JP5135702B2 - Epoxy resin composition, cured product thereof, semiconductor sealing material, and semiconductor device - Google Patents

Description

  The present invention relates to a resin composition for printed circuit boards, a sealing material for electronic parts, particularly an epoxy resin composition suitable for a semiconductor sealing material and a cured product thereof, and a semiconductor sealing material and a semiconductor excellent in moisture resistance and dielectric properties Relates to the device.

  Epoxy resin compositions are widely used in various industrial fields such as paints, adhesives, printed circuit boards, and semiconductor packages because of their excellent adhesion, corrosion resistance, electrical properties, and the like in the cured products. Among these, especially in the field of semiconductor packages, in recent years, the miniaturization and thinning of packages has progressed rapidly, and a ball grid array (BGA) and a chip scale package (CSP) excellent in high-density mounting are newly developed. Accordingly, the spread of IC and LSI chip packages is advancing.

  Such a ball grid array (BGA) package usually has a very narrow bonding wire interval, and the flip chip built-in type also has a very narrow interval between the substrate and the flip chip. And problems such as poor underfill filling have become serious. Since this problem is caused by the high viscosity of the sealing material, in recent years, the demand for low melt viscosity of the epoxy resin itself has become extremely high.

  From such a point, a method (for example, refer to Patent Document 1) in which a biphenyl type epoxy resin is used as a low-viscosity epoxy resin and the inorganic filler is highly filled has been proposed. However, ball grit arrays (BGA) and chip scale packages (CSP) have a serious problem of warping after molding. To prevent this, high inorganic fillers are used to increase the linear expansion coefficient. Where it is necessary to reduce the flow rate, the biphenyl type epoxy resin has insufficient fluidity (viscosity) at the time of molding, and is not satisfactory in warping characteristics (linear expansion coefficient). Accordingly, there is a demand for an epoxy resin having an even lower viscosity in a high-density mounting type semiconductor package.

  As a material that meets such a requirement, for example, a dihydroxynaphthalene type epoxy resin in which a β-methyl group-substituted epoxy group and a β-methyl unsubstituted epoxy group coexist has been proposed (for example, Patent Document 2). reference). Although the epoxy resin is a dihydroxynaphthalene type epoxy resin that exhibits high fluidity, it can improve problems such as a high melting point or crystallinity, which is a drawback thereof, and can be easily adjusted to a semiconductor sealing material. However, in recent years, in the field of electronic materials, due to the dramatic improvement in processing capability based on miniaturization of semiconductor devices and high integration of wiring, heat generation countermeasures and electrical performance in a high frequency region have become problems. This problem is serious in ball grid arrays (BGA) and chip scale packages (CSP). However, since the dihydroxynaphthalene type epoxy resin in which the β-methyl group-substituted epoxy group and the β-methyl unsubstituted epoxy group coexist is a crystalline epoxy resin, it has excellent fluidity and high filler. Although filling was possible, the moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) were not satisfactory.

JP-A-4-218523 JP-A-10-182789

  The problems to be solved by the present invention are that the epoxy resin has good fluidity and can be filled with a high amount of inorganic filler, and that it has moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) in the cured product. It is an object of the present invention to provide an excellent epoxy resin composition and a cured product thereof, and a semiconductor sealing material and a semiconductor device excellent in warpage characteristics, moisture resistance, and dielectric characteristics.

  As a result of intensive studies to solve the above problems, the present inventor used dihydroxynaphthalene as an epoxy resin raw material, and caused β-alkylglycidyl groups to be present in a predetermined proportion or more as epoxy groups in the epoxy resin. The present inventors have found that the moisture resistance and dielectric properties, which are disadvantages of the dihydroxynaphthalene type epoxy resin, can be improved, and have completed the present invention.

  That is, the present invention is an epoxy resin obtained by reacting dihydroxynaphthalenes and β-alkylepihalohydrin as essential monomer components, and β-alkylglycidyl group occupying in all epoxy groups in the epoxy resin. It is related with the epoxy resin composition characterized by using the epoxy resin (A) whose ratio is 95% or more on a molar basis, and a hardening | curing agent (B) as an essential component.

  In addition to the epoxy resin (A) and the curing agent (B), the present invention further comprises the epoxy resin composition containing an inorganic filler (C) in a proportion of 90% by mass or more. It relates to a semiconductor sealing material.

  The present invention further relates to a semiconductor device having a semiconductor chip, a resin package, and an electrode energizing part as essential components, wherein the resin package is made of the semiconductor sealing material. Relates to the device.

  The present invention further provides a cured product obtained by curing the epoxy resin composition.

  According to the present invention, an epoxy resin composition having excellent fluidity of an epoxy resin and capable of being highly filled with an inorganic filler, and having excellent moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) in the cured product, It is possible to provide a cured product, a semiconductor sealing material and a semiconductor device excellent in warpage characteristics, moisture resistance, and dielectric characteristics.

  The epoxy resin (A) used in the present invention is an epoxy resin obtained by reacting dihydroxynaphthalenes and β-alkylepihalohydrin as essential monomer components, and all the epoxy groups in the epoxy resin are bonded to each other. The proportion of β-alkylglycidyl group occupied is 95% or more on a molar basis.

  Here, dihydroxynaphthalene is, for example, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and methyl groups thereof. Or the compound which the nucleus substituted the ethyl group is mentioned. Among these, a crystalline epoxy resin is preferable from the viewpoint of fluidity of the epoxy resin (A), and specifically, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene. Is preferred.

  In the present invention, particularly when 2,7-dihydroxynaphthalene is used, an epoxy resin obtained by epoxidizing the 2,7-dihydroxynaphthalene usually exhibits excellent fluidity, but has a very low melting point and a semiconductor sealing material. In the present invention, β-alkylglycidyl groups are introduced at a ratio of 95% or more on a molar basis with respect to all epoxy groups in the epoxy resin. Thus, the melting point of the epoxy resin itself can be increased to a range suitable for the adjustment of the semiconductor sealing material, specifically, to a range where the melting point measured by DSC is 95 to 120 ° C. Therefore, 2,7-dihydroxynaphthalene, which has heretofore been very difficult to be applied to semiconductor sealing materials, can be put into practical use as a crystalline epoxy resin. Among dihydroxynaphthalenes, 2,7 -Dihydroxynaphthalene is preferred.

  Next, specific examples of the β-alkylepihalohydrin include β-methylepichlorohydrin, β-methylepibromohydrin, β-ethylepichlorohydrin, and β-ethylepibromohydrin. Β-methylepichlorohydrin is preferable from the viewpoint of excellent effect of improving characteristics (low dielectric constant, low dielectric loss tangent).

  Therefore, the compound having a di (β-alkylglycidyloxy) naphthalene structure in the epoxy resin (A) is specifically a compound having a di (β-methylglycidyloxy) naphthalene structure, di (β-ethylglycidyloxy). A compound having a naphthalene structure is exemplified, and a compound having a di (β-methylglycidyloxy) naphthalene structure is particularly preferable. Examples of the β-alkyl glycidyl group in the epoxy resin (A) include a β-methyl glycidyl group and a β-ethyl glycidyl group, and a β-methyl glycidyl group is particularly preferable.

  In addition, the epoxy resin (A) should have a ratio in which the proportion of β-alkylglycidyl groups in all epoxy groups in the epoxy resin (A) is 95% or more on a molar basis. By using all β-alkyl glycidyl groups, the moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) of the cured product are drastically improved. That is, the epoxy resin (A) is obtained by reacting dihydroxynaphthalenes and β-alkyl epihalohydrin as essential monomer components, but in addition, a very small amount of epihalohydrin having no alkyl group such as epichlorohydrin. In this case, an alkyl group unsubstituted glycidyl ether group is introduced into the epoxy resin (A). In the epoxy resin (A), the proportion of β-alkyl glycidyl group in all epoxy groups such as β-alkyl glycidyl group and alkyl group unsubstituted glycidyl ether group is 95% or more on a molar basis. It is preferable that all of them are β-alkylglycidyl groups, so that the moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) of the cured product can be dramatically improved. It expresses.

  Furthermore, when the epoxy resin (A) contains a compound having a di (β-alkylglycidyloxy) naphthalene structure in a range of 75% by mass or more, the epoxy resin (A) itself imparts excellent fluidity. It is preferable because it can be used.

  From the above points, the epoxy resin (A) is specifically represented by the following formula (1):

（式中、ｎは繰り返し数を示す。）で表される構造を有し、かつ、ｎ＝０成分を７５質量％以上含有するものであることが好ましい。

(Where n represents the number of repetitions), and preferably contains 75% by mass or more of n = 0 component.

  The epoxy resin (A) described in detail above is a dihydroxynaphthalene and an epihalohydrin essential for β-alkylepihalohydrin, preferably 1.5 to 20 mol of epichlorohydrin with respect to 1 mol of hydroxyl group of the dihydroxynaphthalene. Can be easily produced by adding 3.0 to 10.0 mol and reacting at 20 to 120 ° C., preferably 50 to 80 ° C. for 2 to 7 hours in the presence of a base.

  Here, the epihalohydrins essentially comprising β-alkyl epihalohydrin are β-alkyl epihalohydrin or a mixture of the β-alkyl epihalohydrin and a β-alkyl group-free epihalohydrin, and in the latter case, β-alkyl epihalohydrin. Is contained at a ratio of 95% or more on a molar basis. In the present invention, as described above, it is preferable to use a β-alkylepihalohydrin alone.

The base used in the epoxidation reaction is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, and the like. Among them, potassium hydroxide Sodium hydroxide is preferred.
At this time, the content of the compound having a di (β-alkylglycidyloxy) naphthalene structure in the resulting epoxy resin (A) by adjusting the excess of β-alkylepihalohydrin relative to the hydroxyl group of dihydroxynaphthalene, particularly the above-mentioned In the case of the epoxy resin represented by Formula 1, the content of the n = 0 component can be adjusted. Specifically, it is desirable to increase the number of moles of β-methylepichlorohydrin to 10 times or more with respect to the hydroxyl group of dihydroxynaphthalene.

  The content of the compound having a di (β-alkylglycidyloxy) naphthalene structure in the epoxy resin (A) or the content of n = 0 component in the case of the epoxy resin represented by the formula 1 is In accordance with general reaction conditions, an epoxy resin intermediate of low purity (75% by mass or less) is produced, and the epoxy resin intermediate is purified by either molecular distillation or recrystallization to contain them. The rate can be increased. Even in this case, although the number of moles of β-methylepichlorohydrin relative to the hydroxyl group of dihydroxynaphthalene does not need to be so high, in order to increase the yield in the subsequent molecular distillation or recrystallization step, it is more than 5 times. It is preferable to enlarge it.

  Further, the production method of obtaining the epoxy resin (A) by purifying the reaction product of dihydroxynaphthalene and β-methylepichlorohydrin by either molecular distillation or recrystallization will be described in detail. 200 to 300 ° C., preferably 1 KPa or less, and recrystallization is preferably performed with a toluene / methanol mixed solvent.

  The epoxy resin (A) has good workability in the epoxy resin composition production process, and further has a melting point measured by DSC of 90 to 90 from the point of being a semiconductor sealing material suitable for a surface-mount type semiconductor device. It is preferably in the range of 120 ° C.

  Similarly, the epoxy resin (A) preferably has a melt viscosity of 10 mPa · s or less measured at 150 ° C. with an ICI viscometer, and in this case, the workability in the epoxy resin composition manufacturing process is good. In addition, it becomes a material suitable for a semiconductor encapsulant in a surface mount type semiconductor device, particularly a semiconductor encapsulant for transfer molding.

  In addition to the crystalline epoxy resin (A) of the present invention, the epoxy resin composition of the present invention may be used in combination with another type of epoxy resin as long as the effects of the present invention are not impaired.

Various other epoxy resins can be used at this time, for example, phenols such as phenol, o-cresol, and catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and aldehydes such as formaldehyde. Phenol novolac epoxy resin or polynaphthol novolak epoxy resin, which is a glycidyl etherified product of the reaction product obtained by condensation of phenols such as phenol, cresol and methyl-t-butylphenol with aromatic aldehydes such as hydroxybenzaldehyde Polyglycidyl ethers of polyphenols containing trityl skeletons; polyphenolic novolacs containing trimethyl skeletons, which are reaction products of polyphenols containing trityl skeletons and formaldehydes Polyglycidyl ethers; phenols such as phenol, o-cresol and catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and polyaralkyl which is a reaction product of xylylene dichloride and (hydroxymethyl) benzenes Polyglycidyl ethers of phenolic resins or polyglycidyl ethers of polyaralkylnaphthol resins; phenols such as phenol, o-cresol and catechol; or naphthols such as hydroxynaphthalene and dihydroxynaphthalene; and non-diethyls such as dicyclopentadiene and limonene Alicyclic hydrocarbon-containing polyphenol resin-type epoxy resin or polynaphthol resin-type epoxy resin that is a glycidyl ether of a reaction product with saturated alicyclic hydrocarbons; Polyphenol resins;
Polyaliphatic hydrogen-containing polyphenol novolak resins or polyglycidyl ethers of polynaphthol novolak resins, which are the reaction products of polynaphthol resins and formaldehyde; obtained by condensation reaction of phenols or naphthols with aromatic carbonyl compounds Glycidyl ether compounds of polyhydric phenols and polyhydric naphthols; phloroglysin, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [ Polyglycidyl ethers of trihydric or higher phenols having (4-hydroxyphenyl) methyl] benzene, 1,4-bis [(4-hydroxyphenyl) methyl] benzene as a basic skeleton; derived from cyclic phenols such as calixarene Glycidyl ether compound And the like;
p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4 ′ -Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, P-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine) Amine-based epoxy resins derived from 1,3-cyclohexanebis (methylamine), N, N-diglycidylaniline, etc .; aromatics such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid Glycidyl ester compounds derived from carboxylic acids; Hydantoin epoxy compounds derived from 5,5-dimethylhydantoin, etc .; 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxy cyclohexylmethyl-3,4-epoxy cyclohexanecarboxylate, etc .; in unsaturated hydrocarbon compounds such as polybutadiene Aliphatic epoxide obtained by oxidizing the double bond of And the like. One or two or more of these epoxy resins may be used.

  The ratio of the crystalline epoxy resin (A) of the present invention to the other epoxy resin used in combination is arbitrary as long as the effects of the present invention are not impaired, and in particular, to maximize the effects of the present invention. It is preferable that the crystalline epoxy resin (A) of the present invention accounts for 50% by mass or more of the entire epoxy resin.

  The curing agent (B) used in the epoxy resin composition of the present invention is not particularly limited, and various curing agents conventionally used as a curing agent for epoxy resins can be used. For example, amine compounds, Examples include acid anhydride compounds, amide compounds, phenol compounds, and the like.

Specific examples of the curing agent (B) include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, and phthalic anhydride , Trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin , Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane Fat, tetraphenylolethane resin, naphthol novolak resin, naphthol - phenol co-condensed novolac resins, naphthol - cresol co-condensed novolac resins, biphenyl-modified phenolic resins, aminotriazine-modified phenolic resins and modified products thereof, imidazo - le, BF _{A 3} -amine complex, a guanidine derivative, etc. are mentioned, These may be used independently and may use 2 or more types together.

  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, because of the excellent flame retardancy of the resulting epoxy resin composition -Phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenol resin are preferable, particularly having a hydroxyl group by a linking group containing an aromatic ring having no hydroxyl group. It is preferably a polyvalent aromatic compound containing a structure in which aromatic rings are linked. For example, an aromatic hydrocarbon formaldehyde resin-modified phenol resin, a phenol aralkyl resin (common name, Iroc resin), naphthol aralkyl 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), aminotriazine Modified phenolic resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) are preferred.

  Although the compounding quantity of the hardening | curing agent (B) in the epoxy resin composition of this invention is not restrict | limited in particular, From the point that the mechanical physical property etc. of the hardened | cured material obtained are favorable, 1 equivalent of epoxy groups of an epoxy resin In contrast, the amount by which the active group in the curing agent is 0.7 to 1.5 equivalents is preferable.

  Moreover, a hardening accelerator can also be suitably used together with the epoxy resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor 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 can be mixed with the inorganic filler (C) in addition to the above-described epoxy resin (A) and curing agent (B) from the viewpoint of good flame retardancy.

  Examples of the inorganic filler (C) include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the blending amount of the inorganic filler (C) is particularly large, it is preferable to use fused silica. The fused silica can be used in either crushed or spherical shape, but the blending amount is increased and the molding material is melted. In order to suppress the increase in viscosity, it is particularly preferable to use mainly spherical ones. In order to further increase the blending amount of the spherical silica, it is preferable that the particle size distribution of the spherical silica is appropriately adjusted so that the average particle size is 5 to 30 μm. The filling rate is preferably 65 to 95% by mass, more preferably 90 to 95% by mass, based on the total amount of the epoxy resin composition, from the viewpoint of good flame retardancy. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can also be used.

  The epoxy resin composition of the present invention is further non-halogen after mixing the above-mentioned epoxy resin (A), the curing agent (B) and the inorganic filler (C) from the viewpoint that the flame retardancy becomes better. It can be obtained by blending a flame retardant (D).

  The epoxy resin composition containing such a non-halogen flame retardant (D) is substantially free of halogen atoms. For example, halogen atoms due to trace amounts of impurities of about 5000 ppm or less derived from epihalohydrin contained in the epoxy resin. May be included.

  Examples of the non-halogen flame retardant (D) include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardant is not limited and may be used alone, or a plurality of flame retardants of the same system may be used, or flame retardants of different systems may be used in combination.

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

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

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydro Examples thereof include cyclic organic phosphorus compounds such as oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, curing agent, non-halogen type When using red phosphorus as a non-halogen flame retardant in 100 parts by mass of the epoxy resin composition (I) or (II) containing all of the flame retardant and other fillers and additives, 0.1-2. It is preferable to mix | blend in the range of 0 mass part, and when using an organophosphorus compound, it is preferable to mix | blend in the range of 0.1-10.0 mass part similarly, Especially 0.5-6.0 mass part It is preferable to mix in the range.

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

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

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

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

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 10 parts by mass in 100 parts by mass. It is particularly preferable to blend in the range of 0.1 to 5 parts by mass.

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

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

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, an epoxy resin (A ), Curing agent (B), non-halogen flame retardant (D), and, if necessary, 0.05 to 20 mass in 100 mass parts of epoxy resin composition containing all of inorganic filler (D) and additives. It is preferable to blend in the range of parts. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

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

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

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

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

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

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

Specific examples of the low-melting-point glass include, for example, 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 The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 20 parts by mass. It is particularly preferable to blend in the range of 0.5 to 15 parts by mass.

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

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

  Various compounding agents, such as a silane coupling agent, an ion trap agent, a mold release agent, and a pigment, can be added to the epoxy resin composition of the present invention as necessary.

  The epoxy resin composition of the present invention includes a semiconductor sealing material, an underfill material, a conductive paste, a resin composition used for a laminate or an electronic circuit board, a resin casting material, an adhesive, and an interlayer insulating material for a build-up substrate. It can be used for coating materials such as insulating paints. Among these various uses, it is particularly suitable for semiconductor sealing materials and underfill materials that are particularly used for electronic components, especially for surface mounting type semiconductor sealing materials such as ball grid array (BGA) and chip scale package (CSP). Can do.

  Further, the cured product of the present invention obtained by curing these is easily obtained by heat curing, specifically, a laminate, a cast product, an adhesive layer, a coating film, a film, etc. It is obtained as a molded cured product.

  Next, the semiconductor encapsulating material of the present invention will be described in detail. The semiconductor encapsulating material of the present invention contains an inorganic filler (C) in addition to the epoxy resin (A) and the curing agent (B) at a filling rate of 90. It consists of the said epoxy resin composition contained in the ratio used as the mass% or more. A method for producing such a semiconductor encapsulating material is a melt-mixing type in which the above-described components and other compounding agents are sufficiently mixed until uniform using an extruder, kneader, roll, or the like. The method of setting it as an epoxy resin composition is mentioned. In this case, since the epoxy resin (A) has an appropriate melting point in the present invention, it is excellent in workability and uniformity during melt kneading.

  In the semiconductor device of the present invention, a semiconductor chip, a resin package, and an electrode energizing part are essential components, and the resin package is made of the semiconductor sealing material. In order to manufacture such a semiconductor device, the semiconductor sealing material is molded using a casting, transfer molding machine, injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours. And a method for obtaining a semiconductor device. In addition, since the epoxy resin (A) has excellent fluidity as described above, the semiconductor device of the present invention is a surface mount semiconductor device such as a ball grid array (BGA) or a chip scale package (CSP). Is preferred.

  When the epoxy resin composition of the present invention is used as a resin composition for electronic circuit boards, it is produced by dissolving the epoxy resin composition of the present invention in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone. can do. The amount of the solvent used in this case is usually in the range of 10 to 70% by mass, preferably 15 to 65% by mass, particularly preferably 35 to 65% by mass in the resin composition for electronic circuit boards. In addition, as a method for obtaining the molded cured product, the resin composition for electronic circuit boards is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and dried by heating. After obtaining and laminating, a method of hot press molding it can be mentioned. Specific examples of the electronic circuit board include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

  When the epoxy resin composition of the present invention is used as a coating material such as an adhesive or paint, the composition may be melted and coated, or a solution obtained by dissolving the composition in the above solvent may be used. After coating by the method, the solvent may be removed by drying and cured. At this time, the curing catalyst may be used as necessary. Moreover, you may mix said inorganic filler etc.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the following, “part” and “%” are based on mass unless otherwise specified. In addition, epoxy equivalent uses perchloric acid method, content of n = 0 component uses gel permeation chromatography (GPC), melting point uses differential thermal scanning calorimeter (DSC), melt viscosity is 150 ° C. It is a value using the ICI viscosity measurement method in

Synthesis Example 1 Synthesis of Epoxy Resin (A) A 4-necked flask equipped with a stirrer, thermometer, Dean Stark trap and condenser was charged with 320 g (2 mol) of 2,7-dihydroxynaphthalene and 1598 g (15 mol) of β-methylepichlorohydrin And n-butanol (300 g) were added, and 359 g of 49% NaOH (4.4 mol) was added dropwise at 50 ° C. over 3 hours. Thereafter, stirring was continued at 50 ° C. for 1 hour to complete the epoxidation reaction, stirring was stopped, and the lower layer was discarded. Next, excess β-methylepichlorohydrin was recovered by distillation, and 1000 g of MIBK and 100 g of n-butanol were added to dissolve the crude resin. To this, 30 g of 10% NaOH was added and stirred at 80 ° C. for 3 hours, stirring was stopped and the lower layer was discarded. 300 g of water was added and washed twice, and 540 g of epoxy resin was obtained through dehydration-filtration-desolvation. This epoxy resin had an epoxy equivalent of 187 g / eq and contained 70% by mass of the n = 0 component in the above formula (1). Further, this epoxy resin was dissolved in 500 g of toluene, 100 g of methanol was gradually added and recrystallized, and the precipitated crystals were separated by filtration, washed with methanol and dried to obtain 270 g of epoxy resin (A). This epoxy resin has an epoxy equivalent of 163 g / eq, 90% by mass of n = 0 component in the above formula (1), a DSC measurement melting point is 115 ° C., and a melt viscosity (150 ° C., ICI viscometer) is 2 mPa · s.

Synthesis Example 2 Synthesis of Epoxy Resin (B) 300 g of the target epoxy resin (B) was obtained in the same manner as in Synthesis Example 1 except that the recrystallization was changed to molecular distillation (260 ° C., 1 KPa or less). This epoxy resin has an epoxy equivalent of 169 g / eq, contains 80 mass of n = 0 component in the above formula (1), has a DSC measurement melting point of 103 ° C., and a melt viscosity (150 ° C., ICI viscometer) of 2 mPa・ It was s.

Synthesis Example 3 Synthesis of Epoxy Resin (C) 540 g of the target epoxy resin (C) was obtained in the same manner as in Synthesis Example 1 except that recrystallization was not performed. This epoxy resin has an epoxy equivalent of 187 g / eq, contains 70 mass of n = 0 component in the formula (1), is semi-solid, and has a melt viscosity (150 ° C., ICI viscometer) of 10 mPa · s. Met.

Synthesis Example 4 Synthesis of Epoxy Resin (D) 275 g of the desired epoxy resin (D) was obtained in the same manner as in Synthesis Example 1 except that 2,7-dihydroxynaphthalene was changed to the same amount of 1,6-dihydroxynaphthalene. . This epoxy resin has an epoxy equivalent of 163 g / eq, 90 mass of n = 0 component in the above formula (1), DSC measurement melting point is 80 ° C., melt viscosity (150 ° C., ICI viscometer) is 2 mPa・ It was s.

Synthesis Example 5 Synthesis of Epoxy Resin (E) 265 g of the desired epoxy resin (E) was obtained in the same manner as in Synthesis Example 1 except that 2,7-dihydroxynaphthalene was changed to the same amount of 1,4-dihydroxynaphthalene. . This epoxy resin has an epoxy equivalent of 163 g / eq, 90 mass of n = 0 component in the above formula (1), DSC measurement melting point is 135 ° C., melt viscosity (150 ° C., ICI viscometer) is 2 mPa・ It was s.

Synthesis Example 6 Synthesis of Epoxy Resin (F) 267 g of the target epoxy resin (F) was obtained in the same manner as in Synthesis Example 1, except that 2,7-dihydroxynaphthalene was changed to the same amount of 1,5-dihydroxynaphthalene. . This epoxy resin has an epoxy equivalent of 163 g / eq, 90 mass of n = 0 component in the above formula (1), DSC measurement melting point is 185 ° C., melt viscosity (150 ° C., ICI viscometer) is measured It was impossible.

Synthesis Example 7 Synthesis of Epoxy Resin (G) 245 g of the target epoxy resin (G) was obtained in the same manner as in Synthesis Example 1 except that β-methylepichlorohydrin was changed to 1388 g (15 mol) of epichlorohydrin. This epoxy resin has an epoxy equivalent of 141 g / eq, 95 mass of n = 0 component in the above formula (1), a DSC measurement melting point of 93 ° C., and a melt viscosity (150 ° C., ICI viscometer) of 1 mPa・ It was s.

Synthesis Example 8 Synthesis of Epoxy Resin (H) Synthesis Example except that 2,7-dihydroxynaphthalene was changed to the same amount of 1,6-dihydroxynaphthalene and β-methylepichlorohydrin was changed to 1388 g (15 mol) of epichlorohydrin. In the same manner as in Example 1, 240 g of the target epoxy resin (H) was obtained. This epoxy resin has an epoxy equivalent of 142 g / eq, 96 mass of n = 0 component in the above formula (1), DSC measurement melting point is 60 ° C., melt viscosity (150 ° C., ICI viscometer) is 1 mPa・ It was s.

Synthesis Example 9 Synthesis of Epoxy Resin (I) Synthesis Example except that 2,7-dihydroxynaphthalene was changed to the same amount of 1,4-dihydroxynaphthalene and β-methylepichlorohydrin was changed to 1388 g (15 mol) of epichlorohydrin. In the same manner as in Example 1, 250 g of the target epoxy resin (I) was obtained. This epoxy resin has an epoxy equivalent of 142 g / eq, contains 95 mass of n = 0 component in the above formula (1), has a DSC measurement melting point of 110 ° C., and a melt viscosity (150 ° C., ICI viscometer) of 1 mPa・ It was s.

Synthesis Example 10 Synthesis of Epoxy Resin (J) Synthesis Example except that 2,7-dihydroxynaphthalene was changed to the same amount of 1,5-dihydroxynaphthalene and β-methylepichlorohydrin was changed to 1388 g (15 mol) of epichlorohydrin. In the same manner as in Example 1, 248 g of the target epoxy resin (J) was obtained. This epoxy resin has an epoxy equivalent of 141 g / eq, contains 95 mass of n = 0 component in the above formula (1), has a DSC melting point of 165 ° C., and a melt viscosity (150 ° C., ICI viscometer) is measured. It was impossible.

Synthesis Example 11 Synthesis of Epoxy Resin (K) 2,7-Dihydroxynaphthalene was changed to the same amount of 1,5-dihydroxynaphthalene and 1598 g (15 mol) of β-methylepichlorohydrin was changed to 479 g (4.5 mol) of β-methylepichlorohydrin. 490 g of the desired epoxy resin (J) was obtained in the same manner as in Synthesis Example 1 except that the mixture was changed to a mixture of 1064 g (11.5 mol) of epichlorohydrin and recrystallization was not performed. This epoxy resin has an epoxy equivalent of 164 g / eq, 81 mass of n = 0 component in the above formula (1), DSC measurement melting point is 128 ° C., melt viscosity (150 ° C., ICI viscometer) is 5 mPa・ It was s. The β-methyl substituted / non-substituted ratio calculated from the C-NMR peak intensity ratio was 47/53.

  The epoxy resins (A) to (K) obtained in Synthesis Examples 1 to 11 and “YX-4000H” (manufactured by Japan Epoxy Resin Co., Ltd.), which is a tetramethylbiphenyl type epoxy resin, are added as a comparison, and the epoxy equivalent, The n = 0 component content, DSC measurement melting point, and melt viscosity (150 ° C., ICI viscometer) in the formula (1) are collectively shown in Table 1.

Examples 1-6 and Comparative Examples 1-6
The epoxy resins (A) to (K) obtained in Synthesis Examples 1 to 11 and YX-4000H were used as the epoxy resin, and “Phenolite TD-2131” (phenol novolac resin, Dainippon Ink & Chemicals, Inc.) as the curing agent. ), A hydroxyl group equivalent of 104 g / eq, a softening point of 80 ° C., and using triphenylphosphine (TPP) as an accelerator, an epoxy composition was prepared according to the blending ratio in Table 2. Next, press molding was performed at 150 ° C. for 20 minutes, and then post-curing (after-curing) was performed at 175 ° C. for further 5 hours to obtain a cured product. The obtained hardened | cured material was cut out to the test size required for each evaluation, and the evaluation test was done with the following method.
(1) Moisture absorption rate Mass change rate before and after the cured specimen was treated for 300 hours under the condition of 85 ° C./85% RH using a constant temperature and humidity device “KCL-2000A” manufactured by Tokyo Rika Co., Ltd. %) Was measured as the moisture absorption (test piece size 75 × 25 × 2 mm).
(2) Linear expansion coefficient Linear expansion when measured with a temperature rise rate of 3 ° C / min using a thermomechanical analyzer “TMA / SS6100” manufactured by Seiko Electronics Industry Co., Ltd. and changed to 40-60 ° C. The coefficient (α1: linear expansion coefficient in the glass region) was measured.
(3) Dielectric properties (dielectric constant, dielectric loss tangent)
Using a method according to JIS-C-6481, the cured material after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies. The dielectric constant and dielectric loss tangent at a frequency of 100 MHz were measured (test piece size 75 × 25 × 2 mm).

Claims (8)

Following formula (1)

(Wherein n represents the number of repetitions), the n = 0 component is contained in an amount of 75% by mass or more, and the melting point measured by DSC is in the range of 95 to 120 ° C. An epoxy resin composition comprising the crystalline epoxy resin (A) and the curing agent (B) as essential components . The epoxy resin (A) is obtained by reacting 2,7-dihydroxynaphthalene and β-alkylepihalohydrin as essential components and further purifying by either molecular distillation or recrystallization. The epoxy resin composition according to 1. The epoxy resin composition of Claim 1 or 2 which contains an inorganic filler (C) as an essential component in addition to the said epoxy resin (A) and a hardening | curing agent (B). The epoxy resin composition according to claim 3 , wherein the filling rate of the inorganic filler (C) is 90% by mass or more. A non-halogen flame retardant (D) is contained, The epoxy resin composition as described in any one of Claims 1-4 characterized by the above-mentioned. Semiconductor sealing material characterized by comprising an epoxy resin composition according to claim 4 or claim 5. A semiconductor device comprising a semiconductor chip, a resin package, and an electrode energizing portion as essential constituent elements, wherein the semiconductor device comprises the semiconductor sealing material according to claim 6 . A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5 .