JP4984451B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention is an epoxy resin composition that is excellent in curability, has good flame retardancy and dielectric properties, and can be suitably used for semiconductor encapsulating materials, printed circuit boards, paints, casting applications, etc. And a cured product thereof.

  The technology that uses polyvalent hydroxy compounds as curing agents for epoxy resins is highly evaluated for the excellent heat resistance and moisture resistance of the resulting cured products, and is widely used in fields such as semiconductor encapsulants and printed circuit boards. As the polyvalent hydroxy compound, a phenol novolak resin (phenol-formaldehyde resin) is generally used.

  By the way, in recent electronics field and high-performance paint field, in order to cope with environmental problems such as dioxin problem and high-speed computing, there is a strong demand for improvement in flame retardancy and dielectric properties. Therefore, the epoxy resin curing agent (polyhydric hydroxy compound) used in these fields is also required to have performance superior to that of the conventional compound, and there is a strong demand for the development of a polyhydric hydroxy compound capable of realizing it.

  As means for meeting these requirements, for example, the following general formula (I)

（式中、Ｒはメチル基またはエチル基を表し、Ｘは水素原子またはメチル基を表す。また、ｎは０〜３の整数を表し、ｍは１〜５の整数を表す。但し、ｎ＝０の化合物の含有率は１０％以下である。）
で表されるアルコキシ基変性フェノールノボラック樹脂が、耐湿性と耐衝撃性の技術課題を解決するものとして開示されている（例えば、特許文献１参照。）。しかしながら、前記特許文献１で提案されたフェノール樹脂をエポキシ樹脂の硬化剤として用いた場合は、硬化性に著しく劣り、実用レベルに達していない。即ち、エポキシ樹脂組成物の硬化性を向上させるために核体数を挙げる手段としてレゾール化反応温度を高めると、最終的に得られる化合物にフェノール性水酸基を含有しない構造の化合物が増加し、官能基濃度が低くなる。又、官能基濃度を高めようとすると、前記特許文献１の実施例１に見られるように、核体数が小さくなり、結果として硬化性に著しく劣るものになる。

(In the formula, R represents a methyl group or an ethyl group, X represents a hydrogen atom or a methyl group, n represents an integer of 0 to 3, and m represents an integer of 1 to 5, provided that n = The content of 0 compound is 10% or less.)
Is disclosed as a solution to the technical problems of moisture resistance and impact resistance (see, for example, Patent Document 1). However, when the phenol resin proposed in Patent Document 1 is used as a curing agent for an epoxy resin, the curability is remarkably inferior and has not reached a practical level. That is, when the resolation reaction temperature is increased as a means of increasing the number of nuclei in order to improve the curability of the epoxy resin composition, the final compound obtained has a structure with no phenolic hydroxyl group, resulting in a functional The base concentration is lowered. Further, if the functional group concentration is to be increased, the number of nuclei decreases as seen in Example 1 of Patent Document 1, resulting in extremely poor curability.

  In addition, the method for producing the alkoxy group-modified phenol novolak resin proposed in Patent Document 1 uses a resol resin obtained by reaction of phenols with formaldehyde using dimethyl sulfate or alkyl halide under alkaline conditions. In this method, after obtaining an alkoxylated resole resin, the desired resin is obtained by dehydration condensation with excess phenols under acidic conditions.

  In the above method, since it is necessary to carry out the reaction in two stages of an alkaline condition and an acidic condition, it takes time for production, and dimethyl sulfate used in the examples as an alkoxylating agent is a deleterious substance and a specific chemistry. It is a substance that has limitations in handling, and is not suitable industrially because it reacts with water (humidity) and corrodes iron and the like. From these points, polyhydric hydroxy compounds obtained by a method that can be industrially produced safely by a simpler method, which are excellent in curability and have a good performance balance of the cured product are required.

JP 2004-10700 A (page 3-5)

  In view of the above situation, the problem of the present invention is excellent in curability, the cured product obtained has good flame retardancy and dielectric properties, and is suitable for semiconductor sealing materials, printed circuit boards, paints, casting applications, etc. It is providing the epoxy resin composition which can be used, and its hardened | cured material.

  As a result of diligent research to solve the above problems, the present inventors have found that a hydroxy group-containing aromatic compound, a monoalkoxybenzene whose alkyl group may be substituted with an aromatic nucleus, and a carbonyl group-containing compound. A polynuclear hydroxy compound obtained by reaction, and a novolak binuclear component and trinuclear component comprising a hydroxy group-containing aromatic compound and a carbonyl group-containing compound in 100 parts by weight of the polyvalent hydroxy compound Has been found that an epoxy resin composition using a compound containing a total weight of 11 parts by weight or more as an epoxy resin curing agent is excellent in curability, and excellent in flame retardancy and dielectric properties of the resulting cured product. The present invention has been completed.

  That is, this invention is an epoxy resin composition containing a polyvalent hydroxy compound (A) and an epoxy resin (B), and the polyvalent hydroxy compound (A) is a hydroxy group-containing aromatic compound (a1). A polyhydroxy compound obtained by reacting a monoalkoxybenzene (a2) whose alkyl group may be substituted with an aromatic nucleus and a carbonyl group-containing compound (a3), and the polyhydroxy compound (A) In 100 parts by weight, a total of 11 parts by weight or more of a novolak dinuclear component and a trinuclear component composed of a hydroxy group-containing aromatic compound (a1) and a carbonyl group-containing compound (a3) are contained. The present invention provides an epoxy resin composition characterized by comprising the following compounds:

  The epoxy resin composition obtained according to the present invention can be dramatically improved in curability as compared with the prior art, and can improve the flame retardancy and dielectric properties of the cured product. Therefore, by using the epoxy resin composition, it is possible to obtain an epoxy resin material that is safe in an environment that can exhibit high flame retardancy without using a halogen-based flame retardant. In addition, its excellent dielectric characteristics can realize high-speed operation speed of high-frequency devices.

Hereinafter, the present invention will be described in detail.
The polyvalent hydroxy compound (A) used in the present invention comprises a hydroxy group-containing aromatic compound (a1), a monoalkoxybenzene (a2) in which an alkyl group may be substituted with an aromatic nucleus, and a carbonyl group-containing compound (a3). Can be obtained by reaction. The polyvalent hydroxy compound (A) obtained by this method is a so-called novolak compound obtained by reacting a hydroxy group-containing aromatic compound (a1) and a carbonyl group-containing compound (a3), or a monoalkoxybenzene ( It is a mixture containing a compound obtained by reacting a2) and a carbonyl group-containing compound (a3), and also a mixture containing a variety of aromatic rings (nuclear number) in one molecule. The polyvalent hydroxy compound (A) used in the epoxy resin composition of the present invention may be used as a mixture, or may be used as a mixture having a smaller number of components using a column or the like. In order to bring the curability of the product to a practical level, two nuclei of novolak comprising a hydroxy group-containing aromatic compound (a1) and a carbonyl group-containing compound (a3) in 100 parts by weight of the polyvalent hydroxy compound (A) It is essential that the body component and the trinuclear component are contained in a total weight of 11 parts by weight or more, and it is preferably contained in an amount of 11 to 50 parts by weight because of excellent balance between flame retardancy and curability. Preferably it is 11-30 weight part. When the content is less than 11 parts by weight, the reactivity with the epoxy resin is inferior and a practical curability cannot be obtained. The content of the novolak component in the polyvalent hydroxy compound (A) is calculated by GPC measurement. The polyvalent hydroxy compound (A) satisfying the above conditions can be obtained by the production method described later, and the hydroxy group-containing aromatic compound (a1) and the carbonyl group-containing compound (a3) in the obtained polyvalent hydroxy compound. In the case where the total weight part of the dinuclear component and the trinuclear component of the novolak is less than 11 parts by weight, a commercially available novolak resin or a separately synthesized novolak resin having a low nuclear number may be used. Is possible.

  As the hydroxy group-containing aromatic compound (a1), any aromatic compound having one or more aromatic hydroxy groups in one molecule can be used, for example, phenol, resorcinol, hydroquinone. Unsubstituted phenols such as cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, t-butylphenol, octylphenol, nonylphenol, phenylphenol and the like; xylenol, methylpropylphenol, methylbutylphenol , Methylhexylphenol, dipropylphenol, dibutylphenol, and other disubstituted phenols; mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, etc. Examples of phenols: naphthols such as 1-naphthol, 2-naphthol, and methylnaphthol; dihydroxybenzenes such as hydroquinone, resorcin, and catechol; bisphenols such as biphenol, tetramethylbiphenol, bisphenol A, bisphenol F, and bisphenol S However, it is not limited to these. Two or more of these can also be mixed and used. Among these, from the viewpoint of particularly excellent flame retardancy of the resulting cured epoxy resin, phenols which may have a substituent and naphthols which may have a substituent are preferable, and the dielectric properties are improved. From the viewpoint of obtaining a particularly excellent cured epoxy resin, phenol having 1-naphthol, 2-naphthol, an alkyl group having 3 to 6 carbon atoms, a phenyl group or a benzyl group as a substituent is particularly preferable.

  Examples of monoalkoxybenzenes (a2) in which the alkyl group may be substituted with an aromatic nucleus include, for example, anisole, ethoxybenzene, 1-methoxy-4-propylbenzene, 1-methoxypropynylbenzene, 1- (4-methoxy Phenyl) -1-propane, 1-propyl-2-methoxy-4-methylbenzene and the like can be exemplified, but are not limited thereto. Two or more of these can also be mixed and used. Among these, anisole is preferable from the viewpoint of excellent flame retardancy and dielectric properties of the obtained cured epoxy resin.

  The carbonyl group-containing compound (a3) is not limited as long as it is a carbonyl group-containing compound having a structure capable of crosslinking the compound (a1) and the compound (a2).

  Examples of the carbonyl group-containing compound (a3) include aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, 4-biphenylaldehyde, naphthylaldehyde, benzophenone, fluorenone, and indanone. A ketone compound is mentioned. Of these, formaldehyde, benzaldehyde, 4-biphenylaldehyde, and naphthylaldehyde are preferable because the cured epoxy resin obtained has excellent flame retardancy.

  This reaction condition will be described in detail. The hydroxy group-containing aromatic compound (a1), the monoalkoxybenzenes (a2) whose alkyl group may have an aromatic nucleus substituted, and the carbonyl group-containing compound (a3) are heated and stirred in the presence of a suitable polymerization catalyst. By doing so, a polyvalent hydroxy compound can be obtained. The polymerization catalyst is not particularly limited, but an acid catalyst is preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, 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. Can be mentioned. The amount used is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the charged raw materials.

  The reaction charge ratio between the hydroxy group-containing aromatic compound (a1) and the monoalkoxybenzene (a2) in which the alkyl group may be substituted with an aromatic nucleus and the carbonyl group-containing compound (a3) is not particularly limited, The total weight of the dinuclear component and the trinuclear component of the novolak composed of the hydroxy group-containing aromatic compound (a1) and the carbonyl group-containing compound (a3) in 100 parts by weight of the polyvalent hydroxy compound (A) is 11 weights. In order to efficiently obtain a compound containing at least a part, the molar ratio (a1) between the hydroxy group-containing aromatic compound (a1) and the monoalkoxybenzene (a2) in which the alkyl group may be substituted with an aromatic nucleus ) / (A2) is 30/70 to 98/2, and the hydroxy group-containing aromatic compound (a1) and the alkyl group may be substituted with an aromatic nucleus. The ratio {(a1) + (a2)} / (a3) of the total number of moles of alkoxybenzenes (a2) to the number of moles of the carbonyl group-containing compound (a3) is 51/49 to 97/3. preferable. By satisfying this condition, it is possible to obtain a cured epoxy resin that is further excellent in flame retardancy and dielectric properties.

  In carrying out this reaction, an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 10 to 500% by weight, preferably 30 to 250% by weight, based on the total weight of the charged raw materials. Moreover, as reaction temperature, it is 40-250 degreeC normally, and the range of 100-200 degreeC is more preferable. The reaction time is usually 1 to 10 hours.

  Further, when the resulting polyvalent hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7. What is necessary is just to perform a neutralization process and a water washing process according to a conventional method. For example, when an acid catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent. At the time of neutralization, a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used. After neutralization or washing with water, unreacted mainly under reduced pressure heating, mainly containing a hydroxy group-containing aromatic compound (a1) and a monoalkoxybenzene (a2) in which the alkyl group may be substituted with an aromatic nucleus The target polyvalent hydroxy compound can be obtained by distilling off raw materials, organic solvents and by-products and concentrating the product. The unreacted raw material recovered here can be reused. Introducing a microfiltration step into the processing operation after the completion of the reaction is a more preferable method because inorganic salts and foreign substances can be purified and removed.

Also as described above, hydroxy group-containing aromatic compound (a1) and also a good monoalkoxy benzenes alkyl group is not aromatic nucleus substituted (a2) and a carbonyl group-containing compound (a3) and the reaction was charged simultaneously Is simple, has a short production time, and is suitable for industrial production. However, 0.05 mol per 1 mol of monoalkoxybenzenes (a2) in which the alkyl group may be substituted with an aromatic nucleus. It is also possible to employ a method in which -30 mol, preferably 2 to 30 mol, of the carbonyl group-containing compound (a3) is substantially completely reacted, and then the hydroxy group-containing aromatic compound (a1) is charged and reacted. it can. By carrying out such a two-step reaction, monoalkoxybenzenes are efficiently introduced into the resin, and either method may be used depending on the intended performance or the like. Here, in the sense that words cormorants same time is a means that is charged with all ingredients until the reaction is accelerated by heating, also means that virtually complete reaction quantitatively alkoxy It does not mean that the group-containing aromatic compound (a2) has disappeared, but means that a sufficient reaction time and reaction temperature have been applied using an excess of the carbonyl group-containing compound (a3). .

  The polyvalent hydroxy compound (A) obtained by the above production method is represented by the following general formula (1) in one molecule, for example.

（式中、Ａｒ_１は置換基を有していてもよい芳香環であり、Ｘ_１はメチレン基、炭素数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基であり、ｍは１又は２である）
で表わされる構造単位と、下記一般式（２）

(In the formula, Ar ₁ is an aromatic ring which may have a substituent, and X ₁ is a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or a methylene group substituted with a phenyl group. A methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, a methylene group substituted with a 9-fluorenyl group, or an alkyl group further on the phenyl group, the naphthyl group or the biphenyl group. A substituted methylene group, and m is 1 or 2)
A structural unit represented by the following general formula (2)

（式中、Ａｒ₂は炭化水素基を置換基として有していてもよいベンゼン骨格、ビフェニル骨格、ナフタレン骨格であり、Ｒ^１は炭素数１〜４のアルキル基であり、Ｘ_２はメチレン基、炭素数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、又は該フェニル基、該ナフチル基若しくは該ビフェニル基上に更にアルキル基が芳香核置換したメチレン基である。）
で表される構造単位を有するものが挙げられる。

(In the formula, Ar ₂ is a benzene skeleton, biphenyl skeleton or naphthalene skeleton which may have a hydrocarbon group as a substituent, R ¹ is an alkyl group having 1 to 4 carbon atoms, and X ₂ is a methylene group. A methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, a methylene group substituted with a biphenyl group, or a 9-fluorenyl group. Or a methylene group in which an alkyl group is further substituted with an aromatic nucleus on the phenyl group, the naphthyl group or the biphenyl group.)
The thing which has a structural unit represented by these is mentioned.

  The following general formula (3) in the general formula (1)

（式中、Ａｒ_１、ｍは前記と同じである。）
で表される構造単位と、前記一般式（２）における下記一般式（４）

(In the formula, Ar ₁ and m are the same as described above.)
And the following general formula (4) in the general formula (2):

（式中、Ａｒ_２及びＲ_１前記と同じである。）
で表される構造単位とのモル比率が前者／後者＝３０／７０〜９８／２の範囲であることが、得られるエポキシ樹脂硬化物の難燃性と誘電特性が一層優れるものになり、好ましいものである。

(Wherein Ar ₂ and R ₁ are the same as described above.)
It is preferable that the molar ratio with the structural unit represented by the formula is in the range of the former / the latter = 30/70 to 98/2 because the flame retardancy and dielectric properties of the obtained cured epoxy resin are further improved. Is.

  The hydroxyl equivalent of the polyvalent hydroxy compound (A) is 110 to 300 g / eq. In that the obtained cured product is excellent in flame retardancy and dielectric properties. Is preferable, 120-160 g / eq. The thing of the range of is more preferable. Furthermore, the thing whose melt viscosity in 150 degreeC measured with the ICI viscometer is the range of 0.3-5.0 dPa * s is preferable at the point which is excellent in the fluidity | liquidity at the time of shaping | molding.

  Specific examples of the general formula (1) include those represented by the following structural formula, but are not limited thereto.

  Specific examples of the general formula (2) include those represented by the following structural formula, but are not limited thereto.

  The polyvalent hydroxy compound (A) may be used singly or as a mixture of two or more kinds. Uses other than those used in the epoxy resin composition of the present invention, for example, photosensitive material uses such as semiconductor photoresists. It can also be used for use as a color developer material.

  In the epoxy resin composition of the present invention, the polyvalent hydroxy compound (A) can be used alone or in combination with other curing agents as long as the effects of the present invention are not impaired. When used in combination, the proportion of the polyvalent hydroxy compound obtained in the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

The other curing agent that can be used in combination is not particularly limited, and various curing agents such as an amine compound, an amide compound, an acid anhydride compound, and a phenol compound may be used. it can. Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like, and amide compounds include dicyandiamide and linolenic acid. And polyamide resins synthesized from ethylenediamine. Examples of 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 novolac 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, aminotriazine-modified phenolic resin are preferred because of excellent flame retardancy, especially high aromaticity such as phenol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, The use of a compound such as a polyhydroxy compound having a high hydroxyl equivalent weight or an aminotriazine-modified phenol resin containing a nitrogen atom results in a hard resin obtained. From the viewpoint of flame retardancy and dielectric characteristics of the object it is excellent.

  The epoxy resin (B) 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, tetramethyl biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy 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-compacted novolak type epoxy resin Naphthol - cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-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, biphenyl type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins and xanthene type epoxy resins described in JP-A No. 2003-201333 are particularly preferable from the viewpoint of excellent flame retardancy and dielectric properties.

  The blending amount of the epoxy resin (B) and the curing agent in the epoxy resin composition of the present invention is not particularly limited, but the epoxy of the epoxy resin (B) is preferable because the obtained cured product has good characteristics. The amount of the active group in the curing agent containing the polyvalent hydroxy compound (A) is preferably 0.7 to 1.5 equivalents with respect to 1 equivalent of the total group.

  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 encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  The epoxy resin composition of the present invention is conventionally used for imparting flame retardancy of a cured product because the polyvalent hydroxy compound (A) itself used as a curing agent has an effect of imparting flame retardancy. Even if the flame retardant used is not added, the cured product has good flame retardancy, but the moldability in the sealing process and the reliability of the semiconductor device are reduced in order to exhibit higher flame retardancy. It is possible to obtain a non-halogen flame retardant resin composition by blending a non-halogen flame retardant which does not substantially contain a halogen atom as long as it does not occur.

  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 the inorganic compound include phosphoric acids such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, which may be surface-treated 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 (i) 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, (ii) 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 a phenol resin, (iii) magnesium hydroxide And a method of double coating with a thermosetting resin such as phenol resin on a coating of an inorganic compound such as aluminum hydroxide, zinc hydroxide or titanium hydroxide, and any of (i) to (iii) 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 (di-2,6-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. 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, (i) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, (ii) phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, and melamine, benzoguanamine, acetoguanamine, formguanamine, etc. A co-condensate of melamines and formaldehyde, (iii) a mixture of the co-condensate of (ii) and a phenol resin such as a phenol formaldehyde condensate, (iv) the above (ii), (iii) Furthermore tung, such as those modified with isomerized linseed oil, 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 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, in particular 0.5 to 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 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.

  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 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 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. However, in order to increase the blending amount of the fused silica and 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. An epoxy resin composition containing an epoxy resin (B), a curing agent containing a polyvalent hydroxy compound (A), and, if necessary, a curing accelerator is easily converted into a cured product by a method similar to a conventionally known method. be able to. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  The use application of the epoxy resin composition of the present invention is not particularly limited, for example, a semiconductor sealing material, a resin composition used for a laminated board or an electronic circuit board, a resin casting material, an adhesive, Examples thereof include interlayer insulating materials for build-up substrates, coating materials such as insulating paints, and the like. Among these, they can be suitably used for semiconductor sealing materials.

  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. For 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 form a semiconductor device which is a molded product. There is a way to get it.

  In order to process the epoxy resin composition of the present invention into a printed circuit board composition, for example, a resin composition for a prepreg can be used. Although it can be used without a solvent depending on the viscosity of the epoxy resin composition, it is preferable to obtain a resin composition for prepreg by varnishing using 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. 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 20 to 60% by weight. When producing a copper-clad laminate using the epoxy resin composition, the prepreg obtained as described above is laminated as described in, for example, JP-A-7-41543, and copper is appropriately added. A copper-clad laminate can be obtained by stacking the foils and thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating to is mentioned.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And 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 an anisotropic conductive adhesive.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 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.

  As a method of obtaining a cured epoxy resin, it may be based on a general curing method of an epoxy resin composition, but the heating temperature condition may be appropriately selected depending on the type and application of the curing agent to be combined, for example, What is necessary is just to heat the composition obtained by the said method in the temperature range of room temperature-about 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, “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 .: in accordance with ASTM D4287 2) Softening point measurement method: JIS K7234
3) GPC:
・ Device: HLC-8220 GPC manufactured by Tosoh Corporation, Column: TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL manufactured by Tosoh Corporation
・ Solvent: Tetrahydrofuran ・ Flow rate: 1 ml / min
・ Detector: RI
4) NMR: NMR GSAR270 manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Synthesis Example 1 [Synthesis of polyvalent hydroxy compound (A-1)]
To a flask equipped with a thermometer, condenser, fractionator, and stirrer was added 188.2 g (2.00 mol) of phenol, 108.1 g (1.00 mol) of anisole, and 3.5 g of methanesulfonic acid to add 60. The temperature was raised to ° C. While raising the temperature from 60 ° C. to 100 ° C. in 60 minutes, 48.9 g (1.50 mol) of 92% paraform was charged in 10 portions. After completion of the charging, the reaction was carried out at 100 ° C. for 2 hours. After completion of the reaction, 700 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Next, after washing with water until the washing water shows neutrality, unreacted phenol and anisole and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure, and the following structural formula

で表される構造単位を有する多価ヒドロキシ化合物（Ａ−１）２３５ｇを得た。これの軟化点は８３℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は２．２ｄＰａ・ｓ、水酸基当量は１３１ｇ／ｅｑ．であった。また、下記一般式（５）で表される多価ヒドロキシ化合物のｒ＝１と２の含有率は１１％であり、分子量分布（ＧＰＣ）Ｍｗ／Ｍｎ＝２．７であった。

235 g of a polyvalent hydroxy compound (A-1) having a structural unit represented by The softening point is 83 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 2.2 dPa · s, and the hydroxyl group equivalent is 131 g / eq. Met. In addition, the content of r = 1 and 2 in the polyvalent hydroxy compound represented by the following general formula (5) was 11%, and the molecular weight distribution (GPC) Mw / Mn = 2.7.

  From the results of the weight measurement of the recovered unreacted phenol and anisole and the measurement results of the hydroxyl group of the obtained polyvalent hydroxy compound, the structural unit represented by the general formula (3) in the compound and the general formula (4 The molar ratio with the structural unit represented by) was the former / the latter = 85/15.

FIG. 1 shows the GPC chart, FIG. 2 shows the ¹³ C-NMR chart, and FIG. 3 shows the MS spectrum. The methoxy group signal observed at 55 ppm in NMR and the hydroxyl group equivalent confirmed that the methoxy group in the compound was not decomposed.

Synthesis Example 2 [Synthesis of polyvalent hydroxy compound (A-2)]
In the examples, the polyvalent hydroxy compound (A-2) was synthesized in the same manner as in Synthesis Example 1 except that 3.5 g of methanesulfonic acid was changed to 6.8 g of oxalic acid and 44.0 g (1.35 mol) of 92% paraform. Got. The softening point is 75 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 1.0 dPa · s, and the hydroxyl group equivalent is 127 g / eq. Met. In addition, the content of r = 1 and 2 in the polyvalent hydroxy compound represented by the general formula (5) was 19%, and the molecular weight distribution (GPC) Mw / Mn = 1.8.

Synthesis example 3
In accordance with Example 1 of JP 2004-010700 A, the following structural formula

で表される構造単位を有する多価ヒドロキシ化合物（Ａ’−１）を得た。これの軟化点は７７℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法，測定温度：１５０℃）は０．８ｄＰａ・ｓ、水酸基当量は１６０ｇ／ｅｑ．であった。また、前記一般式（５）で表される多価ヒドロキシ化合物のｒ＝１と２の含有率は３％であり、分子量分布（ＧＰＣ）Ｍｗ／Ｍｎ＝１．２であった。

The polyvalent hydroxy compound (A'-1) which has a structural unit represented by this was obtained. The softening point is 77 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 0.8 dPa · s, and the hydroxyl equivalent is 160 g / eq. Met. In addition, the content of r = 1 and 2 in the polyvalent hydroxy compound represented by the general formula (5) was 3%, and the molecular weight distribution (GPC) Mw / Mn = 1.2.

Synthesis example 4
While subjecting a flask equipped with a thermometer, dropping funnel, condenser, and stirrer to nitrogen gas purge, Mitsui Chemicals Co., Ltd. Millex XLC-4L 168 g, epichlorohydrin 463 g (5.0 mol), n-butanol 139 g, tetraethylbenzyl 2 g of ammonium chloride was 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% 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. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the following structural formula.

で表される構造単位を有するエポキシ樹脂（Ｂ−１）を得た。該エポキシ樹脂のエポキシ当量は２４１ｇ／ｅｑであった。

The epoxy resin (B-1) which has a structural unit represented by this was obtained. The epoxy equivalent of the epoxy resin was 241 g / eq.

Examples 1-6 and Comparative Examples 1-2
As the epoxy resin, the above B-1 and YX-4000H (tetramethyl biphenol type epoxy resin, epoxy equivalent: 195 g / eq) manufactured by Japan Epoxy Resin Co., Ltd., NC-3000 (biphenyl aralkyl type epoxy resin manufactured by Nippon Kayaku Co., Ltd.,) Epoxy equivalent: 274 g / eq), (A-1), (A-2), (A′-1) as polyhydric phenol compound, triphenylphosphine (TPP) as curing accelerator, condensed phosphoric acid as flame retardant Esters ( PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.), magnesium hydroxide (Echo Mug Z-10 manufactured by Air Water Co., Ltd.), spherical silica (S-COL manufactured by Micron Co., Ltd.) as an inorganic filler, silane coupling agent Γ-glycidoxytriethoxyxysilane (KB made by Shin-Etsu Chemical Co., Ltd.) M-403), carnauba wax (Pearl Wax No. 1-P manufactured by Celalica Noda Co., Ltd.), carbon black, and the composition shown in Table 1, and 5 rolls at a temperature of 85 ° C. using two rolls. The desired composition was obtained by melt-kneading for a minute. The physical properties of the cured product were prepared by using the above composition to prepare a sample for evaluation by the following method, and measuring the curability (gel time), flame retardancy, and dielectric properties by the following method, and the results are shown in Table 1. .

Curability (gel time):
0.15 g of the epoxy resin composition is placed on a cure plate (made by THERMO ELECTRIC) heated to 175 ° C., and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.

Flame retardance:
A sample for evaluation having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was formed by molding at a temperature of 175 ° C. for 90 seconds using a transfer molding machine and then post-curing at a temperature of 175 ° C. for 5 hours. A combustion test was performed using five test pieces having a thickness of 1.6 mm in accordance with the UL-94 test method using the prepared test pieces.

Measurement of dielectric properties:
A sample for evaluation having a width of 25 mm, a length of 75 mm, and a thickness of 2.0 mm was formed by molding at a temperature of 175 ° C. for 90 seconds using a transfer molding machine and then post-curing at a temperature of 175 ° C. for 5 hours. Using the prepared test piece, it was stored in an indoor room at 23 ° C and 50% humidity for 24 hours using the impedance material analyzer "HP4291B" manufactured by Agilent Technologies Co., Ltd., in accordance with JIS-C-6481. Then, the dielectric constant and dielectric loss tangent of the cured product at a frequency of 100 MHz were measured.

Footnotes in Table 1:
* 1: Maximum combustion time (seconds) in one flame contact
* 2: Total burning time of 5 test pieces (seconds)

2 is a GPC chart of a polyvalent hydroxy compound obtained in Synthesis Example 1. 3 is a ¹³ C-NMR spectrum of a polyvalent hydroxy compound obtained in Synthesis Example 1. FIG. 2 is a mass spectrum of a polyvalent hydroxy compound obtained in Synthesis Example 1. FIG.

Claims (11)

An epoxy resin composition containing a polyvalent hydroxy compound (A) and an epoxy resin (B), wherein the polyvalent hydroxy compound (A) substitutes an alkyl group having 3 to 6 carbon atoms, a phenyl group or a benzyl group Yes a good phenols also be and / or naphthols as a base and (a1), and anisole (a2), a polyhydroxy compound obtained by reacting an aldehyde compound (a3), and polyhydric In 100 parts by weight of the hydroxy compound (A), 11 parts by weight or more of a novolak dinuclear component and a trinuclear component composed of phenols and / or naphthols (a1) and an aldehyde compound (a3) are contained. An epoxy resin composition characterized by being a compound. Polyhydroxy compound (A), an alkyl group having 3 to 6 carbon atoms, a phenyl group or optionally phenols also be have a benzyl group as a substituent and / or naphthols and (a1) and anisole (a2) The molar ratio (a1) / (a2) is 30/70 to 98/2, the total number of moles of the hydroxy group-containing aromatic compound (a1) and anisole (a2), and the aldehyde compound (a3) 2. The epoxy resin composition according to claim 1, which is a compound obtained by reacting at a ratio {(a 1) + (a 2)} / (a 3) with the number of moles of 3 / 1.5 to 97/3. Polyhydroxy compound (A) in 100 parts by weight, an alkyl group having 3 to 6 carbon atoms, a phenyl group or optionally phenols also be useful as a substituent a benzyl group and / or naphthols (a1) with an aldehyde compound The epoxy resin composition according to claim 1, wherein the novolak dinuclear component and the trinuclear component (a3) are contained in a total weight of 11 to 50 parts by weight. Aldehyde polyhydroxy compound (A) is an alkyl group having 3 to 6 carbon atoms, a phenyl group or optionally phenols also be have a benzyl group as a substituent and / or naphthols and (a1) and anisole (a2) The epoxy resin composition according to claim 1, which is a compound obtained by using an acid catalyst when reacting with the compound (a3). Polyhydroxy compound (A) is an alkyl group having 3 to 6 carbon atoms, a phenyl group or optionally phenols also be have a benzyl group as a substituent and / or naphthols and (a1), and anisole (a2) , aldehyde compound (a3) and which is a compound obtained by performing the reaction are charged simultaneously claim 1 epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 5, further comprising a non-halogen flame retardant. 7. The non-halogen flame retardant is 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. Epoxy resin composition. The epoxy resin composition according to claim 6 or 7, which is used for a semiconductor sealing material. A cured product obtained by curing the epoxy resin composition according to claim 1. The cured product according to claim 9, which is a semiconductor device. It is an epoxy resin composition containing a curing agent containing a polyvalent hydroxy compound (A) and an epoxy resin (B), and the proportion of the polyvalent hydroxy compound (A) in the curing agent is 30% by weight. The active group in the curing agent containing the polyvalent hydroxy compound (A) is 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of the epoxy groups of the epoxy resin (B). valent hydroxy compound (a) is an alkyl group having 3 to 6 carbon atoms, a phenyl group or optionally phenols also be useful as a substituent a benzyl group and / or naphthols and (a1), and anisole (a2), A polyhydric hydroxy compound obtained by reacting an aldehyde compound (a3) and 100 parts by weight of the polyhydric hydroxy compound (A) with phenols and / or naphthols (a1) and Epoxy resin composition, wherein the binuclear moiety component and trinuclear component of the novolak consisting dehydro compound (a3) is a compound contained 11 parts by weight or more as the total weight.

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