JP6540188B2 - Diluent for epoxy resin, and epoxy resin composition - Google Patents

Description

  The present invention relates to an epoxy resin diluent containing an epoxy compound, and an epoxy resin composition containing the epoxy resin diluent.

Epoxy resins are resins used for a wide range of applications such as adhesive materials, optical materials, electronic materials, etc. because they are excellent in adhesion, corrosion resistance, mechanical properties, heat resistance, electrical properties and the like.
For example, epoxy resin is used for the sealing material used for LED etc. As an epoxy resin for a sealing material, an aliphatic epoxy resin which is more excellent in heat resistance and light resistance than an aromatic epoxy resin is generally used, and in particular, an aliphatic cyclic epoxy resin is excellent in light resistance. It is known as a material which is extremely excellent in heat resistance.

Epoxy resins are also used as heat dissipation materials, and aromatic epoxy compounds are particularly preferably used because of their high heat resistance.
On the other hand, some epoxy resins have high viscosity, and when such an epoxy resin is processed by a method such as molding or coating, the viscosity of the epoxy resin is reduced to dilute it for the purpose of improving processability. Agents are used. Generally, an epoxy resin having a lower viscosity is used as a diluent for the epoxy resin as the main material. For example, a method of using a hydrogenated bisphenol A epoxy resin has been proposed (Patent Document 1).

Japanese Patent Laid-Open No. 2000-143939

  However, when this hydrogenated bisphenol A-type epoxy resin is used as a diluent, although the strength is improved, the heat resistance is lowered and the performance of the aliphatic cyclic epoxy resin is lowered. Thus, while the conventionally used diluent contributes to lowering the viscosity of the epoxy resin which is the main material, it also reduces the curing speed of the epoxy resin, as compared with the case where no diluent is used. There is a problem of reducing the physical properties of the resulting cured product. Specifically, when an epoxy resin having high heat resistance, which is a main material, is diluted with a diluent, although the processability is improved, there is a problem that the heat resistance of the cured product is reduced. With respect to the epoxy resin of the main material, a diluent capable of improving the processability without lowering the heat resistance of the cured product has not been found so far.

  An object of the present invention is to obtain a diluent for epoxy resin applications, which improves processability without impairing the physical properties of the original epoxy resin even when mixed with an epoxy resin and cured.

As a result of intensive studies to solve the above problems, the present inventors obtained an epoxy compound using a butenediol having a specific structure as a starting material, and the present applicant has already filed a patent application for patent application 2013 It has been found that the epoxy resin described in JP-A-212891 becomes a diluent for solving the problem, and the present invention has been achieved.
That is, the gist of the present invention is
[1] A diluent for an epoxy resin, having a structure represented by at least one selected from the following general formulas (1) and (2),

(In Formula (1) and Formula (2), L ¹ and L ² each independently represent a divalent organic group which may have a substituent, and A and B each independently represent hydrogen) It represents a C 1-8 monovalent organic group which may have an atom or a substituent, provided that the substituents on L ¹ and L ² form a ring with A and B, respectively. Well, one of the three epoxy rings may form a carbon-carbon double bond instead of the epoxy ring)
[2] The diluent for an epoxy resin according to the above [1], wherein A and B in the formulas (1) and (2) are hydrogen atoms,
[3] L ¹ and L ^{2 in the} formulas (1) and (2) are alkylene groups represented by — (CH ₂ ) _n — (wherein n represents an integer of 1 to 14), The diluent for epoxy resin as described in the above [1] or [2],
[4] The diluent for an epoxy resin according to the above [3], wherein the n is 1;
[5] The dilution for an epoxy resin according to any one of the above [1] to [4], wherein the ratio of the epoxy equivalent of the diluent to the theoretical epoxy equivalent of the diluent is 1.0 or more and 1.2 or less. Agent,
[6] A diluent for an epoxy resin according to any one of the above [1] to [5] (a), and an epoxy resin (b) other than the diluent for the epoxy resin (a). Epoxy resin composition,
[7] The epoxy resin composition according to the above [6], further comprising a curing agent,
[8] The epoxy resin composition according to the above [6] or [7], further containing a filler.
[9] L ¹ and L ² of the diluent (a) for an epoxy resin are each independently a divalent aliphatic group having 1 to 14 carbon atoms which may have a substituent, and A The epoxy according to any one of the above [6] to [8], wherein each of B and C independently represents a hydrogen atom or a monovalent aliphatic group having 1 to 8 carbon atoms which may have a substituent. Resin composition,
[10] The epoxy resin composition according to any one of the above [6] to [9], wherein the epoxy resin (b) is an aliphatic epoxy resin,
[11] The epoxy resin composition according to any one of the above [6] to [9], wherein the epoxy resin (b) is an epoxy resin having an aromatic group.
[12] An epoxy resin composition for optical materials using the epoxy resin composition according to any one of the above [6] to [11],
[13] An epoxy resin composition for an LED encapsulant using the epoxy resin composition according to any one of the above [6] to [10],
[14] An epoxy resin composition for heat dissipation material using the epoxy resin composition according to the above [11],
[15] A cured product obtained by curing the epoxy resin composition according to any one of the above [6] to [14],
[16] An LED device in which an LED chip is sealed with the epoxy resin composition according to the above [13],
[17] A heat dissipation material using the epoxy resin composition according to the above [14].

  By diluting and using the epoxy resin with the diluent of the present invention, the processability can be improved without impairing the performance of the original epoxy resin, particularly the heat resistance. By using the diluent of the present invention as a diluent for an aliphatic epoxy resin, it is possible to suppress yellow deterioration of the obtained cured product and to lower the coefficient of linear expansion.

5 is a chart of ¹ H-NMR measurement of an epoxy compound obtained in Synthesis Example 2.

Hereinafter, the embodiment of the present invention will be described in more detail, but the description of the constituent requirements described below is an example of the embodiment of the present invention, and the present invention is not limited thereto, and the gist thereof In the range of, it can deform | transform variously and can implement.
In the present specification, "epoxy resin" refers to a compound having two or more epoxy groups in its molecule. The epoxy resin other than the main material (a) diluted with the diluent (a) for an epoxy resin of the present invention is an "epoxy resin (b)", a diluent for an epoxy resin (a) and an epoxy resin (b) The mixture obtained by mixing the epoxy resin composition and the resin obtained by reacting the epoxy resin composition with a curing agent may be referred to as a “cured product”.

<Diluent>
The diluent for epoxy resin of the present invention has a structure represented by at least one selected from the following general formulas (1) and (2).

In formulas (1) and (2), L ¹ and L ² each independently represent a divalent organic group which may have a substituent, and A and B each independently represent a hydrogen atom Or a monovalent organic group having 1 to 8 carbon atoms which may have a substituent. However, the substituent on L ¹ and L ² may form a ring with A and B, respectively, and one of the three epoxy rings forms a carbon-carbon double bond instead of the epoxy ring. It may be

In the present specification, the diluent means one used for diluting the epoxy resin (b) in order to adjust the physical properties of the epoxy resin (b), and in particular, the viscosity of the epoxy resin composition is decreased to process Used to improve gender.
First, compounds having the structures represented by the general formulas (1) and (2) which constitute the diluent of the present invention will be described.

The compounds having the structures represented by the general formulas (1) and (2) are epoxy compounds obtained by being derived from butenediols which may have a substituent. These compounds are novel compounds for which the present applicant has filed patent applications in Japanese Patent Application No. 2013-212891.
In the general formulas (1) and (2), L ¹ and L ² each independently represent a divalent organic group which may have a substituent. Examples of the organic group include divalent hydrocarbon groups such as an alkylene group and an arylene group, a carbonyl group (-CO-), an oxy group (-O-), a thio group (-S-) and an imino group (-NH) -), phosphine-diyl group (-Ph-), a silylene group (-SiH ₂ -) and the like. These divalent organic groups may be used alone or in combination of two or more organic groups.

A carbonyl alkylene group, a carbonyl arylene group, a carbonyloxy alkylene group, an alkylene oxy alkylene group etc. are mentioned as an example of what 2 or more types of bivalent organic groups connected, and a viewpoint of viscosity reduction to a carbonyl alkylene group, alkylene An oxyalkylene group etc. are preferable.
The carbon number of the divalent organic group which may have a substituent is not particularly limited, but is usually 1 to 14 and is preferably 1 to 6 because heat resistance is further improved, and ease of raw material acquisition 1 to 4 are more preferable. When the organic group further has a substituent, this carbon number means the carbon number including the substituent.

Examples of the alkylene group include linear alkylene groups such as methylene group and ethylene group; branched alkylene groups such as isopropylene group and isobutylene group; cyclic alkylene groups such as cyclopentylene group and cyclohexylene group; It can be mentioned.
Examples of the arylene group include phenylene group, naphthylene group, biphenylene group, toluylene group and the like.

When the alkylene group or arylene group has a plurality of substitutable positions, it may be substituted at any substitution position.
The above L ¹ and L ² can be appropriately selected according to the application of the diluent, but when used for applications requiring transparency such as optical materials, the cured product has high transparency and low yellow deterioration. From the viewpoint of forming an alkylene group, a carbonyl group, an oxy group, a thio group, an imino group, a phosphinediyl group, a silylene group, or a combination of two or more of them. Among them, a linear alkylene group having 1 to 14 carbon atoms, A carbonyl group, an oxy group, or a combination of two or more of these is more preferable because the yellow deterioration is further reduced, and a linear alkylene group having 1 to 14 carbon atoms is further preferable because it is easy to produce.

  On the other hand, when it is used for applications where transparency is not required, such as a heat dissipation material, it is preferable that an alkylene group, an arylene group, a carbonyl group, an oxy group, or two or more of these be linked in terms of availability of raw materials. A linear alkylene group having 1 to 14 carbon atoms, a phenylene group, a carbonyl group, an oxy group, or a combination of two or more of these is more preferable, and a diluent having a lower viscosity can be obtained. It is further preferred to use a linear alkylene group.

The substituent which L ¹ and L ² may have is not particularly limited as long as the effect of the diluent of the present invention is not impaired, and examples thereof include an alkyl group, an aryl group, a heterocyclic group, and an alkoxy group. And a hydroxyl group, an amino group, an ester group, a halogen atom, a thiol group, a thioether group, an alkylsilyl group and the like.
Although the substituent which said L ¹ and L ² may have can be suitably selected according to the use of a diluent, when using for uses which require transparency, such as an optical material, it is a hardened material. From the viewpoint of high transparency and low yellowing resistance, aliphatic groups are preferred. Specifically, alkyl groups, alkoxy groups, hydroxyl groups, amino groups, ester groups, halogen atoms, thiol groups, thioether groups, alkylsilyl groups Can be mentioned. On the other hand, in applications where transparency is not required, such as heat radiation materials, alkyl groups, aryl groups, and hydroxyl groups are preferable from the viewpoint of easy availability of raw materials, and from the viewpoint of obtaining a thinner diluent, alkyl Preferred is a group, an ester group, a halogen atom or a thioether group. Further, these substituents may further have a substituent, and the above-mentioned substituents can be mentioned as this substituent.

In the general formulas (1) and (2), the aforementioned A and B each independently represent a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms which may have a substituent. The monovalent organic group is not particularly limited, and examples thereof include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aralkyl group and an ester group.
Although the above A and B can be appropriately selected according to the application of the diluent, particularly when the diluent of the present invention is used for an optical material, the point that the transparency of the cured product is high and the yellowing deterioration becomes low And aliphatic groups such as alkyl groups, alkoxy groups and ester groups are preferable, and aliphatic groups having 1 to 8 carbon atoms are more preferable.

On the other hand, an alkyl group is preferable from the viewpoint that a lower viscosity diluent can be obtained, among which an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is further obtained from the viewpoint of easy availability of raw materials. preferable.
Specifically, examples of the alkyl group include linear alkyl groups such as methyl and ethyl; branched alkyl groups such as isopropyl and isobutyl; and cyclic alkyl groups such as cyclopropyl; Be As an aryl group, a phenyl group, toluyl group, etc. are mentioned, for example. As an alkoxyphenyl group, a methoxyphenyl group etc. are mentioned, for example. Examples of the heterocyclic group include pyridyl group, thienyl group, furyl group, thiazolyl group, oxazolyl group, pyrazolyl group, pyrimidyl group, pyrazinyl group, pyrrolyl group, imidazolyl group, triazolyl group and the like. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example. As an aralkyl group, a benzyl group, a phenylethyl group, etc. are mentioned, for example. As an ester group, an ethyl ester group, a butyl ester group etc. are mentioned, for example.

As a substituent which "the monovalent organic group having 1 to 8 carbon atoms" in A and B may have, the same as the substituents in the above L ¹ and L ² can be mentioned. Among these, an alkyl group, an aryl group and a hydroxyl group are preferable from the viewpoint of easy availability of the raw material.
The substituents on L ¹ and L ² may form a ring with A and B, respectively. Specifically, for example, structures represented by the following structural formulas (3) and (4) in which alkyl groups are linked in general formula (1) can be mentioned.

As Structural Formulas (3) and (4), in General Formula (1), an example in which a carbon six-membered ring in which both of L ¹ and A and L ² and B are bonded is shown. There is no limitation on the number of membered rings in the number of carbon atoms of the substituent, and a compound in which only ^one of L ¹ and A, and L ² and B form a ring is also exemplified as a specific example. Also in the general formula (2), similarly, the number of membered rings is not limited within the number of carbon atoms of the substituent, and for example, one or both of L ¹ and A, L ² and B are bonded And a carbon six-membered ring may be formed. Specifically, for example, structural formula (5) can be mentioned.

As the above L ¹ and L ² , unsubstituted ones represented by — (CH ₂ ) _n — (wherein n represents an integer of 1 to 14) from the viewpoint of obtaining a lower viscosity diluent are preferable. The linear alkylene group is more preferably a group in which n is 1 to 6 and, from the viewpoint of heat resistance, a group in which n is 1 or a methylene group is particularly preferred.
Preferred as A and B are a hydrogen atom and an unsubstituted alkyl group having 1 to 8 carbon atoms in view of availability of raw materials, and among these, a hydrogen atom is particularly preferable in view of high reactivity with a curing agent.
Specifically, the following compounds are preferable as the general formulas (1) and (2).

  Among them, the following compounds are more preferable.

  The diluent of the present invention is at least one selected from epoxy compounds represented by the general formulas (1) and (2), and the epoxy compound is a triepoxy compound having three epoxy rings, and these epoxy compounds Furthermore, it includes a diepoxy compound in which one of the three epoxy rings possessed by the compounds represented by the general formula (1) and the general formula (2) has formed a carbon-carbon double bond instead of the epoxy ring. Also good. Furthermore, each said diepoxy compound may be mixed. Specifically, the diepoxy compound is any of the compounds represented by the following general formula (6).

In the general formula (6), L ¹ , L ² , A and B are as defined in the general formulas (1) and (2). Further, in the general formula (6), the substituent of the carbon-carbon double bond represented by a wavy line represents that any of cis / trans isomers possessed by the double bond may be used.
The triepoxy compound represented by the general formulas (1) and (2) and the diepoxy compound represented by the general formula (6) may contain the respective optical isomers, such as diastereomers and enantiomers. It may contain stereoisomers. Further, the triepoxy compound represented by the general formula (1) may be mixed with the triepoxy compound represented by the general formula (2), and two types of diepoxy compounds represented by the general formula (6) may be used. The above may be mixed. Furthermore, one or more kinds of the triepoxy compound represented by the general formula (1) and the diepoxy compound represented by the general formula (6) may be mixed, and the triepoxy represented by the general formula (2) One or more kinds of the compound and the diepoxy compound represented by the general formula (6) may be mixed.

  When a mixture of the triepoxy compound represented by the above general formula (1) and (2) and the diepoxy compound represented by the above general formula (6) is used as the diluent of the present invention, the effect of the present invention is not impaired The mixing ratio thereof is not particularly limited, and can be appropriately set depending on the purpose of use. However, from the viewpoint of maintaining the heat resistance of the cured product, it is preferable to contain 90% by mass or more of the triepoxy compound, and the epoxy resin composition The diepoxy compound is preferably contained in an amount of 1% by mass or more in order to reduce the viscosity of the product.

Therefore, the ratio of the epoxy equivalent of the diluent of the present invention to the theoretical epoxy equivalent of the triepoxy compound (epoxy equivalent of diluent / theoretical epoxy equivalent of the triepoxy compound) is not particularly limited, but is usually 1.0 or more. It is 2 or less, preferably 1.1 or less.
The epoxy equivalent of the diluent of the present invention can be measured according to JIS method K7236: 2001.

The epoxy compound to be used as a diluent according to the present invention has three epoxy groups in one molecule, so that the epoxy equivalent is small, and a dense network is formed by curing, and it is considered to have high Tg and heat resistance. Be
The Tg of the cured product obtained by curing the epoxy resin composition containing the diluent of the present invention is not particularly limited, and the type of epoxy resin as the main material, the epoxy equivalent thereof, the mixing ratio, the type of curing agent, and the curing The preferred range is different depending on the conditions etc., but usually 100 ° C. or higher, preferably 1
It is 10 ° C. or more, and usually 200 ° C. or less.

Since the epoxy compound used as the diluent of the present invention has a small epoxy equivalent, when it is cured, the number of oxygen atoms per unit volume tends to increase, so high adhesion can be expected.
The epoxy compounds used as diluents in the present invention have low viscosity. Therefore, by mixing the diluent of the present invention, even if the epoxy resin (b) is a high viscosity epoxy resin, the viscosity of the epoxy resin composition can be sufficiently lowered to ensure processability. The viscosity is not limited, but is usually 1 cP or more and 30 cP or less, preferably 20 cP or less, more preferably 10 cP or less, still more preferably 5 cP or less at 70 ° C.

  Some epoxy resins (b) have high viscosity and sometimes have poor processability. Since the diluent (a) of the present invention has a low viscosity, the viscosity of the entire epoxy resin composition can be lowered by mixing it with the epoxy resin (b) to form a composition, and the processability can be increased. become. At the same time, since the diluent (a) of the present invention has a high Tg of a cured product obtained by curing it, it is possible to achieve both processability and heat resistance.

When L ¹ and L ² in the general formulas (1) and (2) are carbon chains having no functional group, the cured product is stable to a base or water and has chemical resistance, Low water absorption. When the diluent of the present invention is represented by the general formula (1) and A and B are hydrogen atoms, the curing reaction rate is fast because the epoxy group is at the end. Further, the epoxy compound of the present invention is excellent in processability because it is liquid, and is also usable as a diluent for aqueous epoxy resin since it has water solubility, and has a feature that processing conditions are wide. That is, by mixing the diluent of the present invention, these properties can be added without impairing the properties of the epoxy resin (b).

<Method of producing diluent>
The method for producing the diluent of the present invention is not particularly limited, and may be appropriately synthesized depending on the substrate to be used and desired physical properties. Specifically, using a butenediol which may have a substituent as a starting material, a method of oxidizing a triolefin compound obtained by linking a hydroxyl group of the butenediol and an organic group having a carbon-carbon double bond. Epichlorohydrin is allowed to act on an alcohol compound obtained by linking an organic group having a hydroxyl group to butenediol or butenediol (hereinafter referred to as production method 1), and the obtained diepoxy compound is further oxidized (hereinafter referred to as Production method 2) and the like can be mentioned.

Among them, the production method 1 is preferable because it hardly generates a high molecular weight due to a side reaction, so that the content ratio of the triepoxy compound is higher, and a low viscosity diluent can be obtained. Further, as in the structure of the general formula (1), since a compound having an epoxy group at an adjacent position in the molecule can be easily synthesized, it is also preferable from the viewpoint of heat resistance.
The manufacturing method according to the above-mentioned manufacturing method 1 is specifically described in the specification of Japanese Patent Application No. 2013-212891, and manufacturing the triepoxy compound used in the present invention based on the methods and conditions described therein. it can.

  In addition, as a method for producing an alcohol compound by connecting an organic group having a hydroxyl group to a butenediol by the production method according to the above-mentioned production method 2, Journal of Combinatorial Chemistry (2001), 3, (2), 154-156, Well-known methods, such as 06-329571 gazette, can be used. Moreover, the method and conditions as described, for example in Synthesis (1985), (6-7), 649-51 etc. can be used for the method of making an epichlorohydrin act on the said alcohol compound, and introduce | transducing an epoxy group.

<Epoxy resin composition>
(Epoxy resin (b))
The epoxy resin composition of the present invention contains the diluent (a) for epoxy resin of the present invention and an epoxy resin (b) other than (a).
In addition, the cured product of the present invention is obtained by curing the epoxy resin composition.

The epoxy resin (b) used in the present invention is not particularly limited as long as the object of the present invention is not impaired, and so-called epoxy resins in general can be used.
The epoxy resin (b) is roughly divided into an epoxy resin having an aromatic group and an aliphatic epoxy resin.
The epoxy resin having an aromatic group is an epoxy resin having an aromatic group in the unit structure thereof, and is not particularly limited. Specifically, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S Ether type epoxy resins such as epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, triphenylmethane type epoxy resins; glycidyl amine type epoxy resins obtained from aromatic amines, aminophenols and the like; Ester type epoxy resin etc .; epoxy resin obtained from phenol novolac, epoxy resin obtained from cresol novolak, novolak epoxy resin of bisphenol A, obtained from phenol and hydroxybenzaldehyde Novolak epoxy resins such as novolac epoxy resins; biphenyl having one plurality of epoxy groups to the aromatic ring of a bisphenol type epoxy resin and a phenoxy resin.

  The aliphatic epoxy compound refers to an epoxy resin other than the above-described epoxy resin having an aromatic group, and specifically refers to an epoxy resin having no aromatic group. For example, a hydrogenated epoxy resin obtained by hydrogenating an aromatic ring of an aromatic group possessed by the epoxy resin having an aromatic group, an alicyclic epoxy resin having an alicyclic group in which a cyclic olefin is epoxidized, Examples thereof include heterocyclic epoxy resins such as 1,3,5-trisglycidyl isocyanuric acid, epoxy resins having a silsesquioxane structure, and the like.

The said epoxy resin (b) can be suitably selected according to the use of an epoxy resin composition, 1 type may be used independently, and 2 or more types may be used together in arbitrary combinations.
When the epoxy resin composition of the present invention is used for optical material applications, aliphatic epoxy resins are preferable in that yellow deterioration of a cured product can be suppressed, and alicyclic epoxy resins and epoxy resins of silsesquioxane structure are preferable. Is more preferred. In particular, in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in a skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is preferable.

Specific examples of these alicyclic epoxy resins include, for example, hydrogenated bisphenol A type epoxy resins, dicyclopentadiene diepoxide and the like, but are not limited thereto (Reference: Review Epoxy Resins) Basic edition I p 76-85). These epoxy resins may be used alone or in combination of two or more.
Specific examples of these alicyclic epoxy resins include, for example, hydrogenated bisphenol A type epoxy resins, alicyclic epoxy resins having a glycidyl ether such as pentaerythritol glycidyl ether; dicyclopentadiene diepoxide, 3 ', 4' Aliphatic acid free from glycidyl ether such as epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2-bis (hydroxymethyl) -1-butanol, etc. And epoxy resins of the formula.

Moreover, when using the epoxy resin composition of this invention for thermal radiation material applications, such as a power device, the epoxy resin which has an aromatic group is preferable from a heat resistant viewpoint, and it contains three or more epoxy groups in 1 molecule. Although an epoxy resin is more preferable, it is easy to obtain the effect of viscosity reduction by the diluent of the present invention particularly when the epoxy resin is a high viscosity.

Examples of these epoxy resins include biphenyl type epoxy resins; bisphenol type epoxy resins; epoxy resins having a polycyclic aromatic structure such as naphthalene ring, anthracene ring and pyrene ring; and phenol novolac type epoxy resins.
The mixing ratio of the diluent (a) of the present invention to the epoxy resin (b) can be appropriately set according to the purpose, but the weight ratio of the diluent (a) is usually 50% by mass or less of the epoxy resin composition 30 mass% or less is preferable, and 10 mass% or less is more preferable.

(Hardening agent, hardening accelerator)
The epoxy resin composition of the present invention may further contain a curing agent.
The curing agent used in the present invention is not particularly limited as long as it can cure the epoxy resin composition to be used, and those generally known as epoxy resin curing agents can be used. For example, addition polymerization type curing agents such as phenol type curing agents, primary and secondary amine type curing agents, acid anhydride type curing agents; tertiary amine type curing agents, imidazole type curing agents, organic phosphine type curing agents, phosphonium Catalyst type curing agents such as salt based curing agents;

  Specific examples of the phenol-based curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, and 1,3-bis. (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol Alk novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butyl catechol, t-butyl hydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2 , 4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2, - dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl compound or polyallyl compound of the dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak and the like.

Specific examples of the primary and secondary amine curing agents 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 ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like can be mentioned. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines and the like.
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 And 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, α- (3-aminophenyl) ethylamine, α- (4-aminophenyl) ) Ethylamine, diaminodiechi Dimethyl diphenylmethane, alpha,. Alpha .'- bis (4-aminophenyl)-p-diisopropylbenzene and the like.

  Specific examples of the acid anhydride-based curing agent include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly (ethyl octadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexenetetracarboxylic acid Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate dianhydride, hetic anhydride, nadic anhydride, methyl nadic anhydride, 5- ( 2, -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Anhydrides, 1-methyl-3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride etc. are mentioned.

Specific examples of tertiary amine curing agents include 1,8-diazabicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) And the like.
Specific examples of the imidazole-based curing agent include 2-phenylimidazole, 2-ethyl-4-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-methyl-1-imidazolyl) -ethyl-s-triazine, 2,4-diamino-6- (2-ethyl-4-methyl-1-imidazolyl) -ethyl-s-triazine, 2, 4-diamino-6- (2-methyl-1-imidazolyl) -ethyl-s-tria 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 mentioned.

Examples of the organic phosphine-based curing agent include tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, diphenyl phosphine, phenyl phosphine and the like, and examples of the phosphonium salt-based curing agent include tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium. Ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate and the like can be mentioned.

In addition, which of these curing agents is used is variously selected according to the balance of various properties such as the curing conditions and the shape of the cured resin, the heat resistance of the cured resin, adhesiveness, water absorbency, and bending strength. .
When the epoxy resin composition of the present invention is used for an optical material, it is preferable to use an acid anhydride as a curing agent from the viewpoint of suppressing yellow deterioration, and particularly in the application of an LED encapsulant, hexahydrophthalic anhydride, It is preferred to use methyl hexahydrophthalic acid anhydride. From the viewpoint of curability, heat resistance and moisture resistance, it is preferable to use the catalyst type curing agent such as organic phosphine type, organic phosphonium salt type or tertiary amine in combination as a curing accelerator.

  In addition, when the epoxy resin composition of the present invention is used for a heat radiation material, an addition polymerization type curing agent is preferable as a curing agent from the viewpoint of heat resistance improvement, and a phenol type curing agent or primary and secondary amine curing It is preferred to use an agent. Among them, a phenol novolac curing agent is more preferable as a phenol-based curing agent, and an aromatic polyamine is more preferable as a primary and secondary amine-based curing agent.

The curing agents listed above may be used alone or in combination of two or more in any combination and ratio.
In the epoxy resin composition of the present invention, the amount of the curing agent used is not particularly limited, but when the curing agent is the addition polymerization type curing agent, the diluent (a) of the present invention and the epoxy resin (b) are mixed. The equivalent ratio of the epoxy group in the epoxy resin to the reaction site that reacts with the epoxy group in the curing agent to form a crosslinked structure is usually 0.8 or more, preferably 0.9 or more, and usually 1.5 or less, Preferably, it is used so as to be 1.2 or less. Within this range, the remaining of the unreacted epoxy group and the reaction site of the curing agent are suppressed, and desired physical properties can be easily obtained.

  When the curing agent is the catalyst type curing agent, the amount used is not particularly limited, and can be appropriately adjusted according to the type of epoxy resin (b) used, the structure, or the mixing ratio with the diluent of the present invention, etc. Is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and usually 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the epoxy resin (b) in the epoxy resin composition Used in By using it in the above-mentioned range, sufficient curing can be achieved, and the heat resistance of the cured product, which is a feature of the diluent of the present invention, can be particularly improved.

In the epoxy resin composition of the present invention, if necessary, a curing accelerator may be used in combination with the curing agent. Moreover, it is also possible to cure only with a curing accelerator without using a curing agent. The curing accelerator used is not particularly limited. For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol, 1 , Tertiary amines such as 8-diaza-bicyclo (5,4,0) undecene-7; phosphines such as triphenylphosphine; tetrabutyl ammonium salt, triisopropyl methyl ammonium salt, trimethyl decanyl ammonium salt, cetyl Examples thereof include quaternary ammonium salts such as trimethyl ammonium salt; and quaternary phosphonium salts such as triphenyl benzyl phosphonium salt, triphenyl ethyl phosphonium salt, tetrabutyl phosphonium salt, methyl tributyl phosphonium salt and the like. The counter anion of the quaternary salt is not particularly specified, such as chloride ion, bromide ion, organic phosphate ion, hydroxide ion and the like, but organic phosphate ion and hydroxide ion are particularly preferable.
When using a hardening accelerator, it is usually 0.01 or more and 10 parts by mass or less with respect to 100 parts by mass of the epoxy resin (b).

(filler)
A filler is added to the epoxy resin composition of the present invention as needed for the purpose of improving various properties such as improving the thermal conductivity of the cured resin and reducing the thermal expansion coefficient. be able to. The filler is not particularly limited, but usually an inorganic compound is used. For example, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, silicon nitride, boron nitride, aluminum nitride, magnesium oxide And zirconia, forsterite, steatite, spinel, titania, powder such as talc, or beads obtained by spheroidizing them. In addition, carbon, aluminum, copper, gold, silicon carbide or the like may be added for the purpose of imparting conductivity. One of these may be used alone, or two or more may be used in combination. You may mix the thing from which a particle size and a shape differ.
Although content of these fillers is not specifically limited in the epoxy resin composition of this invention, The quantity which occupies 1 mass% or more and 95 mass% or less normally is used.

(Diluents other than the diluent of the present invention)
The multifunctional epoxy resin composition of the present invention may contain a diluent other than the diluent of the present invention as long as the effects of the present invention are not impaired, but the multifunctional epoxy resin composition of the present invention may It is preferable not to use a diluent other than the diluent of the present invention, since the viscosity is lowered by the addition of the diluent of the present invention and the processability is sufficient.

(Other additives)
Furthermore, various additives for obtaining desired physical properties can be added to the epoxy resin composition of the present invention as long as the performance is not impaired. For example, flame retardants such as phosphorus-containing compounds; phenols, sulfur Antioxidants such as phosphorus system, light stabilizers such as hindered amine, silane coupling agents, release agents such as stearic acid, palmitic acid, zinc stearate, calcium stearate, etc. butyral resins, acetal resins, Binder resins such as acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicone resins; surfactants, dyes, pigments, UV absorbers, etc. And the like can be added.

The epoxy resin composition of the present invention is suitable as an epoxy resin composition for optical materials, and is particularly suitable as an LED sealing material.
When using it for LED sealing material specifically, fluorescent substance can be added as needed. The phosphor has a function of forming white light by, for example, absorbing a part of blue light emitted from the blue LED element and emitting wavelength-converted yellow light. The phosphor is previously dispersed in the epoxy resin composition, and then the photosemiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used.

  The epoxy resin composition of the present invention is also suitable as an epoxy resin composition for heat dissipation materials, but for the purpose of further improving its functionality, in addition to the various additives described above, plasticizers and solders are also useful. A flux for removing the oxide film, a dispersing agent, an emulsifying agent, a low elasticity agent, an antifoaming agent, an ion trapping agent, etc. may be included.

<Cured product>
The epoxy resin composition of the present invention can be easily cured.
At the time of curing, an epoxy resin composition is obtained in which the curing agent, the curing accelerator, the filler, the additives, etc. are mixed with the epoxy resin (b) and the diluent (a) of the present invention as required.
The mixing method of the said epoxy resin composition is not specifically limited, An extruder, a kneader, a roll etc. can be used.
After sufficiently mixing the epoxy resin composition until it becomes uniform, the resin composition is molded. The molding means is not particularly limited, and it can be molded by potting, casting after melting (in the case of a liquid, it does not require melting), casting, or a transfer molding machine.

Although the curing temperature is not particularly limited, it is usually 80 to 200 ° C.
Although the curing time is not particularly limited, the cured product of the present invention can be obtained by heating generally for 2 to 10 hours.
Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N, N-dimethyl acetamide, N-methyl pyrrolidone and the like to make a varnish, if necessary. Curing of the epoxy resin composition of the present invention by heat press forming a prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heating and drying it. It can be a thing. In this case, the solvent is used in an amount of usually 10% by mass or more, preferably 15% by mass or more, and usually 70% by mass or less in the mixture of the epoxy resin composition of the present invention and the solvent. In the case of a liquid composition, it is also possible to obtain an epoxy resin cured product containing carbon fibers by, for example, RTM (Resin Transfer Molding) molding.

  The epoxy resin composition of the present invention can also be used as a film type composition modifier. Specifically, it can be used to improve the flexibility and the like in the B-stage. When such a film-type resin composition is obtained, such a film-type resin composition was coated on the release film with the epoxy resin composition of the present invention as the varnish, and the solvent was removed under heating. Thereafter, B-staging is performed to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The Tg of the cured product is not particularly limited, and can be appropriately adjusted by the ratio of the epoxy resin (b) to the diluent (a) of the present invention, but is usually 140 ° C. or more, preferably 160 ° C. or more The upper limit is usually the Tg of the epoxy resin (b), preferably 250 ° C. or less, more preferably 220 ° C. or less.
Since the Tg of the diluent of the present invention is high, the resulting cured product can maintain heat resistance without significantly lowering the Tg of the epoxy resin (b).

The diluent of the present invention is less susceptible to yellowing after curing. Therefore, even when the epoxy resin composition is cured, the yellow deterioration of the cured product is not reduced.
The cured product of the present invention can be used in general applications in which a thermosetting resin such as an epoxy resin is used, and, for example, an adhesive, a paint, a coating agent, a molding material (including sheet, film, FRP, etc.) In addition to insulating materials (including printed circuit boards and wire coatings), sealing materials, sealing materials, sealing materials, cyanate resin compositions for substrates, acrylic ester resins as curing agents for resists, and other resins etc. Agents and the like.

  Examples of the adhesive include adhesives for electronic materials as well as adhesives for civil engineering, construction, automobiles, general office work, and medical use. Among these, as adhesives for electronic materials, interlayer adhesives for multilayer substrates such as buildup substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, anisotropic conductive films ( Examples of the adhesive include mounting adhesives such as ACF) and anisotropic conductive paste (ACP).

  As the sealing material, for example, a capacitor, a transistor, a diode, a light emitting diode, potting for IC, LSI, etc., dipping, transfer mold sealing, IC, LSI COB (chip on board), COF (chip on film) , Potting for TAB (Tape Automated Bonding), etc., underfill for flip chip etc., QFP (Quad Flat Package), BGA (Ball Grid Array), IC package for CSP (Chip Size Package) etc. Sealing (including a reinforcing underfill) and the like.

  Among the above-mentioned applications, the epoxy resin composition containing the diluent of the present invention has a low viscosity, and is thus suitably used for applications requiring a reduction in viscosity during molding and processing, and the cured product In particular, multilayer printed wiring board, film adhesive, liquid adhesive, semiconductor sealing material, underfill material, 3D-LSI, since it is characterized by having high heat resistance, strength, low linear expansion and the like. Applications for semiconductor materials such as inter-chip fills, insulating sheets, prepregs, heat dissipation substrates, etc. are more preferable.

  As described above, a filler may be added to the epoxy resin composition for the purpose of improving various properties such as improving the thermal conductivity of the cured resin and reducing the thermal expansion coefficient. it can. In the case of materials for power devices, in particular, there is widely known a method of improving heat dissipation by adding a filler having a high thermal conductivity by providing the heat resistance of a cured product with an epoxy resin, while the blending amount of the filler As the viscosity of the composition increases, the viscosity of the composition increases and the moldability deteriorates. That is, since the blending amount of the filler is limited by the viscosity of the liquid component, the epoxy resin composition is required to have lower viscosity in addition to heat resistance. The epoxy resin composition containing the diluent of the present invention has the same degree of viscosity as when the existing diluent is mixed, but the resulting cured product impairs the heat resistance of the epoxy resin (b) as the main material. It is particularly suitable as a material for power devices because it does not occur.

Here, the “power device” specifically refers to a multilayer printed wiring board, a film adhesive, a liquid adhesive, a semiconductor sealing material, an underfill material, an interchip fill for 3D-LSI, an insulating sheet, a prepreg, It is a heat dissipation board and a heat dissipation sheet.
In addition, since the diluent of the present invention is also excellent in transparency, it can also be used as a diluent for epoxy resins for optical materials. Here, the “optical material” is specifically an optical lens, an optical disc, a light guide plate used for a flat panel display and various films, and in particular, a cured product of an epoxy resin composition containing a diluent of the present invention is a main material Since the heat resistance of the epoxy resin (b) which is the above is not impaired, the use for an optical semiconductor member is suitable. Moreover, although an aliphatic epoxy resin is generally used as an epoxy resin for LED sealing materials from a viewpoint of low yellow deterioration property, L ^{1 of} general formula (1), (2) among the diluents of this invention, When L ² , A and B are all aliphatic organic groups including substituents, the diluent itself is also an aliphatic epoxy resin. Therefore, it is more suitable to use these as a diluent for epoxy resin for LED sealing materials, and the epoxy resin composition containing this is suitable as an epoxy resin composition for LED sealing materials.

  The sealing method may be carried out by a general method, and low pressure transfer molding may be mentioned, but sealing may be carried out by injection molding, compression molding, casting, potting, casting, screen printing or the like. The curing conditions at the time of molding and / or after molding vary depending on the types of the components of the epoxy resin composition and the compounding amount, but generally, the curing temperature is 50 to 200 ° C., and the curing time is preferably 1 minute to 10 hours.

The epoxy resin composition containing the said diluent for LED sealing materials, ie, the epoxy resin composition for LED sealing materials, can be applied to a LED apparatus by sealing an LED light emitting element using this.
The LED light emitting element is not particularly limited, and a conventionally known light emitting element can be used. For example, a light emitting element using a nitride-based LED such as GaN or InGaN can be used.

A conventionally known device configuration can be used as the LED device, and there is no particular limitation, but an epoxy resin composition containing a diluent for the LED sealing material is included as a sealing material, for example, the LED light emitting element, An electrode portion formed in the light emitting element, a lead terminal portion for electrically connecting the electrode portion, a die bonding portion for fixing these in the device, and the like can be provided as necessary.

Hereinafter, the present invention will be more specifically described based on experimental examples (synthetic examples and examples), but the present invention is not limited by the following experimental examples as long as the gist thereof is not exceeded.
Materials in the examples used commercially available reagents unless otherwise noted. Moreover, the various analysis methods in an Example and a comparative example are as follows.

( ¹ H-NMR analysis conditions)
Device: AVKER 400 manufactured by BRUKER, 400 MHz
Solvent: Heavy chloroform containing 0.03% by volume of tetramethylsilane
(Hereafter, gas chromatograph (GC) analysis condition 1)

(Gas chromatography analysis conditions)
Column: ZB-5 (30m × 0.25mmφ, 0.25μm)
Detector: Hydrogen flame ion detector (FID)
Inj temperature: 250 ° C
Det temperature: 280 ° C
Temperature rising conditions: After raising the temperature from 100 ° C. to 270 ° C. at 10 ° C./min, it was held for 5 minutes.
(Hereafter, GC analysis condition 2)
Column: ZB-1 (30 mx 0.25 mm φ, 0.25 μm, Shimadzu LCC) detector: Hydrogen flame ion detector (FID)
Inj temperature: 250 ° C
Det temperature: 280 ° C
Temperature rising condition: After holding for 5 minutes at 100 ° C., the temperature was raised to 250 ° C. at 10 ° C./min and kept for 5 minutes more.

(Epoxy equivalent)
It measured according to JIS K 7236: 2001, and described as a solid content conversion value.

(Viscosity analysis)
Analyzer: Corn plate viscometer (made by Tokai Yagami Co., Ltd.)
One drop of epoxy resin sucked by a 3 mL dropper was dropped on the hot plate of the viscometer adjusted to 70 ° C., and the viscosity was measured at a rotation speed of 750 rpm.

(Measurement of glass transition temperature (Tg) and linear expansion coefficient (α ₁ , α ₂ ))
The cured epoxy resin was measured as a cylindrical specimen having a thickness of about 2 mm and a diameter of about 7 mm.
Analyzer (TMA): EXSTAR 6000E (manufactured by Seiko Instruments Inc.)
Measurement mode: Compression mode heating rate: 2 times at 5 ° C / min, measurement temperature range: 0 ° C to 250 ° C
The glass transition temperature in the second measurement was measured.

(Measurement of YI (Yellowness Index))
The cured resin was measured as a plate-shaped test piece having a thickness of about 2 mm and a piece of about 6 cm.
Analyzer: Nippon Denshoku Kogyo Co., Ltd. Color Meter ZE2000

(Heat resistance deterioration test)
An epoxy resin cured product of about 2 mm in thickness and about 6 cm in one piece is put in an oven 150
After leaving for 96 hours at ° C., it was removed from the oven, and the epoxy cured product was cooled to room temperature and then used for measurement of YI and light transmittance.

(UV resistance test)
Using a metalizing vertical weather meter (manufactured by Suga Test Instruments Co., Ltd.) with a thickness of about 2 mm and a square columnar epoxy resin cured product having a length of about 6 cm, conditions of irradiation intensity 0.4 kW / m 2 and black panel temperature 63 ° C. After UV irradiation for 96 hours, it was removed from the metallizing vertical weather meter, and after curing the epoxy cured product to room temperature, it was used for measurement of YI and light transmittance.

(Measurement of light transmittance)
The cured resin was measured as a plate-like test piece having a thickness of about 2 mm and a length of about 6 cm.
Measuring device: Hitachi spectrophotometer UV Solution U-2010 (Spectro
photometer)
Wavelength: 400 nm
Synthesis Example 1 Synthesis of 3-butene-1,2-diol diallyl ether

A 200 mL three-necked flask equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer was purged with nitrogen, and then 5.0 g (56.7 mmol, manufactured by Mitsubishi Chemical Corporation, GC purity 95.3 of 3-butene-1,2-diol. 5% (Area), 25 mL of tetrahydrofuran, 0.5 g (1.6 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of n-tetrabutylammonium bromide, 17.2 g (142.1 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of allyl bromide and granular 6.8 g (170 mmol) of sodium hydroxide was added and allowed to react at an internal temperature of 60 ° C. for 4.5 hours. After completion of the reaction, 20 mL of ion exchanged water was added and extraction was performed with 75 mL of hexane. Thereafter, the organic layer was washed 5 times with 20 mL of ion-exchanged water and dried over magnesium sulfate, and then the solvent was distilled off to obtain 6.1 g (36 mmol, yield 64%) of a clear liquid product. As a result of analysis under (GC analysis condition 1), the GC purity of 3-butene-1,2-diol diallyl ether was 98.3% (Area%). Moreover, the measurement result of ¹ H-NMR was as follows.

[ ¹ H-NMR] δ = 3.47 ppm (1 H, dd, J = 4.6, 10.4 Hz), 3.53 ppm (1 H, dd, J = 6.6, 10.4 Hz), 3.92- 4.13 ppm (5 H, m), 5.15-5. 20 ppm (2 H, m), 5.25-5. 33 ppm (4 H, m), 5. 75 ppm (1 H, dd, J = 7.1, 10 .4 Hz), 5.86-5.97 ppm (2 H, m)
Synthesis Example 2 Synthesis of 3,4-Epoxy-1,2-butanediol Diglycidyl Ether

  A 100 mL reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer was purged with nitrogen, and then 20.0 g (119 mmol) of 3-butene-1,2-diol diallyl ether synthesized in Synthesis Example 1 and 400 mL of chloroform were added. In addition, 110.43 g (about 416 mmol) of m-chloroperbenzoic acid (manufactured by Tokyo Kasei Co., Ltd.) having a purity of about 65% was added in eight divided portions every 30 minutes while adjusting the internal temperature to 40 ° C to 45 ° C. The reaction was carried out for 11 hours while maintaining the internal temperature at 40-45 ° C. The GC area ratio of the triepoxy compound to the diepoxy compound was 91.8: 8.2.

  After completion of the reaction, 100 mL of dichloromethane was additionally added to bring it to room temperature, and 40.0 g of celite was suspended in 120 mL of water and added, and stirred for 15 minutes. Subsequently, the insoluble matter in the reaction mixture was filtered off through Celite, and the residue was washed with 40 mL of dichloromethane and 200 mL of water. While mixing the washing solution and the filtrate, 30 mL of a saturated aqueous solution of sodium thiosulfate was dropped to the reaction system at an internal temperature of 19 to 25 ° C. After stirring at room temperature for 1 hour, the organic layer and the aqueous layer were separated, and the aqueous layer was reextracted with 40 mL of chloroform. The organic layers were combined and washed three times with 40 mL of 1 N aqueous sodium hydroxide solution. The three aqueous layers were then combined and reextracted with 40 mL chloroform. The organic layers were combined and further washed twice with 40 mL of saturated aqueous sodium chloride solution. Subsequently, the two aqueous layers were combined and reextracted with 40 mL of chloroform. These organic layers are combined, the solvent is distilled off, and a mixture containing 3,4-epoxy-1,2-butanediol diglycidyl ether and its diepoxy compound as a transparent viscous liquid (hereinafter referred to as crude 3,4-epoxy (Referred to as 1,2-butanediol diglycidyl ether). The same operation was repeated to obtain crude 3,4-epoxy-1,2-butanediol diglycidyl ether corresponding to 40.0 g (238 mmol) of 3-butene-1,2-diol diallyl ether.

Column chromatography (silica gel N 60 400 g manufactured by Kanto Chemical Co., Ltd., developing solvent: n-hexane / ethyl acetate = 1/1, crude 3,4-epoxy-1,2-butanediol diglycidyl ether) and adding 2 mL of triethylamine The reaction mixture was purified by lyophilization to obtain 23.7 g (109 mmol) of 3,4-epoxy-1,2-butanediol diglycidyl ether. The yield was 46%. As a result of analysis under (GC analysis condition 2), the GC purity of 3,4-epoxy-1,2-butanediol diglycidyl ether was 98.2% (Area%), and the peak of the diepoxy compound was not observed . ^In the measurement of ¹ H-NMR, the peak of the triolefin-derived olefin contained in the product of Synthesis Example 1 was not observed. The chart of the obtained ¹ H-NMR is shown in FIG. Moreover, the viscosity of the obtained 3,4-epoxy-1,2-butanediol diglycidyl ether was 2 cP at 70 ° C., and the epoxy equivalent was 75 g / equivalent. Moreover, the theoretical epoxy equivalent of the epoxy equivalent / triepoxy compound of the obtained 3, 4- epoxy 1, 2- butanediol diglycidyl ether was 1.0.
Synthesis Example 3 Synthesis of 3,4-Epoxy-1,2-butanediol Diglycidyl Ether

After nitrogen substitution of a 100 mL reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer, 5.0 g (27.0 mmol) of diallyl ether of 3-butene-1,2-diol synthesized in Synthesis Example 1; While adding 50 mL of chloroform and adjusting the internal temperature to 40 ° C. to 45 ° C., 24.9 g (about 93.8 mmol) of m-chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) having a purity of about 65% was added in portions . The reaction was carried out for 8 hours while keeping the internal temperature at 40-45 ° C. As a result of GC analysis, 85.0% (Area%) of the triepoxy compound and 15.0% (Area%) of the diepoxy compound were observed.

  After completion of the reaction, 6 mL of saturated aqueous sodium thiosulfate solution was added little by little to the reaction system so that the internal temperature was 45 ° C. or less, and the precipitated insoluble matter was separated by filtration through Celite. The obtained filtrate is washed 3 times with 20 mL of 1 N aqueous solution of sodium hydroxide and further with 20 mL of water, then the solvent is distilled off and crude 3,4-epoxy-1,2-butanediol diglycidyl ether is obtained as a transparent viscous liquid. Obtained.

Column chromatography (silica gel N 60 200 g, manufactured by Kanto Chemical Co., developing solvent: n-hexane / ethyl acetate = 1/1 → 1/2, crude 3,4-epoxy-1,2-butanediol diglycidyl ether) The reaction solution was purified by adding 4 mL of triethylamine and developed to obtain 3.50 g (16.1 mmol) of 3,4-epoxy-1,2-butanediol diglycidyl ether as a diastereomer mixture. The yield was 61%. As a result of analysis under (GC analysis condition 1), the GC purity was 96.5% (Area%), and the peak of the diepoxy compound was not observed. ^In the measurement of ¹ H-NMR, the same peak as in Synthesis Example 2 was observed. The viscosity of the obtained 3,4-epoxy-1,2-butanediol diglycidyl ether was 2 cP at 70 ° C., and the epoxy equivalent was 74 g / equivalent. The epoxy equivalent of the obtained 3,4-epoxy-1,2-butanediol diglycidyl ether / theoretical epoxy equivalent of the triepoxy compound was 1.0.
Synthesis Example 4 Synthesis of cis-2-butene-1,4-diol diglycidyl ether

  After nitrogen substitution of a 100 mL reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer, 2.0 g (23 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of cis-2-butene-1,4-diol, 20 mL of tetrahydrofuran, 2.0 mL of N, N-dimethylacetamide, 0.73 g (2.3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.7 g (68 mmol) of granular sodium hydroxide are added, and the internal temperature is adjusted to 40 ° C. It warmed up. To this, 5.9 g (64 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) of epichlorohydrin was added in three portions and reacted at an internal temperature of 40 to 45 ° C. for 5 hours. After completion of the reaction, the reaction product is washed twice with 10 mL of water, and after 10 mL of ethyl acetate is added, it is washed once with 10 mL of water and the solvent is distilled off to give cis-2-butene-1,4-diol diglycidyl ether 5.2 g of a yellow liquid (hereinafter referred to as crude cis-2-butene-1,4-diol diglycidyl ether) containing was obtained. When analyzed under (GC analysis condition 1), the GC purity was 76.6% (Area%), and the yield was 87%.

Of the crude cis-2-butene-1,4-diol diglycidyl ether, 4.0 g is purified by column chromatography (100 g of silica gel N60 manufactured by Kanto Chemical Co., developing solvent: hexane / ethyl acetate = 1/2) Thus, 1.8 g of cis-2-butene-1,4-diol diglycidyl ether was obtained. The measurement results of ¹ H-NMR are as follows.
[ ¹ H-NMR] δ = 2.61 ppm (2H, dd, J = 2.5, 4.8 Hz), 2.80 ppm (2H, dd, J = 4.3, 5.0 Hz), 3.13 3.18 ppm (2 H, m), 3.38 ppm (2 H, dd, J = 5.8, 11.4 Hz), 3.75 ppm (2 H, dd, J = 3.0, 11.6 Hz), 4.08 -4.19 ppm (4H, m), 5.
70-5.79 ppm (2H, m)
Synthesis Example 5 Synthesis of cis-2,3-Epoxy-1,4-butanediol Diglycidyl Ether

  After nitrogen substitution of a 100 mL reaction vessel equipped with a reflux condenser, a nitrogen introduction pipe, and a thermometer, 1.0 g of crude cis-2-butene-1,4-diol diglycidyl ether synthesized in Synthesis Example 4 (3. 8 mmol) and 10 mL of chloroform, and adjusting the internal temperature to 40 ° C. to 45 ° C., divide 1.6 g (about 6.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of m-chloroperbenzoic acid having a purity of about 65% into two parts Added. The reaction was carried out at an internal temperature of 40 to 45 ° C. for 3 hours.

  After completion of the reaction, 2 mL of a saturated aqueous sodium thiosulfate solution was added little by little to the reaction system so that the internal temperature was 45 ° C. or less, and the precipitated insoluble matter was separated by filtration through Celite. The obtained filtrate is washed 3 times with 3 mL of 1 N aqueous solution of sodium hydroxide and further with 3 mL of water, and then the solvent is distilled off to obtain a yellow liquid containing cis-2-butene-1,4-diol diglycidyl ether (hereinafter referred to as Crude cis-2-butene-1,4-diol diglycidyl ether was obtained. A clear liquid was obtained.

Column chromatography (silica gel N 60 100 g, manufactured by Kanto Chemical Co., Ltd., developing solvent: n-hexane / ethyl acetate = 1/1 to 1/2, triethylamine in crude cis-2-butene-1,4-diol diglycidyl ether) The reaction mixture was purified by adding 1 mL and developed to obtain 0.29 g (1.3 mmol) of cis-2,3-epoxy-1,4-butanediol diglycidyl ether as a diastereomer mixture. As a result of analysis under (GC analysis condition 1), the GC purity was 98% (Area%), and the yield was 34%. The measurement results of ¹ H-NMR are as follows.

[ ¹ H-NMR] δ = 2.57-2.69 ppm (2H, m), 2.77-2.84 ppm (2H, m), 3.13-3.28 (4H, m), 3.34 -3.41, 3.46-3.53 (2H, m), 3.52-3.64 (2H, m), 3.72-3.92 (4H, m)

Moreover, the viscosity of the obtained cis-2,3-epoxy-1,4-butanediol diglycidyl ether was 2 cP at 70 ° C., and the epoxy equivalent was 84 g / equivalent. Further, the epoxy equivalent of the obtained cis-2,3-epoxy-1,4-butanediol diglycidyl ether / the theoretical epoxy equivalent of the triepoxy compound was 1.2.
Synthesis Example 6 Synthesis of trans-2-butene-1,4-diol diglycidyl ether

After nitrogen substitution of a 300 mL reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer, 8.70 g (98.3 mmol) of trans-2-butene-1,4-diol, cis-2-butene- 2-butene-1,4-diol 10.0 g (113 mmol, manufactured by Mitsubishi Chemical Corporation) containing 1.30 g (14.5 mmol) of 1,4-diol, 100 mL of tetrahydrofuran, 10 mL of N, N-dimethylacetamide, n-tetra 3.66 g (11.4 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of butylammonium bromide and 3.62 g (341 mmol) of granular sodium hydroxide were added, and the mixture was heated to an internal temperature of 48 ° C. To this, 29.4 g (317 mmol) of epichlorohydrin was added in five portions and reacted at an internal temperature of 45 to 48 ° C. for 3 hours. After completion of the reaction, the reaction solution is returned to room temperature, the precipitated solid is separated by filtration, the solid is washed with 20 mL of ethyl acetate, and the washing solution and the filtrate are mixed. The solution was washed twice with 30 mL of saturated aqueous sodium chloride solution, and the separated aqueous layer was reextracted with 20 mL of ethyl acetate. These organic layers are combined, dried by adding 10 g of anhydrous sodium sulfate, and after sodium sulfate is filtered off, the solvent is distilled off and a yellow liquid (trans-2-butene-1,4-diol diglycidyl ether ( Hereinafter, crude trans-2-butene-1,4-diol diglycidyl ether was obtained. The same operation was repeated to obtain crude trans-2-butene-1,4-diol diglycidyl ether corresponding to 26.1 g (295 mmol) of trans-2-butene-1,4-diol. The yellow liquid is purified by column chromatography (500 g of silica gel N60 manufactured by Kanto Chemical Co., Ltd., developing solvent: hexane / ethyl acetate = 2/1 → 1/1 → 1/2), 2-butene-1,4-diol di An ethyl acetate solution containing 29.0 g of glycidyl ether as a mixture of trans and cis isomers was obtained, and analysis according to (GC analysis condition 1) revealed that trans-2-butene-1,4-diol di is excluded except ethyl acetate. The GC purity of glycidyl ether was 81.3% (Area%), and the yield as a mixture was 42.6% .The measurement results of ¹ H-NMR were as follows.

[ ¹ H-NMR] δ = 2.62 ppm (2H, dd, J = 2.5, 4.8 Hz), 2.80 ppm (2H, dd, J = 4.3, 4.8 Hz), 3.15 3.18 ppm (2H, m), 3.40 ppm (2H, dd, J = 5.8, 11.4 Hz), 3.74 ppm (2 H, dd, J = 3.0, 11.6 Hz), 4.05 -4.10 ppm (4H, m), 5.82-5.84 ppm (2H, m)

  Synthesis Example 7 Synthesis of trans-2,3-epoxy-1,4-butanediol diglycidyl ether

A nitrogen-substituted 500 mL reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer is mixed with a mixture of trans and cis isomers of 2-butene-1,4-diol diglycidyl ether synthesized in Synthesis Example 6 .0 g (75.0 mmol) and 10 mL of chloroform are added, and 23.9 g (about 90.0 mmol) of m-chloroperbenzoic acid having a purity of about 65% is divided into four while adjusting to an internal temperature of 40 ° C to 45 ° C added. The reaction was carried out at an internal temperature of 40 to 45 ° C. for 4 hours. After completion of the reaction, 30 mL of a saturated aqueous sodium thiosulfate solution was added little by little to the reaction system so that the internal temperature was 45 ° C. or less, and the precipitated insoluble matter was separated by filtration through Celite. The obtained filtrate was washed once with 30 mL of saturated aqueous sodium thiosulfate solution, and the separated aqueous layer was reextracted with 15 mL of ethyl acetate. These organic layers were combined, washed twice with 30 mL of 1 N aqueous sodium hydroxide solution, and the separated aqueous layer was reextracted with 15 mL of ethyl acetate. These organic layers were combined and further washed twice with 15 mL of saturated aqueous sodium chloride solution, and the separated aqueous layer was reextracted with 15 mL of ethyl acetate. After combining these organic layers and evaporating the solvent, a light yellow liquid containing trans-2,3-epoxy-1,4-butanediol diglycidyl ether (hereinafter referred to as crude trans-2,3-epoxy-1, 4-butanediol diglycidyl ether was obtained. Column chromatography (silica gel N 60 150 g manufactured by Kanto Chemical Co., Ltd., developing solvent: n-hexane / ethyl acetate = 1/1 → 1/2, crude trans-2,3-epoxy-1,4-butanediol diglycidyl The residue is purified by adding 1 mL of triethylamine to ether and then developing to obtain 9.86 g (45.6 mmol) of 2,3-epoxy-1,4-butanediol diglycidyl ether as a mixture of diastereomers as a white waxy solid. The As a result of analysis under (GC analysis condition 1), the GC purity of the mixture was 93% (Area%), and the yield was 61%. The measurement results of ¹ H-NMR are as follows.

[ ¹ H-NMR] δ = 2.62 ppm (2H, dd, J = 2.8, 5.0 Hz), 2.80 ppm (2H, dd, J = 0.8, 4.3 Hz), 3.08- 3.14 ppm (2H, m), 3.15-3.19 ppm (2H, m), 3.43 ppm (2H, ddd, J = 6.0, 11.6, 17.9 Hz), 3.52 ppm (2H , Ddd, J = 5.6, 11.8, 26.5 Hz), 3.79-3.88 ppm (4H, m) 3.53 (2H, m), 3.52-3.64 (2H, m) ), 3.72-3.92 (4H, m)

In addition, trans-2,3-epoxy was found to contain 8.96 g (41.4 mmol) of trans-2,3-epoxy-1,4-butanediol diglycidyl ether as a result of measurement of ¹ H-NMR. As -1, 4- butanediol diglycidyl ether, the total yield of the synthesis example 6 and the synthesis example 7 was 27%.
In addition, the viscosity of the obtained trans-2,3-epoxy-1,4-butanediol diglycidyl ether was 2 cP at 70 ° C., and the epoxy equivalent was 82 g / equivalent. The epoxy equivalent of the obtained trans-2,3-epoxy-1,4-butanediol diglycidyl ether / the theoretical epoxy equivalent of the triepoxy compound was 1.1.

(Resin X) 1,6-Hexanediol diglycidyl ether (YED216D manufactured by Mitsubishi Chemical Corporation)
(Resin Y) Hydrogenated bisphenol A epoxy resin (Mitsubishi Chemical Corporation YX8000)
(Resin Z) 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (Celoxide 2021 P, manufactured by Daicel Corporation)

(Examples 1 to 5 and Comparative Examples 1 to 3) Curing of Epoxy Resin Composition In the compounding ratio shown in Table 1 below, an epoxy resin (diluent (a) and epoxy resin (b)) and 4- as a curing agent Methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30 (MH-700, trade name, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 165 g / equivalent) is mixed until uniform at 40 ° C., followed by curing As an accelerator, methyltributylphosphonium dimethyl phosphate (Hishikorin (registered trademark) PX-4MP, manufactured by Nippon Chemical Industrial Co., Ltd.) was added, stirred and dissolved to obtain an epoxy resin composition. The epoxy resin composition is defoamed under reduced pressure, poured into a mold for test piece preparation of each evaluation test, cured in an oven at 100 ° C. for 3 hours, and then at 140 ° C. for 3 hours to clear cure. I got a thing.
Table 1 shows the evaluation results of physical properties of the epoxy resin and the cured product thereof.

The resin X used in Comparative Example 1 is one which has been conventionally used as a viscosity reducing diluent for epoxy resin compositions. Resins Y and Z used in Comparative Examples 2 and 3 are those generally used as epoxy resins for optical materials such as conventional LED sealing materials.
When Examples 1 to 4 and Comparative Example 1 are compared, it was found that the diluent of the present invention exhibited extremely high Tg of the cured product while having low viscosity equivalent to that of the conventional diluent. This is because the epoxy resin to be the diluent of the present invention has three epoxy groups in one small molecule while having a small molecular weight and a low viscosity, and since the epoxy equivalent is small, a dense network is obtained by curing. It is thought that it is because it is formed. From this, it is considered that the use of the diluent of the present invention can maintain the Tg of the cured product at a higher level than when a conventional diluent is used.

Furthermore, in Example 5, by adding the diluent of the present invention to the resin Y used in Comparative Example 2, the viscosity is significantly lower than when the resin Y alone, but the Tg of the cured product does not change. It was shown.
Further, it was found that the Tg of Examples 1 and 2 was higher than that of Examples 3 and 4. This is because the epoxy group possessed by each epoxy resin is located at two ends and one inside in Example 1 and Example 2 in the inside, while all three are located at the end in Example 3, therefore, it is more cured Is considered to be one of the reasons for its high reactivity.

The Tgs of the cured products of Examples 1 to 4 were found to be equal to or higher than Comparative Example 2 and relatively high. Moreover, the viscosity of the diluent of Examples 1-4 was lower than the viscosity of resin Y and Z. Therefore, it is considered that adding the diluent of the present invention to the resins X and Y can lower the viscosity and maintain the Tg of the cured product high.
From the above results, when the diluent of the present invention is used as a diluent for an epoxy resin, the cured product of the epoxy resin composition obtained can be able to lower the viscosity without losing the heat resistance. Therefore, the epoxy resin composition of the present invention is suitable as a semiconductor application for which moldability is required.

Table 2 shows the evaluation results of physical properties required as an optical material for the cured products obtained in Example 2 and Comparative Examples 2 and 3.
As a result, it was found that the cured product of Example 2 had a low linear expansion coefficient in a temperature range (α2) higher than Tg and was lower than that of a conventional epoxy resin.

From the above results, when the diluent of the present invention is mixed with the epoxy resin, the viscosity of the epoxy resin composition can be reduced, and the molding processability can be improved. Further, the cured product not only does not impair the heat resistance of the epoxy resin but also has a low coefficient of linear expansion, so it can be said that it is a highly reliable sealing material with few cracks. Therefore, although the use for a semiconductor sealing agent is anticipated, since this diluent is also an aliphatic epoxy resin, its yellow deterioration property is low, and it is suitable also for the optical material use represented by the sealing agent of LED especially.

  The epoxy resin composition of the present invention can be applied to various fields such as adhesives, paints, materials for civil engineering and construction, insulation materials for electric and electronic parts, etc. In particular, insulation casting and lamination materials in the electric and electronic fields It is useful as a sealing material etc. Examples of the application include a multilayer printed wiring board, a film adhesive, a liquid adhesive, a semiconductor sealing material, an underfill material, an interchip fill for 3D-LSI, an insulating sheet, a prepreg, a heat dissipation substrate and the like.

Claims (16)

A diluent for an epoxy resin, having a structure represented by at least one selected from the following general formula (1) and the general formula (2).

(In the general formula (1) and the general formula (2), L ¹ and L ² are each independently — (CH ₂ ) _n —
(Wherein n represents an integer of 1 to 14) represents an alkylene group, and A and B represent
Each independently represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms which may have a substituent. ) The diluent for epoxy resins according to claim 1, wherein A and B in the general formula (1) and the general formula (2) are hydrogen atoms.   The diluent for epoxy resins according to claim 1 or 2, wherein n is 1. The ratio of the epoxy equivalent of the diluent to the theoretical epoxy equivalent of the diluent is 1.0 or more,
The diluent for epoxy resin according to any one of claims 1 to 3, which is 1.2 or less. It has a structure represented by at least one selected from the general formula (1) and the general formula (2)
The diluent for epoxy resin according to any one of claims 1 to 4, which contains 90% by mass or more of the triepoxy compound. An epoxy resin composition comprising: a diluent (a) for an epoxy resin according to any one of claims 1 to 5; and an epoxy resin (b) other than the diluent (a) for an epoxy resin. object.   The epoxy resin composition according to claim 6, further comprising a curing agent.   The epoxy resin composition according to claim 6, further comprising a filler. The epoxy resin composition according to any one of claims 6 to 8, wherein the epoxy resin (b) is an aliphatic epoxy resin. The epoxy resin composition according to any one of claims 6 to 8, wherein the epoxy resin (b) is an epoxy resin having an aromatic group. The epoxy resin composition for optical materials using the epoxy resin composition of any one of Claims 6-10. The epoxy resin composition for LED sealing materials using the epoxy resin composition of any one of Claims 6-9.   The epoxy resin composition for heat-radiation materials which used the epoxy resin composition of Claim 10.   A cured product obtained by curing the epoxy resin composition according to any one of claims 6 to 13. The LED device with which the LED chip is sealed by the epoxy resin composition of Claim 12.   A heat dissipation material using the epoxy resin composition according to claim 13.

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