JP2007002053A - Epoxy resin composition and cured article of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition imparting a cured article with excellent flame retaradancy while not using a halogen-based flame retardant, and excellent in moisture resistance and to provide a cured article of the same. <P>SOLUTION: The epoxy resin composition comprises (A) the epoxy resin, (B) a curing agent, and (C) an aromatic compound containing a thioether group represented by general formula (1). The invention relates to the cured article obtained by curing the epoxy resin composition. In the formula, Ar is a (substituted)aromatic ring (with the proviso that the substituent is a 1-3C alkyl group, an aryl group, an aralkyl group or a 1-3C alkoxy group), R is a 1-4C alkyl or phenyl group, n is 1 or 2. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is excellent in moisture resistance, the cured product obtained has good flame retardancy, an epoxy resin composition that can be suitably used for semiconductor sealing materials, printed circuit boards, paints, casting applications, etc., and its curing Related to things.

  Conventionally, epoxy resin compositions have been widely used in various industrial fields such as paints, adhesive properties, and electrical and electronic properties because they are excellent in adhesion, corrosion resistance, electrical properties, and the like of the cured products obtained. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, they are used as sealing materials and substrate materials, and demands for higher performance are increasing with technological innovation in these fields. .

  For example, semiconductor packages have been rapidly reduced in size and thickness, and BGAs with excellent high-density mounting have been newly developed, and have become the mainstream of IC and LSI chip packages. In such a mounting method, the entire semiconductor device package is exposed to a high temperature, and if the moisture resistance of the sealing resin is low, peeling between the sealing resin and the semiconductor chip or between the sealing resin and the lead frame may occur. A phenomenon occurs in which moisture that has absorbed moisture explodes during solder reflow and cracks occur. Furthermore, in recent years, the use of lead-free solder that does not contain lead has been promoted from the viewpoint of environmental protection. However, lead-free solder has a high melting point, which increases the reflow temperature, resulting in higher reflow resistance reliability than before. It has been demanded. That is, an epoxy resin composition for a sealing material having excellent moisture resistance is required.

  Moreover, when using an epoxy resin composition as a sealing material, halogen-type flame retardants, such as a bromine, are mix | blended with the antimony compound in order to provide a flame retardance. However, in recent environmental and safety efforts, environmentally and flame-resistant flame retardants that do not use halogen-based flame retardants that may cause dioxins and do not use antimony compounds that are suspected of carcinogenicity. There is a strong demand for the development of a conversion method. Further, non-halogenation of the semiconductor sealing material is expected to be a technology that greatly contributes to improvement of the reliability of the semiconductor device left at high temperature.

  For example, a thiodiphenol-containing epoxy resin composition has been disclosed as one that is excellent in low melt viscosity, moisture resistance, and moldability, which are performance required as a semiconductor encapsulant (see, for example, Patent Document 1). Although the effect of improving the moisture resistance and moldability of the cured product obtained using the resin composition is recognized, it does not improve the moisture resistance to a satisfactory level, and further improvement in flame retardancy is also achieved. It has been demanded.

  That is, a cured product capable of exhibiting sufficient flame retardancy can be obtained using a non-halogen epoxy resin composition, and the composition having a well-balanced moisture resistance of the cured product has not yet been presented. Currently.

JP 2002-212270 A

  The problem to be solved by the present invention has been made in view of the above circumstances, and is excellent in flame retardancy of a cured product obtained without using a halogen-based flame retardant and has good moisture resistance. An object is to provide an epoxy resin composition and a cured product thereof.

  In order to solve the above-mentioned problems, the present inventors have eagerly studied for an epoxy resin composition excellent in the above-mentioned properties, and as a result, an epoxy resin, a curing agent, and an epoxy compound containing a thioether group-containing aromatic compound as essential components. The present inventors have found that a resin composition solves the above problems and have completed the present invention.

  That is, the present invention includes an epoxy resin (A), a curing agent (B), and the following general formula (1).

〔式中、Ａｒは置換基を有していてもよい芳香環（但し、置換基は炭素数１〜３のアルキル基、アリール基、アラルキル基又は炭素数１〜３のアルコキシ基である。）であり、Ｒは炭素数１〜４のアルキル基又はフェニル基であり、ｎは１又は２である。〕
で表されるチオエーテル基含有芳香族化合物（Ｃ）を含有することを特徴とするエポキシ樹脂組成物、及びその硬化物を提供するものである。

[In the formula, Ar is an aromatic ring which may have a substituent (provided that the substituent is an alkyl group having 1 to 3 carbon atoms, an aryl group, an aralkyl group, or an alkoxy group having 1 to 3 carbon atoms). R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
The epoxy resin composition characterized by containing the thioether group containing aromatic compound (C) represented by these, and its hardened | cured material are provided.

  As can be seen from this example, the epoxy resin composition of the present invention can have both the flame retardancy and moisture resistance of the cured product as compared with the conventional epoxy resin composition. Therefore, by using the epoxy resin composition, high flame retardancy can be expressed without using a halogen flame retardant, and an epoxy resin material that is safe for the environment can be obtained. Moreover, the sealing material excellent in solder crack resistance can be obtained due to the excellent moisture resistance of the cured product. In addition to the above applications, it can also be suitably used for photosensitive material applications such as semiconductor photoresists and color developer materials.

The present invention provides an epoxy resin composition that provides a cured product excellent in flame retardancy and moisture resistance by using an epoxy resin (A), a curing agent (B), and a thioether group-containing aromatic compound (C) as essential components. It is obtained.
Hereinafter, the present invention will be described in detail.

  The epoxy resin (A) used in 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, bisphenol S 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-condensed novolak type Poxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl novolac type epoxy resin, hydroquinone type epoxy resin, stilbene type epoxy resin, alkyl modified triphenolmethane type epoxy resin Is mentioned. In addition, the epoxy resin described in the epoxy resin technical review, the epoxy resin described in the epoxy resin, the epoxy resin described in the new epoxy resin edited by Hiroshi Kakiuchi, the epoxy resin described in the handbook of the epoxy resin edited by Masaki Shinbo, etc. Pitch-type epoxy resins, furfural-modified epoxy resins described in JP-A-2001-064339, hydrazine-modified epoxy resins described in JP-A-2002-212265, xanthene-type epoxy resins described in JP-A-2003-201333, and JP-A-2004-010724 Disulfide-containing epoxy resin, epoxy resin derived from glyoxal described in JP-A-2004-010877, bismethylol-modified epoxy resin described in JP-A-2004-339313, etc., fluorene described in JP-A-2005-15696, etc. Type epoxy resins, anthracene type epoxy resins in JP 2005-97473 described. 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 preferred from the viewpoint of excellent flame retardancy and moisture resistance. Furthermore, it is particularly preferable that the epoxy resin (A) has an epoxy equivalent of 150 to 500 g / eq.

The curing agent (B) used in the present invention is not particularly limited, and various curing agents such as an amine compound, an amide compound, an acid anhydride compound, and a phenol compound are used. it can. 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. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydroanhydride. Examples thereof include phthalic acid, methyl nadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples of phenolic compounds include phenol novolac resins and high orthophenol novolac. Resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (common name, zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol Novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (phenol nuclei in bismethylene groups are Linked polyvalent naphthol compound), aminotriazine modified phenolic resin (melamine, benzoguanamine, etc.) Polyphenol compounds such as compounds), and their modified products, bisphenol compounds, and the phenol resin described in p175-p185 of the Epoxy Resin Technology Basic Edition I First Edition, furfural modification described in JP-A-2001-064339 Phenol resin, dihydric phenol-modified phenol resin described in JP-A-2003-277485, modified phenol resin described in JP-A-2004-010700, dithiophenol resin described in JP-A-2004-010724, pyridine aldehyde-modified phenol described in JP-A-2004-161872 Resin, a thiophenol-containing phenol resin described in JP-A-2004-244526, a modified phenol resin described in JP-A-2004-269553, and a thioaldehyde-modified phenol resin described in JP-A-2004-339277. It is not limited to these. These may be used alone or in combination of two or more.

  Among these, phenol novolak resin, high ortho phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol- Cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because of their excellent flame retardancy. Polyhydric hydroxy compounds such as biphenyl-modified naphthol resins are preferred because the resulting cured product has excellent flame retardancy. There.

  Although it does not restrict | limit especially as a compounding quantity of the epoxy resin (A) and the hardening | curing agent (B) in the epoxy resin composition of this invention, From the point that the hardened | cured material characteristic obtained is favorable, an epoxy resin (A The amount of active groups in the curing agent (B) is preferably 0.5 to 2.0 equivalents, particularly preferably 0.7 to 1.5 equivalents, based on a total of 1 equivalent of epoxy groups.

  As the thioether group-containing aromatic compound (C) used in the present invention, an aromatic compound having 1 to 2 thioether groups in one molecule and having no hydroxy group on the aromatic ring having a thioether group Various thioanisoles which may have a substituent, ethylphenyl sulfides which may have a substituent, and diphenyl sulfides which may have a substituent ( However, each substituent is an alkyl group having 1 to 3 carbon atoms, an aryl group, an aralkyl group, or an alkoxy group having 1 to 3 carbon atoms.), For example, thioanisole, ethylphenyl sulfide, t-butylphenyl Sulfide, 2-methylthioanisole, 3-methylthioanisole, 4-methylthioanisole, 2-ethylthioanisole, 3-e Ruthioanisole, 4-ethylthioanisole, diphenyl sulfide, 1-methoxy-2- (methylthio) benzene, 1-methoxy-4- (methylthio) benzene, 2-thiomethylnaphthalene, 2-thioethylnaphthalene, 1,2- Although benzenedimethanethiol etc. can be illustrated, it is not limited to these. Two or more of these can also be mixed and used. Among these, thioanisole, ethylthiosulfide, and diphenylsulfide are preferable from the viewpoint of excellent flame retardancy of the cured product to be obtained, and thioanisole is particularly preferable.

  Although the amount of the thioether group-containing aromatic compound (C) represented by the general formula (1) is not particularly limited, for example, the thioether group-containing aromatic compound with respect to the entire epoxy resin composition It is preferable that the blending amount of (C) is 0.05% by weight or more because the effect of exhibiting the flame retardancy of the cured product of the epoxy resin composition is remarkable, and with respect to the entire epoxy resin composition The blending amount of the thioether group-containing aromatic compound (C) is preferably 15% by weight or less because a good cured product is easily obtained. Among these ranges, 0.1 to 10% by weight is particularly preferable.

  When preparing an epoxy resin composition using the thioether group-containing aromatic compound (C), the thioether group-containing aromatic compound may be mixed in advance with an epoxy resin or a phenol resin. They may be used without mixing as they are. When an epoxy resin having a similar structure and a phenol resin are compared, the epoxy resin generally has a higher softening point than the phenol resin. Therefore, when mixing the above-mentioned epoxy resin and phenol resin in advance, it is preferable to mix with phenol resin because it is easy to handle. As for the amount to be mixed, the entire amount of the thioether group-containing aromatic compound to be blended may be used, or a part thereof may be mixed first.

  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, triphenylphosphine, tetraphenylphosphonium tetrakisphenylborate, tetraphenylphosphonium are used as phosphorus compounds because of their excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc. For tetrakis (4-methylphenyl) borate, an adduct of a phosphine compound and a quinone compound, and a tertiary amine, 1,8-diazabicyclo- [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 thioether group-containing aromatic compound (C) itself has an effect of imparting flame retardancy. Even if a flame retardant is not added, the cured product has good flame retardancy, but in order to exhibit higher flame retardancy, it does not reduce the moldability in the sealing process and the reliability of the semiconductor device Thus, it is possible to obtain a non-halogen flame retardant resin composition by blending a non-halogen flame retardant (D) substantially containing no halogen atom.

  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 (D) is not limited as long as it is a compound that does not substantially contain a halogen atom such as chlorine or bromine and has a function as a flame retardant or a flame retardant aid. For example, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organometallic salt-based flame retardants, and the like are not limited in any way. Even if it is used alone, a plurality of flame retardants of the same type 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 There is a method of doubly coating with a thermosetting resin such as phenol resin on a coating of an inorganic compound such as aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc., 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 No. 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-phos Examples thereof include cyclic organophosphorus compounds such as faphenanthrene = 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, 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 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 In combination with inorganic powders described in JP-A 2000-156437, etc., in combination with butadiene rubber described in JP-A 2000-156437, etc., high acid value polyethylene wax and long-chain alkyl phosphate ester compounds described in JP-A 2000-053875, etc. A conventional method such as a combination of these 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. 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 ratio 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 the epoxy 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 an anisotropic conductive film composition. 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.

  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 application of the curing agent to be combined. For example, the method of heating the composition obtained by the said method in the temperature range of about room temperature-250 degreeC is mentioned. 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.

Examples 1-2 and Comparative Example 3
As an epoxy resin, NC-3000 manufactured by Nippon Kayaku Co., Ltd. (biphenylaralkyl type epoxy resin, epoxy equivalent: 276 g / eq), and as a curing agent, Phenolite TD-2131 manufactured by Dainippon Ink & Chemicals, Inc. (phenol novolac resin, hydroxyl group) Equivalent: 104 g / eq), thioanisole as a thioether group-containing aromatic compound, bis (4-hydroxyphenyl) sulfide as a comparative thiodiphenol compound, triphenylphosphine (TPP) as a curing accelerator, spherical as an inorganic filler Silica (S-COL manufactured by Micron Co., Ltd.), γ-glycidoxytriethoxyxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, Carnauba wax (PEARL WAX No. 1 manufactured by Celalica Noda Co., Ltd.) -P ), And the composition shown in Table 1 using carbon black, and melt kneading for 5 minutes at a temperature of 85 ° C. using two rolls to obtain the desired composition. Regarding the physical properties of the cured product, a sample for evaluation was prepared by the following method using the above composition, the moisture resistance and flame retardancy were measured by the following method, and the results are shown in Table 1.

Moisture resistance (moisture absorption rate)
An evaluation sample having a width of 75 mm, a length of 25 mm, and a thickness of 2.4 mm was molded at 175 ° C. for 5 hours using a press molding machine to obtain a test piece. Using the prepared test piece, the weight change (wt%) before and after treatment for 300 hours in a constant temperature and humidity apparatus of 85 ° C./85% RH was measured as the moisture absorption rate.

Flame Retardancy Create a sample for evaluation with a width of 12.7mm, a length of 127mm, and a thickness of 1.6mm by molding for 90 seconds at a temperature of 175 ° C using a transfer molding machine and then post-curing at a temperature of 175 ° C for 5 hours. did. 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.

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

Claims (17)

Epoxy resin (A), curing agent (B), and the following general formula (1)

[In the formula, Ar is an aromatic ring optionally having a substituent (wherein the substituent is an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or an alkoxy group having 1 to 10 carbon atoms). R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is 1 or 2. ]
The epoxy resin composition characterized by containing the thioether group containing aromatic compound (C) represented by these. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) has an epoxy equivalent of 150 to 500 g / eq. The epoxy resin (A) comprises a phenol novolac type epoxy resin, a high ortho phenol novolak type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl novolac type epoxy resin and a xanthene type epoxy resin. The epoxy resin composition according to claim 1, wherein the epoxy resin composition is one or more epoxy resins selected from the group consisting of: The epoxy resin composition according to claim 1, wherein the curing agent (B) is a phenol compound. The epoxy resin composition according to any one of claims 1 to 4, wherein the thioether group-containing aromatic compound (C) is 0.05 to 15% by weight based on the whole epoxy resin composition. In the general formula (1), R is a methyl group, an ethyl group or a phenyl group, n is 1, and Ar may have a substituent, a benzene ring or a naphthalene ring (provided that the substituent is carbon The epoxy resin composition according to claim 1, which represents a C 1-3 alkyl group, an aryl group, an aralkyl group, or a C 1-3 alkoxy group. The epoxy resin composition according to any one of claims 1 to 6, further comprising a non-halogen flame retardant (D). The non-halogen flame retardant (D) is one or more flame retardants selected from the group consisting of phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants and organometallic salt flame retardants. The epoxy resin composition according to claim 7. The epoxy resin composition according to claim 7 or 8, which is used for a semiconductor encapsulant. The epoxy resin composition according to claim 7 or 8, which is used for a printed circuit board. The epoxy resin composition according to claim 7 or 8, which is used for resist ink. The epoxy resin composition according to claim 7 or 8, which is used for a conductive paste. The epoxy resin composition according to claim 7 or 8, which is used for an interlayer insulating material. A cured product obtained by curing the epoxy resin composition according to claim 1. The cured product according to claim 14, which is a semiconductor device. 16. The semiconductor device according to claim 15, which is a BGA type. The cured product according to claim 14, which is a printed circuit board device.