JP5689230B2 - Epoxy resin composition, cured product thereof, semiconductor sealing material, semiconductor device, and epoxy resin - Google Patents

Description

The present invention relates to an epoxy resin, an epoxy resin composition, a cured product, and a semiconductor encapsulating material that provide a cured product having low viscosity, excellent continuity formation, non-halogen, and having high flame retardancy and solder crack resistance. About.

Epoxy resin compositions containing an epoxy resin and its curing agent as essential components are excellent in various properties such as electrical insulation, high heat resistance, moisture resistance, and dimensional stability. Substrates, electronic components such as resist ink, conductive adhesives such as conductive paste and other adhesives, liquid sealing materials such as underfill, liquid crystal sealing materials, flexible substrate coverlays, matrix for composite materials, paints, photoresists Widely used in materials and color developing materials. 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 the demand for higher performance is increasing with technological innovation in these fields.
In recent years, in various applications, particularly advanced materials, there has been a demand for higher heat resistance of cured products. For example, in the field of semiconductor sealing materials, the transition to surface mount packages such as BGA and CSP, and lead-free solder As a result, the temperature of the reflow treatment is increased, and therefore, there is a demand for an electronic component encapsulating resin material that is more excellent in moisture resistance and solder resistance than ever before.
As an electronic component sealing material that meets such required characteristics, for example, an epoxy resin in which a phenol resin obtained by reacting a hydroxy group-containing aromatic compound, an alkoxy group-containing aromatic compound, and a carbonyl group-containing compound is reacted with epihalohydrin is disclosed. (See Patent Document 1 below).

JP 2006-274236 A

However, although the epoxy resin disclosed in Patent Document 1 is excellent in the heat resistance of the cured product, it has a high melt viscosity at the time of molding the epoxy resin itself, and is inferior in continuity formation after composition adjustment. For this reason, the effect of improving the solder crack resistance in the electronic component sealing material application is not sufficient.
Therefore, the problems to be solved by the present invention are excellent in heat resistance of the cured product, low in melt viscosity at the time of molding of the epoxy resin itself, excellent in continuity formation after composition adjustment, and electronic component sealing material An object of the present invention is to provide an epoxy resin composition having drastically improved solder crack resistance in use.

  As a result of intensive studies to solve the above problems, the present inventors have found that a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), and a methylene group. Each having a structural site of a divalent hydrocarbon group (X) selected from an alkylidene group and an methylene group containing an aromatic hydrocarbon structure, and the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) And the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group. An epoxy resin obtained by reacting a mixture of a phenol resin (ph1) having a bonded structure in its molecular structure and 4,4′-biphenol in advance with epihalohydrin, Finding that it is a viscosity and has excellent curability and continuous moldability when it is a composition with a curing agent, and that it can impart excellent solder cracking resistance to the cured product. It came.

That is, this invention is an epoxy resin composition which has an epoxy resin (A) and a hardening | curing agent (B) as an essential component, Comprising: The said epoxy resin (A) is,
2 selected from a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), and a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group. Each having a structural site of a valent hydrocarbon group (X), the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) Is a phenol resin (ph1) having a structure in which the molecular structure is bonded via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group 70 mass % to 90 wt% and, 4,4'-biphenol epoxy resin sets, characterized in that a mixture of 10% to 30% by weight is obtained by reacting an epihalohydrin On things.
The present invention further relates to a cured product obtained by curing the epoxy resin composition.
The present invention further provides a semiconductor sealing material using the epoxy resin composition.
The present invention further uses the semiconductor sealing material.
The present invention further includes a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene. Each having a structural part of a divalent hydrocarbon group (X) selected from a group, and the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic group Phenol having a structure in which a hydrocarbon group (B) is bonded via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group in the molecular structure Resin (ph1) 70 mass% to 90 mass% ,
The present invention relates to an epoxy resin having a molecular structure obtained by reacting a mixture of 10% by mass to 30% by mass of 4,4′-biphenol with epihalohydrin.

  According to the present invention, the cured product has excellent heat resistance, low melt viscosity at the time of molding of the epoxy resin itself, excellent continuity formation after composition adjustment, and resistance to solder cracks in electronic component sealing material applications. It is possible to provide an epoxy resin composition having dramatically improved properties.

FIG. 1 is a GPC chart of the epoxy resin (A-1) obtained in Example 1. FIG. 2 is a GPC chart of the epoxy resin (A-2) obtained in Example 2. FIG. 3 is a GPC chart of the epoxy resin (A-3) obtained in Example 3.

Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the present invention is an epoxy resin obtained by reacting a mixture of the phenol resin (ph1) and 4,4′-biphenol with epihalohydrin.

The phenol resin (ph1), which is one component of the raw material of the epoxy resin (A) used in the epoxy resin composition for semiconductor encapsulation of the present invention,
Selected from phenolic hydroxyl group-containing aromatic hydrocarbon group (P), alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), and methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group It has each structural site of a divalent hydrocarbon group (X), and the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B ) Is a phenol resin having in its molecular structure a structure bonded via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group. It is a feature.

  Here, the phenol resin includes a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), a methylene group, an alkylidene group, and an aromatic hydrocarbon. Each structural unit of a divalent hydrocarbon group (X) selected from structure-containing methylene groups (hereinafter simply referred to as “methylene group etc. (X)”) is represented by “P”, “B”, When represented by “X”, the following structural site A1

であらわされる構造部位を必須として分子構造内に含むものである。

The structural part represented by is included in the molecular structure as essential.

  In this invention, since it has such a characteristic chemical structure, the aromatic content rate in a molecular structure becomes high.

  Here, the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) can have various structures, specifically, phenol, naphthol represented by the following structural formulas of P1 to P16, and An aromatic hydrocarbon group formed from a compound having an alkyl group as a substituent on these aromatic nuclei is preferable from the viewpoint of excellent dielectric performance.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  The phenolic hydroxyl group-containing aromatic hydrocarbon group (P) described in detail above, particularly those having a methyl group as a substituent on the aromatic nucleus can impart excellent flame retardancy to the cured epoxy resin itself, This makes it possible to design halogen-free materials that are highly demanded in the field of electronic components.

  Further, the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) has a methyl group in the ortho position of the phenol skeleton as represented by the structural formulas P6, P7, P8, and P9. The improvement effect of heat resistance and dielectric properties is remarkable, which is preferable.

  Next, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) contained in the phenol resin structure is a monovalent or polyvalent aromatic having an alkoxy group as a substituent on the condensed polycyclic aromatic nucleus. A hydrocarbon group, specifically, an alkoxyquinephthalene structure represented by the following structural formulas B1 to B15 or an alkoxyanthracene represented by the following structural formula B16.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Among the alkoxy group-containing condensed polycyclic aromatic hydrocarbon groups (B) described in detail above, those having an alkoxynaphthalene type structure are particularly preferable from the viewpoint that the heat resistance of the cured epoxy resin is good. In particular, the epoxy resin cured product is excellent in flame retardancy, and in recent years, it has become possible to design a halogen-free material that is highly demanded in the field of electronic components, so that a methoxy group represented by the structural formulas B1 to B13 or An aromatic hydrocarbon group formed from a naphthalene structure having an ethoxy group as a substituent and a structure further having a methyl group as a substituent is preferable.

  Next, the divalent hydrocarbon group (X) selected from the methylene group, the alkylidene group, and the aromatic hydrocarbon structure-containing methylene group in the phenol resin structure is, for example, an methylene group or an alkylidene group. Are ethylidene group, 1,1-propylidene group, 2,2-propylidene group, dimethylene group, propane-1,1,3,3-tetrayl group, n-butane-1,1,4,4-tetrayl group, An n-pentane-1,1,5,5-tetrayl group may be mentioned. In addition, examples of the aromatic hydrocarbon structure-containing methylene group include those having the following structures X1 to X9.

これらの中でも特に誘電効果に優れる点からメチレン基であることが好ましい。

Among these, a methylene group is preferable from the viewpoint of excellent dielectric effect.

  The phenol resin used in the present invention can take any combination of the structures shown in the specific examples of the structural sites (P), (B), and (X). As described above, the molecular structure of the phenol resin composed of each of such constituent parts is as follows: phenolic hydroxyl group-containing aromatic hydrocarbon group (P), alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), And when each structural unit of (X) such as methylene group is represented by “P”, “B”, “X”, the following structural site A1

であらわされる構造部位を必須として分子構造内に含むものであるが、更に具体的には、下記構造式Ａ２及びＡ３で表される構造、

The structure represented by the formula is essentially included in the molecular structure, more specifically, structures represented by the following structural formulas A2 and A3,

で表される構造を繰り返し単位とするノボラック構造の分子末端に、下記構造式Ａ６ Structural formula A4 or A5

At the molecular end of the novolak structure having the structure represented by

で表される構造を有する構造、その他下記構造式Ａ７〜Ａ８

Other structures having the structure represented by the following structural formulas A7 to A8

で表される構造を繰り返し単位とする交互共重合体構造が挙げられる。

The alternating copolymer structure which makes the structure represented by repeating unit a repeating unit is mentioned.

  In the present invention, the phenolic resin (ph1) can have various structures as described above. By having the structure represented by the structural formula A6 at the molecular end, the dielectric loss tangent of the cured epoxy resin is obtained. Can be significantly reduced. Therefore, in particular, the phenol resin having the structure of the structural formula A3 or the phenol resin having the structure represented by the structural formula A6 at the molecular end of the A4 or A7 as a repeating unit is particularly preferable. From the point that the effect of the above appears remarkably, the phenol resin having the structure of the structural formula A3, or the phenol resin having the structure represented by the structural formula A6 at the molecular end of the A4 as a repeating unit is preferable. .

  Furthermore, the phenol resin (ph1) is produced by reacting a hydroxy group-containing aromatic compound (a1), an alkoxy group-containing aromatic compound (a2), and a carbonyl group-containing compound (a3) as described later. In this case, in addition to the various structures described above, a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), a methylene group, and the like ( When each structural unit of X) is represented by “P”, “B”, and “X”,

で表される構造の化合物も同時に生成し、該フェノール樹脂中に含まれる。本発明では該化合物の含有量が比較的高い方が、該フェノール樹脂自体の溶融粘度を低減でき、かつ得られるエポキシ樹脂硬化物の誘電特性に優れたものとなる為好ましく、具体的には該樹脂中、１〜３０質量％となる範囲でフェノール樹脂中に含まれることが好ましい。特に、このような効果が顕著なものとなる点から、３〜２５質量％、なかでも３〜１５質量％の範囲であることが好ましい。

A compound having a structure represented by the following formula is simultaneously generated and contained in the phenol resin. In the present invention, a relatively high content of the compound is preferable because the melt viscosity of the phenol resin itself can be reduced and the resulting epoxy resin cured product has excellent dielectric properties. It is preferable that it is contained in a phenol resin in the range which becomes 1-30 mass% in resin. In particular, from the point that such an effect becomes remarkable, the range of 3 to 25% by mass, particularly 3 to 15% by mass is preferable.

  Similarly, as a result of reacting the hydroxy group-containing aromatic compound (a1), the alkoxy group-containing condensed polycyclic aromatic compound (a2), and the carbonyl group-containing compound (a3), the product is a phenol resin. In addition, when the structural units of the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) and the methylene group (X) are represented by “B” and “X” respectively,

で表される構造を有する化合物が混入する場合がある。本発明では、エポキシ樹脂硬化物の耐熱性の点から、かかる化合物の含有率は低いことが望ましく、できれば全く存在しないことが好ましい。よって、フェノール樹脂（ｐｈ１）中に占める該化合物の含有率は、５質量％以下、なかでも３質量％以下、特に２質量％以下であることが好ましい。

In some cases, a compound having a structure represented by In the present invention, from the viewpoint of heat resistance of the cured epoxy resin, it is desirable that the content of such a compound is low, and it is preferable that it is not present at all. Therefore, the content of the compound in the phenol resin (ph1) is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

  The phenol resin (ph1) has a melt viscosity at 150 ° C. measured with an ICI viscometer in the range of 0.1 to 5.0 dPa · s, and has fluidity during molding and heat resistance of the cured product. Etc. are preferable in that they are excellent. Furthermore, the phenol resin has a hydroxyl group equivalent of 120 to 500 g / eq. Those in the range are preferable from the viewpoint of further improving the flame retardancy and dielectric properties of the cured product. Moreover, in this invention, what comprises the conditions of such a hydroxyl equivalent and melt viscosity becomes the novel phenol resin of this invention here. The hydroxyl equivalent is particularly 150 to 350 g / eq. Within this range, the balance between the dielectric properties of the cured product and the curability of the composition is particularly excellent.

  Further, the phenol resin (ph1) has a molar ratio of the abundance ratio of the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B). / The latter = 30/70 to 98/2 is preferable because the flame retardancy and dielectric properties of the cured product are further improved.

  The phenol resin (ph1) can be produced by reacting a hydroxy group-containing aromatic compound (a1), an alkoxy group-containing aromatic compound (a2), and a carbonyl group-containing compound (a3).

Specific examples of the hydroxy group-containing aromatic compound (a1) used in the above production method include unsubstituted phenols such as phenol, resorcinol and hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol, and iso-propyl. Monosubstituted phenols such as phenol and t-butylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol and dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2 , 3,6-trimethylphenol and the like, and naphthols such as 1-naphthol, 2-naphthol and methylnaphthol.
Two or more of these may be used in combination.

  Among these, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint of a cured product and flame retardancy.

Next, the alkoxy group-containing aromatic compound (a2) specifically includes 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy-2-methylnaphthalene, 1,3. , 5-trimethyl-2-methoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-ethoxynaphthalene,
1,4-dimethoxynaphthalene, 1-t-butoxynaphthalene, 1-methoxyanthracene, and the like can be given.
Among these, 1-methoxynaphthalene and 2-methoxynaphthalene are preferable because the hardness during molding can be increased.

  Next, the carbonyl group-containing compound (a3) specifically includes aliphatic aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, dialdehydes such as glyoxal, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, Examples thereof include aromatic aldehydes such as 4-biphenylaldehyde and naphthylaldehyde, and ketone compounds such as benzophenone, fluorenone and indanone.

  Among these, formaldehyde, benzaldehyde, 4-biphenylaldehyde, and naphthylaldehyde are preferable because the cured product obtained has excellent flame retardancy.

As a method of reacting the hydroxy group-containing aromatic compound (a1), the alkoxy group-containing condensed polycyclic aromatic compound (a2), and the carbonyl group-containing compound (a3), specifically,
1) A hydroxy group-containing aromatic compound (a1), an alkoxy group-containing condensed polycyclic aromatic compound (a2), and a carbonyl group-containing compound (a3) are charged substantially simultaneously and in the presence of a suitable polymerization catalyst. A method of performing the reaction by heating and stirring, and
2) After reacting 0.05 to 30 mol, preferably 2 to 30 mol, of the carbonyl group-containing compound (a3) with respect to 1 mol of the alkoxy group-containing condensed polycyclic aromatic compound (a2), a hydroxy group Method of charging and reacting containing aromatic compound (a1) 3) Hydroxy group-containing aromatic compound (a1) and alkoxy group-containing condensed polycyclic aromatic compound (a2) are mixed in advance, The method of reacting by adding a carbonyl group containing compound (a3) in a system continuously thru | or intermittently is mentioned. Here, “substantially simultaneously” means that all raw materials are charged until the reaction is accelerated by heating.

  Next, the epoxy resin (A) of the present invention is obtained by mixing the above-described phenol resin (ph1) and 4,4′-biphenol to obtain a mixture, and then reacting it with epihalohydrin. .

  Here, the mixing ratio of the phenol resin (ph1) and 4,4′-biphenol is 10% by mass to 30% by mass of 4,4′-biphenol with respect to 70% by mass to 90% by mass of the phenol resin (ph1). The amount of 4,4′-biphenol is preferably 15% by mass or more and 25% by mass or less with respect to 75% by mass or more and 85% by mass or less of the phenol resin (ph1). If the amount of 4,4'-biphenol used is too small, a sufficiently low melt viscosity cannot be obtained, and improvement of continuous moldability is less effective. Further, since the obtained epoxy resin does not crystallize, the softening point is low and there is a problem in workability. Here, the melt viscosity of the epoxy resin (A) of the present invention is preferably in the range of 0.1 to 1.0 dPa · s, particularly in the range of 0.1 to 0.7 dPa · s, at an ICI viscosity of 150 ° C. . On the other hand, if the amount of 4,4'-biphenol used is too large, the melt viscosity will be low, but the functional group concentration will be high, the hygroscopicity will be increased, and usable solder crack resistance will not be obtained. As a result, 4,4 ′-(2,3-epoxypropoxy) biphenol is not compatible during kneading, and a cured product exhibiting sufficient characteristics cannot be obtained.

  Specifically, the method of reacting the mixture with epihalohydrin is such that 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the mixture, and further 0.9 to 2 to 1 mol of phenolic hydroxyl group. A method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding 0.0 mol of a basic catalyst. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. It is possible to adopt a method in which the mixture is further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  Among these, in order to suppress crystallization of the biphenol skeleton-containing compound during the reaction, it is preferable to react at an alkali concentration of 30% by mass or less and a reaction temperature of 60 ° C. or more.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

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

  The epoxy resin (A) thus obtained itself has a low melt viscosity. Specifically, the epoxy resin (A) has a melt viscosity in an ICI viscometer at 150 ° C. of 0.1 to 1.0 dPa · s and an epoxy equivalent of 220 g / eq. -300 g / eq. It is preferable from the point of being excellent in the continuity forming property after the composition adjustment and the solder crack resistance in the electronic component sealing material application being drastically improved.

  The epoxy resin composition of the present invention can be used in combination with other epoxy resins as long as it does not impair the characteristics of the present invention, in addition to the epoxy resin (A) described above as an epoxy resin component. In this case, the epoxy resin (A) is preferably contained in an amount of 30% by mass or more, more preferably 50% by mass or more, based on 100% by mass of the total epoxy resin.

  The other epoxy resin 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, bisphenol AD type Bifunctional type such as epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, sulfur containing epoxy resin, stilbene type epoxy resin Epoxy resin, triglycidyl isosocyanurate, methoxynaphthalene modified aralkyl epoxy resin, methoxynaphthalene modified novolak resin, phenol novolac epoxy resin, cresol novo Type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin (commonly known as epoxide of zylock resin), naphthol formaldehyde condensation type epoxy Resin, naphthol novolac epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin epoxy resin, biphenyl modified novolak Type epoxy resin (epoxidized polyhydric phenol resin in which phenol nucleus is linked by bismethylene group), biphenyl modified naphthol type epoxy resin ( (Epoxy compound of polyvalent naphthol resin in which naphthol nuclei are linked by smethylene group), alkoxy group-containing novolac type epoxy resin, alkoxy group-containing phenol aralkyl resin, tetrabromobisphenol A type epoxy resin, Examples thereof include epoxy resins derived from various 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide described in JP-A-11-166035. Moreover, the said epoxy resin may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins are preferable in terms of particularly low viscosity, and phenol aralkyl-type epoxy resins and biphenyls are preferable in terms of excellent flame retardancy. A modified novolac type epoxy resin is preferred.

  As the curing agent (B) used in the epoxy resin composition of the invention, various curing agents for epoxy resins can be used, such as amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Examples include a curing agent for epoxy resin.

Specifically, polyamide resin synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyrone anhydride Mellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified Phenol resin, dicyclopentadiene phenol addition resin; phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified A polyvalent aromatic compound having a structure in which a hydroxyl group-containing aromatic structure is linked with bisaralkyl as a nodule group such as an enol aralkyl resin; a phenol trimethylol methane resin, a tetraphenylol ethane resin, a naphthol novolak resin, a naphthol-phenol co-polymer Condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin, alkoxy group-containing aromatic ring-modified novolak resin (polyhydric phenol compound in which phenol nucleus and alkoxy group-containing aromatic ring are connected with formaldehyde And the like, and modified products thereof, imidazoles, BF ₃ -amine complexes, guanidine derivatives, and the like. Moreover, these hardening | curing agents may be used independently and may mix 2 or more types.

  Among these curing agents, polyvalent aromatic compounds having a structure in which a hydroxyl group-containing aromatic structure is linked with bisaralkyl as a nodule group, the above-described phenol resin (ph1), an aromatic hydrocarbon formaldehyde resin-modified phenol resin , Aminotriazine-modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked with melamine or benzoguanamine), alkoxy group-containing aromatic ring-modified novolak resin (polyhydric phenol in which phenol nucleus and alkoxy group-containing aromatic ring are linked with formaldehyde) Polyhydric phenol compounds such as (compound) are preferred from the viewpoint of excellent flame retardancy, and aralkyl type phenol resins are preferred. For example, when it is desired to improve moldability, a phenol novolac resin is preferable, and the curing agent can be used in combination as appropriate depending on the application and required characteristics.

  Specific examples of the polyvalent aromatic compound having a structure in which a hydroxyl group-containing aromatic structure is linked using bisaralkyl as a nodule group include the following general formula (1)

（式中、Ｘ^１はベンゼン環、ナフタレン環、若しくはこれらの芳香核にアルキル基を有する構造部位であり、Ａｒ^１はベンゼン骨格、ビフェニル骨格、ナフタレン骨格、若しくはこれらの芳香核にアルキル基を有する構造部位であり、Ｒ^１は同一でも異なっていてもよい水素原子又は炭素数１〜６の炭化水素基であり、ｎは１〜４である。）で表されるアラルキル型フェノール類；

(In the formula, X ¹ is a benzene ring, a naphthalene ring, or a structural part having an alkyl group in an aromatic nucleus thereof, and Ar ¹ has an alkyl group in a benzene skeleton, a biphenyl skeleton, a naphthalene skeleton, or an aromatic nucleus thereof. An aralkyl-type phenol represented by the following formula: R ¹ is a hydrogen atom which may be the same or different or a hydrocarbon group having 1 to 6 carbon atoms, and n is 1 to 4.

As the aromatic hydrocarbon formaldehyde resin-modified phenol resin, specifically, the following general formula (2)

（式中、Ｘ^２は置換基を有していてもよい芳香環であり、Ａｒ^２はフェニル基、ビフェニル基、ナフチル基、若しくはこれらの芳香核にアルキル基を有する構造部位でありｎは１〜４である。）で表されるフェノール樹脂が挙げられる。
これらの硬化剤はそれぞれ単独で用いてもよく、また、２種以上併用してもよい。

(In the formula, X ² is an aromatic ring which may have a substituent, Ar ² is a phenyl group, a biphenyl group, a naphthyl group, or a structural site having an alkyl group in the aromatic nucleus, and n is 1 To 4)).
These curing agents may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as a compounding quantity of the hardening | curing agent (B) in the epoxy resin composition of this invention, From the point that the mechanical physical property etc. of the hardened | cured material obtained are favorable, epoxy resin (A) and The amount of the active group in the curing agent is preferably 0.5 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups with other epoxy resins used in combination as necessary.

  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.

  Since the epoxy resin composition of the present invention described in detail above has an excellent flame retardancy imparting effect, the flame retardant of the cured product can be obtained without adding a conventionally used flame retardant. Good properties. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. A non-halogen flame retardant (C) may be added.

  The epoxy resin composition containing such a non-halogen flame retardant (C) 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 (C) include:
Phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organometallic salt flame retardants, etc., are not limited in any way, and even if used alone A plurality of flame retardants of the same system may be used, and different types of flame retardants may be used in combination.

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

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

  Examples of the organic phosphorus compound 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- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -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 In 100 parts by mass 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 mass 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 mass, particularly in the range of 0.5 to 6.0 parts by mass. Is preferred.

  Also, when using the phosphorus flame retardant, hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. are used in combination with the phosphorus flame retardant. Also good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and 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, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.

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

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

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

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

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

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

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

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

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

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

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

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

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

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

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

  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. In consideration of flame retardancy, the filling rate is preferably as high as possible, and is particularly preferably 65% by mass, more preferably 85% by mass to 95% by mass 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, an ion trap agent, a pigment, an emulsifier, can be added to the epoxy resin composition of this invention as needed.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above-described components. 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 made into a cured product by a conventionally known method according to various uses. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications for which the epoxy resin composition of the present invention is used include semiconductor sealing materials, laminates, interlayer insulating materials for build-up substrates, die attach agents, underfills, grab top materials, liquid sealing materials for TCP, and conductive adhesives. Resin composition used for electronic circuit boards such as adhesives, liquid crystal sealing materials, flexible substrate coverlays, resist inks, optical waveguides, resin casting materials, composite materials, adhesives, insulating paints, etc. that require a high refractive index Among these, among these, it can be suitably used as 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 mass per 100 parts by mass 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 mass or more, and in order to significantly increase these effects, 80 parts by mass 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 mass 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 mass. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  When using the epoxy resin composition of the present invention as a resist ink, for example, the epoxy resin is used as a curing agent for resins containing various unsaturated double bonds or unsaturated double bonds and carboxyl groups in the molecule, A method of preparing a resist ink composition by adding a cationic polymerization catalyst, a pigment, talc, and a filler, and then applying the resist ink composition on a printed circuit board by a screen printing method, followed by a method of forming a resist ink cured product.

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

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

  The method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. What is necessary is just to heat the composition obtained by the said method in the temperature range of about room temperature-250 degreeC. As the molding method and the like, a general method of the epoxy resin composition is used, and a condition specific to the epoxy resin composition of the present invention is not particularly required.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The melt viscosity at 150 ° C. was measured according to ASTM D4287. GPC was measured under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Synthesis Example 1 [Synthesis of phenol resin (B-1)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 432.4 g (4.00 mol) of o-cresol and 158.2 g (1.00 mol) of 2-methoxynaphthalene 179.3 g (2.45 mol) of 41% formaldehyde aqueous solution was added, 9.0 g of oxalic acid was added, the temperature was raised to 100 ° C., and the mixture was reacted at 100 ° C. for 3 hours. Subsequently, 73.2 g (1.00 mol) of a 41% aqueous formaldehyde solution was added dropwise over 1 hour while collecting water with a fractionating tube. After completion of the dropwise addition, the temperature was raised to 150 ° C. over 1 hour and further reacted at 150 ° C. for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Subsequently, after washing with water until the washing water showed neutrality, unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone were removed from the organic layer under heating and reduced pressure to obtain a phenol resin (B-1). The softening point of the obtained phenol resin was 76 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 1.0 dPa · s, and the hydroxyl group equivalent was 164 g / eq. Met.

Synthesis Example 2 [Synthesis of phenol resin (B-2)]
The phenol resin (B-2) was prepared in the same manner as in Synthesis Example 1 except that 324.3 g (3.00 mol) of o-cresol and 132.3 g (1.83 mol) of the first 41% formaldehyde aqueous solution used were used. Obtained. The obtained phenol resin had a softening point of 71 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.4 dPa · s, and a hydroxyl group equivalent of 178 g / eq. Met.

Example 1 [Synthesis of Epoxy Resin (A-1)]
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 113.8 g (0.69 equivalents of hydroxyl group) of the phenol resin (B-1) obtained in Synthesis Example 1 4,4′-biphenol (hydroxyl equivalent 0.31 equivalent), epichlorohydrin 463 g (5.0 mol), n-butanol 139 g and tetraethylbenzylammonium chloride 2 g were charged and dissolved. After the temperature was raised to 70 ° C., 220 g (1.1 mol) of a 20% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. Then, 1000 g of methyl isobutyl ketone and 350 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 176 g of an epoxy resin (A-1). The resulting epoxy resin (A-1) has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.4 dPa · s, and an epoxy equivalent of 230 g / eq. Met. The GPC chart of the obtained epoxy resin (A-1) is shown in FIG.

Example 2 [Synthesis of Epoxy Resin (A-2)]
In Example 1, the phenol resin (B-1) and 4,4′-biphenol were converted into 137.1 g (hydroxyl group 0.84 equivalent) of phenol resin (B-1) and 15.3 g (hydroxyl group) of 4,4′-biphenol. Except for using 0.16 equivalent), 185 g of epoxy resin (A-2) was obtained in the same manner as in Example 1. The resulting epoxy resin (A-2) has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.6 dPa · s, and an epoxy equivalent of 240 g / eq. Met. The GPC chart of the obtained epoxy resin (A-2) is shown in FIG.

Example 3 [Synthesis of Epoxy Resin (A-3)]
In Example 1, the phenol resin (B-1) and 4,4′-biphenol were mixed with 97.9 g of phenol resin (B-2) (hydroxyl group 0.55 equivalent) and 41.9 g of 4,4′-biphenol (hydroxyl group equivalent). Except that 0.45 equivalent) was used, 178 g of an epoxy resin (A-3) was obtained in the same manner as in Example 1. The resulting epoxy resin (A-3) has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.2 dPa · s and an epoxy equivalent of 225 g / eq. Met. The GPC chart of the obtained epoxy resin (A-3) is shown in FIG.

Comparative Example 1 [Synthesis of Epoxy Resin (A-4)]
In Example 1, instead of the mixture of phenol resin (B-1) and 4,4′-biphenol, only 164.0 g of phenol resin (B-1) (hydroxyl equivalent 1.0 equivalent) was used. In the same manner as in Example 1, an epoxy resin (A-4) was obtained. The resulting epoxy resin (A-4) has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 1.0 dPa · s and an epoxy equivalent of 252 g / eq. Met.

Comparative Example 2 [Synthesis of Epoxy Resin (A-5)]
In Example 1, instead of the mixture of the phenol resin (B-1) and 4,4′-biphenol, only 93.0 g (hydroxyl equivalent 1.0 equivalent) of 4,4′-biphenol was used. A similar reaction was attempted, but crystals were precipitated during the dropwise addition of sodium hydroxide, and an epoxy resin could not be obtained.

Comparative Example 3 [Synthesis of Epoxy Resin (A-6)]
In Example 1, a mixture of the phenol resin (B-1) and 4,4′-biphenol was mixed with 90.6 g (0.76 equivalent) of orthocresol borac resin and 22.8 g (hydroxyl group) of 4,4′-biphenol. 150 g of epoxy resin (A-6) was obtained in the same manner as in Example 1 except that 0.25 equivalent) was used. The resulting epoxy resin (A-6) has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 1.0 dPa · s, and an epoxy equivalent of 195 g / eq. Met.

Examples 4 to 12 and Comparative Examples 4 and 5
Various materials shown in Table 1 were used and melt-kneaded for 10 minutes at a temperature of 80 ° C. using two rolls to obtain an epoxy resin composition. About the obtained epoxy resin composition, gel time was measured with the following method, and sclerosis | hardenability evaluation and spiral flow evaluation were performed. The epoxy resin composition was subjected to a transfer molding machine under conditions of a mold temperature of 175 ° C., a molding pressure of 7.0 MPa, a ram speed of 5 cm / second, and a curing time of 180 seconds. After further curing at 175 ° C. for 5 hours, the physical properties of the cured product were confirmed by the following method. The physical properties of the obtained cured product are summarized in Tables 3 to 5.

Gel time: 0.15 g of the epoxy resin composition is placed on a cure plate heated to 175 ° C. (manufactured by THERMO ELECTRIC), and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.
Spiral flow: Using a spiral flow measuring mold in accordance with EMEI-1-66, the epoxy resin composition kneaded with the two rolls has a mold temperature of 175 ° C., a molding pressure of 7.0 MPa, and a ram speed of 5 cm / sec. The flow distance (cm) was determined under the conditions.
Shore D: It was molded into a disk-shaped mold having a diameter of 50 mm and a thickness of 3 mm, and immediately after molding, it was measured using a Shore D type hardness meter.
Continuous moldability: Molded into a disk-shaped mold having a diameter of 50 mm and a thickness of 3 mm, and the package surface and mold surface after 300, 500 and 700 shot molding were visually evaluated for dirt.
Those that were not stained up to 700 shots were marked with ◎, those that were not stained up to 500 shots were marked with ○, those that were not smudged up to 300 shots were marked with Δ, and those that were smudged before 300 shots were marked with ×.
Solder crack: 80-pin quad flat package with silicon chip sealed with epoxy resin composition under conditions of mold temperature of 175 ° C., molding pressure of 7.0 MPa, ram speed of 5 cm / sec and curing time of 180 sec. (80pQFP; Cu lead frame, package outer dimension: 14 mm × 20 mm × 2 mm thickness, pad size: 6.5 mm × 6.5 mm, chip size 6.0 mm × 6.0 mm × 0.35 mm thickness) It was.
The molded package was post-cured by heat treatment at 175 ° C. for 8 hours, and then humidified for 168 hours at 85 ° C. and 60% relative humidity, and then immersed in a solder bath at 260 ° C. for 10 seconds. The adhesion state of the interface between the 20 semiconductor elements immersed in the solder and the cured epoxy resin composition is observed with an ultrasonic flaw detector (mi-scope 10 manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), and peeling occurs. The rate [(number of peeled packages) / (total number of packages) × 100] was calculated. The judgment criteria for solder resistance are ◎ for those where no peeling occurred, ◯ for peeling occurrence rates of 5% or more and less than 10%, ◯ for 10% or more, less than 20%, △, or 20% or more. The thing was set as x.
Peel strength (index of adhesion): A test piece of 100 mm × 70 mm × 3 mm on a 30 μm thick aluminum foil under conditions of a mold temperature of 175 ° C., a molding pressure of 7.0 MPa, a ram speed of 5 cm / second, and a curing time of 180 seconds. Molded and cut into a width of 10 mm to prepare a test piece. The peel strength was measured by the method based on JIS-K6481 using the obtained test piece.
Flame retardancy: Based on the UL-94 test method, a flame test was conducted using five test pieces having a thickness of 1.6 mm.

  The abbreviations in Table 1 are as follows.

  In Examples 4 to 8, 11 and 12 using the epoxy resin composition of the present invention, a sufficient flame retardancy was exhibited in the obtained cured product without blending a flame retardant, and a semiconductor sealing material, In particular, it was confirmed that it can be suitably used for an area array type semiconductor device. However, Comparative Example 1 has not only poor fluidity but also poor continuity formation and solder crack resistance. In Comparative Example 2, 4,4 ′-(2,3-epoxypropoxy) biphenol crystals remained and an evaluation cured product was not obtained. Comparative Example 3 was not only poor in fluidity and solder crack resistance, but also did not show sufficient flame retardancy. As is clear from these comparative examples, it was confirmed that the epoxy resin compositions used in the comparative examples were not sufficiently satisfactory in performance of the cured products.

  In Examples 9 and 10 obtained by blending non-halogen flame retardants, it was confirmed that the fluidity, continuous moldability, and solder cracking properties were excellent.

Claims (12)

An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, the epoxy resin (A) being
2 selected from a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), and a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group. Each having a structural site of a valent hydrocarbon group (X), the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) Is a phenol resin (ph1) having a structure in which the molecular structure is bonded via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and methylene group containing an aromatic hydrocarbon structure. Epoxy resin composition obtained by reacting a mixture of 10% by mass to 90% by mass and 10% by mass to 30% by mass of 4,4′-biphenol with epihalohydrin object.   The epoxy resin (A) has a melt viscosity of 0.1 to 1.0 dPa · s and an epoxy equivalent of 220 g / eq. -300 g / eq. The composition according to claim 1, wherein the composition is in the range.   The epoxy resin composition according to claim 1, wherein the curing agent (B) is a hydroxy aromatic compound having a structure in which a hydroxyl group-containing aromatic structure is linked with bisaralkyl as a nodule group.   Furthermore, the epoxy resin composition of Claim 1 containing a hardening accelerator.   The epoxy resin composition according to claim 1, further comprising an inorganic filler.   The epoxy resin composition according to claim 1, further comprising a non-halogen flame retardant (C).   Non-halogen flame retardant (C) is phosphorus flame retardant (c1), nitrogen flame retardant (c2), silicone flame retardant (c3), inorganic flame retardant (c4), organometallic flame retardant (c5). The epoxy resin composition according to claim 6, which is at least one flame retardant selected from the group consisting of:   Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-7.   A semiconductor encapsulating material using the epoxy resin composition according to claim 1.   A semiconductor device using the semiconductor sealing material according to claim 9.   2 selected from a phenolic hydroxyl group-containing aromatic hydrocarbon group (P), an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B), and a methylene group, an alkylidene group, and an aromatic hydrocarbon structure-containing methylene group. Each having a structural site of a valent hydrocarbon group (X), the phenolic hydroxyl group-containing aromatic hydrocarbon group (P) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) Is a phenol resin (ph1) having a structure in which the molecular structure is bonded via a divalent hydrocarbon group (X) selected from the methylene group, alkylidene group, and methylene group containing an aromatic hydrocarbon structure. Epoxy having a molecular structure obtained by reacting a mixture of 10% by mass to 90% by mass with 4,4′-biphenol and 10% by mass to 30% by mass with epihalohydrin Fat. The melt viscosity in an ICI viscometer at 150 ° C. is 0.1 to 1.0 dPa · s, and the epoxy equivalent is 220 g / eq. -300 g / eq. Claim 1 1 Symbol mounting epoxy resin and characterized in that.

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