JP2007262398A - Epoxy resin composition and electronic component device - Google Patents

Abstract

（Ｒ_１〜Ｒ_８は、水素原子、炭素数１〜１０の炭化水素基、炭素数１〜１０のアルコキシ基のいずれかよりそれぞれ独立に選ばれ、互いに同じであっても異なっていても良い。）
【選択図】なしAn epoxy resin composition having excellent productivity, moldability such as fluidity and curability, heat dissipation of a package and other reliability, and an electronic component device provided with an element sealed thereby. To do.
(A) An epoxy resin having a structure represented by the following general formula (I), (B) a curing agent having any one of structures represented by specific general formulas (IIa) to (IId), (C) An epoxy resin composition containing an inorganic filler.
(Chemical formula 1)

(R _{1 to} R ₈ are independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and may be the same as or different from each other. .)
[Selection figure] None

Description

  The present invention relates to an epoxy resin composition and an electronic component device including an element sealed with the epoxy resin composition.

  Conventionally, in the field of element sealing of electronic component devices such as transistors, ICs, and LSIs, sealing with a resin has been the mainstream in terms of productivity and cost, and epoxy resin compositions have been widely used. This is because the epoxy resin is balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

  In recent years, in order to improve the performance and functionality of electronic component devices, high-density mounting of elements, miniaturization of wiring, multilayering, increase in the number of pins, increase in the area occupied by the element package, etc. have been progressing. . Also, in electronic devices such as the automobile field, an increase in so-called power-related elements that consume a large amount of power is observed, and in addition to the high-density mounting of the elements, the problem of heat generation of the elements is closed up. High heat dissipation is also required for the epoxy resin composition for stopping.

  In order to increase the heat dissipation of the epoxy resin composition for sealing, crystalline silica, alumina, aluminum nitride, etc. as inorganic fillers have higher thermal conductivity than silica normally used in epoxy resin compositions for sealing In the past, a method of adding a substance having a heat resistance has been reported. However, when a large amount of crystalline silica, alumina, aluminum nitride or the like is added in order to obtain sufficient heat dissipation, the fluidity of the epoxy resin composition for sealing can be increased. In many cases, the moldability such as curability is lowered, or the reliability of the package is lowered due to an increase in elastic modulus. Regarding compatibility between moldability and heat dissipation when alumina is used as the inorganic filler of the epoxy resin composition for sealing, there is also a report such as a technique using alumina having a specific particle size distribution (for example, Patent Document 1). However, the problems such as difficulty in filling fine alumina with a composition with a large amount of filler and the problem of reduced reliability due to an increase in elastic modulus have not been sufficiently solved.

In recent years, reports on attempts to increase the heat dissipation of the epoxy resin composition for sealing have come to be seen from the structure side of the resin with respect to the approach from the inorganic filler. For example, a so-called mesogenic resin having a biphenyl skeleton and the like and a novolak resin such as catechol and resorcinol are combined to increase the orientation of the resin skeleton, thereby reducing the internal thermal resistance and improving the heat dissipation of the epoxy resin composition. However, novolak resins such as catechol and resorcinol are easy to gel during resin synthesis, have a high softening point, and it is difficult to produce an epoxy resin composition for sealing. There are problems such as accompanying.
Japanese Patent No. 2874089

  When an inorganic filler such as alumina is blended in the epoxy resin composition for sealing in order to improve the heat dissipation of the package, generally the moldability such as fluidity and curability, the reliability of the package, etc. are lowered. The higher the blending ratio of the inorganic filler such as, the more remarkable. Also, if we try to increase the heat dissipation of the package by increasing the orientation of the cured resin skeleton (decreasing the internal thermal resistance), it will be difficult to synthesize raw material resins and produce epoxy resin compositions for sealing. It will be difficult to sex.

  The present invention has been made in view of such circumstances, and an epoxy resin composition excellent in productivity, moldability such as fluidity and curability, heat dissipation and other reliability of a package, and sealed with this. An electronic component device provided with an element is to be provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used the above-described epoxy resin composition containing an epoxy resin having a specific structure and a curing agent having a specific structure. The inventors have found that the object can be achieved and have completed the present invention.

The present invention includes (1) (A) an epoxy resin having a structure represented by the following general formula (I), and (B) a cured resin having any structure represented by the following general formulas (IIa) to (IId). The epoxy resin composition containing an agent and (C) inorganic filler.

(R _{1 to} R ₈ are independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and may be the same as or different from each other. .)

(In the general formulas (IIa) to (IId), m and n represent a positive number, and Ar represents one of the following general formulas (IIIa) or (IIIb).)

(R ₁₁ and R ₁₄ in the general formulas (IIIa) and (IIIb) are each independently selected from a hydrogen atom or a hydroxyl group, and R ₁₂ and R ₁₃ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. (The binding sites in general formulas (IIIa) and (IIIb) are not limited.)
The present invention is also obtained by reaction of (2) (A) an epoxy resin having a structure represented by the following general formula (I), (B ′) hydroxybenzenes and aldehydes, and the hydroxyl equivalent is an average value. It is related with the epoxy resin composition containing the phenol resin composition which is 65 or more and 130 or less, and (C) inorganic filler.

(R _{1 to} R ₈ are independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and may be the same as or different from each other. .)
Further, the present invention provides (3) the above (1) or (2), wherein the (C) inorganic filler contains at least one selected from crystalline silica, alumina, aluminum nitride, silicon nitride, and boron nitride. It relates to the epoxy resin composition described.

  Moreover, this invention relates to the electronic component apparatus provided with the element sealed with the epoxy resin composition in any one of (4) said (1)-(3).

  The epoxy resin composition of the present invention is excellent in productivity, moldability, heat dissipation and reliability of the package, etc. If this epoxy resin composition is used to seal electronic components such as IC and LSI, heat dissipation and An electronic product device excellent in reliability and the like can be obtained, and its industrial value is great.

  The epoxy resin composition of the present invention comprises (A) an epoxy resin having a structure represented by the following general formula (I), and (B) any structure represented by the following general formulas (IIa) to (IId). And (C) an inorganic filler.

  Each component will be described below.

(A) Epoxy resin In the present invention, by using an epoxy resin having a structure represented by the following general formula (I), the orientation of the resin can be enhanced, and high heat dissipation can be realized.

In general formula (I), R _{1 to} R ₈ are independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and may be the same as each other. It may be different. The hydrocarbon group having 1 to 10 carbon atoms is a saturated or unsaturated hydrocarbon group which may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group , Tertiary butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, vinyl group, etc., among these, from the viewpoint of orientation of the resin, a lower alkyl group is preferable. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a tertiary riboxy group. From the viewpoint of the orientation of the resin, Again, a lower alkoxy group is preferred.

The biphenyl structure represented by the general formula (I) has a two-dimensional planar structure by forming sp ² hybrid orbitals of all carbon atoms constituting the biphenyl skeleton, and the z-axis direction (in the molecular structure plane) In contrast, it is easy to orient (resin skeleton) in the vertical direction. Such a feature is advantageous for lowering the thermal resistance after curing of the epoxy resin composition, and as a result, increases the heat dissipation of the cured product and provides high heat dissipation.

As an epoxy resin which has a structure represented by general formula (I), the compound etc. which are represented by the following general formula (IV) can be illustrated, for example.

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N is 0 to 3). Indicates an integer.)
From the viewpoint of fluidity, n is preferably 0 to 2 in the above general formula (IV), more preferably n is 0 or 1, and particularly preferably n is 0. In the epoxy resin represented by the general formula (IV), R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen, and n = 0 is the main component. “Epicoat YX4000H” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), R ¹ , R ³ , R ⁶ , R ⁸ are methyl groups, R ² , R ⁴ , R ⁵ , R ⁷ are hydrogen, n = “Epicoat YL6121H” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixture of a compound having 0 as a main component and a compound having R ^{1 to} R ⁸ as hydrogen and n = 0 as main components Available on the market.

  In order to sufficiently obtain the effects of the present invention, the blending amount of the epoxy resin having the structure represented by the general formula (I) is preferably 60% by mass or more, more preferably 70% by mass or more of the entire epoxy resin. Is more preferable, and 80% by mass or more is particularly preferable.

  In the present invention, in addition to the epoxy resin having the structure represented by the general formula (I), the epoxy resin (A) is generally used in an epoxy resin composition for sealing as long as the effects of the present invention are not impaired. It is possible to use the epoxy resin used together. Examples of the epoxy resins that can be used in combination include phenols such as phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and / or α-naphthol, Epoxylated novolak resin obtained by condensation or cocondensation of naphthols such as β-naphthol and dihydroxynaphthalene with compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde in the presence of an acidic catalyst. , Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, bisphenol A / D, phenols and / or naphthols and dimeth Glycidyl obtained by reaction of polychlorinated acid such as epoxidized phenol / aralkyl resin synthesized from xiparaxylene or bis (methoxymethyl) biphenyl, stilbene type epoxy resin, hydroquinone type epoxy resin, phthalic acid, dimer acid and epichlorohydrin Ester-type epoxy resin, diaminodiphenylmethane, isocyanuric acid and other polyamines and epichlorohydrin, glycidylamine-type epoxy resin, dicyclopentadiene-type epoxy resin that is an epoxidized product of co-condensation resin of cyclopentadiene and phenol, hydroxynaphthalene and Epoxy compounds such as dihydroxy naphthalene dimer, triphenolmethane type epoxy resin, trimethylolpropane type epoxy resin, terpene modified epoxy Resins, linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, alicyclic epoxy resins, sulfur atom-containing epoxy resins, and these epoxy resins based on silicone, acrylonitrile, butadiene, isoprene Examples thereof include epoxy resins modified with rubber, polyamide-based resins, and the like.

(B) Curing Agent In order to enhance the effects of the present invention, particularly the heat dissipation of the package, (B) a curing agent having at least one structure represented by the following general formulas (IIa) to (IId) as a curing agent Must be used alone or in combination. The hydroxyl equivalent of such a curing agent is preferably 60 to 130, more preferably 65 to 120, and particularly preferably 70 to 110. The softening point of the curing agent is preferably 50 to 120 ° C, more preferably 60 to 100 ° C, and particularly preferably 70 to 90 ° C.

In the general formulas (IIa) to (IId), m and n represent positive numbers, and Ar represents one of the following general formulas (IIIa) or (IIIb).

R ₁₁ and R ₁₄ in the general formulas (IIIa) and (IIIb) are each independently selected from a hydrogen atom or a hydroxyl group, and R ₁₂ and R ₁₃ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Chosen independently. The binding site in the general formulas (IIIa) and (IIIb) is not limited. Examples of the alkyl group having 1 to 8 carbon atoms of R ₁₂ and R ₁₃ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, A heptyl group and an octyl group are mentioned.

  For each of the general formulas (IIa) to (IId), Ar may be the same atomic group or may contain two or more atomic groups. The constituents represented by the general formulas (IIa) to (IId) may be included randomly or regularly in the main chain skeleton or side chain of the curing agent (B). However, it may be included in a block shape.

In order to realize the effect of the present invention, particularly high heat dissipation, Ar in the general formulas (IIa) to (IId) is dihydroxybenzene (in the general formula (IIIa), R ₁₁ is a hydroxyl group, R ₁₂ and R ₁₃ are hydrogen atoms. Or dihydroxynaphthalene (in the general formula (IIIb), R ₁₄ is a hydroxyl group), and Ar is dihydroxybenzene from the viewpoint of productivity and fluidity of the epoxy resin composition. It is more preferable that it is at least one of 1,2-dihydroxybenzene (catechol) and 1,3-dihydroxybenzene (resorcinol).

  Further, from the viewpoint of moldability such as heat dissipation and fluidity, the structures represented by the general formulas (IIa) to (IId) are not particularly superior or inferior as long as at least one of these structures is included. Further, Ar in the general formulas (IIa) to (IId) may be one type of the structure represented by the general formula (IIIa) or (IIIb), or may be a plurality of types.

  In the general formulas (IIa) to (IId), m and n are preferably m / n = 20/1 to 1/5, more preferably 10/1 to 1/3, and 5/1. It is especially preferable that it is -1/2. Further, (m + n) is preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less. If m / n is greater than 20/1 or (m + n) exceeds 20, the viscosity of the compound may increase, which may adversely affect the fluidity of the epoxy resin composition, and m / n is 1/5. If it becomes smaller, it may be disadvantageous in terms of heat dissipation.

In order to improve the effect of the present invention, particularly the heat dissipation of the package, the blending amount of the curing agent having a structure represented by the general formulas (IIa) to (IId) should be 60% by mass or more of the entire curing agent. Is preferable, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. By setting the blending amount of the curing agent to 60% by mass or more of the entire curing agent, the orientation of the epoxy resin is helped, and as a result, the heat dissipation of the package is easily improved.
The curing agent having a structure represented by the general formulas (IIa) to (IId) is particularly preferable when Ar is at least one of substituted or unsubstituted dihydroxybenzene and substituted or unsubstituted dihydroxynaphthalene. Compared with a resin obtained by simply novolakizing dihydroxynaphthalene or the like, its synthesis is easy, and since a curing agent having a low softening point can be obtained, an epoxy resin composition can be easily produced.

The method for obtaining the curing agent having the structure represented by the general formulas (IIa) to (IId) is not particularly limited. For example, the following method using an intramolecular ring closure reaction by autooxidation of dihydroxybenzene can be used. . That is, for example, phenols and aldehydes containing 20 to 90 mol% of catechol (1,2-dihydroxybenzene, a compound in which R ₁₁ is a hydroxyl group, R ₁₂ and R ₁₃ are hydrogen in the general formula (IIIa)), Like a general novolak resin, the reaction is carried out under an acid catalyst such as oxalic acid. When formalin is used as the aldehyde, the reflux reaction is performed at around 100 ° C. This reaction is performed for 1 to 8 hours, and then the temperature is raised to 120 to 180 ° C. while removing water from the system. The atmosphere at this time is an oxidizing atmosphere (for example, in an air stream). By continuing this state for 2 to 24 hours, a compound represented by the general formula (IIa) or (IIb) is generated in the system. Thereafter, the desired curing agent can be obtained by removing water and the like in the system.

  A mixture of compounds represented by the general formulas (IIa) to (IId) is produced by reacting resorcinol, catechol, and aldehydes in the same manner using the intramolecular ring closure reaction by autooxidation of dihydroxybenzene. In addition, resorcinol and aldehydes are similarly reacted to produce a mixture of compounds represented by the general formulas (IIa), (IIc), and (IId). Moreover, the mixture of the compound represented by general formula (IIa) and (IIb) produces | generates by reacting hydroquinone, catechol, and aldehydes similarly.

  From another point of view, the curing agent used in the present invention is a phenol resin composition obtained by reacting dihydroxybenzenes and aldehydes in the presence of an acidic catalyst, and the hydroxyl group equivalent is the theoretical hydroxyl group equivalent of a novolak resin of dihydroxybenzenes. It is a large phenol resin composition compared with (around 60). By using such a resin composition as a curing agent, the effect of assisting the orientation of the epoxy resin and, as a result, enhancing the heat dissipation of the epoxy resin composition can be obtained. The hydroxyl equivalent is preferably 65 or more and 130 or less in terms of the average value of the phenol resin composition. More preferably, it is 65-120, Most preferably, it is 70-110. Preferably, at least one of the phenol resins having the structure represented by the general formulas (IIa), (IIb), (IIc), and (IId) is included. The reason why the hydroxyl group equivalent becomes larger than the theoretical value is considered to be because dihydroxybenzenes undergo an intramolecular ring-closing reaction during the reaction and contain phenolic resins such as the above general formulas (IIa) to (IId). Examples of the dihydroxybenzenes include monocyclic dihydroxyarenes such as catechol, resorcin, and hydroquinone, and polycyclic such as dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 1,4-dihydroxynaphthalene. The formula dihydroxyarene is mentioned, and these may be used in combination. Examples of the aldehydes include aldehydes used for phenol resin synthesis such as formaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde, and the aldehydes may be used alone or in combination of two or more. In the presence of an acid catalyst, these dihydroxybenzenes and aldehydes are preferably reacted in an amount of 0.3 to 0.9 mol with respect to 1 mol of dihydroxybenzenes. More preferably, the reaction is performed at 0.4 to 0.8 mol. When the aldehydes are less than 0.3 mol, novolak resins are produced, but the content of dibenzoxanthene derivatives is low, and the amount of unreacted dihydroxybenzenes tends to increase and the amount of resin produced tends to decrease. When the amount of aldehyde exceeds 0.9 mol, it is advantageous in terms of the amount of resin produced, but gelation tends to occur in the reaction system and the reaction tends to be very difficult to control. Acids used as catalysts include organic carboxylic acids such as oxalic acid and acetic acid, strong acids such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid and trifluoroacetic acid, and super acids such as trifluoromethanesulfonic acid and methanesulfonic acid. A strong acid may be mentioned. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is preferably 0.0001 mol to 0.1 mol with respect to the dihydroxybenzene to be used. More preferably, 0.001 to 0.05 mol is used. When the amount of the catalyst is less than 0.0001 mol, the process of performing intramolecular dehydration and ring closure at 120 to 180 ° C. tends to take a long time. In a system that dislikes ionic impurities, the catalyst removal process tends to be more complicated. For example, when formalin is used as the aldehyde, a reflux reaction is performed at around 100 ° C., this reaction is performed for 1 to 8 hours, and then an oxidizing atmosphere (for example, air stream) is taken while removing water from the system. In this case, by continuing this state for 2 to 24 hours after raising the temperature to 120 to 180 ° C., a phenol resin composition having an average hydroxyl value of 65 or more and 130 or less can be obtained.

  In this invention, in the range which does not impair the effect of this invention, it can use together with the hardening | curing agent generally used for the epoxy resin composition for sealing. Examples of curing agents that can be used in combination include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and formaldehyde. , Benzaldehyde, salicylaldehyde, and other compounds having an aldehyde group condensed or co-condensed in the presence of an acidic catalyst, synthesized by copolymerization from a novolac-type phenolic resin, phenols and / or naphthols, and cyclopentadiene. Examples include dicyclopentadiene type phenol resins such as pentadiene type phenol novolac resin and naphthol novolac resin, terpene modified phenol resin, and triphenolmethane type phenol resin. I can get lost.

  The equivalent ratio of (A) epoxy resin to (B) curing agent, that is, the ratio of the number of epoxy groups in the epoxy resin / the number of hydroxyl groups in the curing agent is not particularly limited, but to suppress each unreacted component to a small amount. Is preferably set in the range of 0.5 / 1 to 2/1, more preferably 0.6 / 1 to 1.5 / 1. In order to obtain an epoxy resin molding material having excellent moldability and reliability, it is more preferable to set the ratio in the range of 0.8 / 1 to 1.2 / 1.

(C) Inorganic filler In the present invention, in addition to increasing the heat dissipation of the package, it is necessary to add (C) an inorganic filler for hygroscopicity, reduction of linear expansion coefficient, improvement of strength, and the like. . Examples of inorganic fillers include silicas such as fused silica, crystalline silica, and synthetic silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, Examples include zirconia, zircon, fosterite, steatite, spinel, mullite, titania and the like. The shape of these inorganic fillers is not particularly limited, and may be any of powder, beads obtained by spheroidizing these, glass fiber, and the like. These inorganic fillers may be used alone or in combination of two or more.

  From the viewpoint of increasing the heat dissipation of the package, it is preferable that a part or all of the inorganic filler is at least one of crystalline silica, alumina, aluminum nitride, silicon nitride, and boron nitride. From the viewpoint of increasing the heat dissipation of the package, the average particle diameter of the inorganic filler is preferably 5 to 20 μm, the component (C1) having an average particle diameter of about 10 to 50 μm, and an average particle diameter of 0.5. It is more effective to use at least two components of the component (C2) having an average particle diameter of about 3 μm. From the viewpoint of fluidity, it is preferable that the inorganic filler has a spherical shape or a shape similar thereto. From the viewpoint of fluidity of the epoxy resin composition, a part of the inorganic filler is at least one of crystalline silica, spherical alumina, spherical aluminum nitride, spherical silicon nitride, and spherical boron nitride, and then spherical fused silica, spherical It is preferable to use synthetic silica or the like in combination. The crystalline silica in the present invention refers to silica having a crystallinity of 70% or more.

  From the viewpoint of fluidity and reliability of the epoxy resin composition, the blending amount of the (C) inorganic filler is preferably 60 to 97% by mass, and preferably 65 to 96% by mass of the entire epoxy resin composition. It is more preferable that the content be 70 to 95% by mass. (C) If the blending amount of the inorganic filler is less than 60% by mass, the moisture absorption characteristics and mechanical strength of the package may be insufficient. Conversely, if it exceeds 97% by mass, the flow characteristics will be insufficient. there is a possibility.

  From the viewpoint of the balance between the heat dissipation of the package and other reliability, (C) the total amount of the inorganic filler is within the above range, and crystalline silica, alumina, aluminum nitride, silicon nitride, boron nitride The blending amount of at least one is preferably 10 to 100% by mass of component (C), more preferably 20 to 100% by mass, and particularly preferably 30 to 100% by mass. If the blending amount of at least one of crystalline silica, alumina, aluminum nitride, silicon nitride, and boron nitride is less than 10%, there is a possibility that high heat dissipation of the package may be insufficient.

  In the present invention, in addition to the components (A) to (C), a curing accelerator usually used in an epoxy resin composition for sealing may be used without particular limitation for the purpose of improving productivity. it can. Examples of curing accelerators include, for example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutyl. Cycloamidine compounds such as amino-1,8-diaza-bicyclo (5,4,0) undecene-7 and these compounds, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone Quinone compounds such as diazophenylmethane, phenolic resins and other compounds having an intramolecular polarization formed by adding a compound having a π bond, such as benzyldimethylamine, trie Tertiary amine compounds such as noramine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole and their derivatives , Tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and other organic phosphines, and maleic anhydride, quinone compounds, diazophenylmethane, phenol Organic phosphorus compounds such as compounds with intramolecular polarization formed by adding compounds with π bonds such as resins, tetraphenylphosphonium tetraphenylborate, triphenylphosphine And tetraphenylboron salts such as tin tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, and derivatives thereof, and two or more of these may be used alone. May be used in combination. From the viewpoint of reliability and moldability, an organophosphorus compound is preferred.

  Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if the hardening acceleration effect is achieved, 0.1-10 mass% is preferable with respect to (A) epoxy resin, More preferably, 1 ˜5 mass%. When the blending amount of the curing accelerator is less than 0.1% by mass, the curability in a short time tends to be inferior. Tend to be difficult.

  The epoxy resin composition of the present invention includes epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane as necessary in order to enhance the adhesion between the resin component comprising the epoxy resin and the curing agent and the inorganic filler. Various known silane compounds such as vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. These may be used alone or in combination of two or more. The blending amount of the coupling agent is preferably 0.05 to 5% by mass and more preferably 0.1 to 2.5% by mass with respect to (B) the inorganic filler. If the blending amount of the inorganic filler is less than 0.05% by mass, the moisture resistance tends to decrease, and if it exceeds 5% by mass, the moldability of the package tends to decrease.

  In the present invention, in order to ensure smooth releasability from the mold when the epoxy resin composition is molded, higher fatty acid wax such as stearic acid and montanic acid, stearic acid ester, montanic acid ester and the like. Conventionally known release agents used for the epoxy resin composition for sealing, such as higher fatty acid ester wax and polyethylene wax, can be used.

  An anion exchanger can also be added to the epoxy resin composition of the present invention from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The anion exchanger is not particularly limited and conventionally known anion exchangers can be used. For example, hydrotalcite, hydrous oxide of an element selected from antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum These can be used, and these can be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, if necessary, halogen flame retardant such as brominated epoxy resin, antimony flame retardant such as antimony trioxide, antimony tetroxide, antimony pentoxide, phosphate ester, etc. Conventionally known flame retardants and the like can be added to the epoxy resin composition, such as phosphorous flame retardants, metal hydroxide flame retardants such as magnesium hydroxide and aluminum hydroxide.

  Further, the epoxy resin composition of the present invention includes colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, bengara, imidazole, triazole, tetrazole, and triazine within a range not impairing the effects of the present invention. And their derivatives, anthranilic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, and derivatives thereof, aliphatic acid amide compounds, dithiocarbamate, thiadiazole derivatives, silicone-based or non- A silicone-based low stress agent or the like can be blended as necessary.

  The epoxy resin composition of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed, but as a general method, raw materials of a predetermined blending amount are sufficiently mixed by a mixer or the like. Thereafter, a method of melting and kneading with a mixing roll, a kneader, an extruder or the like, followed by cooling and pulverization can be exemplified. It is easy to use if it is tableted with dimensions and mass that match the molding conditions.

  In addition, the epoxy resin composition of the present invention can be used as a liquid epoxy resin composition by dissolving in various organic solvents. The liquid epoxy resin composition is applied thinly on a plate or film, and the resin curing reaction is caused. It can also be used as a sheet-like or film-like epoxy resin composition obtained by volatilizing an organic solvent under conditions that do not progress so much.

  As an electronic component device obtained by sealing an element with the epoxy resin composition obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, a support member such as a semiconductor chip, a transistor An electronic component device in which an active element such as a diode or thyristor, a passive element such as a capacitor, a resistor, or a coil is mounted and a necessary portion is sealed with the epoxy resin composition of the present invention can be used. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, the terminal part of the element such as a bonding pad and the lead part are connected by wire bonding or bump, and then the epoxy resin composition of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outer Package), SOJ (Small Outer Jap) , TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. A semiconductor chip connected to a carrier by a bump is connected to a TCP (Tape Carrier Package) encapsulated with the epoxy resin composition of the present invention, a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering, or the like. COB (Chip On Board) module, hybrid IC, in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin composition of the present invention The device is mounted on the organic substrate on which the terminals for connecting the multichip module and the wiring board are formed, and after connecting the device and the wiring formed on the organic substrate by bump or wire bonding, the device is connected with the epoxy resin composition of the present invention. Sealed BGA (Ball Gri Array), CSP (Chip Size Package) and the like. The epoxy resin composition of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin composition of the present invention, a low-pressure transfer molding method is most common, but an injection molding method, a compression molding method, or the like may be used. When the epoxy resin composition is liquid or paste at normal temperature, a dispensing method, a casting method, a printing method, and the like can be given. Also, not only a general sealing method for directly sealing an element with a resin, but also a hollow package system in which an epoxy resin composition for sealing an electronic component is not in direct contact with the element, sealing for a hollow package It can be suitably used as an epoxy resin composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited by a following example.

(Examples 1-10, Comparative Examples 1-9)
Hereinafter, various raw materials used in each example and each comparative example are shown.

(A) Epoxy resin Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 192 and a melting point of 105 ° C. (trade name “Epicoat YX4000H” manufactured by Japan Epoxy Resin Co., Ltd.).

  Comparative epoxy resin 1: bisphenol F type epoxy resin having an epoxy equivalent of 195 and a melting point of 70 ° C. (trade name “YSLV-80XY” manufactured by Toto Kasei Co., Ltd.).

  Comparative epoxy resin 2: Sulfur-containing epoxy resin having an epoxy equivalent of 245 and a melting point of 115 ° C. (trade name “YSLV-120TE” manufactured by Toto Kasei Co., Ltd.).

(B) Curing agent Curing agent 1: a mixture of the above general formulas (IIa) and (IIb), wherein Ar is the general formula (IIIa) and R ₁₁ = hydroxyl group and R ₁₂ = R ₁₃ = hydrogen 1,2 -Compound containing a curing agent (hydroxyl equivalent 112, softening point 85 ° C, number average molecular weight 400, mass average molecular weight 550) which is dihydroxybenzene (catechol) Curing agent 2: a mixture of the above general formulas (IIa) to (IId) A curing agent (hydroxyl group), wherein Ar is 1,2-dihydroxybenzene (catechol) or 1,3-dihydroxybenzene (resorcinol) wherein R ₁₁ = hydroxyl group and R ₁₂ = R ₁₃ = hydrogen in the general formula (IIIa) Equivalent 108, softening point 72 ° C., number average molecular weight 540, mass average molecular weight 1,000) Comparative curing agent 1: softening point 85 ° C., hydroxyl group equivalent of 105 Phenol novolac resin (Maywa Kasei Co., Ltd., trade name “H-100”).

  Comparative curing agent 2: A naphthol novolak resin having a softening point of 85 ° C. and a hydroxyl group equivalent of 180 (trade name “SN-170L” manufactured by Tohto Kasei Co., Ltd.).

Comparative curing agent 3: catechol novolak resin (hydroxyl equivalent 70, softening point 135 ° C.)
Comparative curing agent 4: resorcinol novolak resin (hydroxyl equivalent 72, softening point 126 ° C.)
(C) Inorganic filler C1 component: spherical alumina having an average particle size of 40 μm (trade name “DAW-45” manufactured by Denki Kagaku Kogyo Co., Ltd.).

  C2 component: spherical alumina having an average particle diameter of 5 μm (trade name “DAW-05” manufactured by Denki Kagaku Kogyo Co., Ltd.).

  C3 component: spherical alumina having an average particle size of 0.4 μm (trade name “AO-502” manufactured by Admatechs Co., Ltd.).

  C4 component: spherical aluminum nitride having an average particle size of 1.8 μm (manufactured by Tokuyama Corporation).

C5 component: crystalline silica having an average particle size of 15 μm (trade name “EC-15N” manufactured by Tokai Mineral Co., Ltd.).

C6 component: fused spherical silica having an average particle diameter of 12 μm and a specific surface area of 5.0 m ² / g (trade name “FB-105” manufactured by Denki Kagaku Kogyo Co., Ltd.).

C7 component: Synthetic spherical silica having an average particle size of 0.5 μm and a specific surface area of 6.5 m ² / g (manufactured by Admatechs Co., Ltd., trade name “SO-25R”).

(Other additives)
Curing accelerator: an adduct of triphenylphosphine and benzoquinone.

  Release agent: oxidized polyethylene.

  Coupling agent: γ-glycidoxypropyltrimethoxysilane (epoxysilane).

  Colorant: Carbon black.

  Flame retardant: Brominated epoxy resin, antimony trioxide.

  The curing agent 1 and the curing agent 2 were synthesized by the following methods, respectively.

(Curing agent 1)
Catechol 220g, 37% formalin 81.1g, oxalic acid 2.5g, and water 100g were placed in a 2L separable flask equipped with a stirrer, cooler and thermometer. The temperature was raised to 100 ° C while heating in an oil bath. Warm up. The mixture was refluxed at around 104 ° C., and the reaction was continued at the reflux temperature for 3 hours. Thereafter, the temperature in the flask was raised to 150 ° C. while distilling off water. The reaction was continued for 12 hours while maintaining 150 ° C. After the reaction, concentration was performed under reduced pressure for 20 minutes to remove water in the system and obtain the desired resin. The change in weight average molecular weight during synthesis is shown in FIG. 1, and the change in monomer (dimer, trimer) and other (tetramer or higher) content (number of molecular nuclei) is shown in FIG. It was. The GPC chart of the obtained phenol resin is shown in FIG.

  Note that the change in content shown in FIG. 2 was obtained by taking out the product at regular intervals, performing gel filtration, and obtaining from the chart as shown in FIG. 3, and the monomer, dimer, trimer and tetramer. The above shows that the last peak of the GPC chart shown in FIG. 3 is a monomer, the second peak from the last is a dimer, the third peak from the last is a trimer, and the previous peak is a tetramer or higher. The content rate is obtained from the area. Therefore, even if it says a dimer and a trimer, it is not necessarily the same component, but is considered to be a phenol resin mixture.

  As the reaction progresses, the weight average molecular weight decreases as shown in FIG. 1, the stable dimer and trimer form as shown in FIG. 2, and the hydroxyl equivalent of the theoretical value (around 60). It is considered that a phenol resin having the structure of the general formula (IIa) and the formula (IIb) was obtained from the point of use of catechol and the like. A compound having the structure of the general formula (IIa) can be obtained, and a compound having the structure of the general formula (IIb) can be obtained by further dehydration reaction.

(Curing agent 2)
462 g of resorcinol, 198 g of catechol, 316.2 g of 37% formalin, 15 g of oxalic acid and 300 g of water are placed in a 3 L separable flask equipped with a stirrer, a cooler and a thermometer, and heated to 100 ° C. while heating in an oil bath. Warm up. The mixture was refluxed at around 104 ° C., and the reaction was continued at the reflux temperature for 4 hours. Thereafter, the temperature in the flask was raised to 170 ° C. while distilling off water. The reaction was continued for 8 hours while maintaining 170 ° C. After the reaction, concentration was performed under reduced pressure for 20 minutes to remove water in the system and obtain the desired resin.

  The above-mentioned various raw materials are blended in parts by mass shown in Table 1 and Table 2 below, and roll kneading is performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Examples 1 to 10 and Comparative Examples 1 to 9 The corresponding epoxy resin composition was prepared. The comparative curing agent 3 and the comparative curing agent 4 had a high softening point, and it was predicted that it would be difficult to produce a material by roll kneading. Therefore, the total amount was preliminarily mixed with the total amount of the epoxy resin as the component (A). Used above. The preliminary mixing was performed by stirring and mixing in a flask at 150 ° C./30 minutes.

  FIG. 4 shows the change in weight average molecular weight during synthesis, and FIG. 5 shows the change in the content of monomer, dimer, trimer and tetramer or higher. A GPC chart of the obtained phenol resin is shown in FIG.

  Since catechol and resorcinol are used, it is thought that the phenol resin which has a structure of general formula (IIa)-(IId) was obtained. A compound having the structure of the general formula (IIa) is formed, and further, a compound having the structure of the general formulas (IIb) to (IId) is obtained by dehydration reaction.

  In addition, the measurement of the said hardening | curing agent was performed as follows. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using a high performance liquid chromatography L6000 manufactured by Hitachi, Ltd. and a data analyzer C-R4A manufactured by Shimadzu. G2000HXL and G3000HXL manufactured by Tosoh Corporation were used as analytical GPC columns. The sample concentration was 0.2%, the mobile phase was tetrahydrofuran, and the measurement was performed at a flow rate of 1.0 ml / min. A calibration curve was prepared using a polystyrene standard sample, and the number average molecular weight and the like were calculated using the polystyrene conversion value.

The hydroxyl equivalent was measured by acetyl chloride-potassium hydroxide titration method. The titration end point was determined by potentiometric titration instead of coloration with an indicator because the solution color was dark. Specifically, the hydroxyl group of the measurement resin is acetylated in a pyridine solution, the excess reagent is decomposed with water, and the resulting acetic acid is titrated with a potassium hydroxide / methanol solution.

  The produced epoxy resin compositions of Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Tables 3 and 4.

  The epoxy resin composition was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, unless otherwise specified. Further, post-curing was performed at 175 ° C. for 6 hours.

(1) Spiral flow (fluidity index)
An epoxy resin molding material was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was determined.

(2) Heat hardness (curability index)
An epoxy resin composition is molded into a disk 30 mm in diameter and 4 mm in thickness under the above conditions using a Mitsumi Metal Co., Ltd. Bali mold having a central portion of 30 mm in diameter and 4 mm in depth. Immediately after that (5 seconds after the lower mold of the transfer press began to open, the mold was taken out and immediately thereafter), the Shore D hardness of the molded product (the cull portion at the center of the mold) was measured.

(3) Flexural modulus (at room temperature) (index of flexural properties)
Using a test piece obtained by molding and post-curing the epoxy resin composition under the above conditions, the measurement was performed in accordance with JIS K 7171 (3-point bending test). The test piece size was 127 mm × 12.7 mm × 4.0 mmt, and the flexural modulus was obtained from the measured average value at N = 4.

(4) Thermal conductivity (index of heat dissipation)
An epoxy resin composition is molded under the above conditions to prepare a 50 mm × 100 mm × 15 mmt test piece, and after post-curing, the thermal conductivity is measured using a QTM-500 (device name) manufactured by Kyoto Electronics Industry Co., Ltd. It was.

  Comparative Examples 6 to 9 that do not contain the component (A) of the present invention or Comparative Examples 1 to 5 that do not contain the component (B) are either heat dissipation, fluidity, curability, or mechanical properties (bending properties), Or inferior to multiple items. On the other hand, Examples 1 to 10 including both the component (A) and the component (B) of the present invention are excellent in mechanical properties such as heat dissipation and bending properties, and also in moldability such as fluidity and curability. It turns out that it is excellent.

FIG. 1 is a graph showing changes in the weight average molecular weight of the phenol resin in the reaction of the curing agent 1. FIG. 2 is a graph showing changes in the number of nuclei (content) of phenol resin molecules in the curing agent 1. FIG. 3 is a GPC chart graph of the phenol resin obtained with the curing agent 1. FIG. 4 is a graph showing a change in the weight average molecular weight of the phenol resin in the reaction of the curing agent 2. FIG. 5 is a graph showing changes in the number of nuclei (content) of phenol resin molecules in the curing agent 2. FIG. 6 is a GPC chart graph of the phenol resin obtained with the curing agent 2.

Claims (4)

(A) An epoxy resin having a structure represented by the following general formula (I), (B) a curing agent having any one of the structures represented by the following general formulas (IIa) to (IId), and (C) inorganic filling An epoxy resin composition containing an agent.

(R _{1 to} R ₈ are independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and may be the same as or different from each other. .)

(In the general formulas (IIa) to (IId), m and n represent a positive number, and Ar represents one of the following general formulas (IIIa) or (IIIb).)

(R ₁₁ and R ₁₄ in the general formulas (IIIa) and (IIIb) are each independently selected from a hydrogen atom or a hydroxyl group, and R ₁₂ and R ₁₃ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. (The binding sites in general formulas (IIIa) and (IIIb) are not limited.) (A) An epoxy resin having a structure represented by the following general formula (I), (B ′) a phenol resin obtained by a reaction between hydroxybenzenes and aldehydes and having an average hydroxyl value of 65 or more and 130 or less An epoxy resin composition comprising a composition, (C) an inorganic filler.

(R _{1 to} R ₈ are independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and may be the same as or different from each other. .)   The epoxy resin composition according to claim 1 or 2, wherein the (C) inorganic filler contains at least one selected from crystalline silica, alumina, aluminum nitride, silicon nitride, and boron nitride.   The electronic component apparatus provided with the element sealed with the epoxy resin composition in any one of Claims 1-3.

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