JP2016172852A - Nitrogen-containing epoxy resin, epoxy resin composition, cured product, and electric and electronic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which has low viscosity and is excellent in moldability, workability and storage stability, is excellent in heat resistance and insulating properties when cured, and is formed into a cured product suitable for an electric and electronic material.SOLUTION: There are provided a nitrogen-containing epoxy resin which is represented by general formula (1), has a molecular weight of 380 or less, and has an epoxy equivalent of 0.9 times or more and 1.5 times or less a theoretical value; an epoxy resin composition containing the nitrogen-containing epoxy resin; a cured product formed by subjecting the epoxy resin composition to curing reaction; an electric and electronic material having the cured product; and a method for producing the nitrogen-containing epoxy resin. In formula (1), Arepresents a monovalent organic group; and each of Rto Reach independently represents a hydrogen atom or a methyl group.SELECTED DRAWING: None

Description

  The present invention relates to a novel nitrogen-containing epoxy resin, an epoxy resin composition containing the resin, a cured product obtained by curing the epoxy resin composition, and an electric / electronic material having the cured product. In particular, the present invention is an epoxy having a low viscosity, excellent moldability, processability and storage stability, and excellent in heat resistance and insulation when cured, and is a cured product suitable for electrical and electronic materials. The present invention relates to a resin composition.

Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties, so they are used in various fields such as adhesives, paints, civil engineering and building materials, and insulation materials for electrical and electronic equipment. It is used. In particular, in the electric / electronic field, it is widely used in insulating materials, laminated materials, sealing materials and the like.
In recent years, especially for electrical and electronic equipment materials such as multilayer circuit boards, miniaturization, weight reduction, and high functionality of equipment have progressed, and further multilayering, high density, thinning, weight reduction, reliability, and molding processing. There is a need for improvements in properties. And the improvement of heat resistance, insulation, and storage stability is also calculated | required also about the epoxy resin used for these uses.

  As a high heat resistance epoxy resin, a polyfunctional epoxy resin or the like is known. Specific examples include novolak type epoxy resins such as phenol novolak type, cresol novolak type, and bisphenol A novolak type, and low molecular nitrogen-containing epoxy resins such as tetraglycidyldiaminodiphenylmethane and triglycidylaminophenol. (Refer nonpatent literature 1). Further, nitrogen-containing epoxy resins having a sulfonyl group are known as resins having a structure similar to a glycidylamine type epoxy resin (see Patent Documents 1 and 2).

Plastic Functional Materials Dictionary (Industry Research Committee), 448-465 pages

JP-A-62-84070 JP-A-62-84071

  However, as a result of detailed studies by the present inventors, the novolak type epoxy resin has a high viscosity at the time of melting, and aminophenol triglycidyl ether, which is a nitrogen-containing epoxy resin, increases in viscosity when stored at 150 ° C. It became clear that there was a need to improve sex. In addition, the glycidyl compound having a sulfonyl group has a high viscosity, and the cured product obtained by curing the glycidyl compound has low heat resistance and volume resistance, and is suitable for electrical and electronic equipment materials that require high heat resistance and insulation. Not found out.

  The present invention has been made in view of the above background art and the knowledge obtained by the present inventors. That is, the present invention is an epoxy resin composition having a low viscosity, excellent moldability, processability and storage stability, excellent heat resistance and insulation when cured, and a cured product suitable for electrical and electronic materials. The issue is to provide goods.

  The inventors of the present invention have repeatedly studied the above problems. As a result, it has been found that the above problem can be solved by a nitrogen-containing epoxy resin represented by a specific structure manufactured by a specific method. Furthermore, it has been found that the nitrogen-containing epoxy resin represented by a specific structure produced by this specific method has a specific molecular weight and a specific epoxy equivalent, so that the above problem can be solved. It came to.

  That is, the first gist of the present invention is a nitrogen-containing epoxy resin represented by the following general formula (1), having a molecular weight of 380 or less and an epoxy equivalent of 0.9 times or more of the theoretical value. It exists in the nitrogen-containing epoxy resin characterized by being 5 times or less.

(In the formula, A ¹ represents a monovalent organic group, and each of R ^{1 to} R ³ independently represents a hydrogen atom or a methyl group.)
The second gist of the present invention resides in the nitrogen-containing epoxy resin described in the first gist, wherein A ¹ is an aromatic ring group which may have a substituent. The third gist of the present invention is the nitrogen-containing epoxy resin described in the first or second gist, wherein the epoxy equivalent is not less than 0.9 times and not more than 1.2 times the theoretical value. It exists in epoxy resin.

  Moreover, the 4th summary of this invention exists in the epoxy resin composition containing the nitrogen-containing epoxy resin described in any one 1st thru | or 3 summary. A fifth aspect of the present invention is the epoxy resin composition described in the fourth aspect, wherein the nitrogen-containing epoxy resin described in any one of the first to third aspects is used as the epoxy resin composition. It exists in the epoxy resin composition which contains 10 weight% or more with respect to the total amount of the epoxy resin contained in it. The sixth aspect of the present invention resides in the epoxy resin composition described in the fourth or fifth aspect, which contains a curing agent and a filler. A seventh aspect of the present invention is the epoxy resin composition described in the sixth aspect, wherein the filler is contained in an amount of 10% by weight to 95% by weight with respect to the total solid content in the epoxy resin composition. It exists in an epoxy resin composition.

And the 8th summary of this invention exists in the hardened | cured material formed by carrying out hardening reaction of the epoxy resin composition described in any one of the 4th thru | or 7th summary. The ninth aspect of the present invention resides in an electric / electronic material having a cured product described in the eighth aspect.
The tenth gist of the present invention is a method for producing a nitrogen-containing epoxy resin, which is obtained by reacting a compound represented by the following general formula (2). Exist in the manufacturing method.

(In the formula, A ¹ represents a monovalent organic group, and each of R ^{1 to} R ³ independently represents a hydrogen atom or a methyl group.)

  According to the present invention, an epoxy resin composition having a low viscosity, excellent moldability, workability and storage stability, and excellent heat resistance and insulation properties when cured, which becomes a cured product suitable for electrical and electronic materials. Can be provided.

Embodiments of the present invention will be described in detail below. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following descriptions unless it exceeds the gist. It is not something.
In the present invention, the epoxy resin means a compound having an epoxy group or a composition containing the same. In the present invention, the theoretical value of epoxy equivalent represents a value (unit: g / equivalent) obtained by dividing the molecular weight of the compound by the total number of epoxy groups of the structure. [Nitrogen-containing epoxy resin]
The nitrogen-containing epoxy resin of the present invention is represented by the following general formula (1).

(In the formula, A ¹ represents a monovalent organic group, and each of R ^{1 to} R ³ independently represents a hydrogen atom or a methyl group.)
In the general formula (1), A ¹ represents a monovalent organic group. A ¹ is not particularly limited as long as it is an organic group having a molecular weight of 380 or less of the nitrogen-containing epoxy resin of the present invention. The number of carbon atoms A ¹ has is preferably large in terms of easily controlling the balance of processability and heat resistance, while it is preferred that less from the viewpoint of excellent workability by lowering the viscosity of the nitrogen-containing epoxy resin. Therefore, the number of carbon atoms A ¹ has is preferably 3 or more, and more preferably 6 or more. On the other hand, it is preferably 12 or less, and more preferably 10 or less.

A ¹ is preferably a hydrocarbon group which may have a substituent.
The hydrocarbon group may be saturated or unsaturated, may be chain or cyclic, may be linear or branched, and may be aliphatic or aromatic. Examples of the saturated hydrocarbon group include saturated chain hydrocarbon groups such as a methyl group, an ethyl group, and a propyl group, and saturated cyclic hydrocarbon groups such as a cyclohexyl group. Examples of the unsaturated hydrocarbon group include unsaturated chain hydrocarbon groups such as vinyl group, allyl group, and ethynylmethyl group, and unsaturated cyclic hydrocarbon groups such as cyclohexenyl group. In addition, examples of the aromatic hydrocarbon group include a phenyl group, a pyridyl group, a thiophene group, and a naphthyl group. Of these, A ¹ is the cured product obtained by curing a composition containing a nitrogen-containing epoxy resins of the present invention (hereinafter sometimes referred to as "cured product of the present invention".) From the viewpoint of excellent heat resistance An aromatic hydrocarbon group which may have a substituent is preferable, more preferably a 5- or 6-membered aromatic hydrocarbon group or a condensed ring thereof, and a 6-membered aromatic hydrocarbon group is More preferred are phenyl and biphenyl, most preferred is phenyl.

In the case where A ¹ is a hydrocarbon group having a substituent, the substituent is not particularly limited as long as the molecular weight of the nitrogen-containing epoxy resin of the present invention is 380 or less, but has 10 or less carbon atoms. Is preferred. Specifically, a saturated or unsaturated alkyl group; an aryl group; an alkyloxy group or an aryloxy group; an alkylcarbonyloxy group or an arylcarbonyloxy group; an alkyloxycarbonyl group or an aryloxycarbonyl group; an acyl group and a substituent. A sulfonyl group and the like which may be present is preferable.

  Examples of the saturated or unsaturated alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclopentyl, hexyl, and cyclohexyl. An alkyl group not substituted with a heteroatom such as a group; an alkyl group substituted with a heteroatom such as a hydroxymethyl group, a methoxymethyl group, an acetyloxymethyl group, a methoxyethyl, a trifluoromethyl group; a vinyl group, 1-propenyl An alkenyl group not substituted with a heteroatom such as a group, allyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 2-methyl-1-propenyl group, 1-hexenyl group, 1-cyclohexenyl; 2-hydroxyethenyl group, 2-methoxycarbonylethenyl group, 2-cyanoetheth Alkenyl groups substituted with heteroatoms such as ruthel groups; alkynyls not substituted with heteroatoms such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 1-hexynyl And an alkynyl group substituted with a hetero atom such as a 2-hydroxyethynyl group, a 2-methoxyethynyl group, and a 2-trimethylsilylethynyl group. Among these, an alkenyl group is preferable, an alkenyl group having 4 or less carbon atoms is more preferable, and an alkenyl group having 3 or less carbon atoms is particularly preferable.

  Examples of the aryl group include an aryl group not substituted with a hetero atom such as a phenyl group, a 1-methylphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, and a 2,5-dimethylphenyl group, and 1-methoxy group. Examples thereof include an aryl group substituted with a hetero atom such as a phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 1-fluorophenyl group, a 2-fluorophenyl group, and a 3-fluorophenyl group. Of these, a phenyl group is preferred.

  Examples of the alkyloxy group or aryloxy group include a methoxy group, an ethoxy group, an allyloxy group, a cyclohexyloxy group, a phenyloxy group, an alkyloxy group or an aryloxy group that does not contain a hetero atom, a methoxymethyloxy group, and an acetylethyl group. Examples thereof include an alkyloxy group or an aryloxy group containing a hetero atom such as an oxy group, a glycidyloxy group, and an o-pyridyloxy group.

Examples of the alkylcarbonyloxy group or arylcarbonyloxy group include an acetyl group, an ethylcarbonyloxy group, an allylcarbonyloxy group, a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group, an alkylcarbonyloxy group or an aryloxy group that does not contain a heteroatom. And an alkylcarbonyloxy group or an aryloxy group containing a heteroatom such as a methoxymethylcarbonyloxy group, an acetylethylcarbonyloxy group, a glycidylcarbonyloxy group, or an o-pyridylcarbonyloxy group.

  Examples of the alkyloxycarbonyl group or aryloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an allyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a phenyloxycarbonyl group that do not contain heteroatoms. And an alkyloxycarbonyl group or an aryloxy group containing a hetero atom such as a methoxymethyloxycarbonyl group, an acetylethyloxycarbonyl group, a glycidyloxycarbonyl group, or an o-pyridyloxycarbonyl group.

  The acyl group is substituted with a hetero atom such as an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an iso-propylcarbonyl group, an n-butylcarbonyl group, a t-butylcarbonyl group, a cyclohexylcarbonyl group, or a phenylcarbonyl group. And an acyl group substituted with a hetero atom such as a trifluoromethylcarbonyl group and a p-fluorophenylcarbonyl group. Among these, an acyl group having 4 or less carbon atoms is preferable, and an acyl group having 3 or less carbon atoms is more preferable.

Examples of the sulfonyl group which may have a substituent include alkylsulfonyl groups such as methanesulfonyl group, ethanesulfonyl group and butanesulfonyl group, and arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group. It is done. Of these, a methanesulfonyl group and a p-toluenesulfonyl group are preferable.
Among these substituents, a substituent containing an epoxy group is particularly preferable in terms of improving heat resistance when a cured product is obtained.

R ^{1 to} R ³ each independently represents a hydrogen atom or a methyl group. R ^{1 to} R ³ are preferably hydrogen atoms from the viewpoint of excellent storage stability of the nitrogen-containing epoxy resin of the present invention.
Specific examples of the nitrogen-containing epoxy resin of the present invention are shown below.

  Of these, the following nitrogen-containing epoxy resins are particularly preferable.

  The nitrogen-containing epoxy resin of the present invention has a molecular weight of 380 or less. When the molecular weight of the nitrogen-containing epoxy resin of the present invention is 380 or less, it is considered that both the processability of the epoxy resin and the heat resistance of a cured product obtained by curing the epoxy resin can be achieved. The molecular weight is preferably high in that the epoxy resin has low volatility and a cured product obtained by curing the epoxy resin has high heat resistance, and on the other hand, it is preferably low in terms of reducing the viscosity of the epoxy resin. . Therefore, the molecular weight of the nitrogen-containing epoxy resin of the present invention is preferably 230 or more, more preferably 260 or more, and on the other hand, preferably 370 or less, more preferably 350 or less. .

  The nitrogen-containing epoxy resin of the present invention has an epoxy equivalent of 0.9 times to 1.5 times the theoretical value. The lower limit of the epoxy equivalent is preferably 0.95 times the theoretical value, and on the other hand, it is preferably 1.2 times or less of the theoretical value, and more preferably 1.15 times or less. preferable. In the nitrogen-containing epoxy resin of the present invention, as shown in the examples described later, the nitrogen-containing epoxy resin of the present invention has a low viscosity, and the cured product of the composition containing this has excellent heat resistance and insulation.

  In addition, an epoxy equivalent can be obtained as solid content conversion value by measuring by the method of JISK7236: 2001. Here, solid content means components other than volatile components, such as a solvent contained in the nitrogen-containing epoxy resin of this invention. The theoretical value represents a value (unit is g / equivalent) obtained by dividing the molar mass of the molecule in the general formula (1) by the number of epoxy groups of the general formula (1).

The shear viscosity of the nitrogen-containing epoxy resin of the present invention is preferably low in view of excellent moldability and processability. Specifically, it is preferably 20 mPa · s or less.
On the other hand, since it is difficult for the nitrogen-containing epoxy resin of the present invention to volatilize, it is preferably 2 mPa · s or more. Here, the shear viscosity is obtained when a parallel plate is rotated so that 1.45 g of a nitrogen-containing epoxy resin has a thickness of 0.5 mm in a plate having a diameter of 50 mm, 150 ° C., and the outer peripheral portion is 150 rpm. Represents viscosity.

[Method for producing nitrogen-containing epoxy resin]
The nitrogen-containing epoxy resin according to the present invention is preferably produced by epoxidizing a compound represented by the following general formula (2) in that it is easy to obtain an epoxy resin having an epoxy equivalent in a specific range (hereinafter, It may be referred to as “a method for producing a nitrogen-containing epoxy resin of the present invention”).

(In the formula, A ¹ represents a monovalent organic group, and each of R ^{1 to} R ³ independently represents a hydrogen atom or a methyl group.)
Here, even when the epoxidation is performed using an inorganic oxidizing agent such as oxygen or hydrogen peroxide, an organic oxidizing agent such as tert-butyl peroxide, peracetic acid, m-chloroperbenzoic acid, or dimethyldioxirane is used. You may go. In addition, for example, the reaction conditions described in “Comprehensive Organic Transformations” (2nd edition, Wiley-VCH, 1999) pages 915-929 may be used. Of these, hydrogen peroxide or peracetic acid is preferably used in terms of easy production on a larger scale, and m-chloroperbenzoic acid is used on a small scale and easy to epoxidize safely. It is preferable to carry out. In particular, when the cured product of the present invention is used as an electric / electronic material, from the viewpoint of easily reducing the chlorine atom concentration in the nitrogen-containing epoxy resin according to the present invention, chlorine atoms such as hydrogen peroxide and peracetic acid are used. It is preferable to use an oxidizing agent not contained.

  Further, the nitrogen-containing epoxy resin according to the present invention is a known method such as bringing a corresponding sulfonamide compound into contact with epichlorohydrin and condensing with a base, as shown in Examples described later (see Patent Documents 1 and 2). The nitrogen-containing epoxy resin produced in (1) can also be obtained by purification by a method such as crystallization, distillation, column chromatography purification, or the like. That is, also when the epoxy equivalent of the resulting epoxy resin becomes 1.5 times or more of the theoretical value due to the occurrence of side reactions such as intermolecular crosslinking, such as this condensation reaction, it is purified. Thus, the nitrogen-containing epoxy resin according to the present invention can be obtained.

  In addition, a trace amount by-product etc. may remain in the nitrogen-containing epoxy resin according to the present invention. Examples of such by-products include unreacted raw materials and oligomers formed by reacting unreacted raw materials with generated epoxy. Even if the low-molecular-weight or high-molecular-weight by-product is contained in the nitrogen-containing epoxy resin according to the present invention, the above-mentioned epoxy equivalent is usually high, and a reactive agent containing an epoxy group such as epichlorohydrin is used. When included, the above epoxy equivalent is usually low.

[Epoxy resin composition]
The epoxy resin composition of the present invention contains the nitrogen-containing epoxy resin of the present invention. By containing the nitrogen-containing epoxy resin of the present invention, the epoxy resin composition of the present invention has a low viscosity and is excellent in processability, moldability and storage stability sufficient to be applied to processes such as film molding and coating. . Moreover, when it hardens | cures, it is easy to express heat resistance. Therefore, it is suitable for adhesives, paints, civil engineering and building materials, electrical / electronic materials, and the like.

The epoxy resin composition of the present invention has an epoxy resin other than the nitrogen-containing epoxy resin of the present invention (hereinafter referred to as “others”) unless the effect expressed by containing the nitrogen-containing epoxy resin of the present invention is significantly hindered. It may be referred to as an “epoxy resin”), a curing agent, a filler, other additives and a solvent. When the epoxy resin composition of the present invention contains a component other than the nitrogen-containing epoxy resin of the present invention, the content thereof does not significantly hinder the effect that is usually manifested by containing the nitrogen-containing epoxy resin of the present invention. Within the range, the amount is such that the effect of including components other than the nitrogen-containing epoxy resin of the present invention can be exhibited.

  The content ratio of the nitrogen-containing epoxy resin of the present invention relative to the total solid content contained in the epoxy resin composition of the present invention is preferably large in that it is easy to sufficiently develop the characteristics of the nitrogen-containing epoxy resin of the present invention. It is preferable that the amount of the component other than the nitrogen-containing epoxy resin of the present invention is small in that the characteristics of the component are sufficiently expressed. Therefore, it is usually 0.1% by weight or more, preferably 0.2% by weight or more, particularly preferably 0.4% by weight or more, and usually 95% by weight or less, preferably 90% by weight or less, particularly preferably. It is good that it is 80 weight% or less. In addition, when the 2 or more types of nitrogen-containing epoxy resin of this invention is contained in the epoxy resin composition of this invention, it is preferable that the total amount is the said range.

[Other epoxy resins]
As another epoxy resin which may be contained in the epoxy resin composition of the present invention, one having two or more epoxy groups in the molecule is preferable. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane Examples thereof include various epoxy resins such as a type epoxy resin and a dicyclopentadiene type epoxy resin. In addition, “Plastic Functional Polymer Material Dictionary” (1st edition, Industrial Research Council, 2004), pages 448-465, “Review Epoxy Resins Volumes 1 to 4” (1st edition, Epoxy Resin Technology Association, 2003) and “Review Epoxy Resin Recent Progress I” (1st Edition, Epoxy Resin Technology Association, 2009), etc. may be used. These may be used alone or in combination of two or more in any ratio.

  When another epoxy resin is contained in the epoxy resin composition of the present invention, the content of the nitrogen-containing epoxy resin of the present invention relative to the total amount of the epoxy resin including the nitrogen-containing epoxy resin of the present invention in the composition is: Many are more likely to exhibit the excellent moldability, processability, storage stability, and heat resistance effect of curing a composition containing the nitrogen-containing epoxy resin of the present invention. Effects such as processing controllability of the epoxy resin and controllability of physical properties when a composition containing the epoxy resin is cured are easily exhibited. Therefore, specifically, the content of the nitrogen-containing epoxy resin of the present invention relative to the total amount of the epoxy resin in the composition is usually 0.1% by weight or more, preferably 10% by weight or more, more preferably 20% by weight. Above, particularly preferably 40% by weight or more, and on the other hand, preferably 95% by weight or less, particularly preferably 90% by weight or less.

  Moreover, the total content of the epoxy resin including the nitrogen-containing epoxy resin of the present invention relative to the total solid content contained in the epoxy resin composition of the present invention is often high in that the characteristics of the epoxy resin are sufficiently developed. Preferably, it is preferably small in that the physical properties of components other than the epoxy resin are sufficiently expressed. Therefore, it is usually 1% by weight or more, preferably 3% by weight or more, particularly preferably 5% by weight or more, and usually 95% by weight or less, preferably 80% by weight or less, particularly preferably 70% by weight or less. That is good.

[Curing agent]
The curing agent that may be contained in the epoxy resin composition of the present invention may be any substance that contributes to the crosslinking reaction of the epoxy group of the nitrogen-containing epoxy resin of the present invention, and is generally referred to as an epoxy resin curing agent. In addition to known curing agents, those generally known as curing accelerators are also included. That is, the curing agent according to the present invention is a substance that contributes to the cross-linking reaction between epoxy groups of the epoxy resin contained in the epoxy resin composition of the present invention, or the cross-linking of epoxy resins contained in the epoxy resin composition of the present invention. It is a substance that expresses the function of promoting the reaction and the addition reaction between the epoxy resin and the curing agent.

Curing agents generally referred to as epoxy resin curing agents include, for example, phenolic curing agents, ester curing agents, benzoxazine curing agents, acid anhydride curing agents, primary and secondary amines. Examples thereof include a system curing agent, a mercaptan curing agent, an amide curing agent, and a blocked isocyanate curing agent. It is also possible to use a phenoxy resin as a curing agent.
Various known phenolic curing agents can be used as the phenolic curing agent. Specific examples include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin, phenol Polyhydric phenols such as aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, naphthol novolac resins, brominated bisphenol A, brominated phenol novolac resins; Benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxy Polyhydric phenol resins obtained by condensation reaction with aldehydes such as alcohol; polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols; heavy oils and pitches, phenols and formaldehydes And phenol resins such as co-condensation resins. Of these, phenol novolac resin, phenol aralkyl resin, trisphenol methane resin, biphenyl aralkyl resin, naphthol aralkyl resin, phenol / benzaldehyde / xylylene dimethoxide polycondensate, phenol / benzaldehyde / 4,4′-dimethoxybiphenyl polycondensation A thing etc. are preferable.

The ester curing agent is generally roughly classified into an active ester curing agent and a cyanate ester resin.
The active ester curing agent has a highly reactive ester group such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, a compound in which a heterocyclic hydroxy group is esterified, and has a curing action on an epoxy resin. Say the substance you have. The active ester curing agent is preferably a compound having two or more active ester groups. In particular, from the viewpoint of improving the heat resistance of a cured product obtained by curing the epoxy group resin composition of the present invention, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is more preferable, and the carboxylic acid compound and the phenol compound or An active ester compound obtained from a naphthol compound is more preferred. Further, an aromatic compound having two or more active ester groups obtained from a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group is more preferred, and has at least two compounds having a carboxylic acid and a phenolic hydroxyl group. Particularly preferred are aromatic compounds having two or more active ester groups obtained from aromatic compounds. The active ester curing agent may be linear or hyperbranched. Here, if the compound having at least two carboxylic acids is a compound containing an aliphatic chain, the compatibility with the epoxy resin can be increased, and if the compound has an aromatic ring, the compound of the present invention can be used. The heat resistance of the cured product obtained by curing the epoxy resin composition can be increased. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of improving the heat resistance of a cured product obtained by curing the epoxy resin composition of the present invention. Isophthalic acid, terephthalic acid Is more preferable. Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o -Cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetra Hydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like. Among these, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methyl are used from the viewpoint of improving solubility and improving heat resistance of a cured product obtained by curing the epoxy resin composition of the present invention. Bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol Dicyclopentadienyl diphenol and phenol novolak are preferred, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphth Rene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac are more preferable, α-naphthol, β-naphthol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac are more preferable, α-naphthol, β-naphthol , Dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadieni Diphenols, phenol novolak is particularly preferred, alpha-naphthol, beta-naphthol, dicyclopentadienyl diphenol, phenol novolac especially preferred, alpha-naphthol, beta-naphthol, dicyclopentadienyl diphenol is most preferred. Moreover, as an active ester compound, the active ester compound currently disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and various commercial items may be used. As a commercial item, for example, "EXB-9451" and "EXB-9460" manufactured by DIC Corporation are included as those containing a dicyclopentadienyl diphenol structure, and acetylated products of phenol novolac are Mitsubishi Chemical Corporation. “DC808” manufactured by Mitsubishi Electric Corporation, and “YLH1026” manufactured by Mitsubishi Chemical Co., Ltd. can be cited as benzoylated products of phenol novolac.

  Specific examples of the cyanate ester resin include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether; phenol Novolac, cle Polyfunctional cyanate resins derived from arn novolac, etc. Examples include prepolymers in which these cyanate resins are partially triazines .. Commercially available cyanate ester resins include phenol novolac type polyfunctional cyanate ester resins (manufactured by Lonza Japan Ltd.) Examples include “PT30”, cyanate equivalent 124), and a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified to form a trimer (“BA230” manufactured by Lonza Japan Co., Ltd., cyanate equivalent 232).

Specific examples of the benzoxazine-based curing agent include Fa, Pd (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.
Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride,
Tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol Bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid Anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate An acid dianhydride etc. are mentioned.

  Specific examples of the primary and secondary amine curing agents include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and polyoxypropylene triamines. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine , Diaminodiethyl And rudimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene, and the like.

  A known phenoxy resin can be used as the phenoxy resin. The phenoxy resin is preferably an epoxy resin having a weight average molecular weight of 5,000 to 200,000 and an epoxy equivalent of 2,000 g / equivalent to 100,000 g / equivalent. By including a phenoxy resin in the epoxy resin composition of the present invention, when the cured product obtained by curing the epoxy resin composition of the present invention is a film, its flexibility can be improved. Specific examples of the phenoxy resin include “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YX8100”, “YX6954 (YL6954)”, and “YL6974” manufactured by Mitsubishi Chemical Corporation.

The content of these curing agents contained in the epoxy resin composition of the present invention is such that the epoxy groups contained in the epoxy resin composition of the present invention do not remain unreacted and are easily cured sufficiently in a short time. A larger number is preferable in terms. On the other hand, it is preferable that the number of sites that react with the epoxy group of the curing agent remains unreacted in the cured product obtained by curing the epoxy resin composition of the present invention. Specifically, the epoxy group contained in the epoxy resin composition of the present invention and the reaction site in the curing agent (hydroxyl group of phenolic curing agent, ester group of ester curing agent, NO group of benzoxazine curing agent, acid The equivalent ratio of the anhydride-based curing agent to the acid anhydride group, the amine-based curing agent amino group, etc.) is preferably 0.3 or more, and more preferably 0.8 or more. More preferably, it is particularly preferably used so as to be 0.9 or more. On the other hand, it is preferably used so as to be 1.5 or less, and more preferably used so as to be 1.2 or less. Note that only one type of curing agent may be used, or two or more types may be used in any combination and ratio. As for the content in the case of using 2 or more types of hardening | curing agents, it is preferable that the total amount is said preferable range.

Curing agents that are often referred to as curing accelerators generally include imidazole curing accelerators, tertiary amine curing accelerators, organic phosphine curing accelerators, phosphonium salt curing accelerators, and tetraphenyl boron salts. Examples thereof include a system curing accelerator, a metal curing accelerator, an organic acid dihydrazide, and a boron halide amine complex.
Specific examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2 ' -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium succinic acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Le benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin.

  Specific examples of the tertiary amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol. And tertiary amine compounds such as 1,8-diazabicyclo (5,4,0) -undecene and adducts of these tertiary amine compounds and epoxy resins.

  The content of the imidazole-based curing accelerator and the amine-based curing accelerator contained in the epoxy resin composition of the present invention is preferably large in that the epoxy resin composition of the present invention can be sufficiently cured in a short time. . On the other hand, it is preferable that the storage stability of the epoxy resin composition of the present invention, the low coefficient of thermal expansion, and the effect of the curing agent on the cured product are difficult to occur. Specifically, it is preferably used so as to be 0.1 parts by weight or more, and used so as to be 0.2 parts by weight or more with respect to 100 parts by weight of the epoxy resin contained in the epoxy resin composition of the present invention. More preferably, it is preferably used so as to be 20 parts by weight or less, more preferably 10 parts by weight or less.

Organic phosphine curing accelerators, phosphonium salt curing accelerators, tetraphenyl boron salt curing accelerators include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine ,
Tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris ( Organic phosphines such as tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; complexes of these organic phosphines with organic borons; maleic anhydride, 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4- Nzokinon, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, compound compound is added, such as diazo methane and the like. The content of these curing accelerators contained in the epoxy resin composition of the present invention is used so as to be 0.001 part by weight or more with respect to 100 parts by weight of the epoxy resin contained in the epoxy resin composition of the present invention. Preferably, it is used so that it may become 0.005 weight part or more, and on the other hand, it is used so that it may become 20 weight part or less, and it is further used so that it may become 10 weight part or less. It is particularly preferable to use it so as to be 5 parts by weight or less.

  Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Among these, from the viewpoint of solvent solubility and curability of the epoxy resin composition of the present invention, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, Iron (III) acetylacetonate is preferred, and cobalt (III) acetylacetonate and zinc naphthenate are particularly preferred. The content of the metal-based curing accelerator contained in the epoxy resin composition of the present invention is preferably large in that a conductor layer having excellent peel strength can be easily formed on the surface of the low-roughness insulating layer. On the other hand, it is preferable that the epoxy resin composition of the present invention is small in terms of excellent storage stability and insulation. Therefore, the metal-based curing agent-derived metal is preferably 500 ppm or less, more preferably 200 ppm or less, on the other hand, preferably 20 ppm or more, and 30 ppm relative to the nonvolatile content in the composition. It is still more preferable that it is above.

Among these, particularly when using a cyanate ester resin, it is easy to efficiently cure the cyanate ester resin and the epoxy resin, so that a metal curing agent, an imidazole curing agent, an amine curing agent, etc. are used in combination. Is preferred.
Also, "Review Epoxy Resin Vol. 1" (1st edition, Epoxy Resin Technology Association, 2003), pages 119-209 and "Review Epoxy Resin Recent Progress I" (1st edition, Epoxy Resin Technology Association, 2009). ), Pages 43-84, and curing agents and curing accelerators may be used.
The type and combination of curing agents and the amount thereof may be selected according to the balance of curing conditions, the shape of the cured product, physical properties such as the adhesiveness and bending strength of the cured product, and the like.

[filler]
When the epoxy resin composition of the present invention contains a filler, by curing the epoxy resin composition of the present invention, fillers such as low linear expansion coefficient, high thermal conductivity, flame retardancy, and conductivity can be obtained. The physical properties possessed can be imparted to the cured product.
The type of filler may be selected according to desired physical properties. For example, when it is desired to obtain an insulating composition at a low cost, it is preferable to use an insulating filler such as alumina, aluminum nitride, boron nitride, silicon nitride, and silica, and among these, a composition having particularly high thermal conductivity. In the case where it is desired to obtain, alumina, aluminum nitride, boron nitride and the like are preferable. When it is desired to obtain a conductive composition, it is preferable to use an electrically conductive filler such as aluminum, silver, copper, carbon, silicon carbide, etc. Among these, when it is desired to obtain a composition that is particularly excellent in workability. Silver is preferred.

  The shape and particle size of the filler are not particularly limited as long as the desired effect due to the inclusion of the filler is exhibited without significantly impairing the excellent physical properties of the epoxy resin composition of the present invention. However, with regard to the shape of the filler, when it is desired to obtain a composition with excellent processability, a filler having a small surface area such as a sphere is fibrous, etc. in that the functions such as the thermal conductivity of the filler are easily exhibited. A filler having a large surface area is preferably a filler having an intermediate surface area such as a flat shape in that it is easy to balance the two.

  The particle size of the filler is preferably small in that voids are not easily generated in a cured product obtained by curing the epoxy resin composition of the present invention. On the other hand, it is preferable that the filler is large in that it does not aggregate and is easily dispersed. Therefore, specifically, the particle size is preferably 0.05 μm or more, more preferably 0.1 μm or more, particularly preferably 0.5 μm or more, and on the other hand, 1000 μm or less. Preferably, it is 200 micrometers or less, and it is especially preferable that it is 100 micrometers or less. The particle size can be measured by a method such as a laser diffraction scattering method or a sedimentation method.

  When the epoxy resin composition of the present invention contains a filler, the content of the filler is preferably large in that the effect of using the filler is easily exhibited. On the other hand, it is preferable that the epoxy resin composition of the present invention is small in that it tends to be excellent in processability. Therefore, specifically, the filler content is preferably 10% by weight or more, preferably 20% by weight or more, and on the other hand, preferably 95% by weight or less, 90% by weight. % Or less is more preferable. A filler may be used only by 1 type, or may be used 2 or more types by arbitrary combinations and ratios. As for the content in the case of using two or more kinds of fillers, the total amount is preferably in the above-mentioned preferable range.

[Other additives]
Examples of other additives that may be included in the epoxy resin composition of the present invention include the following additives. Adhesion between the epoxy resin composition of the present invention and a cured product obtained by curing the epoxy resin composition and the substrate, and when the epoxy resin composition of the present invention contains an inorganic filler, the glycidylamine compound of the present invention and the inorganic Coupling agents such as silane coupling agents and titanate coupling agents used to improve adhesiveness with fillers; UV inhibitors, antioxidants, plasticizers used to improve storage stability; oxide films on solder Flux for removal; flame retardant; colorant; dispersant; emulsifier; low elasticity agent; diluent; defoaming agent;

Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyl Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, etc. An aminosilane; mercaptosilane such as 3-mercaptopropyltrimethoxysilane; p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (8-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ- Examples include vinyl silanes such as methacryloxypropyltrimethoxysilane; epoxy-based, amino-based, and vinyl-based polymer type silanes.

  As titanate coupling agents, isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl) Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

  When the epoxy resin composition of the present invention contains a coupling agent, the content of the coupling agent is preferably large in that it is easy to obtain an adhesive effect due to the coupling agent blending. On the other hand, it is preferable that the coupling agent is small in that it is difficult to bleed out. Therefore, specifically, the content of the coupling agent with respect to the total solid content in the epoxy resin composition of the present invention is preferably 0.1% by weight or more and 2.0% by weight or less. A coupling agent may be used only by 1 type, or may be used 2 or more types by arbitrary combinations and ratios. As for the content in the case of using 2 or more types of coupling agents, the total amount is preferably within the above-mentioned preferable range.

[solvent]
The epoxy resin composition of the present invention may contain a solvent for adjusting the viscosity at the time of processing and handling properties when cured. As the solvent, the solvent used when producing the nitrogen-containing epoxy resin of the present invention may be used. Examples of the solvent contained in the epoxy resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; N Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; alcohols such as methanol, ethanol and isopropanol; alkanes such as hexane and cyclohexane; aromatics such as toluene and xylene. The amount of the solvent used is preferably not used or small so that voids are not easily formed in the cured product due to residual solvent. On the other hand, it is preferable that the number of cracks accompanying the increase in the viscosity of the composition is less likely to occur. These solvents may be used alone or in combination of two or more in any ratio.

[Cured product]
The cured product of the present invention can be obtained by curing the epoxy resin composition of the present invention. The cured product of the present invention is excellent in heat resistance because the epoxy resin composition of the present invention is cured. The curing method and conditions are not particularly defined as long as the epoxy resin composition of the present invention can be cured. However, thermosetting is preferable because it is easy to mold.

  The cured product of the present invention has a high glass transition temperature and excellent heat resistance because the composition containing the nitrogen-containing epoxy resin of the present invention is cured. The glass transition temperature measured by differential calorimetry of the cured product of the present invention is usually 50 ° C. when, for example, PSM6200 (manufactured by Gunei Chemical Co., Ltd.) and triphenylphosphine are used as a curing agent and cured at 175 ° C. As mentioned above, Preferably it is 100 degreeC or more, More preferably, it is 140 degreeC or more. The upper limit of the glass transition temperature is usually 350 ° C.

[Usage]
The nitrogen-containing epoxy resin and the composition containing the same of the present invention have sufficient processability to be applied to processes such as coating, mixing, and film forming. Further, it can be preferably used for other resin modifiers, various raw materials for chemicals such as adducts and thermoplastic resins.
And the hardened | cured material which hardened this composition is excellent in heat resistance and heat conductivity. Therefore, it can be applied as materials in various fields such as adhesives, paints, materials for civil engineering and construction, and insulating materials in the electric / electronic field. In particular, it is useful as an insulating casting, laminate material, sealing material, etc. in the electric / electronic field. Examples of the use of the composition containing the nitrogen-containing epoxy resin of the present invention and the cured product thereof include multilayer printed wiring boards, film adhesives, liquid adhesives, semiconductor sealing materials, underfill materials, and 3D-LSI interfaces. A chip fill, an insulating sheet, a prepreg, a heat dissipation board, etc. are mentioned.

[Reason for manifesting properties]
The nitrogen-containing epoxy resin (composition) of the present invention has a low viscosity and is excellent in processability, moldability and storage stability sufficient to be applied to processes such as film molding and coating, and has heat resistance when cured. Insulation is easy to develop. The reason is estimated as follows.
First, as shown in the Example mentioned later, the nitrogen-containing epoxy resin of this invention was low viscosity compared with the nitrogen-containing epoxy resin manufactured by the method using the epichlorohydrin disclosed by patent document 2. FIG. From this, it was suggested that in the production reaction of the epoxy resin, the viscosity changes due to the difference in the acidity or basicity of the nitrogen atom of the epoxy resin raw material.

  Since low molecular nitrogen-containing epoxy resins such as tetraglycidyldiaminodiphenylmethane and triglycidylaminophenol disclosed in Non-Patent Document 1 have basic nitrogen atoms in the resin, they serve as their own curing catalysts. Since it works, the storage stability at high temperature becomes insufficient. In contrast, the glycidyl compound having a sulfonyl group (nitrogen-containing epoxy resin having a sulfonyl group) disclosed in Patent Documents 1 and 2 has a nitrogen atom in the resin that is acidic due to the electron withdrawing property of the sulfonyl group. It is thought that the storage stability at high temperature is improved. However, the addition of epichlorohydrin and sulfonamide (main reaction) and the cross-linking reaction between added epoxy and other sulfonamides (side reactions) due to changes in the acidity of nitrogen atoms in the epoxy resin raw material. ) And the reaction rate balance have also changed.

  On the other hand, in the nitrogen-containing epoxy resin (composition) of the present invention, in the method for producing the nitrogen-containing epoxy resin, the acidic nitrogen atom of the raw material of the epoxy resin enhances the oxidation activity of the alkenyl group of the raw material. A highly pure nitrogen-containing epoxy resin can be obtained in a yield. Moreover, in the manufacturing method of this nitrogen containing epoxy resin, since the nitrogen atom of a raw material is tinged with acidity, it is difficult for a side reaction that a nitrogen atom itself receives an oxidation reaction and becomes N-oxide to occur together.

  This indicates that the epoxy equivalent of the nitrogen-containing epoxy resin (Comparative Example 1) produced by the method using epichlorohydrin disclosed in Patent Document 2 was significantly higher than the theoretical value, as shown in the Examples described later. In contrast, the nitrogen-containing epoxy resin produced by the method for producing a nitrogen-containing epoxy resin of the present invention (Examples 1 and 5) and the nitrogen-containing product produced by the method using epichlorohydrin disclosed in Patent Document 2 This is supported by the fact that the epoxy equivalent of the purified epoxy resin (Example 2) was close to the theoretical value.

The nitrogen-containing epoxy resin (composition) of the present invention thus obtained has both the characteristics of a nitrogen-containing epoxy resin that is low molecular weight and easy to be multifunctional, and the characteristic that the nitrogen atom is acidic due to the sulfonyl group. It is considered that it has low viscosity, storage stability at high temperature, and can achieve both heat resistance when cured. Moreover, it is thought that the conductive effect derived from the various by-products in a manufacturing process can be suppressed, and it can also have insulation by being a highly purified epoxy resin.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to these.
Various analyzes in Examples and Comparative Examples were performed as follows.
[Epoxy equivalent]
By measuring by the method of JISK7236: 2009, it obtained as solid content conversion value.

[Nuclear magnetic resonance spectrum (NMR) analysis]
The nuclear magnetic resonance spectrum was measured using a Bruker nuclear magnetic resonance spectrum apparatus “400 Ultrashield” (400 MHz). The sample was dissolved in deuterated chloroform and used for measurement.

[Viscosity analysis]
The viscosity was measured using a viscoelasticity measuring device “MCR-301” manufactured by Anton Paar. Specifically, a 1.45 g sample was placed in a disposable aluminum dish having a diameter of 50 mm, and the shear viscosity at 150 ° C. was determined under the following conditions.
Plate: 50mm diameter aluminum parallel plate Gap: 0.50mm
Shear rate: 150 times / minute (outer periphery)

[Glass transition point (Tg)]
The glass transition point was measured using a differential calorimeter “DSC 6220” manufactured by SII Nano Technology. Specifically, a 5 mg sample was analyzed under the following conditions, and the peak top of the observed endothermic behavior was taken as the glass transition point.
Container: Au-plated SUS pressure-resistant sample container Atmosphere: Under nitrogen atmosphere Temperature rising condition: 5-200 ° C
Temperature increase rate: 10 ° C / min

[Volume resistance]
The volume resistance value at an applied voltage of 500 V was measured using a “HIRESTA UX HT-800” volume resistance measuring device manufactured by Mitsubishi Chemical Analytech.

<Example 1>
A nitrogen-containing epoxy resin having the structure of the following general formula (3) was synthesized.

7.0 g (28 mmol) of 4-diallylaminosulfonyltoluene was dissolved in 110 cm ³ of chloroform. 70 g% of m-chloroperbenzoic acid 21 g (84 mmol) was added and reacted at room temperature (15-25 ° C.) for 3 hours, and then the internal temperature was raised to 50 ° C. and reacted for 3 hours. The resulting reaction mixture was cooled to room temperature, 5 wt% aqueous sodium thiosulfate solution was added to stop the reaction, and the oil layer was washed with aqueous sodium hydrogen carbonate solution and water. Water was removed by filtration after adding anhydrous sodium sulfate, and then the solvent was distilled off by reducing the pressure. The obtained residue was purified by silica gel column chromatography to obtain 7.1 g of a colorless liquid.

The obtained liquid was analyzed by nuclear magnetic resonance spectrum measurement, and the following results were obtained. Thus, it was confirmed that this liquid was a nitrogen-containing epoxy resin having the structure of the general formula (3). The yield was 89%.
¹ H NMR (deuterated chloroform, δ): 7.72 (d, J = 9.0 Hz, 2H), 7.33 (d, J = 9.0 Hz, 2H), 3.61 (m, 2H), 3 .14 (m, 4H), 2.79 (m, 2H), 2.59 (m, 2H), 2.44 (s, 3H)
The epoxy equivalent of this nitrogen-containing epoxy resin was 146 g / equivalent (theoretical value 142 g / equivalent), the molecular weight was 283, and the shear viscosity at 150 ° C. was 3.2 mPa · s. The nitrogen-containing epoxy resin was held at 150 ° C. for 1 hour, but the properties were not changed.

<Comparative Example 1>
A nitrogen-containing epoxy resin having the structure of the following general formula (4) was synthesized by the method described in Patent Document 2.

4-hydroxybenzenesulfonamide 10 g (60 mmol), epichlorohydrin 70 cm ³ (900 mmol) and benzyltrimethylammonium chloride 0.55 g (3.0 mmol) were mixed, and the mixture was heated and stirred at 90 ° C. for 4 hours. The obtained mixture was cooled to 50 ° C., and 17 cm ³ (210 mmol) of a 50 wt% aqueous sodium hydroxide solution was added dropwise thereto over 30 minutes. After dropping, the mixture was stirred with heating at 80 ° C. for 2 hours. The resulting mixture was cooled to room temperature, extracted with ethyl acetate, and washed with water. Water was removed by filtering the oil layer after adding anhydrous sodium sulfate, and then the solvent was distilled off by reducing the pressure. A liquid nitrogen-containing epoxy resin was obtained as a residue.
The epoxy equivalent of this nitrogen-containing epoxy resin was 177 g / equivalent (theoretical value 114 g / equivalent), the molecular weight was 341, and the shear viscosity at 150 ° C. was 23 mPa · s. The nitrogen-containing epoxy resin was held at 150 ° C. for 1 hour, but the properties were not changed.

<Example 2>
The nitrogen-containing epoxy resin obtained in Comparative Example 1 was purified by silica gel column chromatography to obtain 6.5 g of a colorless liquid.
The obtained liquid was analyzed by nuclear magnetic resonance spectrum measurement, and the following results were obtained. Thus, it was confirmed that this liquid was a nitrogen-containing epoxy resin having the structure of the general formula (4).
¹ H NMR (deuterated chloroform, δ): 7.79 (d, J = 9.0 Hz, 2H), 7.02 (d, J = 9.0 Hz, 2H), 4.35 (d, J = 8. 5Hz, 1H), 3.97 (m, 1H), 3.63 (m, 2H) 3.38 (m, 1H), 3.15 (m, 4H), 2.94 (t, J = 4. 5Hz, 1H), 2.78 (m, 3H), 2.59 (m, 2H)
The epoxy equivalent of this nitrogen-containing epoxy resin was 124 g / equivalent (theoretical value 114 g / equivalent), the molecular weight was 341, and the shear viscosity at 150 ° C. was 9.1 mPa · s. The nitrogen-containing epoxy resin was held at 150 ° C. for 1 hour, but the properties were not changed.

<Comparative example 2>
Triglycidylaminophenol “jER630” (epoxy equivalent: 98 g / equivalent) manufactured by Mitsubishi Chemical Corporation is a resin that is liquid at room temperature, but because it thickens by heating at 100 ° C. or higher, the shear viscosity at 150 ° C. is It was not possible to measure. The results are summarized in Table 1.

  Since the 150 ° C. shear viscosity of the nitrogen-containing epoxy resins of Examples 1 and 2 was lower than that of the bisphenol A novolac type epoxy resin and did not deteriorate upon heating at 150 ° C., the nitrogen-containing epoxy resin of the present invention had a low viscosity and a high temperature. It was confirmed that the storage stability was excellent.

<Example 3>
500 mg of the nitrogen-containing epoxy resin of general formula (3) obtained in Example 1, 353 mg of a phenolic curing agent “PSM6200” (OH value: 103 g / equivalent) manufactured by Gunei Chemical Industry Co., Ltd., and Tokyo Chemical Industry Co., Ltd. 5 mg of triphenylphosphine manufactured was melt-mixed to obtain a composition. The composition was cured by heating at 175 ° C. for 6 hours to obtain a cured product having a thickness of 200 μm. The glass transition point of this cured product was 115 ° C.

<Example 4>
600 mg of the nitrogen-containing epoxy resin of the general formula (4) obtained in Example 2, 502 mg of phenolic curing agent “PSM6200” (OH value: 103 g / equivalent) manufactured by Gunei Chemical Industry Co., Ltd., and Tokyo Chemical Industry Co., Ltd. 6 mg of triphenylphosphine manufactured was melt mixed to obtain a composition. The composition was cured by heating at 175 ° C. for 6 hours to obtain a cured product having a thickness of 200 μm. This cured product had a glass transition point of 174 ° C. and a volume resistance value of 5 × 10 ¹⁴ Ωcm.

<Comparative Example 3>
600 mg of the nitrogen-containing epoxy resin obtained in Comparative Example 1, 349 mg of a phenolic curing agent “PSM6200” (OH value: 103 g / equivalent) manufactured by Gunei Chemical Industry Co., Ltd. and 6 mg of triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd. Melt mixing was performed to obtain a composition. The composition was cured by heating at 175 ° C. for 6 hours to obtain a cured product having a thickness of 200 μm. The cured product had a glass transition point of 141 ° C. and a volume resistance of 2 × 10 ¹⁴ Ωcm.

<Comparative example 4>
500 mg of triglycidylaminophenol “jER630” (epoxy equivalent: 98 g / equivalent) manufactured by Mitsubishi Chemical Corporation, 526 mg of phenolic curing agent “PSM6200” (OH value: 103 g / equivalent) manufactured by Gunei Chemical Industry Co., Ltd. and Tokyo Chemical Industry 5 mg of triphenylphosphine manufactured by Kogyo Co., Ltd. was melt-mixed to obtain a composition. The composition was cured by heating at 175 ° C. for 6 hours to obtain a cured product having a thickness of 200 μm. The glass transition point of this cured product is 164.
° C. The results are summarized in Table 2.

  In particular, since the glass transition point and volume resistance of Example 4 were higher than those of Comparative Example 3, it was confirmed that the cured product of the present invention was excellent in heat resistance and insulation.

<Example 5>
A nitrogen-containing epoxy resin having the structure of the general formula (4) was synthesized from 4-diallylaminosulfonylallyloxybenzene. 4-Diallylaminosulfonylallyloxybenzene used for the synthesis was obtained by allylating 4-hydroxybenzenesulfonamide with allyl bromide and potassium carbonate.

4.4 g (15 mmol) of 4-diallylaminosulfonylallyloxybenzene was dissolved in 150 cm ³ of chloroform. 16.7 g (68 mmol) of 70% by weight m-chloroperbenzoic acid was added and reacted at 40 ° C. for 10 hours, and then the internal temperature was raised to 50 ° C. and reacted for 5 hours. After cooling the obtained reaction mixture to room temperature, 12 wt% sodium thiosulfate aqueous solution was added to stop the reaction, and then the oil layer was washed with sodium carbonate aqueous solution and water. Water was removed by filtration after adding anhydrous magnesium sulfate, and then the solvent was distilled off by reducing the pressure. A liquid nitrogen-containing epoxy resin was obtained as a residue.
The epoxy equivalent of this nitrogen-containing epoxy resin was 122 g / equivalent (theoretical value 114 g / equivalent), the molecular weight was 341, and the shear viscosity at 150 ° C. was 12 mPa · s.

<Comparative Example 5>
A nitrogen-containing epoxy resin having the structure of the general formula (4) was synthesized in the same manner as in Comparative Example 1.
The epoxy equivalent of this nitrogen-containing epoxy resin was 188 g / equivalent (theoretical value 114 g / equivalent), the molecular weight was 341, and the shear viscosity at 150 ° C. was 28 mPa · s. The results are summarized in Table 3.

<Example 6>
400 mg of the nitrogen-containing epoxy resin obtained in Example 5, 338 mg of a phenolic curing agent “PSM6200” (OH value: 103 g / equivalent) manufactured by Gunei Chemical Co., Ltd. and 20 mg of triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd. Melt mixing was performed to obtain a composition. The composition was cured by heating at 175 ° C. for 6 hours to obtain a cured product having a thickness of 200 μm. The glass transition point of this cured product was 166 ° C.

<Comparative Example 6>
500 mg of the nitrogen-containing epoxy resin obtained in Comparative Example 5, phenolic curing agent “PSM6200” (OH value: 103 g / equivalent) manufactured by Gunei Chemical Co., Ltd., and 25 mg of triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd. Melt mixing was performed to obtain a composition. The composition was cured by heating at 175 ° C. for 6 hours to obtain a cured product having a thickness of 200 μm. The glass transition point of this cured product was 140 ° C. The results are summarized in Table 4.

  From the above results, the nitrogen-containing epoxy resin of the present invention has low viscosity and excellent storage stability, and the epoxy resin composition of the present invention contains the nitrogen-containing epoxy resin of the present invention, so that the film can be formed with low viscosity. It was confirmed that the processability, moldability and storage stability sufficient for application to processes such as coating were excellent, and the cured product obtained by curing this composition was excellent in heat resistance and insulation.

  The epoxy resin composition of the present invention can be applied to various uses such as adhesives, paints, materials for civil engineering and construction, and insulating materials for electric / electronic parts. Further, it is useful as an insulating material, laminated material, sealing material, etc. in the electric / electronic field. Moreover, it is applicable also to uses, such as 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, and a heat dissipation board.

Claims (10)

A nitrogen-containing epoxy resin represented by the following general formula (1), having a molecular weight of 380 or less and an epoxy equivalent of 0.9 times or more and 1.5 times or less of a theoretical value Contains epoxy resin.

(In the formula, A ¹ represents a monovalent organic group, and each of R ^{1 to} R ³ independently represents a hydrogen atom or a methyl group.) A nitrogen-containing epoxy resin according to claim 1, the nitrogen-containing epoxy resin wherein A ¹ is a aromatic ring group which may have a substituent.   The nitrogen-containing epoxy resin according to claim 1 or 2, wherein the epoxy equivalent is 0.9 times or more and 1.2 times or less of a theoretical value.   An epoxy resin composition comprising the nitrogen-containing epoxy resin according to any one of claims 1 to 3.   It is the epoxy resin composition described in Claim 4, Comprising: The nitrogen-containing epoxy resin described in any one of Claims 1 thru | or 3 is used with respect to the total amount of the epoxy resin contained in the said epoxy resin composition. An epoxy resin composition containing 10% by weight or more.   The epoxy resin composition according to claim 4 or 5, wherein the epoxy resin composition contains a curing agent and a filler.   7. The epoxy resin composition according to claim 6, wherein the filler is contained in an amount of 10 wt% to 95 wt% with respect to the total solid content in the epoxy resin composition.   Hardened | cured material formed by making the epoxy resin composition as described in any one of Claims 4 thru | or 7 cure-react.   An electric / electronic material having the cured product according to claim 8. A method for producing a nitrogen-containing epoxy resin, which is obtained by epoxidizing a compound represented by the following general formula (2).

(In the formula, A ¹ represents a monovalent organic group, and each of R ^{1 to} R ³ independently represents a hydrogen atom or a methyl group.)