JP2006316024A - Polyhydroxy compound, epoxy resin, method for producing them, and epoxy resin composition and cured material of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop an epoxy resin and a curing agent, capable of exhibiting sufficient flame retardance even without using a halogen-based flame retardant, also capable of reducing the using amount of a non-halogen-based flame retardant, an epoxy resin composition, the use of the same, a cured material obtained by curing the same, and a method capable of producing the epoxy resin and curing agent in high yields. <P>SOLUTION: This polyhydroxy compound is expressed by general formula (1) [wherein, Ar is an aromatic group which may have a substituent; R<SB>11</SB>, R<SB>12</SB>, R<SB>21</SB>, R<SB>21</SB>are each independently H, a 1-4C alkyl or phenyl]. The epoxy resin obtained by epoxydizing the polyhydroxy compound, and the method for producing the same are also provided. The epoxy resin composition contains these resins. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyvalent hydroxy compound and an epoxy resin which are excellent in heat resistance, moisture resistance and the like, and give a cured product excellent in flame retardancy without using a flame retardant represented by a brominated flame retardant.

Conventionally, epoxy resins have been widely used in various industrial fields such as electricity, paints and adhesives. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, epoxy resin compositions containing curing agents, flame retardants, fillers, and the like are used as resin compositions for binders for sealing materials and board materials. ing. Conventionally, halogen-containing flame retardants such as bromine and antimony compounds have been used as the flame retardants, and in particular, the halogen flame retardants that are feared to generate dioxins in recent efforts for environmental problems. The methods used in combination are avoided, and the development of flame retardant methods using new non-halogen compounds is required. In order to solve the above problems, as a non-halogenated flame retardant technique for semiconductor encapsulating materials in recent years, a technique using red phosphorus (for example, see Patent Document 1), a technique using a phosphoric ester compound (for example, Patent Document). 2), a method using magnesium hydroxide (for example, see Patent Document 3), and the like have been proposed. However, in any case, it is a combination with a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, etc., which have been generally used in the past, and is sufficient in flame retardancy, for example, a general index In order to achieve V-0 grade of UL94 flame retardant test, 2 parts by weight or more for red phosphorus, 7 parts by weight or more for phosphoric acid ester compounds, 150 weights for magnesium hydroxide with respect to 100 parts by weight of the epoxy resin. It is necessary to add a large amount of these non-halogen flame retardants, and problems such as defects in the moldability in the sealing process and reliability of the semiconductor device are likely to occur, and improvements are eagerly desired. .
JP-A-8-151427 (page 2-4) JP-A-9-235449 (pages 5-6 and 10-12) JP 2002-212392 A (pages 8 and 10-12)

  In view of the above circumstances, an epoxy resin and a curing agent that can exhibit sufficient flame retardancy without using a halogen-based flame retardant and can reduce the amount of non-halogen-based flame retardant used The present invention provides an epoxy resin composition that can solve the above-described problems, its use, and a cured product obtained by curing the epoxy resin composition, and the production method of the epoxy resin and the curing agent in a high yield. It is to provide a way that can be done.

  As a result of intensive studies to solve the above problems, the present inventor has found that a curing agent having a skeleton of the following general formula (1) or an epoxy resin having a skeleton of the following general formula (6) contains a halogen flame retardant. The present invention has been completed by finding that it is not necessarily required and that sufficient flame retardancy can be exhibited without adding a large amount of non-halogen flame retardant.

  That is, the present invention provides a polyvalent hydroxy compound represented by the following general formula (1).

（式中、Ａｒは置換基を有していてもよい芳香族炭化水素基を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２はそれぞれ独立に水素原子または炭素数１〜４のアルキル基、或いはフェニル基を示す。）

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group.)

  In addition, the present invention provides a compound obtained by reacting the compound represented by the general formula (3) and the general formula (4) in the presence of a basic catalyst, and the compound represented by the general formula (5) is acidic. There is also provided a method for producing a polyvalent hydroxy compound characterized by reacting under a catalyst.

（式中、Ａｒは置換基を有していてもよい芳香族炭化水素基を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２はそれぞれ独立に水素原子または炭素数１〜４のアルキル基、或いはフェニル基を示す。）

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group.)

  The present invention also provides an epoxy resin represented by the general formula (6).

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be the same or different.

  Moreover, this invention is an epoxy resin composition and its hardened | cured material which have the polyhydric phenol compound represented by General formula (1) and / or the epoxy resin represented by General formula (6) as an essential component, those It also provides uses.

  According to the present invention, a polyvalent hydroxy compound and an epoxy resin excellent in flame retardancy of a cured product can be obtained in a high yield without using a halogen-based flame retardant. A stop material and a semiconductor device using the same can be provided.

The present invention will be described in detail below.
Although the synthesis method of the polyhydric phenol compound represented by General formula (1) is not specifically limited, For example, it is compoundable by reaction of the following two steps.

  That is, as the first-stage reaction, the compounds represented by the following general formula (3) and general formula (4) are reacted in the absence of a catalyst or a basic catalyst. Next, as the second-stage reaction, the compound obtained by the first-stage reaction is reacted with a compound represented by the following general formula (5) in the presence of an acidic catalyst to give a polyvalent compound represented by the general formula (1). A phenolic compound can be obtained.

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group.)

  Here, specific examples of the general formula (3) used for obtaining the compound of the general formula (1) include 1,2-epoxyethylbenzene, 1,2-epoxyethylbiphenyl, 1,2-epoxyethyltoluene, 1, Examples include 2-epoxyethyl xylene, 1,2-epoxyethyl-1-naphthalene, 1,2-epoxyethyl-2-naphthalene, but are not limited thereto. Among these, 1,2-epoxyethylbenzene is preferable because the balance between flame retardancy, heat resistance and curability is improved.

Specific examples of the compounds represented by the general formula (4) and the general formula (5) used for obtaining the compound of the general formula (1) include phenol, orthocresol, 2,6-xylenol, 2-methyl -6-ethyl-phenol, 2,6-diethyl-phenol, 2-methyl-6-propyl-phenol, 2-ethyl-6-propyl-phenol, 2,6-dipropyl-phenol, 2,6-dibutyl-phenol 2,6-diphenyl-phenol and the like, but are not limited thereto. Of these, it is preferable to use 2,6-xylenol for both general formula (4) and general formula (5) because the balance between flame retardancy, heat resistance and curability is improved.

A case where the first-stage reaction is performed will be described.
The first stage reaction proceeds in the absence of a catalyst or in the presence of a catalyst. Various catalysts can be used as the catalyst. For example, basic catalysts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and other alkali (earth) metal hydroxides, sodium carbonate, potassium carbonate and other alkali metal carbonates, triphenylphosphine, etc. Phosphorus compounds such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium chloride, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium chloride Quaternary ammonium salts such as bromide and iodide, triethylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo (5.4.0) undecene, 1,4-di Zabishikuro (2.2.2) tertiary amines such as octane, 2-ethyl-4-methylimidazole, imidazoles such as 2-phenylimidazole, and the like. These may use together 2 or more types of catalysts. Of these, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds quickly and the effect of reducing the amount of impurities.

  Although the usage-amount of these catalysts is not specifically limited, It is preferable to use 0.005-0.05 mol with respect to 1 mol of phenolic hydroxyl groups of the compound represented by General formula (3). The form of these catalysts is not particularly limited, and the catalyst may be used in the form of an aqueous solution or in the form of a solid.

  When represented by the general formula (3) used in the first-stage reaction, the reaction ratio with the compound represented by the general formula (4) is not particularly limited, but when represented by the general formula (3), the general formula The molar ratio [general formula (3)] / [general formula (4)] with the compound represented by (4) is preferably 1/1 to 0.1 / 1 (molar ratio).

  The first stage reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol. The amount of the organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight, based on the total weight of the charged raw materials. These organic solvents can be used alone or in combination of several kinds. In order to carry out the reaction promptly, a solvent-free is preferable. On the other hand, dimethyl sulfoxide is preferably used in order to reduce impurities in the final product.

  The reaction temperature for carrying out the first stage reaction is usually 50 to 180 ° C., and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 80 to 150 ° C. in order to reduce impurities in the final product. Moreover, when the coloring of the compound obtained is large, in order to suppress it, you may add antioxidant and a reducing agent. Although it does not specifically limit as antioxidant, For example, a hindered phenol type compound, such as a 2, 6- dialkylphenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. are mentioned. Can do. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  After completion of the first stage reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. What is necessary is just to perform a neutralization process and a water washing process in accordance with a conventional method. For example, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium monohydrogen phosphate, p-toluenesulfonic acid, oxalic acid and the like can be used as a neutralizing agent. After neutralization or washing with water, the compound can be obtained by concentrating the product by distilling off the solvent and unreacted substances under reduced pressure heating if necessary.

Next, the case where the second-stage reaction is performed will be described.
When performing the second-stage reaction, various catalysts can be used. For example, acidic catalysts such as inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, lactic acid, succinic acid And organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These may use together 2 or more types of catalysts. Of these, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid are preferred because the reaction proceeds quickly and the effect of reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but 0.1 to 30% by weight of the total weight of the compound obtained by the first-stage reaction and the compound represented by the general formula (4) is used. preferable. The form of these catalysts is not particularly limited and may be used in the form of an aqueous solution or in the form of a solid.

  The reaction ratio between the product of the first-stage reaction used in the second-stage reaction and the compound represented by the general formula (5) is not particularly limited, but the product of the first-stage reaction and the general formula (5 It is preferable that the molar ratio [product of the first stage reaction] / [general formula (5)] is 1/1 to 0.1 / 1.

  The second stage reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, and dimethyl sulfoxide. The amount of the organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight, based on the total weight of the charged raw materials. These organic solvents can be used alone or in combination of several kinds. Among these, no solvent is preferable because the steps such as solvent distillation can be omitted. Water or alcohols generated during the reaction are distilled off using a fractionation tube outside the system, and the reaction is promptly performed. For this purpose, use of toluene or xylene is preferred.

The reaction temperature for carrying out the second stage reaction is usually 80 to 180 ° C., and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 80 to 150 ° C. in order to reduce impurities in the final product.
Moreover, when the coloring of the compound obtained is large, in order to suppress it, you may add antioxidant and a reducing agent. Although it does not specifically limit as antioxidant, For example, a hindered phenol type compound, such as a 2, 6- dialkylphenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. are mentioned. Can do. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  After completion of the second stage reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. What is necessary is just to perform a neutralization process and a water washing process in accordance with a conventional method. For example, when an acidic catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent. After neutralization or washing with water, if necessary, the solvent and unreacted substances are distilled off under reduced pressure and the product is concentrated to obtain the compound of the general formula (1). At this time, the reaction product may contain a compound represented by the following general formula (2).

  In that case, it is possible to reduce the content of the compound represented by the following general formula (2) by purifying the obtained reaction product after completion of the second-stage reaction. The content of the compound represented by the general formula (2) is preferably 50 mol% or less of the whole from the viewpoint of maintaining the heat resistance of the cured product, and further preferably 10 mol% or less of the whole. More preferable. The purification method can be carried out according to various methods. For example, a column chromatography separation method using a difference in polarity, a distillation fractionation method using a difference in boiling point, an alkaline aqueous extraction method using a difference in solubility in alkaline water, and the like can be mentioned. Among these, an alkaline aqueous extraction method that does not involve thermal alteration is preferable in terms of efficiency.

（式中、Ａｒは置換基を有していてもよい芳香族を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２はそれぞれ独立に水素原子または炭素数１〜４のアルキル基、或いはフェニル基を示す。）

(In the formula, Ar represents an aromatic group which may have a substituent, and R _11, R ₁₂ , R ₂₁ and R ₂₂ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Is shown.)

  The epoxy resin represented by the general formula (6) of the present invention can be obtained by reacting the polyhydric phenol compound represented by the general formula (1) with an epihalohydrin. In this case, a reaction product containing a compound represented by the following general formula (2) may be reacted with epihalohydrin.

  The conditions for carrying out the epoxy resin reaction can be carried out according to various methods. For example, 2 to 10 mol of epihalohydrin is added to 1 mol of the phenolic hydroxyl group of the compound of the general formula (1), and 0.9 to about 1 mol of the phenolic hydroxyl group of the compound of the general formula (1) is added to this mixture. The reaction is carried out at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding 2.0 mol of a basic catalyst. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  When industrial production is performed, the first batch of epoxy resin production uses all of the prepared epihalohydrin, but after the next batch, the epihalohydrin recovered from the crude reaction product and the amount consumed in the reaction. It is preferable to use in combination with a new epihalohydrin corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferable because it is easily available. The basic catalyst is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent catalytic activity for the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide, potassium hydroxide, and calcium hydroxide. In use, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples thereof include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After washing the reaction product of these epoxidation reactions, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by weight based on the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin and a polyvalent hydroxy compound represented by general formula (1), or an epoxy resin represented by general formula (6) and cured. It is an epoxy resin composition containing an agent.

  At this time, the polyvalent hydroxy compound represented by the general formula (1) may include a compound represented by the general formula (2). Further, the content is preferably 50 mol% or less of the whole from the viewpoint of maintaining the heat resistance of the cured product, and more preferably 10 mol% or less of the whole because of excellent heat resistance.

  In the epoxy resin composition containing the epoxy resin and the polyvalent hydroxy compound represented by the general formula (1) of the present invention, the polyvalent hydroxy compound represented by the general formula (1) of the present invention is an epoxy resin. Acts as a curing agent. In this case, the polyvalent hydroxy compound represented by the general formula (1) of the present invention can be used alone or in combination with other curing agents as long as the characteristics are not impaired. When used in combination, the proportion of the polyvalent hydroxy compound represented by the general formula (1) of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Other curing agents that can be used in combination with the polyvalent hydroxy compound represented by the general formula (1) of the present invention are not particularly limited, and examples thereof include amine compounds, amide compounds, acid anhydride compounds, phenols, and the like. Various curing agents such as a ruthenium compound can be used. Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like. Examples of amide compounds include dicyandiamide and linolenic acid. And polyamide resins synthesized from ethylenediamine, and acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl Examples include tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol Condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol 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) ), Polyphenol compounds such as aminotriazine-modified phenol resins (polyphenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.), and Examples of these modified products include, but are not limited to, these. These may be used alone or in combination of two or more.

  Among these, 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 resin, Biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenolic resin are preferable because they are excellent in flame retardancy, especially aromatic hydrocarbon formaldehyde resin-modified phenolic resin, phenol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenolic resin, biphenyl. Hydroxyl by a linking group containing an aromatic ring not having a hydroxyl group such as a modified naphthol resin or an aminotriazine-modified phenol resin It is preferred particularly from the viewpoint of excellent flame retardancy polyvalent aromatic compound containing an aromatic ring are linked structure with.

  In the epoxy resin composition of the present invention, the epoxy resin represented by the general formula (6) of the present invention can be used alone or in combination with other epoxy resins as long as the properties are not impaired. When used in combination, the proportion of the epoxy resin represented by the general formula (6) of the present invention in the total epoxy resin is preferably 30% by weight or more, and particularly preferably 40% by weight or more.

  In addition, as the melt viscosity of the epoxy resin represented by the general formula (6), the viscosity value by an ICI cone / plate viscometer at 150 ° C. is 5 dPa · It is preferable that it is s or less.

  The epoxy resin used in the epoxy resin composition of the present invention is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl Type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol 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 novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type Carboxymethyl resins, do not aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resin is not limited thereto. Moreover, these epoxy resins may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins are preferable in terms of particularly low viscosity, and phenol aralkyl-type epoxy resins and biphenyls are preferable in terms of excellent flame retardancy. A modified novolac type epoxy resin is preferred.

  In addition, the epoxy resin composition containing the epoxy resin represented by the general formula (6) and the curing agent contains various curing agents containing the epoxy resin represented by the general formula (6) as an essential component. is there. In this case, the curing agent is not particularly limited, and examples thereof include a polyvalent hydroxy compound represented by the general formula (1) or the other curing agent.

  In addition, the epoxy resin composition containing the epoxy resin represented by the general formula (6) and a curing agent can be used in combination with other epoxy resins as long as the properties are not impaired. A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, di Cyclopentadiene-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 type epoxy resin, naphthol-crezo Le co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resins are not limited thereto. Moreover, these epoxy resins may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins are preferable in terms of particularly low viscosity, and phenol aralkyl-type epoxy resins and biphenyls are preferable in terms of excellent flame retardancy. A modified novolac type epoxy resin is preferred.

  The blending amount of the epoxy resin and the curing agent in the epoxy resin composition of the present invention is not particularly limited, but from the viewpoint of good mechanical properties of the resulting cured product, the epoxy group of the epoxy resin. The amount by which the active groups in the curing agent are 0.7 to 1.5 equivalents with respect to 1 equivalent in total.

  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 application, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., triphenylphosphine is used for phosphorus compounds, and 1,8-diazabicyclo- is used for tertiary amines. (5,4,0) -undecene is preferred.

The epoxy resin composition of the present invention is a cured product because the polyvalent hydroxy compound represented by the general formula (1) used and the epoxy resin itself represented by the general formula (6) have flame retardancy. The flame retardant of the cured product is good without adding a conventionally used flame retardant to impart the flame retardant, but in order to exhibit a higher degree of flame retardant, sealing process It is also possible to obtain a non-halogen flame retardant resin composition by blending a non-halogen flame retardant that does not substantially contain a halogen atom within a range that does not reduce the moldability and reliability of the semiconductor device. is there.
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.

  The non-halogen flame retardant is a compound that does not substantially contain a halogen atom such as chlorine or bromine, and is not limited as long as it has a function as a flame retardant or a flame retardant aid. There are, for example, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organometallic salt flame retardants, etc. Even when used, a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, both inorganic and organic compounds can be used as long as they are compounds containing phosphorus atoms. Examples of inorganic compounds include phosphoric acids such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, which may be subjected to surface treatment for the purpose of preventing hydrolysis and the like. Examples thereof include inorganic nitrogen-containing phosphorus compounds such as ammonium and phosphoric acid amide.

  Examples of the surface treatment method of red phosphorus include (1) coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. A method of treating, (2) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and a thermosetting resin such as phenol resin, (3) magnesium hydroxide In addition, there is a method of doubly coating with a thermosetting resin such as a phenol resin on a coating of an inorganic compound such as aluminum hydroxide, zinc hydroxide, titanium hydroxide, and any one of (1) to (3) What was processed by the method of can also be used.

  Examples of the organic phosphorus compounds include phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, and organic nitrogen-containing phosphorus compounds. Specific examples of the phosphoric ester compound include triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (di2,6-xylenol phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate). ), Resorcinyl diphenyl phosphate and the like.

  Specific examples of the phosphonic acid compound include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, and phosphonic acid metal salts described in JP-A No. 2000-226499.

  Specific examples of the phosphinic acid compound include diphenylphosphinic acid, methylethylphosphinic acid, a compound described in JP-A-2001-55484, 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phospha Examples thereof include cyclic organophosphorus compounds such as phenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

Specific examples of the phosphine oxide compound include triphenylphosphine oxide, tris (3-hydroxypropyl) phosphine oxide, diphenylphosphinyl hydroquinone, JP-A No. 2000-186186, JP-A No. 2002-080484, JP-A No. 2002. -097248 gazette etc. are mentioned.
Specific examples of the phosphorane compound include compounds described in JP-A No. 2000-281871.

  Examples of organic nitrogen-containing phosphorus compounds include JP 2002-60720, JP 2001-354686, JP 2001-261792, JP 2001-335703, JP 2000-103939, and the like. And the phosphazene compounds described.

  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 In 100 parts by weight of the epoxy resin composition containing all of the flame retardant and other fillers and additives, when using red phosphorus as a non-halogen flame retardant, in the range of 0.1 to 2.0 parts by weight It is preferable to mix, and when using an organophosphorus compound, it is also preferable to mix in the range of 0.1 to 10.0 parts by weight, particularly in the range of 0.5 to 6.0 parts by weight. Is preferred.

  Further, the method of using the phosphorus-based flame retardant is not particularly limited. For example, JP 2002-080566 A, JP 2002-053734 A, JP 2000-248156 A, and JP 9-9 A. No. 235449, etc., hydrotalcite used together, Japanese Patent Application Laid-Open No. 2001-329147, etc., magnesium hydroxide used together, Japanese Patent Application Laid-Open No. 2002-23989, Japanese Patent Application Laid-Open No. 2001-323134, etc. Compound combination, zirconium oxide combination described in JP-A No. 2002-069271, etc., black dye combination described in JP-A No. 2001-123047, etc., calcium carbonate described in JP-A No. 2000-281873, etc. Combined use, combined use of zeolite described in JP-A-2000-281873, etc., JP-A-200 Used in combination with zinc molybdate described in JP-A No. -248155, etc., used in combination with activated carbon described in JP-A No. 2000-212392, JP-A No. 2002-348440, JP-A No. 2002-265758, and JP-A No. 2002-180053. Conventional methods such as surface treatment methods described in JP-A No. 2001-329147, JP-A No. 2001-226564, JP-A No. 11-269345, and the like can be applied.

  The nitrogen-based flame retardant is not particularly limited as long as it is a compound containing a nitrogen atom, and examples thereof include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like. Triazine compounds, cyanuric acid compounds An isocyanuric acid compound is preferred.

  Specific examples of the triazine compound include, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and derivatives thereof. For example, (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, (2) phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, and melamine, benzoguanamine, acetoguanamine, formguanamine, etc. A co-condensate of melamines and formaldehyde, (3) a mixture of the co-condensate of the above (2) and a phenol resin such as a phenol formaldehyde condensate, (4) the above (2), (3) is further paulownia oil, Modified with isomerized linseed oil, etc. And the like.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine. Specific examples of the isocyanuric acid compound include tris (β-cyanoethyl) isocyanurate, diallyl monoglycidyl isocyanuric acid, monoallyl diglycidyl isocyanuric acid, and the like.

Further, the compound containing a nitrogen atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. May be.

  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 weight in 100 parts by weight 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 weight.

  Further, the method of using the nitrogen-based flame retardant is not particularly limited. For example, the metal hydroxide described in JP-A-2001-234036 and the like, JP-A-2002-003577, JP-A Conventional methods such as combined use of molybdenum compounds described in JP 2001-098144 A can be applied.

  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. Specific examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether-modified silicone oil, and the like. Specific examples of the silicone rubber include methyl silicone rubber and methylphenyl silicone rubber. Specific examples of the silicone resin include methyl silicone, methyl phenyl silicone, and phenyl silicone.

The organic compound containing a silicon atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. You may do it.

  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 weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives.

Further, the method of using the silicone-based flame retardant is not particularly limited. For example, a combination of molybdenum compounds described in JP 2001-011288 A, alumina described in JP 10-182941 A, and the like. A conventional method such as a combination of these can be applied.
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, for example, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, JP 2002-212391 A, and JP 2001. Examples thereof include composite metal hydroxides described in JP-A No. 335681 and JP-A No. 2001-32050.

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, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  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 an amount of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives, and particularly 0.5 to 20 parts by weight. It is preferable to mix in the range of 15 parts by weight.

  Further, the method of using the inorganic flame retardant is not particularly limited. For example, the method for controlling the specific surface area described in JP-A-2001-226564, JP-A-2000-19595, JP-A-2000. 191886, JP-A-2000-109647, JP-A-2000-038776, etc., methods for controlling the shape, particle size, and particle size distribution, JP-A-2001-32050, JP-A-2000-095956 JP, 10-279813, JP 10-251486, a method for performing surface treatment, JP 2002-030200, JP 2001-279063, etc. Combined use, combined use of zinc borate described in JP 2001-049084 A, etc., JP 2000-195994 A A combination of inorganic powders described in JP-A-2000-156437, a butadiene rubber described in JP-A-2000-156437, a high acid value polyethylene wax described in JP-A-2000-053875 and a long-chain alkyl phosphate ester compound Conventional methods such as combined use can be applied.

  Examples of the organometallic salt-based flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  Specific examples of the acetylacetonate metal complex include compounds described in JP-A No. 2002-265760. Specific examples of the organometallic carbonyl compound include compounds described in JP-A No. 2002-371169.

  Specific examples of the organic cobalt salt compound include, for example, a cobalt naphthenic acid complex, a cobalt ethylenediamine complex, a cobalt acetoacetonate complex, a cobalt piperidine complex, a cobalt cyclohexanediamine complex, a cobalt tetraazacyclotetradodecane complex, and a cobalt ethylenediaminetetraacetic acid complex. , Cobalt tetraethylene glycol complex, cobalt aminoethanol complex, cobalt cyclohexadiamine complex, cobalt glycine complex, cobalt triglycine complex, cobalt naphthidirine complex, cobalt phenanthroline complex, cobalt pentanediamine complex, cobalt pyridine complex, cobalt salicylic acid complex, cobalt Salicylaldehyde complex, cobalt salicylideneamine complex, cobalt complex porphyrin, cobalt thiourea complex And the like can be given.

  Specific examples of the organic sulfonic acid metal salt include potassium diphenylsulfone-3-sulfonate.

  Specific examples of the compound in which the metal atom and the aromatic compound or heterocyclic compound are ion-bonded or coordinate-bonded include compounds described in JP-A-2002-226678.

  The amount of the organic metal salt-based flame retardant is appropriately selected according to the type of the organic metal 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 weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin, curing agent, non-halogen flame retardant, and other fillers and additives.

  An inorganic filler can be blended in the epoxy resin composition of the present invention as necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by weight or more with respect to the total amount of the epoxy resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the epoxy resin composition of this invention as needed.
The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention, in which the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator are blended, can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, insulation paints Among these, it can be suitably used for a semiconductor sealing material.

  In order to produce an epoxy resin composition prepared for a semiconductor encapsulant, an epoxy resin, a curing agent, a compounding agent such as a filler, and the like, if necessary, an extruder, a kneader, a roll, etc. It is sufficient to obtain a melt-mixed type epoxy resin composition by mixing well until it is uniform. At that time, silica is usually used as the filler, and the filling rate is preferably in the range of 30 to 95% by weight per 100 parts by weight of the epoxy resin composition. In order to improve moisture resistance and solder crack resistance and to reduce the linear expansion coefficient, it is particularly preferably 70 parts by weight or more, and in order to significantly increase these effects, 80 parts by weight or more further enhances the effect. be able to.

  With semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to obtain a molded product. it can.

In order to make the curable resin composition of the present invention into a resin composition for a prepreg for printed circuit boards, it can be used without a solvent depending on the viscosity of the curable resin composition, but it can be varnished with an organic solvent. It is preferable to use a resin composition for prepreg. 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 or the like which does not contain an alcoholic hydroxyl group, and it can be used alone or as a mixed solvent of two or more kinds. A solvent containing an alcoholic hydroxyl group is not preferable because it reacts with vinyl ethers depending on conditions. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.
In order to obtain a resin composition for a copper-clad laminate from the curable resin composition of the present invention, it is the same as the method for preparing the resin composition for a prepreg, and the obtained prepreg is, for example, JP-A-7-41543. As described in the above, a copper-clad laminate can be obtained by laminating copper foils as appropriate, and thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. .

  When the curable resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A-5-186567, a resist ink composition is prepared, and then a printed circuit board is printed by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating on top is mentioned.

  When the curable resin composition of the present invention is used as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition to form a composition for anisotropic conductive film. A paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And a method of using an anisotropic conductive adhesive.

A method for obtaining an interlayer insulating material for a build-up substrate from the curable resin composition of the present invention is not particularly limited. For example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960 Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the curable resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then 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.
The method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. What is necessary is just to heat the composition obtained by the said method in the temperature range of about room temperature-250 degreeC. As the molding method and the like, a general method of the epoxy resin composition is used, and a condition specific to the epoxy resin composition of the present invention is not particularly required.

Next, the present invention will be specifically described with reference to examples and comparative examples. In the following, unless otherwise specified, “parts” indicate parts by weight.
GPC measurement method:
Equipment Tosoh Corporation HLC-8220 GPC
Column: Tosoh Corporation TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL
Solvent: Tetrahydrofuran Flow rate: 1 ml / min
Detector: RI

Example 1 [Synthesis of polyvalent hydroxy compound (A-1)]
<First stage reaction>
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 366 parts of 2,6-xylenol and 360 parts of 1,2-epoxyethylbenzene previously heated and melted at 80 ° C. while purging with nitrogen gas. Stirring while heating to 90 ° C. 8 parts of triphenylphosphine was slowly added so as not to exceed 100 ° C. while paying attention to heat generation. Thereafter, the mixture was heated to 120 ° C. and reacted for 2 hours. Thereafter, 4 parts of triphenylphosphine was added, and the mixture was further reacted for 5 hours. After completion of the reaction, p-toluenesulfonic acid was added until the system became neutral to obtain the product (a). When the mass spectrum was measured, the corresponding M + = 242 was confirmed. A C ₁₃ -NMR chart is shown in FIG.

<Second stage reaction>
260 parts of 2,6-xylenol previously heated and melted at 80 ° C. and 300 parts of the product (a) 300 were subjected to nitrogen gas purging in a flask equipped with a temperature-separating pipe and a separator cock attached to the lower part. The mixture was charged and stirred while heating to 90 ° C. in an oil bath. 3 parts of p-toluenesulfonic acid was slowly added so as not to exceed 100 ° C. while paying attention to heat generation. Thereafter, the mixture is heated to 120 ° C. and reacted for 4 hours. Unreacted 2,6-xylenol is distilled off under reduced pressure, and then a product (A−), which is a mixture of the structures of the formulas (7) and (8). 1) was obtained. The obtained polyvalent hydroxy compound had a hydroxyl group equivalent of 220 g / eq. When the mass spectrum was measured, the corresponding M + = 346 was confirmed. The mass spectrum is shown in FIG. 2, and the C ₁₃ -NMR chart is shown in FIG. The content of the structure of the formula (8) calculated from the C ₁₃ -NMR chart was 30 mol%.

Example 2 [Synthesis of Epoxy Resin (B-1)]
219 parts of the polyvalent hydroxy compound (A-1) obtained in Example 1 while purging nitrogen gas purge to a flask equipped with a separatory cock at the lower part equipped with a thermometer, a dropping funnel, a condenser, and a stirrer 463 g (5.0 mol), 139 g of n-butanol, and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49 wt% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. Then, 510 g of methyl isobutyl ketone and 170 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% by weight aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 150 g of water was repeated three times until the pH of the washing solution became neutral. Subsequently, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain a product (B-1) that is a mixture of the structures of the formulas (9) and (10) 270 parts were obtained. The epoxy equivalent of the obtained epoxy resin was 319 g / eq. When the mass spectrum was measured, corresponding M + = 402 and 452 were confirmed. A mass spectrum is shown in FIG. 4, and a C ₁₃ -NMR chart is shown in FIG.

Example 3 Synthesis of polyvalent hydroxy compound (A-2)
<First stage reaction>
The product (a) was obtained in the same manner as in Example 1.
<Second stage reaction>
The product (A-1) was obtained in the same manner as in Example 2.
Thereafter, 400 parts of the product (A-1) was dissolved in 800 parts of toluene, and water washing was repeated with 400 parts of water until the pH of the cleaning liquid became neutral. From this washed toluene solution, the polyvalent hydroxy compound (A-2) and unreacted 2,6-xylenol were extracted five times using 400 parts of a 5% aqueous sodium hydroxide solution. Hydrochloric acid was added to 2000 parts of a 5% aqueous sodium hydroxide solution from which this polyhydroxy compound (A-2) and unreacted 2,6-xylenol had been extracted until PH in the system was 1, and toluene 1000 Then, the polyvalent hydroxy compound (A-2) and unreacted 2,6-xylenol were extracted into toluene. The toluene solution was repeatedly washed with 400 parts of water until the pH of the washing solution became neutral, and after toluene and 2,6-xylenol were distilled off under reduced pressure, the toluene solution of the present invention represented by the above formula (7) was used. A mixture (A-2) containing a polyvalent hydroxy compound was obtained. The obtained mixture (A-2) had a hydroxyl equivalent of 175 g / eq. A C ₁₃ -NMR chart is shown in FIG. It was calculated from the C ₁₃ -NMR chart. As a result, the content of the structure of the formula (7) was 97 mol%, and the content of the structure of the formula (8) was 3 mol%.

Example 4 [Synthesis of Epoxy Resin (B-2)]
In Example 2, 175 parts of the mixture (A-2) obtained in Example 3 was used instead of the product (A-1) which is a mixture of the structures of the formulas (7) and (8). Produced 224 parts of epoxy resin (B-2) in the same manner as in Example 2. The epoxy equivalent of the obtained epoxy resin (B-2) was 245 g / eq. A C ₁₃ -NMR chart is shown in FIG.

Examples 5 to 8 and Comparative Example 1
Using the various materials shown in Table 1, the composition shown in Table 2 was melt kneaded for 10 minutes at a temperature of 100 ° C. using two rolls to obtain the desired composition. About the obtained epoxy resin composition, gel time was measured with the following method and sclerosis | hardenability was tested. In addition, this was press-molded at 180 ° C. for 10 minutes, and then further cured at 180 ° C. for 5 hours. Then, a test piece having a thickness of 1.6 mm in accordance with the UL-94 test method was prepared and cured by the following method. The physical properties of the material were confirmed.

  Moisture absorption rate (%): The weight increase rate after treatment for 300 hours under the condition of 85 ° C./85% RH was determined.

Glass transition temperature: Measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, temperature rising rate 3 ° C./min).
Flame retardancy: Based on the UL-94 test method, a flame test was performed using five test pieces having a thickness of 1.6 mm.

  Examples 1-4 which are the epoxy resin curing agent and epoxy resin of the present invention have excellent flame retardancy, heat resistance, and moisture resistance.

2 is a ¹³ C-NMR spectrum of the compound (a) obtained by the first-stage reaction in Example 1. FIG. 2 is a mass spectrum of the polyvalent hydroxy compound obtained in Example 1. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 1. FIG. 2 is a mass spectrum of the polyvalent hydroxy compound obtained in Example 2. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 2. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 3. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 4.

Claims (21)

The following general formula (1)

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Or a phenyl group.) A polyvalent hydroxy compound represented by: The polyvalent hydroxy compound according to claim 1, wherein R _11, R ₁₂ , R ₂₁ , and R _{22 in the} general formula (1) are methyl groups. The polyvalent hydroxy compound according to claim 1 or 2, wherein Ar in the general formula (1) has a benzene skeleton, a biphenyl skeleton, or a naphthalene skeleton. The polyhydroxy compound according to claim 1, 2 or 3 and the compound represented by the following general formula (2) are contained, and the content of the compound represented by the general formula (2) is 50 mol% of the whole. A polyhydric hydroxy compound mixture which is:

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group.) Reacting a compound represented by the general formula (5) with a compound obtained by reacting the compound represented by the general formula (3) and the general formula (4) under a basic catalyst with an acid catalyst. A process for producing a polyvalent hydroxy compound characterized in that

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group.) An epoxy resin represented by the general formula (6).

(In the formula, Ar represents an aromatic hydrocarbon group which may have a substituent, R _11, R ₁₂ , R ₂₁ and R ₂₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Alternatively, it represents a phenyl group, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be the same or different. A method for producing an epoxy resin, comprising reacting the polyvalent hydroxy compound according to claim 1, 2 or 3 with an epihalohydrin. A method for producing an epoxy resin, comprising reacting the polyhydroxy compound mixture according to claim 4 with an epihalohydrin. An epoxy resin composition comprising the polyvalent hydroxy compound according to claim 1, 2 or 3 or the polyhydric hydroxy compound mixture according to claim 4 and an epoxy resin. The epoxy resin composition containing the epoxy resin of Claim 6. An epoxy resin composition comprising an epoxy resin derived from the polyhydroxy compound mixture according to claim 4 and an epihalohydrin. The epoxy resin composition according to claim 9, 10 or 11, which contains substantially no halogen-based flame retardant. Furthermore, it contains at least one flame retardant selected from the group consisting of phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organometallic salt flame retardants as non-halogen flame retardants. The epoxy resin composition according to claim 9, 10 or 11. The epoxy resin composition according to any one of claims 9 to 13, which is prepared for a semiconductor sealing material. The epoxy resin composition according to any one of claims 9 to 13, which is prepared for a circuit board resin composition. The epoxy resin composition according to any one of claims 9 to 13, which is prepared for resist ink. The epoxy resin composition according to claim 9, which is prepared for a conductive paste. The epoxy resin composition according to any one of claims 9 to 13, which is prepared for an interlayer insulating material. Hardened | cured material obtained by hardening the epoxy resin composition as described in any one of Claims 9-18. A semiconductor device or a circuit board on which the epoxy resin cured product according to claim 19 is mounted as a component. The circuit board which mounts the epoxy resin hardened | cured material of Claim 19 as components.

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