JP2014034680A - Epoxy resin composition, cured article and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition in which a chlorine content is small and crystallization is suppressed.SOLUTION: An epoxy resin composition includes an epoxy resin, α-glycols, a compound having a structure represented by formula (1) and a compound having a structure represented by formula (2). In the formulae, X, Y represent a divalent group including an oxygen atom and/or a nitrogen atom, and Rrepresents a 1-10C organic group.

Description

  The present invention relates to an epoxy resin composition, a cured product, and an electronic member.

  A cured product obtained from an epoxy resin composition containing an epoxy resin and a curing agent is excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical properties, etc., and is used in various applications. . In recent years, as an epoxy resin used in the electric / electronic field, an epoxy resin having a low content of chlorine-containing impurities is desired from the viewpoint of corrosion resistance and electrical reliability.

  Patent Document 1 discloses a method for reducing the total chlorine content by using a high-concentration metal hydroxide aqueous solution. Patent Document 2 discloses a resin in which the total amount of chlorine is reduced by using a powdery alkali metal hydroxide. Patent Document 3 discloses a technique for reducing the total amount of chlorine by using a sulfoxide compound as a solvent at the time of dechlorination reaction. Patent Document 4 discloses a technique for reducing the total amount of chlorine by an extraction method.

Japanese Patent No. 3986445 Japanese Patent Publication No. 06-062596 Japanese Examined Patent Publication No. 03-012088 JP 2005-519147 A

  However, the conventional technique may be able to obtain a liquid epoxy resin composition having a low total chlorine content, but has a problem that crystallization is likely to occur during long-term storage because crystallization cannot be sufficiently suppressed. In view of the above circumstances, an object of the present invention is to provide an epoxy resin composition having a small amount of chlorine and suppressed crystallization.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by adding a compound having a specific structure to a specific epoxy resin, and have completed the present invention.

That is, the present invention is as follows.
[1]
Epoxy resin,
α-glycols;
A compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2);
And an epoxy resin composition that satisfies the following conditions (1) to (4):
(1) The number average molecular weight of the epoxy resin composition is 150 or more and 1000 or less,
(2) The total chlorine content of the epoxy resin composition is 200 mass ppm or less,
(3) The content of the α-glycols in the epoxy resin composition is 150 meq / kg or less,
(4) The total content of the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) in the epoxy resin composition is 10 mass ppm or more and 10,000. The mass is ppm or less.

(In the formula, X represents a divalent group containing an oxygen atom and / or a nitrogen atom.)


(In the formula, Y represents a divalent group containing an oxygen atom and / or a nitrogen atom, and R ₁ represents an organic group having 1 to 10 carbon atoms.)
[2]
The epoxy according to [1], wherein the sum of the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) is 50 mass ppm or more and 5000 mass ppm or less. Resin composition.
[3]
The epoxy resin composition according to [1] or [2], wherein a viscosity at 25 ° C. is 0.1 Pa · s or more and 20 Pa · s or less.
[4]
The epoxy resin composition according to any one of [1] to [3], further including a curing agent.
[5]
Hardened | cured material obtained by hardening the epoxy resin composition as described in [4].
[6]
The electronic member containing the hardened | cured material as described in [5].

  According to the present invention, it is possible to provide an epoxy resin composition with a small amount of chlorine and suppressed crystallization.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

The epoxy resin of the present embodiment includes an epoxy resin, α-glycols, a compound having a structure represented by the following formula (1), and a compound having a structure represented by the following formula (2), And it is an epoxy resin composition that satisfies the following conditions (1) to (4);
(1) The number average molecular weight of the epoxy resin composition is 150 or more and 1000 or less,
(2) The total chlorine content of the epoxy resin composition is 200 mass ppm or less,
(3) The content of α-glycols in the epoxy resin composition is 150 meq / kg or less,
(4) The total content of the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) in the epoxy resin composition is 10 mass ppm or more and 10000 mass ppm or less. It is.

(In the formula, X represents a divalent group containing an oxygen atom and / or a nitrogen atom.)


(In the formula, Y represents a divalent group containing an oxygen atom and / or a nitrogen atom, and R ₁ represents an organic group having 1 to 10 carbon atoms.)

  Condition (1): The number average molecular weight of the epoxy resin composition of this embodiment is 150 or more and 1000 or less. When the number average molecular weight is less than 150, the heat resistance of the cured product becomes insufficient. When the number average molecular weight exceeds 1000, the viscosity becomes too high and the moldability is poor. From the viewpoint of moldability at the time of curing, the number average molecular weight is preferably 200 or more and 800 or less, more preferably 300 or more and 600 or less. The number average molecular weight can be measured by gel permeation chromatography (GPC).

  Condition (2): The total chlorine amount of the epoxy resin composition of this embodiment is 200 mass ppm or less. If the total chlorine content of the epoxy resin exceeds 200 ppm by mass, the corrosion of the metal by the cured product of the epoxy resin composition will proceed. From the viewpoint of long-term reliability when used for semiconductor devices and copper-clad laminates, the total chlorine content is preferably 150 ppm by mass or less, more preferably 100 ppm by mass or less. The total chlorine content can be measured by the method described in the examples.

Condition (3): The content of α-glycols in the epoxy resin composition of the present embodiment is 150 meq / kg or less. The α-glycols referred to here are compounds having a structure represented by the following formula (3). When the content of α-glycols exceeds 150 meq / kg, the content of the highly reactive primary hydroxyl group is too high, so that when a modification reaction of a resin such as a phenol resin or an isocyanate resin is performed, the molecular weight is increased. Undesirable reactions such as gelation occur. Furthermore, from the viewpoint of water absorption, the content of α-glycols is preferably 100 meq / kg or less, and more preferably 50 meq / kg or less. The content of α-glycols can be measured by the method described in Examples described later.

(Wherein R ₂ represents a monovalent organic group)

R ₂ is not particularly limited as long as it is a monovalent organic group. Examples of R ₂ include a monovalent substituent obtained by removing a hydrogen atom from a phenol resin, and a monovalent substituent obtained by removing a hydrogen atom from a primary amine or a secondary amine.

  Examples of α-glycols include, for example, glycol added to bisphenol A, condensed with glycerin, glycidol added to bisphenol F, condensed with glycerin, glycidol added to diaminodiphenylmethane, Or the thing condensed with glycerin etc. is mentioned.

Condition (4): The total content of the compound having the structure represented by Formula (1) and the compound having the structure represented by Formula (2) in the epoxy resin composition of the present embodiment is 10 masses. It is ppm or more and 10000 mass ppm or less. If the total content of the above compounds is less than 10 ppm by mass, crystallization cannot be sufficiently suppressed. If the total content of the above compounds exceeds 10,000 ppm by mass, the physical property balance such as long-term reliability, heat resistance and water absorption of the cured product will be poor. The sum total of content of the said compound becomes like this. Preferably they are 50 mass ppm or more and 5000 mass ppm or less, More preferably, they are 100 mass ppm or more and 2000 mass ppm or less. If the total content of the above compounds is not less than the above lower limit, crystallization tends to be further suppressed, and if it is not more than the above upper limit, the physical property balance such as long-term reliability, heat resistance and water absorption of the cured product is more. Further improve.

(In the formula, X represents a divalent group containing an oxygen atom and / or a nitrogen atom.)

(In the formula, Y represents a divalent group containing an oxygen atom and / or a nitrogen atom, and R ₁ represents an organic group having 1 to 10 carbon atoms.)

  X in Formula (1) should just be a bivalent group containing an oxygen atom and / or a nitrogen atom, and is not limited. Among these, from the viewpoint of the purity of the compound having the structure represented by Formula (1) and the compound having the structure represented by Formula (2), a divalent group containing an oxygen atom is preferable. A divalent group containing an oxygen atom and having few bonding groups is preferred, and an oxygen atom is more preferred.

  Y in formula (2) is not particularly limited as long as it is a divalent group containing an oxygen atom and / or a nitrogen atom. Among these, from the viewpoint of the purity of the compound having the structure represented by Formula (1) and the compound having the structure represented by Formula (2), a divalent group containing an oxygen atom is preferable. A divalent group containing an oxygen atom and having few bonding groups is preferred, and an oxygen atom is more preferred.

R ₁ in Formula (2) is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms. Specific examples of R ₁ are preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- group, from the viewpoint of suppressing crystallization. It is a butyl group.

  Preferable specific examples of the compound having the structure represented by the formula (1) include a compound represented by the following formula (4) having a bisphenol A skeleton and a following formula (6) having a bisphenol F skeleton. Compounds.

Preferable specific examples of the compound having the structure represented by the formula (2) include a compound represented by the following formula (5) having a bisphenol A skeleton and a following formula (7) having a bisphenol F skeleton. Compounds.

(In the formula, G ₁ represents a hydrogen atom or a glycidyl group.)

(In the formula, G ₁ represents a hydrogen atom or a glycidyl group, and R ₂ represents an organic group having 1 to 10 carbon atoms.)

(In the formula, G ₁ represents a hydrogen atom or a glycidyl group.)

(Wherein, _{G 1} represents a hydrogen atom or a glycidyl group, _{R 3} represents an organic group having 1 to 10 carbon atoms.)

In the formula, G ₁ may be a hydrogen atom or a glycidyl group, and is preferably a glycidyl group from the viewpoint of reactivity. Wherein, R ₂ may be any organic group having 1 to 10 carbon atoms is not particularly limited. Specific examples of R ₂ are preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of suppression of crystallization, and more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- It is a butyl group. Wherein, R ₃ may be any organic group having 1 to 10 carbon atoms is not particularly limited. Specific examples of R ₃ are preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- group, from the viewpoint of suppressing crystallization. It is a butyl group.

  In the epoxy resin composition of the present embodiment, the total chlorine content in the epoxy resin composition is 200 ppm or less, and the content of α-glycols in the epoxy resin composition is 150 meq / kg or less. Usually, in the case of an epoxy resin composition having such a small amount of total chlorine, the contained epoxy resin molecules tend to be densely arranged and tend to be crystallized. However, in this embodiment, surprisingly, the content of α-glycols, the content of the compound having the structure represented by Formula (1), and the content of the compound having the structure represented by Formula (2) are controlled. By doing, crystallization of an epoxy resin composition can be suppressed. Although it is not clear why the crystallization is suppressed, it is considered that satisfying such a condition breaks down the molecular arrangement of the epoxy resin itself and makes it difficult to crystallize (however, the effect of this embodiment is Not limited to this.)

  In addition, content of the compound which has a structure represented by Formula (1), and the compound which has a structure represented by Formula (2) can be measured by the method as described in the Example mentioned later.

  The viscosity at 25 ° C. of the epoxy resin composition of the present embodiment is preferably 0.1 Pa · s or more and 20 Pa · s or less. When the viscosity of the epoxy resin composition is within the above range, the flowability is further improved when the epoxy resin composition of the present embodiment is used as a mounting material such as a liquid resin composition for sealing.

  As another epoxy resin contained in the epoxy resin composition of the present embodiment, for example, a compound having an average of two or more active hydrogens per molecule, an epichlorohydrin compound, an alkali metal hydroxide, or the like And epoxy resins obtained by condensation reaction in the presence of.

  Examples of compounds having active hydrogen include various phenols such as bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, dihydroxydiphenyl ether, and dihydroxynaphthalene; Examples include various amino compounds such as diaminodiphenylmethane, aminophenol, and xylenediamine; various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid. Among these, from the viewpoint of the balance between the viscosity of the epoxy resin and the heat resistance of the cured product, phenols are preferable, and among the phenols, bisphenols such as bisphenol A and bisphenol F are more preferable.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and rubidium hydroxide, and sodium hydroxide and potassium hydroxide are preferable from the viewpoint of reaction rate and handleability.

  The epoxy resin of this embodiment can be an epoxy resin composition further containing other components. Hereinafter, other components added to the epoxy resin of the present embodiment will be described.

  For example, in the present embodiment, other epoxy resins can be added to the above-described epoxy resin. Other epoxy resins are not particularly limited, and various known resins can be appropriately selected and used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hindered type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol A novolac type epoxy resin and an epoxy resin obtained by halogenating these can be used, such as diglycidyl ether which is an adduct of polyethylene glycol, polypropylene glycol, butanediol, hexanediol, cyclohexanedimethanol and epichlorohydrin. Further, when selecting from polyfunctional epoxy resins having 3 or more epoxy groups in the molecule, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bis A novolac type epoxy resin, dicyclopentadiene / Phenol epoxy resin, alicyclic amine epoxy resin, aliphatic amine epoxy resin and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of other epoxy resins can be appropriately adjusted within a range in which the effects of the present embodiment can be obtained. Usually, the content of other epoxy resins is preferably 75% by mass or less of the epoxy resin composition.

  The epoxy resin composition of this embodiment may further contain a curing agent. The curing agent is not particularly limited, and various known materials can be appropriately selected and used. From the viewpoint of the reaction rate during curing, a guanidine derivative, an aromatic amine compound, a novolac type phenol resin, and It is preferably at least one selected from the group consisting of imidazole curing agents.

  Specific examples of guanidine derivatives include dicyandiamide derivatives such as dicyandiamide, dicyandiamide-aniline adduct, dicyandiamide-methylaniline adduct, dicyandiamide-diaminodiphenylmethane adduct, dicyandiamide-diaminodiphenyl ether adduct, guanidine nitrate, guanidine carbonate, phosphorus Guanidine acid, guanidine sulfamate, aminoguanidine bicarbonate, acetylguanidine, diacetylguanidine, propionylguanidine, dipropionylguanidine, cyanoacetylguanidine, guanidine succinate, diethylcyanoacetylguanidine, dicyandiamidine, N-oxymethyl-N′- Examples include guanidine salts such as cyanoguanidine and N, N′-dicarboethoxyguanidine. Is not particularly limited et.

  Specific examples of the aromatic amine compound include, for example, metaphenylene diamine, paraphenylene diamine, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl methane, 4, 4 ′. -Diamino diphenyl ether etc. are mentioned, However, It does not specifically limit to these.

  Specific examples of the novolak type phenol resin include, but are not limited to, phenol novolak, bisphenol A novolak, cresol novolak, naphthol novolak, and the like.

  Specific examples of the imidazole curing agent include 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and the like, but are not particularly limited thereto. Among these, it is preferable to use 2-methylimidazole from the viewpoint of a reaction active point.

  In the epoxy resin composition of the present embodiment, the content of the curing agent is preferably 0.7 to 1.5 equivalents, more preferably 0.8 to 1.3, with respect to 1 equivalent of epoxy groups of the epoxy resin. Equivalent, more preferably 0.9 to 1.1 equivalent. By setting the content of the curing agent in the above range, the curing proceeds sufficiently, and thus better cured physical properties tend to be obtained.

  The epoxy resin composition of this embodiment may further contain a curing accelerator. Thereby, hardening can be promoted. Specific examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,5-diazabicyclo [4. .3.0] Non-5-ene, tertiary amines such as 1,8-diazabicyclo [5.4.0] undec-7-ene, phosphorus compounds such as triphenylphosphine, organic acid metal salts, Examples include Lewis acids and amine complex salts. The imidazoles described here are used as a curing accelerator for phenol curing.

  Preferably content of a hardening accelerator is 0.1-5.0 mass parts with respect to 100 mass parts of total amounts of the epoxy resin contained in an epoxy resin composition. By setting the content of the curing accelerator in the above range, curing of the epoxy resin proceeds sufficiently and good cured properties tend to be obtained.

  The epoxy resin composition of this embodiment can further contain an inorganic filler as necessary. Specific examples of the inorganic filler include, for example, fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride and the like. The content of the inorganic filler is preferably 90% by mass or less of the epoxy resin composition. By setting the content of the inorganic filler in the above range, the viscosity is sufficiently low and the handleability tends to be excellent.

  Moreover, the epoxy resin composition of this embodiment may further contain other additives, such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as needed.

  Examples of the flame retardant include a halide, a phosphorus atom-containing compound, a nitrogen atom-containing compound, and an inorganic flame retardant compound.

  Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3 -Black Propyl methyl dimethoxy silane, 3-chloropropyl silane coupling agents such as trimethoxysilane. Among these, from the viewpoint of bonding strength, polymerizable functional group silane coupling agent having a preferably.

  Examples of phosphorus atom-containing compounds include 9,10-dihydro-9-oxa-10-phosphananthrene-10-oxide and epoxy derivatives thereof, triphenylphosphine and derivatives thereof, phosphate esters, condensed phosphate esters, and phosphazene compounds. From the viewpoint of heat resistance, phosphazene compounds are preferable.

  Examples of the nitrogen atom-containing compound include guanidine flame retardant, triazine structure-containing phenol, melamine polyphosphate, isocyanuric acid and the like.

  Examples of the inorganic flame retardant compound include magnesium hydroxide and aluminum hydroxide, and magnesium hydroxide is preferable from the viewpoint of heat resistance.

  As an example of the manufacturing method of the epoxy resin composition of this embodiment, it has the process of adding the compound which has a structure represented by Formula (1), and the compound which has a structure represented by Formula (2) to an epoxy resin. A manufacturing method is mentioned. In addition, as another production method, for example, an epoxy resin having a total chlorine content of more than 200 ppm by mass is selected by the production conditions, whereby the compound having the structure represented by the formula (1) and the formula (2) are used. The manufacturing method which has the process made into the epoxy resin composition containing the compound which has a structure represented is mentioned. Hereinafter, these manufacturing methods will be described.

In the case of the manufacturing method which has the process of adding the compound which has a structure represented by Formula (1), and the compound which has a structure represented by Formula (2) to an epoxy resin, first, the epoxy resin to be used is the following process (a ) To (c).
(A) a step of reacting a compound having active hydrogen with epichlorohydrin in the presence of an alkali to obtain a reaction product containing a crude epoxy resin;
(B) removing unreacted epichlorohydrin from the reaction product;
(C) A step of proceeding a ring closure reaction of an epoxy ring by adding an alkali to the reaction product obtained in the step (2).
That is, in this case, as the method for producing the epoxy resin composition of the present embodiment, the epoxy resin prepared by the method having steps (a) to (c) is a compound having a structure represented by the formula (1). And a method for producing an epoxy resin composition, which includes a step of adding a compound having a structure represented by the formula (2). Hereinafter, each step will be described.

(A) A step of reacting a compound having active hydrogen with epichlorohydrin in the presence of an alkali to obtain a reaction product containing a crude epoxy resin

  Examples of compounds having active hydrogen include various phenols such as bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, dihydroxydiphenyl ether, and dihydroxynaphthalene; Examples include various amino compounds such as diaminodiphenylmethane, aminophenol, and xylenediamine; various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid. Among these, from the viewpoint of the balance between the viscosity of the epoxy resin and the heat resistance of the cured product, phenols are preferable, and among the phenols, bisphenols such as bisphenol A and bisphenol F are more preferable.

  Examples of the alkali used in the step (a) include alkali metal hydroxides. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and rubidium hydroxide, and sodium hydroxide and potassium hydroxide are preferable from the viewpoint of reaction rate and handleability.

  It is preferable to make it react, stirring the reaction conditions of the (a) process under the temperature of 50-70 degreeC. In the step (a), a solvent may be used as necessary. Examples of the solvent include alcohol and acrylonitrile.

  The reaction product containing the crude epoxy resin is obtained by the step (a). The crude epoxy resin here is an epoxy resin having a low purity, and is usually a crude epoxy resin having a total chlorine amount exceeding 200 mass ppm. In this embodiment, a commercially available crude epoxy resin may be used instead of the step (a). Usually, the total amount of chlorine of the commercially available epoxy resin exceeds 200 mass ppm, but it is also possible to reduce the total amount of chlorine through the steps (b) and (c).

(B) Step of removing unreacted epichlorohydrin from the reaction product (a) From the reaction product obtained in step (corresponding to a crude epoxy resin or the like when a commercial product is used), unreacted epi Remove chlorohydrin. Examples of the method for removing epichlorohydrin include a method in which the reaction product is washed with water and epichlorohydrin is removed by distillation. As the conditions in that case, heating is performed at 150 ° C. or higher under reduced pressure and distillation is performed.

(C) Step of advancing the ring-closing reaction of the epoxy ring by adding an alkali to the reaction product obtained in step (b). Examples of the alkali used in step (c) include alkali metal hydroxides. . Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and rubidium hydroxide, and sodium hydroxide and potassium hydroxide are preferable from the viewpoint of reaction rate and handleability. The addition amount of the alkali metal hydroxide is usually 0.5 to 5 equivalents, preferably 1 to 3 equivalents, per 1 equivalent of hydrolyzable halogen. Usually, the reaction temperature of the ring closure reaction is preferably in the range of 60 to 120 ° C., and the reaction time is preferably in the range of 0.5 to 3 hours.

  In the present embodiment, in addition to the steps (a) to (c), other steps such as pretreatment, post treatment, and purification may be performed as necessary. For example, it is preferable to further perform a post-processing step after the step (c). As the post-treatment process, for example, a method in which chlorine ions are dissolved in purified water and separated from the reaction solution, a method in which chlorine ions are separated from the reaction solution using an ion exchange resin, or chlorine ions are separated by molecular distillation of an epoxy resin. It may be separated. Among the above, when separating and washing with purified water, it is preferable to neutralize in advance using an acid such as phosphoric acid, carbonic acid, or nitric acid. Thereby, isolation | separation with an organic layer and an aqueous layer becomes favorable.

  The epoxy resin composition of the present embodiment is added to the epoxy resin obtained by the above steps by adding a compound having the structure represented by the formula (1) and a compound having the structure represented by the formula (2). Can be obtained. The addition order, method, conditions, etc. of the compound having the structure represented by formula (1) and the compound having the structure represented by formula (2) are not particularly limited.

  An example of a method for producing a compound having a structure represented by the formula (1) is a method in which methyl epichlorohydrin is β-added to phenols to separate impurities.

  As an example of the manufacturing method of the compound which has a structure represented by Formula (2), the method of making phenols and glycidyl ether manufactured from alcohol etc. react is mentioned.

  In addition, in this embodiment, an epoxy resin composition can be manufactured also by the following methods other than the above-described manufacturing method. For example, a crude epoxy resin having a total chlorine content of more than 200 ppm by mass is obtained by selecting a production condition to obtain a compound having a structure represented by formula (1) and a compound having a structure represented by formula (2). The manufacturing method made into the epoxy resin composition containing only above-mentioned content is mentioned. Examples of the production conditions described above include adding a metal alkoxide and causing a reaction by heating.

  Examples of the metal alkoxide include lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium propoxide, sodium propoxide, potassium propoxide, lithium butoxide, sodium butoxide, potassium. Examples include butoxide and isomers thereof. These may be used individually by 1 type and may use 2 or more types together.

  Although it does not specifically limit as addition amount of a metal alkoxide, Usually, it is preferable that it is 1-20 molar equivalent with respect to the total chlorine amount contained in a crude epoxy resin, and it is 2.5- from a viewpoint of reaction rate. It is more preferably 20 molar equivalents, and further preferably 2.5 to 15 molar equivalents from the viewpoint of facilitating oil-water separation when washing impurity ions.

  Examples of the reaction solvent include a keto group-containing solvent, an ether group-containing solvent, and an amide group-containing solvent. Among these, a keto group-containing solvent or an amide group-containing solvent is preferable. Examples of the keto group-containing solvent include chain ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; cyclopentanone, cyclohexanone, and cyclohepta. Examples include non-cyclic ketones. Examples of the amide group-containing solvent include N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and γ-caprolactam. By using an amide group-containing solvent, an increase in viscosity can be suppressed. In particular, when acetone or methyl ethyl ketone is used, the reaction with the metal alkoxide can be performed efficiently.

  The epoxy resin composition of the present embodiment can be cured to obtain a cured product. As a method for producing a cured product, a known method can be used. For example, it can be cured by heating after filling, or cured by thermocompression bonding of a film obtained by drying after coating, or a B stage. For example, after forming into a prepreg, the resin is pressure-molded and cured.

  The cured product of this embodiment can be used as an electronic member. Examples of the electronic member include an underfill material, a die attach material, a heat dissipation material, and a laminated material.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited at all by these Examples. In the following description, “part” and the like are based on mass unless otherwise specified.

First, each measurement method, evaluation method, and test method will be described.
(1) Number average molecular weight To a gel permeation chromatography apparatus (“GPC-8020” manufactured by Tosoh Corporation), “shodex A-804”, “shodex A-803”, “shodex A-802” manufactured by Showa Denko KK “Shodex A-802” was used as a column, tetrahydrofuran was used as a carrier solvent, and the number average molecular weight was determined from comparison with the elution time of polystyrene having a known molecular weight.

(2) Epoxy equivalent The epoxy equivalent was measured according to JIS K7236. The sample was dissolved in a mixed solution of propyl alcohol and benzyl alcohol, potassium iodide was added, and 1N hydrochloric acid titration was performed on the mixed solution.

(3) Total chlorine content Total chlorine content was measured according to JIS K7246. A sample was dissolved in diethylene glycol monobutyl ether, 1N potassium hydroxide-propylene glycol solution was added, and the mixture was boiled for 20 minutes, and then silver nitrate titration was performed.

(4) Content of α-glycols The content of α-glycols in the sample was determined according to JIS K7146. That is, an epoxy resin (or an epoxy resin composition) was dissolved in chloroform and reacted with a periodic acid solution, and then sulfuric acid and potassium iodide were added to perform sodium thiosulfate titration.

(5) Identification and quantification of compound having structure represented by formula (1) and compound having structure represented by formula (2) After separating each component from the sample by preparative GPC, ¹ H- Each compound was identified and quantified by NMR. An epoxy resin (or epoxy resin composition) was dissolved in chloroform to prepare a solution. The fraction of the compound having the structure represented by formula (1) and the fraction of the compound represented by formula (2) from the prepared solution using HPLC (manufactured by Nippon Analytical Industrial Co., Ltd., “LC-908 type”) The fractions were collected and the respective contents were calculated. Then, after replacing the chloroform solvent heavy chloroform, nuclear magnetic resonance apparatus (JEOL Ltd., "JNM-ECS400") was analyzed by ¹ H-NMR spectrum using. A compound having a structure represented by the formula (1) is identified by the presence or absence of a peak at a chemical shift of 4.3 to 4.6 ppm, and is represented by the formula (2) by the presence or absence of a peak near a chemical shift of 1.11 ppm. A compound having the following structure was identified: Further, from the ¹ H-NMR spectrum, the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) were quantified.

(6) Viscosity measuring method A Cannon Fenceke viscosity tube containing 15 g of the sample was placed in a constant temperature water bath set at 25 ° C., and allowed to stand for 30 minutes, and then the outflow time of the sample was measured to measure the viscosity.

(7) Days until crystallization Take 5 g of each 3g sample in a 10mL screw tube, put in a refrigerator at 4 ° C, measure the number of days until 3 of the 5 become cloudy, and count the number of days until crystallization. It was.

(8) Evaluation of heat resistance of cured product (glass transition temperature)
Dicyandiamide was added to the epoxy resin composition so that the amine equivalent was 0.6 times the epoxy equivalent and heated at 180 ° C. for 45 minutes to obtain a cured product. The glass transition temperature (° C.) of the obtained cured product was measured at a temperature rising rate of 10 ° C./min using differential scanning calorimetry (“DSC 6220” manufactured by Seiko Instruments Inc.).

(9) HAST test (Highly accelerated temperature and humidity stress test)
The HAST test was performed according to IEC 68-2-66. That is, dicyandiamide was added to the epoxy resin composition so that the amine equivalent was 0.6 times the epoxy equivalent and heated at 180 ° C. for 45 minutes to obtain a cured product. The evaluation board | substrate was produced from the obtained hardened | cured material, and the time until it short-circuits by migration was applied by applying the voltage of 100V under the conditions of 85 degreeC and 85% RH.

(Synthesis Example 1; synthesis of a compound having a structure represented by Formula (1))
After 100 parts by mass of bisphenol A was dissolved in 100 parts by mass of ethanol, 29.2 parts by mass of 2-chloromethyl-2-methyloxirane was further added and heated to 40 ° C. Thereafter, 7.2 parts by mass of a 48.5% aqueous sodium hydroxide solution was further added and heated at 40 ° C. for 2 hours. As a result, 120 parts by mass of the compound (a) represented by the following formula (a) (corresponding to the compound represented by the formula (4)) was obtained.

After adding 287 parts by mass of epichlorohydrin to 120 parts by mass of the obtained compound (a) and dissolving it by heating at 55 ° C., 72.4 parts by mass of 48.5% aqueous sodium hydroxide solution was added over 2 hours. After adding and reacting, 100 parts by mass of purified water is added, the resulting salt is washed, epichlorohydrin is distilled off, silica gel chromatography (solvent: tetrahydrafuran, silica gel used: manufactured by Fuji Sicilia, product By the name “Chromatolex BW”), a compound A represented by the following formula (A) (corresponding to a compound represented by formula (4)) was obtained. The structure was confirmed by NMR measurement.

(Synthesis Example 2; synthesis of a compound having a structure represented by Formula (2))
After 100 parts by mass of bisphenol A was dissolved in 100 parts by mass of ethanol, 57 parts by mass of tert-butyl glycidyl ether was further added and heated to 40 ° C. Thereafter, 7.2 parts by mass of a 48.5% aqueous sodium hydroxide solution was further added and heated at 40 ° C. for 2 hours. As a result, 120 parts by mass of the compound (b) represented by the following formula (b) (corresponding to the compound represented by the formula (5)) was obtained.

After adding 287 parts by mass of epichlorohydrin to 120 parts by mass of the obtained compound (b) and dissolving it by heating at 55 ° C., 72.4 parts by mass of a 48.5% aqueous sodium hydroxide solution was added over 2 hours. After adding and reacting, 100 parts by mass of purified water is added, the resulting salt is washed, epichlorohydrin is distilled off, silica gel chromatography (solvent: tetrahydrafuran, silica gel used: manufactured by Fuji Sicilia, product The compound B represented by the following formula (B) (corresponding to the compound represented by the formula (5)) was separated and purified from the obtained reaction solution by the name “Chromatolex BW”). The structure was confirmed by NMR measurement.

(Synthesis Example 3; synthesis of a compound having a structure represented by Formula (2))
The compound C was synthesized in the same manner as in Synthesis Example 2 except that methyl glycidyl ether was used instead of tert-butyl glycidyl ether, and corresponded to compound C represented by the following formula (C) (corresponding to the compound represented by formula (5)) ) The structure was confirmed by NMR measurement. In the obtained compound C, a peak was confirmed at 3.30 ppm in ¹ H-NMR measurement.

(Synthesis Example 4; synthesis of a compound having a structure represented by Formula (2))
The compound D was synthesized in the same manner as in Synthesis Example 2 except that isopropyl glycidyl ether was used instead of tert-butyl glycidyl ether, and the compound D represented by the following formula (D) (corresponding to the compound represented by formula (5)) ) The structure was confirmed by NMR measurement. In the obtained compound D, a peak was confirmed at 3.19 ppm in ¹ H-NMR measurement.

(Synthesis Example 5; synthesis of a compound having a structure represented by Formula (1))
Synthesis was performed in the same manner as in Synthesis Example 1 except that bisphenol F was used in place of bisphenol A to obtain compound E (corresponding to the compound represented by formula (6)) represented by the following formula (E). . The structure was confirmed by NMR measurement.

(Synthesis Example 6; synthesis of a compound having a structure represented by Formula (2))
The compound F was synthesized in the same manner as in Synthesis Example 2 except that bisphenol F was used instead of bisphenol A to obtain a compound F represented by the following formula (F) (corresponding to a compound represented by the formula (7)). . The structure was confirmed by NMR measurement.

(Synthesis Example 7)
Bisphenol A type epoxy (Asahi Kasei Epoxy, “AER260”, epoxy equivalent 188 g / eq, total chlorine content 1566 mass ppm, hydrolyzable chlorine content 517 mass ppm, α-glycol content 18 meq / kg, hereinafter “BisA -Ep ".) 50 parts by mass was dissolved in 100 parts by mass of dehydrated acetone at room temperature of 25 ° C to obtain a solution. To the resulting solution, 0.10 parts by mass of potassium tert-butoxide was added as a powder and reacted at 40 ° C. for 90 minutes. Thereafter, 20 parts by mass of water was added to the solution to stop the reaction, and then neutralized by adding 0.087 parts by mass of an alkali equivalent of phosphoric acid, and acetone was recovered under reduced pressure. Thereafter, 100 parts by mass of toluene was added to the solution, followed by washing with water three times to separate the oil layer and the aqueous layer. Toluene was recovered from the oil layer under reduced pressure to obtain an epoxy resin composition G. The obtained epoxy resin composition G had an epoxy equivalent of 189 g / eq, a total chlorine content of 172 mass ppm, an α-glycol content of 25 meq / kg, and a number average molecular weight of 397. Further, by the above-described measurement method, the compound G1 represented by the following formula (G1) (corresponding to the compound represented by the formula (4)) and the compound G2 represented by the following formula (G2) (formula (5)) It was confirmed that the content of the compound G1 was 260 mass ppm and the content of the compound G2 was 640 mass ppm.

(Synthesis Example 8)
Bisphenol F type epoxy instead of bisphenol A type epoxy (DIC Corporation, “Epiclon 830”, epoxy equivalent 172 g / eq, total chlorine content 3015 mass ppm, hydrolyzable chlorine content 1416 mass ppm, α-glycol content An epoxy resin composition H was obtained in the same manner as in Synthesis Example 5 except that 18 meq / kg (hereinafter also referred to as “BisF-Ep”) was used. The obtained epoxy resin composition H had an epoxy equivalent of 175 g / eq, a total chlorine content of 128 mass ppm, an α-glycol content of 25 meq / kg, and a number average molecular weight of 368. Further, by the above-described measurement method, a compound represented by the following formula (H1) (corresponding to a compound represented by the formula (6)) and a compound represented by the following formula (H2) (represented by the formula (7)). The content of compound H1 was 480 ppm by mass, and the content of compound H2 was 870 ppm by mass.

(Synthesis Example 9)
Bisphenol A type epoxy (Asahi Kasei Epoxy, “AER260”, epoxy equivalent 188 g / eq, total chlorine content 1566 mass ppm, hydrolyzable chlorine content 517 mass ppm, α-glycol content 18 meq / kg, hereinafter “BisA Epoxy resin I was obtained according to the method described in Example 1 of JP-B-06-062596. That is, 100 parts by mass of BisA-Ep was dissolved in 400 parts by mass of toluene, suspended by adding 2 parts by mass of fine powder potassium hydroxide having a purity of 95% and an average particle size of 150 μm or less, and stirred at 110 ° C. for 4 hours. . Thereafter, 400 parts by mass of hexane was added to the solution, followed by filtration. The purified epoxy resin composition I was obtained by concentrating the filtrate from which the insoluble matter had been separated under reduced pressure. The obtained epoxy resin composition I had an epoxy equivalent of 182 g / eq, a total chlorine content of 45 mass ppm, an α-glycol content of 20 meq / kg, and a number average molecular weight of 385. Moreover, by the above-mentioned measuring method, the compound I1 represented by the following formula (I1) and the compound I2 represented by the following formula (I2) were quantified, the content of the compound I1 was 82 mass ppm, It was confirmed that it was not included. The structure was confirmed by NMR measurement.

(Synthesis Example 10)
Bisphenol F type epoxy instead of bisphenol A type epoxy (DIC Corporation, “Epiclon 830”, epoxy equivalent 172 g / eq, total chlorine content 3015 mass ppm, hydrolyzable chlorine content 1416 mass ppm, α-glycol content An epoxy resin composition J was obtained in the same manner as in Synthesis Example 9 except that 18 meq / kg (hereinafter also referred to as “BisF-Ep”) was used. The obtained epoxy resin composition J had an epoxy equivalent of 168 g / eq, a total chlorine content of 43 mass ppm, an α-glycol content of 20 meq / kg, and a number average molecular weight of 375. Moreover, the compound J1 represented by the following formula (J1) and the compound J2 represented by the following formula (J2) are quantified by the measurement method described above, and the content of the compound J1 is 54 ppm by mass. It was confirmed that it was not included. The structure was confirmed by NMR measurement.

(Synthesis Example 11)
Bisphenol A type epoxy (Asahi Kasei Epoxy, “AER2502”, epoxy equivalent 185 g / eq, total chlorine content 952 mass ppm, hydrolyzable chlorine content 18 mass ppm, α-glycol content 35 meq / kg, hereinafter “BisA Epoxy resin K was obtained according to the method described in Example 15 of JP-B-03-012088. That is, 100 parts by mass of BisA-Ep was dissolved in 200 parts by mass of dimethyl sulfoxide, and this was stirred for 30 minutes at 50 ° C. with potassium tert-butoxide. After that, the epoxy was purified by concentrating the solvent under reduced pressure after washing with warm water. A resin composition K was obtained. The obtained epoxy resin composition K had an epoxy equivalent of 189 g / eq, a total chlorine content of 129 mass ppm, an α-glycol content of 170 meq / kg, and a number average molecular weight of 388. In addition, by the measurement method described above, the compound K1 represented by the following formula (K1) and the compound K2 represented by the following formula (K2) were quantified, and the content of the compound K1 was 22 mass ppm. It was confirmed that the content was 25 ppm by mass.

Example 1
Epoxy resin composition I To 99.94 parts by mass, 0.03 parts by mass of compound A and 0.03 parts by mass of compound B were mixed at a room temperature (25 ° C.) using an autorotation / revolution mixer (manufactured by THINKY, “Aritori Kentaro”). And kneading for 5 minutes, defoaming for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Example 2)
Epoxy resin composition I To 99.97 parts by mass, 0.01 part by mass of compound A and 0.02 part by mass of compound C were mixed at room temperature (25 ° C.) using an autorotation / revolution mixer (manufactured by THINKY, “Aritori Kentaro”). And kneading for 5 minutes, defoaming for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Example 3)
After 99.55 parts by mass of the epoxy resin composition I, 0.45 parts by mass of the compound D was kneaded at room temperature (25 ° C.) for 5 minutes using an autorotation / revolution mixer (THINKY, “Awatori Nertaro”), Defoaming was performed for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

Example 4
Epoxy resin composition J To 99.94 parts by mass, 0.03 part by mass of compound E and 0.03 part by mass of compound F were mixed at room temperature (25 ° C.) using a revolving / revolving mixer (manufactured by THINKY, “Awatori Nertaro”). And kneading for 5 minutes, defoaming for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Example 5)
After 99.70 parts by mass of epoxy resin composition J, 0.30 part by mass of compound F was kneaded at room temperature (25 ° C.) for 5 minutes using an autorotation / revolution mixer (THINKY, “Awatori Nertaro”), Defoaming was performed for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Example 6)
After 99.45 parts by mass of the epoxy resin composition J, 0.55 parts by mass of compound B was kneaded at room temperature (25 ° C.) for 5 minutes using an autorotation / revolution mixer (THINKY, “Aritori Netaro”), Defoaming was performed for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Example 7)
Epoxy resin composition I To 99.48 parts by mass, 0.26 parts by mass of compound A and 0.26 parts by mass of compound D were mixed at room temperature (25 ° C.) using an autorotation / revolution mixer (THINKY, “Awatori Kentaro”). And kneading for 5 minutes, defoaming for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Example 8)
The epoxy resin composition G was used as it was and its physical properties were evaluated.

Example 9
The epoxy resin composition H was used as it was, and its physical properties were evaluated.

(Comparative Example 1)
The epoxy resin composition I was used as it was, and its physical properties were evaluated.

(Comparative Example 2)
The epoxy resin composition J was used as it was, and its physical properties were evaluated.

(Comparative Example 3)
The epoxy resin composition K was used as it was, and its physical properties were evaluated.

(Comparative Example 4)
After 99.00 parts by mass of the epoxy resin composition I, 1.00 parts by mass of compound A was kneaded at room temperature (25 ° C.) for 5 minutes using an autorotation / revolution mixer (THINKY, “Aritori Nertaro”), Defoaming was performed for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Comparative Example 5)
Epoxy resin composition I To 98.92 parts by mass, 0.26 parts by mass of compound A and 0.76 parts by mass of compound B were mixed at a room temperature (25 ° C.) using an autorotation / revolution mixer (manufactured by THINKY, “Aritori Nertaro”). ) For 5 minutes and then defoamed for 3 minutes to obtain an epoxy resin composition. The physical properties of the obtained epoxy resin composition were evaluated.

(Comparative Example 6)
An epoxy resin composition L was obtained by charging 100 parts by mass of epoxy resin composition I and 31 parts by mass of bisphenol A (Idemitsu Kosan Co., Ltd.) into a 1 L separable flask and heating at 180 ° C. for 6 hours. The resulting epoxy resin composition L is a solid resin having an epoxy equivalent of 622 g / eq, a total chlorine content of 105 mass ppm, an α-glycol content of 120 meq / kg, and a number average molecular weight of 1350, and flows at room temperature. There was no sex.

  The evaluation results of each example and each comparative example are shown in Table 1.

In Table 1, “ND” indicates that it was below the measurement limit, “Structure of Formula 1 (ppm)” indicates the content of the compound having the structure represented by Formula 1, and “Formula 2” "Structure (ppm)" indicates the content of the compound represented by Formula 2.

  As shown in Table 1, in each example, crystallization of the epoxy resin composition was suppressed, and it was confirmed that the cured product had good results in the heat resistance and long-term reliability tests.

  The epoxy resin of the present invention can be used as a material for various members including electronic members such as underfill materials, die attach materials, heat radiating materials, and laminated materials.

Claims (6)

Epoxy resin,
α-glycols;
A compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2);
And an epoxy resin composition that satisfies the following conditions (1) to (4):
(1) The number average molecular weight of the epoxy resin composition is 150 or more and 1000 or less,
(2) The total chlorine content of the epoxy resin composition is 200 mass ppm or less,
(3) The content of the α-glycols in the epoxy resin composition is 150 meq / kg or less,
(4) The total content of the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) in the epoxy resin composition is 10 mass ppm or more and 10,000. The mass is ppm or less.

(In the formula, X represents a divalent group containing an oxygen atom and / or a nitrogen atom.)

(In the formula, Y represents a divalent group containing an oxygen atom and / or a nitrogen atom, and R ₁ represents an organic group having 1 to 10 carbon atoms.)   2. The epoxy according to claim 1, wherein the sum of the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) is 50 mass ppm or more and 5000 mass ppm or less. Resin composition.   The epoxy resin composition of Claim 1 or 2 whose viscosity in 25 degreeC is 0.1 Pa.s or more and 20 Pa.s or less.   The epoxy resin composition according to any one of claims 1 to 3, further comprising a curing agent.   Hardened | cured material obtained by hardening the epoxy resin composition of Claim 4.   The electronic member containing the hardened | cured material of Claim 5.