JP2009035586A - Epoxy resin composition, cured product thereof, varnish for printed circuit board, new epoxy resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition having excellent flame retardance and excellent toughness and to provide a new epoxy resin imparting the performances to a cured product. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin (A) and a curing agent (B). The epoxy resin (A) is a bifunctional type epoxy resin prepared by reacting a bifunctional type epoxy resin (a) with a monofunctional active hydrogen-containing phosphorus compound (b) and a diisocyanate compound (c) and having a phosphorus atom and a urethane bond in the molecular structure. The bifunctional type epoxy resin has an epoxy equivalent thereof within the range of 300-2,000 g/equivalent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is excellent in flame retardancy of the resulting cured product, and can be suitably used for semiconductor encapsulant, printed circuit board, paint, casting application, etc., cured product thereof, and the epoxy resin composition The present invention relates to a novel epoxy resin that can be suitably used for products and a method for producing the same.

  Epoxy resins provide cured products with excellent shrinkage during curing, dimensional stability of cured products, electrical insulation and chemical resistance, etc., and are highly functional in the electronics field such as semiconductor encapsulants and printed circuit boards. Widely used in the paint field. In the field of electronics and high-performance paints, high flame retardancy is required, and epoxy resin compositions applied to these fields are epoxy resins such as bisphenol A type epoxy resin and novolac type epoxy resin. In general, the curing agent is adjusted by blending a halogen-based flame retardant and an antimony compound.

However, among recent environmental and safety initiatives, there is a concern that halogen flame retardants generate dioxins. On the other hand, antimony compounds are also suspected of having carcinogenic properties, and there has been a strong demand for the development of flame retardant methods that are environmental and safety alternatives to halogen-based flame retardants and antimony compounds. As a means for meeting these requirements, various techniques for imparting flame retardancy to the epoxy resin itself have been studied. For example, 9,10-dihydro-9-oxa-10-phos is added to a bisphenol type epoxy resin. A bifunctional phosphorus atom-containing epoxy resin obtained by reacting dihydroxybenzene or dihydroxynaphthalene having phenanthrene-10-oxide (hereinafter abbreviated as “HCA”) as a substituent on the aromatic nucleus is used. Techniques are known (see, for example, Patent Documents 1 and 2). However, such a bifunctional phosphorus atom-containing epoxy resin knots a bisphenol-type epoxy resin at a phosphorus atom-containing structural site, so that the epoxy equivalent becomes large and the distance between cross-linking points after curing becomes long, resulting in a cured product itself. Had reduced toughness. As another flame retardant method, a technique using an epoxy resin obtained by directly reacting an HCA with an epoxy group of a novolak type epoxy resin is known (for example, Patent Document 3). However, when such an epoxy resin is used as a main component, the resin structure itself becomes rigid, leading to a decrease in tensile strength and tensile elongation, which is also inferior in toughness of the cured product.
In this way, when the toughness of the cured product is not sufficiently expressed, especially when used as a varnish for printed circuit boards, defects such as peeling and cracking are unavoidable in the solder treatment process after moisture absorption during printed wiring board manufacture. Met.

Japanese Patent No. 3613724

  The problem to be solved by the present invention is to provide an epoxy resin composition having excellent flame retardancy and excellent toughness in the cured product, and a novel epoxy resin that provides these properties to the cured product. There is.

  As a result of intensive studies to solve the above problems, the present inventors have introduced a urethane bond together with phosphorus atoms into a resin structure of a high molecular weight bifunctional epoxy resin, and have excellent flame retardancy and advanced It has been found that toughness can be imparted to the cured product, and the present invention has been completed.

  That is, the present invention is a bifunctional epoxy resin having a phosphorus atom and a urethane bond in the molecular structure, and an epoxy resin (A) having an epoxy equivalent in the range of 300 to 2000 g / equivalent, and curing It is related with the epoxy resin composition characterized by making an agent (B) into an essential component.

The present invention further relates to a varnish for a printed circuit board comprising the epoxy resin composition.
The present invention further includes the following structural formula 1

（式中、Ｇはグリシジル基、Ａｒ^１は、ナフチレン基、又は、下記構造式２

(In the formula, G is a glycidyl group, Ar ¹ is a naphthylene group, or the following structural formula 2

（構造式２中、Ｘは炭素原子数１〜３のアルキリデン基又はスルホニル基を表し、Ｒ^１〜Ｒ^４はそれぞれ独立的に水素原子又はメチル基を表す。）で表される２価の有機基、Ａｒ^２は芳香族炭化水素基、Ｙは有機ホスファニル基、ｎは繰り返し単位の平均で０．０５〜２．８である。）
で表される構造を有する新規エポキシ樹脂に関する。
本発明は、更に、前記エポキシ樹脂組成物を硬化させてなる硬化物に関する。

(In Structural Formula 2, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group.) Group, Ar ² is an aromatic hydrocarbon group, Y is an organic phosphanyl group, and n is 0.05 to 2.8 on the average of the repeating units. )
It relates to a novel epoxy resin having a structure represented by:
The present invention further relates to a cured product obtained by curing the epoxy resin composition.

  According to the present invention, it is possible to provide an epoxy resin composition having excellent flame retardancy and excellent toughness in the cured product, and a novel epoxy resin that imparts these performances to the cured product.

Hereinafter, the present invention will be described in detail.
The epoxy resin composition of the present invention is a bifunctional epoxy resin having a phosphorus atom and a urethane bond in the molecular structure, and an epoxy resin (A) having an epoxy equivalent in the range of 300 to 2000 g / equivalent. Is used as a main agent.
Since the epoxy resin (A) has a phosphorus atom in its molecular structure, it exhibits excellent flame retardancy and is a bifunctional epoxy resin having an epoxy equivalent of 300 to 2000 g / equivalent, so that a cured product is obtained. In this case, an appropriate toughness can be formed, and an excellent toughness can be exhibited since it has a urethane bond in the molecule.

  The content of phosphorus atoms in the epoxy resin (A) is preferably in a range of 0.5 to 10% by mass from the viewpoint that the flame retardant effect becomes remarkable. In addition, the content of urethane bonds in the epoxy resin (A) is a ratio of 0.1 to 5.6 on average in one molecule of the epoxy resin, because the toughness of the cured product is improved. preferable.

  Examples of a method for incorporating a phosphorus atom and a urethane bond into the resin structure of the epoxy resin (A) include, for example, reacting a bifunctional epoxy resin (a) with a monofunctional active hydrogen-containing phosphorus compound (b), The method of making the diisocyanate compound (c) react with the produced | generated hydroxyl group is mentioned.

  Examples of the bifunctional epoxy resin (a) used here include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol A type epoxy resin, tetramethyl bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Biphenyl type epoxy resin; biphenyl type epoxy resin such as biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy resin; phenol aralkyl type epoxy resin; diglycidyloxynaphthalene; molecular structure of xanthene skeleton The epoxy resin which it has is mentioned.

  Among these, a bisphenol type epoxy resin is particularly preferable from the viewpoint that the effect of the present invention is remarkable, and a liquid bisphenol type epoxy resin is particularly preferable from the viewpoint of easy production of the epoxy resin (A). Further, among the liquid bisphenol-type epoxy resins, those having a binuclear content of 80% by mass or more have a low three-dimensional branching property during the production of the epoxy resin (A), and contain a large amount of phosphorus atoms. However, since there are few problems that lead to excessive thickening and gelation, it is particularly preferable.

  Next, as the monofunctional active hydrogen-containing phosphorus compound (b), phosphinic acids such as dimethylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid and bis (p-tolyl) phosphinic acid; dialkyl such as dimethylphosphine and dioctylphosphine Phosphines; aromatic phosphine compounds such as diphenylphosphine, diphenylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like. Among these, aromatic phosphine compounds are preferable from the viewpoint of high reactivity with epoxy groups, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is particularly preferable.

  Next, as the polyfunctional isocyanate compound (c), any kind can be used as long as it is a compound containing one or more isocyanate groups in one molecule. Illustrative examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, and the like.

  Among these, the flame retardant effect of the cured product is particularly remarkable when it is an aromatic diisocyanate compound such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or 4,4′-diphenylmethane diisocyanate. It is preferable from the point of becoming. Moreover, in this invention, the balance of adhesiveness and toughness can be aimed at by using together aliphatic diisocyanate, such as 1, 6- hexane diisocyanate, with the said aromatic diisocyanate compound suitably.

  An epoxy resin (A) obtained by reacting the bifunctional epoxy resin (a) with the monofunctional active hydrogen-containing phosphorus compound (b) and then reacting the generated hydroxyl group with the diisocyanate compound (c), More specifically, the following structural formula 1

Structural formula 1

（構造式１中、Ｇはグリシジル基、Ａｒ^１は、ナフチレン基、又は、下記構造式２

(In Structural Formula 1, G is a glycidyl group, Ar ¹ is a naphthylene group, or the following Structural Formula 2

（構造式２中、Ｘは炭素原子数１〜３のアルキリデン基又はスルホニル基を表し、Ｒ^１〜Ｒ^４はそれぞれ独立的に水素原子又はメチル基を表す。）で表される２価の有機基、Ａｒ^２は芳香族炭化水素基、Ｙは有機ホスファニル基をそれぞれ表し、ｎは繰り返し単位の平均で０．０５〜２．８である。）
で表される構造を有する本発明の新規エポキシ樹脂であることが本発明の効果が顕著なものとなる点から好ましい。

(In Structural Formula 2, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group.) Group, Ar ² represents an aromatic hydrocarbon group, Y represents an organic phosphanyl group, and n is 0.05 to 2.8 on the average of the repeating units. )
It is preferable that it is the novel epoxy resin of this invention which has a structure represented by these from the point where the effect of this invention becomes remarkable.

  Among the epoxy resins (A) represented by the structural formula 1, in particular, the following structural formula 3

（構造式３中、Ｘは炭素原子数１〜３のアルキリデン基又はスルホニル基を表し、Ｒ^１〜Ｒ^４はそれぞれ独立的に水素原子又はメチル基を表し、Ａｒ^２は芳香族炭化水素基を表し、Ｙは有機ホスファニル基を表し、ｎは繰り返し単位の平均で０．０５〜２．８である。）で表されるものが、硬化物の靱性向上の効果が顕著なものとなる点から好ましい。

(In Structural Formula 3, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group, and Ar ² represents an aromatic hydrocarbon group. Y represents an organic phosphanyl group, and n is 0.05 to 2.8 on the average of repeating units.) From the point that the effect of improving the toughness of the cured product becomes remarkable. preferable.

  Here, specific examples of the organic phosphanyl group represented by “Y” in Structural Formula 1 or Structural Formula 3 include those represented by the following structural formulas p1 to p3.

これらのなかでもエポキシ樹脂（Ａ）の製造が容易であり、かつ、該エポキシ樹脂（Ａ）の難燃効果が顕著なものとなる点から前記ｐ１で表されるものが好ましい。

Among these, the one represented by p1 is preferable from the viewpoint that the production of the epoxy resin (A) is easy and the flame retardant effect of the epoxy resin (A) becomes remarkable.

  In addition, “X” in Structural Formula 2 or Structural Formula 3 is an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group as described above, and examples of the alkylidene group having 1 to 3 carbon atoms include a methylidene group and an ethylidene group. Group, and 2,2-propylidene group. Among these, a 2,2-propylidene group is preferable because the effects of the present invention are remarkable.

The method for producing the epoxy resin (A) detailed above is as follows:
(i) a method in which the bifunctional epoxy resin (a), the monofunctional active hydrogen-containing phosphorus compound (b) and the polyfunctional isocyanate compound (c) are mixed and reacted all at once, or
(ii) reacting the bifunctional epoxy resin (a) with the monofunctional active hydrogen-containing phosphorus compound (b) (step 1), and then reacting the resulting reaction product with the diisocyanate compound (c) (step) 2) A method is mentioned.

  Here, in the methods (i) and (ii), the reaction ratio between the bifunctional epoxy resin (a) and the monofunctional active hydrogen-containing phosphorus compound (b) is the same as that in the bifunctional epoxy resin (a). The ratio in which the active hydrogen in the monofunctional active hydrogen-containing phosphorus compound (b) is in the range of 0.2 to 0.8 equivalent, particularly in the range of 0.3 to 0.6 equivalent, relative to 1 equivalent of the epoxy group It is preferable that the ratio is such that the phosphorus atom concentration can be adjusted to an appropriate range, the flame retardancy is good, and the moisture resistance reliability of the epoxy resin (A) is also good.

  The amount of the diisocyanate compound (c) used is such that the isocyanate group in the diisocyanate compound (c) is 0.2 to 0.8 equivalent relative to 1 equivalent of the epoxy group in the bifunctional epoxy resin (a). It is preferable from the point that the toughness of the hardened | cured material of an epoxy resin (A) will be favorable that it is a ratio used as the range, especially the range used as the range of 0.3-0.6 equivalent.

  Among the above-described methods, the latter method (ii) is particularly preferable because an epoxy compound having a high reaction selectivity and a molecular structure having a high linear structure can be obtained. Hereinafter, the method (ii) will be described in detail.

As the reaction conditions of step 1 of method (ii), for example, a bifunctional epoxy resin (a) and a monofunctional active hydrogen-containing phosphorus compound (b) are mixed, and the reaction condition is 1 in a temperature range of 50 to 200 ° C. Intermediates can be obtained by stirring for ~ 20 hours. In that case, an organic solvent can also be used as needed. Examples of organic solvents used include aromatic organic solvents such as xylene and toluene,
Ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohol organic solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol and cyclohexanol, ether organic solvents such as methyl cellosolve and ethyl cellosolve, acetic acid Examples thereof include ester organic solvents such as methyl, ethyl acetate and propyl acetate, and aliphatic hydrocarbon organic solvents such as normal hexane. It is preferable that the usage-amount is a ratio used as 10-500 mass parts with respect to 100 mass parts of raw materials.

  Moreover, a catalyst can also be used as needed. Examples of the catalyst that can be used here include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, and tris (2,6-dimethoxyphenyl) phosphine. Phosphinium salts, phosphonium salts such as ethyltriphenylphosphonium bromide, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, Lewis acids such as boron trifluoride, anhydrous aluminum chloride, zinc chloride, dibutyltin maleate, dibutyltin dilaurate And organic acid metal salts such as zinc 2-ethylhexanoate. The addition amount is preferably in the range of 10 ppm to 1% by mass with respect to the total of the raw material components.

  Next, as the step 2, in the reaction step of the intermediate and the polyfunctional isocyanate compound (c), both are mixed and stirred at a temperature of 50 to 200 ° C. for 1 to 20 hours to contain the target phosphorus atom. A urethane-modified epoxy resin can be obtained. In that case, an organic solvent can also be used as needed. Specific examples of the organic solvent used include aromatic organic solvents such as xylene and toluene, ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, n-butanol, and methoxypropanol. Alcohol organic solvents such as cyclohexanol, ether organic solvents such as methyl cellosolve and ethyl cellosolve, ester organic solvents such as methyl acetate, ethyl acetate and propyl acetate, and aliphatic hydrocarbon organic solvents such as normal hexane. Can be mentioned. It is preferable that the usage-amount is a ratio used as 10-500 mass parts with respect to 100 mass parts of raw materials.

Moreover, a catalyst can also be used as needed. Examples of the catalyst that can be used here include organometallic compounds such as tin octylate and dibutyltin laurate, 1,4-diaza-2,2,2-bicyclooctane, triethylamine, dimethylcyclohexylamine,
And tertiary amines such as diazabicycloundecane and diethylbenzylamine.
The addition amount is preferably in a range of 5 to 1000 ppm with respect to the total of the raw material components.

  The epoxy resin composition of the present invention may use other epoxy resins in combination with the epoxy resin (A).

Examples of other types of epoxy resins that can be used here include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, and cresol novolak type epoxy resins. Resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy Resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde Fat-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types. In particular, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl novolac type epoxy resin, and an epoxy resin having a xanthene skeleton in the molecular structure are particularly preferable from the viewpoint of excellent flame retardancy.
It is preferable that the usage-amount of said other epoxy resin mentioned above is 5-70 mass% in an epoxy resin composition, especially 5-60 mass%.

  Next, examples of the curing agent (B) used in the present invention include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like.

Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine.

  Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride.

  Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins (commonly known as “Zylock resins”), naphthol aralkyl resins, trimethylol. Methane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenol compound in which phenol nucleus is linked by bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenolic resin (melamine or benzogua) Min polyhydric phenol compound phenol nuclei are connected by, etc.) the polyhydric phenol compound such as, and and modified products thereof. These may be used alone or in combination of two or more.

  Among these, dicyandiamide, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak Resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because they are excellent in flame retardancy, and are particularly highly aromatic such as phenol aralkyl resins, naphthol aralkyl resins, biphenyl-modified phenol resins, and biphenyl-modified naphthol resins. , High hydroxyl equivalent polyvalent hydroxy compounds, and compounds such as aminotriazine-modified phenolic resins containing nitrogen atoms DOO is, from the viewpoint of flame retardancy of the cured product obtained is excellent.

  The compounding quantity of the said hardening | curing agent (B) in the epoxy resin composition of this invention is a point in the hardening | curing agent (B) with respect to a total of 1 equivalent of the epoxy group of an epoxy resin from the point that the hardened | cured material characteristic obtained is favorable. The amount of the active group is preferably 0.7 to 1.5 equivalents. In the catalyst curing system such as imidazole, the range of 0.5 to 10% by mass with respect to the epoxy resin is preferable.

  Moreover, a hardening accelerator can also be suitably used together with the epoxy resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor sealing material, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine is used for phosphorus compounds, and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  Since the epoxy resin composition of the present invention has the effect of imparting flame retardancy as described above, the epoxy resin (A) itself has good flame retardancy in the cured product even if no flame retardant is added. Although it can be expressed, in order not to lower the moldability in the sealing process and the reliability of the semiconductor device in order to exhibit a higher degree of flame retardancy, it is substantially free of halogen atoms. It is preferable to blend a halogen-based flame retardant.

  The flame retardant resin composition substantially not containing a halogen atom as used herein means a resin composition exhibiting sufficient flame retardancy without blending a halogen-based compound for the purpose of imparting flame retardancy. For example, halogen atoms due to a small amount of impurities of about 5000 ppm or less derived from epihalohydrin contained in an epoxy resin may be contained.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydro And cyclic organic phosphorus compounds such as oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, curing agent, non-halogen type In 100 parts by mass of epoxy resin composition containing all of flame retardant and other fillers and additives, etc., when red phosphorus is used as a non-halogen flame retardant, it is blended in the range of 0.1 to 2.0 parts by mass. In the case of using an organophosphorus compound, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and particularly in the range of 0.5 to 6.0 parts by mass. preferable.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, among which triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, melam sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine, and formaldehyde, (iii) (Ii) a mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) or (iii) above with paulownia oil, isomerized linseed oil, etc. .

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass, especially in the range of 0.05 to 10 parts by mass, in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by mass.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

  Specific examples of the low-melting-point glass include, for example, Shipley (Bokusui Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3-based, ZnO-P2O5-MgO-based, P2O5-B2O3-PbO-MgO-based, Examples thereof include glassy compounds such as P—Sn—O—F, PbO—V 2 O 5 —TeO 2, Al 2 O 3 —H 2 O, and lead borosilicate.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, cured It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition in which all of the agent, non-halogen flame retardant and other fillers and additives are blended. It is preferable to mix in the range of 15 parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the epoxy resin, the curing agent, the non-halogen flame retardant, and other fillers and additives.

  The epoxy resin composition of the present invention includes a semiconductor sealing material, an underfill material, a conductive paste, a varnish for a printed circuit board, a resin casting material, an adhesive, an interlayer insulating material for a build-up board, a coating material such as an insulating paint, etc. It can be applied to various uses.

  Among these, particularly when the epoxy resin composition of the present invention is used as a varnish for a printed circuit board, the excellent toughness of the cured product effectively prevents peeling and cracking in the soldering process after moisture absorption in printed wiring board production. It is preferable because it is possible.

  Examples of the method for producing a varnish for a printed circuit board from the epoxy resin composition of the present invention include a method in which each of the above-described components is varnished with an organic solvent. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds.

  To produce a copper clad laminate for a printed circuit board from the printed circuit board varnish described above, first, the printed circuit board varnish is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass. A prepreg which is a cured product is produced by impregnating various reinforcing base materials such as roving cloth and heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. At this time, the mass ratio of the epoxy resin composition and the reinforcing base is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Next, the prepreg obtained in this manner is laminated by a conventional method, and copper foil is appropriately laminated, and then subjected to thermocompression bonding under a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours. A stretched laminate can be obtained.

  Examples of a method for obtaining an interlayer insulating material for a build-up board from the epoxy resin composition of the present invention include, for example, a spray coating method, a curtain, and the like on a wiring board on which a circuit is formed by using the curable resin composition appropriately blended with rubber, filler and the like. After applying using a coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

Moreover, the epoxy resin composition of this invention can manufacture a semiconductor sealing material or an electrically conductive paste by mix | blending an inorganic filler with said each component further.
Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like for semiconductor sealing materials, and conductive filler such as silver powder and copper powder for conductive paste applications. Agents.

  Here, it is preferable that the compounding quantity of the said inorganic filler is the range of 70-95 mass% of fillers with respect to 100 mass parts of epoxy resin compositions especially for a semiconductor sealing material use.

  When the epoxy resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the epoxy resin composition to obtain a composition for anisotropic conductive film, liquid at room temperature And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  Moreover, the epoxy resin composition of the present invention can also be used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent (B) are blended with the epoxy resin (A), and a pigment, talc and filler are further added to form a resist. A method for forming a resist ink cured product after coating on a printed circuit board by a screen printing method after an ink composition is used.

  In the epoxy resin composition of the present invention, various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be appropriately added according to the various uses described above.

  The epoxy resin composition of the present invention can be cured by a conventional method in accordance with the purpose or application to be used to obtain a cured product. Under the present circumstances, the method of obtaining hardened | cured material adds the various compounding components to the epoxy resin composition of this invention, and also mix | blends the composition obtained by mix | blending a hardening accelerator suitably, The temperature range of about 20-250 degreeC. The method of heating at is preferred. A general method of an epoxy resin composition can also be adopted as a molding method. The cured product thus obtained forms a laminate, cast product, adhesive layer, coating film, film and the like.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. The melt viscosity at 150 ° C., GPC measurement, NMR, and MS spectrum were measured under the following conditions.
1) Melt viscosity at 150 ° C .: Conforms to ASTM D4287 2) Softening point measurement method: JIS K7234
3) GPC:
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
4) NMR: NMR “GSX270” manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.
The phosphorus content was measured by the following method.

[Phosphorus content measurement method]
Nitric acid (25 ml) and perchloric acid (10 ml) are added to 1 g of the material, and the contents are thermally decomposed to 5 to 10 ml. This solution is diluted with distilled water in a 1000 ml volumetric flask. Add 10 ml of this sample solution to a 100 ml volumetric flask, add 10 ml of nitric acid, 10 ml of 0.25% ammonium vanadate solution and 10 ml of 5% ammonium molybdate solution, dilute to the mark with distilled water, mix well, and leave to stand. This color developing solution is placed in a quartz cell, and the absorbance of the sample and the phosphor standard solution is measured using a spectrophotometer under the condition of a wavelength of 440 nm using the blank solution as a control. Phosphorus standard solution is prepared by adding 10 ml of a solution prepared by adjusting potassium phosphate to P = 0.1 mg / ml with distilled water, and diluting with distilled water.
Next, the phosphorus content is obtained from the following equation.
Phosphorus content (%) = absorbance of sample / absorbance of phosphor standard solution / sample (g)

Example 1 (Synthesis of phosphorus atom-containing urethane-modified epoxy resin (A-1))
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was added to a bisphenol A type liquid epoxy resin (epoxy equivalent 188 g / eq, hydroxyl value 19.3 KOH mg / g, Dainippon Ink and Chemicals, Inc. 188 g (epoxy group 1.0 equivalent)) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA: Sanko Chemical Co., Ltd.) 72.1 g (PH group concentration of 0.3 equivalent) was added, 0.135 g of triphenylphosphine was added, the temperature was raised to 150 ° C., the mixture was stirred for 7 hours, and HCA was substantially determined by epoxy equivalent and GPC measurement. After confirming disappearance, an intermediate was obtained. Next, 27.5 g (isocyanate group 0.3 equivalent) of tolylene diisocyanate (TDI: NCO equivalent 87 g / eq., Manufactured by Mitsui Chemicals Polyurethane Co., Ltd .: Cosmonate T-100) was added to the reaction system at 130 ° C. The mixture was stirred for 3 hours, and it was confirmed by IR measurement that the isocyanate group had substantially disappeared. Thus, the target phosphorus atom-containing urethane-modified epoxy resin (A-1) was obtained. The epoxy equivalent of the obtained epoxy resin was 440 g / eq., Softening point 92 ° C., and phosphorus atom content 3.5% by mass. A mass spectrum diagram of the obtained epoxy resin (A-1) is shown in FIG. 1, a ¹³ C-NMR chart is shown in FIG. 2, and a GPC chart is shown in FIG.

Example 2 (Synthesis of phosphorus atom-containing urethane-modified epoxy resin (A-2))
Instead of bisphenol A type liquid epoxy resin, 170 g of bisphenol F type liquid epoxy resin (epoxy equivalent 170 g / eq, hydroxyl value 18.3 KOH mg / g, “Epichlor 830S” manufactured by Dainippon Ink & Chemicals, Inc.), tolylene diisocyanate (TDI) ) Was used in the same manner as Example 1 except that 39.6 g (isocyanate group 0.3 equivalent) of diphenylmethane diisocyanate (MDI: NCO equivalent 125 g / eq., “Millionate MT” manufactured by Nippon Polyurethane Industry Co., Ltd.) was used. Thus, the target phosphorus atom-containing urethane-modified epoxy resin (A-2) was obtained. The epoxy equivalent of the obtained epoxy resin was 438 g / eq, the softening point was 89 ° C., and the phosphorus atom content was 3.6% by mass.

Example 3 (Synthesis of phosphorus atom-containing urethane-modified epoxy resin (A-3))
Instead of bisphenol A liquid epoxy resin, 1,6-dihydroxynaphthalene type epoxy resin (epoxy equivalent 151 g / eq, “Epicron HP-4032” manufactured by Dainippon Ink & Chemicals, Inc.), instead of tolylene diisocyanate (TDI) Except that 34.6 g (isocyanate group 0.3 equivalent) of 1,5-diisocyanate naphthalene (NDI: NCO equivalent 105 g / eq, “Cosmonate ND” manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was used, the same procedure as in Example 1 was performed. Thus, the target phosphorus atom-containing urethane-modified epoxy resin (A-3) was obtained. The epoxy equivalent of the obtained epoxy resin was 410 g / eq, the softening point was 97 ° C., and the phosphorus atom content was 3.9% by mass.

Example 4 (Synthesis of phosphorus atom-containing urethane-modified epoxy resin (A-4))
Except for using 300 g of bisphenol S type epoxy resin (epoxy equivalent 300 g / eq, hydroxyl value 74.8 KOH mg / g, “Epicron EXA-1514” manufactured by Dainippon Ink & Chemicals, Inc.) instead of bisphenol A liquid epoxy resin. The target phosphorus atom-containing urethane-modified epoxy resin (A-4) was obtained in the same manner as in Example 1. The epoxy equivalent of the obtained epoxy resin is 620 g / eq. The softening point was 112 ° C. and the phosphorus atom content was 2.6% by mass.

Example 5 (Synthesis of phosphorus atom-containing urethane-modified epoxy resin (A-5))
The target phosphorus was obtained in the same manner as in Example 1 except that 130.9 g of HCA (PH group concentration 0.6 equivalent) and 52.2 g of tolylene diisocyanate (TDI) (isocyanate group 0.6 equivalent) were used. An atom-containing urethane-modified epoxy resin (A-5) was obtained. The epoxy equivalent of the obtained epoxy resin was 940 g / eq, the softening point was 125 ° C., and the phosphorus atom content was 5.1% by mass.

Example 6 (Synthesis of phosphorus atom-containing urethane-modified epoxy resin (A-6))
An intermediate was obtained in the same manner as in Example 1 except that 157.3 g of HCA (PH group concentration 0.7 equivalent) was used, and then 63.3 g of tolylene diisocyanate (TDI) (isocyanate group) in the reaction system. 0.7 equivalent) and toluene was added so that the solid content concentration in the reaction solution became 80%, and the mixture was stirred at 130 ° C. for 3 hours. By IR measurement, it was confirmed that the isocyanate group was substantially disappeared. The phosphorus atom-containing urethane-modified epoxy resin (A-6) was obtained. The epoxy equivalent of the obtained epoxy resin was 1600 g / eq, the softening point was 143 ° C., and the phosphorus atom content was 5.5% by mass.

Comparative Example 1
A cresol novolak epoxy resin (epoxy equivalent: 206 g / eq, “Epicron N-665” manufactured by Dainippon Ink & Chemicals, Inc.) is attached to a flask equipped with a thermometer, cooling pipe, fractionating pipe, nitrogen gas introduction pipe, and stirrer. 206 g and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA: manufactured by Sanko Chemical Co., Ltd.) 54.2 g were added, and 0.05 g of triphenylphosphine was added. The mixture was heated to 0 ° C., stirred for 4 hours, and it was confirmed by epoxy equivalent and GPC measurement that HCA substantially disappeared to obtain a phosphorus atom-containing epoxy resin (B-1). The epoxy equivalent of the obtained epoxy resin was 380 g / eq., Softening point 65 ° C., and phosphorus atom content 3.9% by mass.

Examples 7 to 9 and Comparative Examples 2 and 3
As a curing agent with 100 parts of the epoxy resin obtained in Examples 1, 5 and 6, phenol novolak resin (phenolic hydroxyl group equivalent 105 g / eq, softening point 85 ° C., “TD-2090” manufactured by Dainippon Ink & Chemicals, Inc. ) In an equivalent amount, triphenylphosphine (TPP) as a curing accelerator, condensed phosphoric acid ester ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.) as a flame retardant, magnesium hydroxide (air water Echo Mug “Z-10” manufactured by Co., Ltd.), spherical silica (“S-COL” manufactured by Micron Co., Ltd.) as inorganic filler, and γ-glycidoxytriethoxyxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as silane coupling agent KBM-403 "), Carnauba wax (" PEARLWAX No. 1-P "manufactured by Celalica Noda Co., Ltd.) Were blended with compositions shown in Table 1 using the carbon black, to obtain an epoxy resin composition was 5 minutes melt-kneaded at a temperature of 85 ° C. using two rolls. As for the physical properties of the cured product, a sample for evaluation was prepared by the following method using the above composition, and the flame retardancy, Tg and tensile properties were measured by the following method, and the results are shown in Table 1.

[Flame retardance] Conforms to UL standards.
[Tg (glass transition temperature)] Measured by DMA method. Temperature rising speed 3 ° C./min [Tensile strength / elongation rate] Conforms to JIS-K6911.

1 is a mass spectrum diagram of the phosphorus atom-containing urethane-modified epoxy resin obtained in Example 1. FIG. 2 is a ¹³ C-NMR spectrum of the phosphorus atom-containing urethane-modified epoxy resin obtained in Example 1. FIG. 3 is a GPC chart of the phosphorus atom-containing urethane-modified epoxy resin obtained in Example 1. FIG.

Claims (15)

An epoxy resin (A) having a phosphorus atom and a urethane bond in the molecular structure and having an epoxy equivalent in the range of 300 to 2000 g / equivalent, and a curing agent (B) are essential. An epoxy resin composition characterized in that it is a component. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) contains a phosphorus atom in a proportion of 0.5 to 10% by mass. 3. The epoxy resin (A) is obtained by reacting a bifunctional epoxy resin (a) with a monofunctional active hydrogen-containing phosphorus compound (b) and a diisocyanate compound (c). Epoxy resin composition. The epoxy resin composition according to claim 3, wherein the bifunctional epoxy resin (a) is a liquid bisphenol type epoxy resin. The epoxy resin composition according to claim 3 or 4, wherein the monofunctional active hydrogen-containing phosphorus compound (b) is an aromatic phosphine compound. The hardener (B) is at least one phenol resin selected from the group consisting of a nitrogen atom-containing phenol resin, a phenol aralkyl resin, and a biphenyl aralkyl type phenol resin. The epoxy resin composition described in 1. The epoxy resin composition according to any one of claims 1 to 6, further comprising a non-halogen flame retardant in addition to the epoxy resin (A) and the curing agent (B). The epoxy resin composition according to any one of claims 1 to 7, further comprising an organic solvent in addition to the epoxy resin (A) and the curing agent (B). A varnish for a printed circuit board comprising the epoxy resin composition according to claim 8. Structural formula 1

(In the formula, G is a glycidyl group, Ar ¹ is a naphthylene group, or the following structural formula 2

(In Structural Formula 2, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group.) Group, Ar ² is an aromatic hydrocarbon group, Y is an organic phosphanyl group, and n is 0.05 to 2.8 on the average of the repeating units. )
A novel epoxy resin having a structure represented by Reacting the bifunctional epoxy resin (a) with the monofunctional active hydrogen-containing phosphorus compound (b) (step 1), and then reacting the resulting reaction product with the diisocyanate compound (c) (step 2). A method for producing an epoxy resin characterized by the following. The reaction ratio of the bifunctional epoxy resin (a) and the monofunctional active hydrogen-containing phosphorus compound (b) in the step 1 is monofunctional with respect to 1 equivalent of the epoxy group in the bifunctional epoxy resin (a). Active hydrogen in the active active hydrogen-containing phosphorus compound (b) is in a ratio of 0.2 to 0.8 equivalent, and the amount of the diisocyanate compound (c) used in the step 2 is the bifunctional epoxy. The production method according to claim 11, wherein the isocyanate group in the diisocyanate compound (c) is in a ratio of 0.2 to 0.8 equivalent to 1 equivalent of the epoxy group in the resin (a). The method according to claim 11 or 12, wherein the bifunctional epoxy resin (a) is a liquid bisphenol type epoxy resin. The production method according to claim 12 or 13, wherein the monofunctional active hydrogen-containing phosphorus compound (b) is an aromatic phosphine compound. Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-9.

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