were prepared, and the release pet film side of these glass plates was used as the inner surface, and the distance between the glass plates was adjusted to 5 mm to prepare a casting plate.
50 g of the epoxy resin composition was cast on this casting plate at 80 ° C., and cured by heating at 120 ° C. for 2 hours and then at 175 ° C. for 6 hours to obtain a cured product. The product from which a 5 cm square cured product having a thickness of 5 mm was obtained had good castability, and the product not obtained had poor castability and was evaluated as x.

The following evaluations were carried out on the products from which cured products were obtained, and the results are shown in Table 2.
[Blocking test of composition]
In the composition of Table 2, the epoxy resin and the curing agent were heated to 100 ° C. and stirred until uniform, and cooled at 5 ° C. for 30 minutes to obtain a composition. After that, it was crushed with a hammer, and after passing a 5 mm square mesh, it was placed in a cylinder 5 cm long and 15 cm long and left at 20 ° C. for 72 hours. Then, the thing which passed the mesh of 1 cm square made it as O as a composition which did not block the thing of 50% or more, and the thing which passed the mesh of 1 cm square made it as X which was a composition which blocked the thing of 50% or less .

[Heat resistance: 5% thermal weight loss temperature (° C)]
100 mg of the cured product was scraped off, and 10 mg was weighed therefrom to obtain a sample. About this sample, a thermal analyzer (TG / DTA: EXSTAR manufactured by Seiko Instruments Inc.)
Thermal analysis was performed using 7200) (heating rate: 5 ° C./min, measurement temperature range: 30 ° C. to 600 ° C., air: flow rate 200 mL / min). The temperature at which the weight of the cured product decreased by 5% was measured as the 5% weight loss temperature.

[Measurement of elastic modulus at high temperature (250 ° C. (E ')])
The cured product was cut into a length of 5 cm, a width of 1 cm, and a thickness of 5 mm to obtain a test piece. Analysis was carried out by a thermomechanical analyzer (DMS: EXSTAR 6100 manufactured by Seiko Instruments Inc.) in a three-point bending mode by the following measurement method, and 250 ° C. (E ′) at 1 Hz was taken as the elastic modulus at high temperature.
[Measurement of water absorption rate]
The cured product was cut into a length of 3 cm, a width of 3 cm, and a thickness of 5 mm to obtain a test piece. A test piece of 168 hr was put in a thermostatic chamber adjusted to 85 ° C. and 85%, and a weight change rate due to the test piece absorbing water was regarded as a water absorption rate.

[Evaluation of results]
From Table 1, the epoxy resins of Examples 1 to 3 which produced the epoxy resin of the present invention having an epoxy equivalent and n number within the specified range of the present invention were hydrolyzable to the epoxy resins of Comparative Examples 1 and 2. It turns out that it is superior to chlorine. On the other hand, Comparative Example 3 is lower in hydrolyzable chlorine but higher in melt viscosity than Examples 1 to 3 and has problems in handling.

  From Table 2, the epoxy resin cured products of Examples 4 to 6 using the epoxy resin of the present invention in which the epoxy equivalent n number is within the specified range of the present invention are as compared to the epoxy resin cured products of Comparative Examples 4 and 5. It turns out that it is excellent in blocking resistance, heat resistance, heat stress resistance, and water absorption resistance. Furthermore, it turns out that casting property is excellent with respect to the epoxy resin hardened | cured material of Comparative Example 6.

Claims (9)

The epoxy resin which is represented by following formula (1) and whose epoxy equivalent is 332-664 .

( Wherein n is the average number of repeating units shown in the above parenthesis;
It is a value determined from the formula weight of the structural formula of formula (1) . )   The epoxy resin according to claim 1, which has a softening point of 50 to 92 ° C. The epoxy resin according to claim 1, wherein the melt viscosity at 150 ° C. is 5.4 Pa · s or less. The epoxy resin according to any one of claims 1 to 3, wherein the content of hydrolyzable chlorine is 190 ppm or less based on the epoxy resin. An epoxy resin composition comprising 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 claims 1 to 4. The epoxy resin composition according to claim 5, 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 5 or 6, further comprising an epoxy resin different from the epoxy resin according to any one of claims 1 to 4. A cured product obtained by curing the epoxy resin composition according to any one of claims 5 to 7. An electric / electronic component obtained by curing the epoxy resin composition according to any one of claims 5 to 7.