JP5169288B2 - Epoxy resin composition for semiconductor encapsulation and semiconductor device - Google Patents

Description

  The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device.

  In recent years, as electronic components such as integrated circuits (ICs), large scale integrated circuits (LSIs), and very large scale integrated circuits (VLSIs) and semiconductor devices have been increased in density and integration, their mounting methods have been changed from insertion mounting. It is changing to surface mounting. Along with this, there is a demand for a multi-pin lead frame and a narrow lead pitch. Surface mount type QFP (Quad Flat Package), which is small, light, and compatible with multi-pin use, is used in various semiconductor devices. It has been. And since the semiconductor device is excellent in the balance of productivity, cost, reliability and the like, it is mainly sealed with an epoxy resin composition.

These epoxy resin compositions for encapsulating semiconductors are required to have flame retardancy. For this reason, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, and the like as flame retardancy imparting components apart from the main components. The brominated epoxy resin and antimony oxide were combined in combination.
However, in recent years, there has been an increasing trend to regulate the use of halogen-containing compounds that are likely to generate dioxin-like compounds and highly toxic antimony compounds from the viewpoint of environmental protection. For this reason, regarding the composition for semiconductor sealing, the technique which achieves a flame retardance, without using halogen compounds and antimony oxides including the above-mentioned brominated epoxy resin came to be examined. In addition, when a semiconductor device is stored at a high temperature of 150 to 200 ° C. for a long time, it is known that a brominated epoxy resin or an antimony compound that is a flame retardant causes an increase in the resistance value of the semiconductor element or a breakage of the gold wire. Also from this viewpoint, development of an epoxy resin composition for semiconductor encapsulation which is excellent in high-temperature storage characteristics without using brominated epoxy resin or antimony compound is required. Under these circumstances, flame retardants of metal oxides such as aluminum hydroxide and magnesium hydroxide, which are used as brominated epoxy resins and antimony compounds, have been used. There existed the subject of the fall of the continuous moldability by deterioration and the fall of solder resistance.

  From the above situation, an epoxy resin composition using an epoxy resin having a biphenylaralkyl skeleton has been proposed as a semiconductor epoxy resin composition that can obtain good flame retardancy without adding a flame retardant imparting agent. (For example, refer to Patent Documents 1 and 2.) Although these epoxy resin compositions have a low water absorption, a low elastic modulus during heat, a high adhesiveness, and excellent flame retardancy, a highly reliable semiconductor device can be obtained. There was the difficulty that it cost.

JP 2004-203911 A Japanese Patent Application Laid-Open No. 2004-155841

  The present invention relates to an epoxy resin composition for semiconductor encapsulation, which does not use a brominated epoxy resin and an antimony compound, has excellent flame resistance at low cost, and has good fluidity, continuous moldability, and solder resistance, and its A semiconductor device in which a semiconductor element is sealed with a cured product is provided.

The epoxy resin composition for semiconductor encapsulation of the present invention comprises (A) an epoxy resin having a structure represented by the following general formula (1), (B) a compound containing two or more phenolic hydroxyl groups, and (C) It contains an inorganic filler, (D) a curing accelerator, and (E) a tolylene diisocyanate-modified oxidized wax.

(In the above general formula (1), Ar is an aromatic group having 6 to 20 carbon atoms, and may be the same or different from each other. R1 is a hydrocarbon group having 1 to 6 carbon atoms. And R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, R3 is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or An aromatic group having 6 to 20 carbon atoms, which may be the same or different from each other, a is an integer of 0 to 10, b is an integer of 1 to 3, m and n are molar ratios; (0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / n is 1/10 to 1/1).

  In the epoxy resin composition for semiconductor encapsulation of the present invention, the epoxy resin having the structure represented by the general formula (1) is a phenolic hydroxyl group-containing aromatic, an aldehyde, the following general formula (2) The epoxy resin obtained by co-condensing the compound (J) represented by glycidyl ether with epichlorohydrin can be used.

(However, in the said General formula (2), Ar is a C6-C20 aromatic group, R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 Is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, a is an integer of 0 to 10, and b is an integer of 1 to 3).

  In the epoxy resin composition for semiconductor encapsulation of the present invention, the epoxy resin having the structure represented by the general formula (1) is an epoxy resin having a structure represented by the following general formula (3). Can be.

(However, in the said General formula (3), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group, W1 is an oxygen atom or a sulfur atom, c is an integer of 0 to 5, d is an integer of 0 to 3, m and n represent a molar ratio, and 0 ≦ m <1, 0 <n ≦ 1 M + n = 1 and m / n is 1/10 to 1/1.)
In the epoxy resin composition for semiconductor encapsulation of the present invention, the epoxy resin having a structure represented by the general formula (3) is an epoxy resin having a structure represented by the following general formula (4). be able to.

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. C is an integer of 0 to 5 and d is an integer of 0 to 3. m and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / N is 1/10 to 1/1.)

In the epoxy resin composition for semiconductor encapsulation of the present invention, the dropping point of the tolylene diisocyanate-modified oxidized wax may be 70 ° C. or higher and 120 ° C. or lower.
In the epoxy resin composition for semiconductor encapsulation of the present invention, the acid value of the tolylene diisocyanate-modified oxidized wax may be 10 mgKOH / g or more and 50 mgKOH / g or less.
In the epoxy resin composition for semiconductor encapsulation of the present invention, the curing accelerator (D) is a compound represented by the following general formula (5), a compound represented by the following general formula (6), the following general formula ( 7) and at least one selected from the compound represented by the following general formula (8).

(In the general formula (5), P represents a phosphorus atom and Si represents a silicon atom. R4, R5, R6 and R7 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Wherein X1 is an organic group bonded to the groups Y1 and Y2, and X2 is an organic group bonded to the groups Y3 and Y4. Y2 represents a group formed by releasing a proton from a proton donating group, and groups Y1 and Y2 in the same molecule are combined with a silicon atom to form a chelate structure.Y3 and Y4 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y3 and Y4 in the same molecule are bonded to a silicon atom to form a chelate structure.X1 and X2 may be the same or different from each other, Y1, Y2, Y And Y4 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

(However, in the said General formula (6), P represents a phosphorus atom. R8, R9, R10, and R11 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

(However, in the said General formula (7), X3 represents a C1-C3 alkyl group, Y5 represents a hydroxyl group. E is an integer of 0-5, f is an integer of 0-3.)

(However, in the said General formula (8), P represents a phosphorus atom. R12, R13, and R14 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R15, R16 and R17 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R15 and R16 are bonded to form a cyclic structure. May be.)

The epoxy resin composition for semiconductor encapsulation according to the present invention may include a compound in which the compound (B) containing two or more phenolic hydroxyl groups is represented by the following general formula (9).
(However, in the said General formula (9), R18 represents a C1-C4 hydrocarbon group, and they may mutually be same or different. G is an integer of 0-3. H The average value of is a positive number of 0 or 8 or less.)

The epoxy resin composition for semiconductor encapsulation of this invention can contain the said inorganic filler (C) 80 to 92 weight% of the whole said resin composition.
The epoxy resin composition for semiconductor encapsulation of the present invention further comprises (F) a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and / or a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and an epoxy. It may contain a reaction product (F2) with a resin.
The epoxy resin composition for semiconductor encapsulation of the present invention further comprises (G) an organopolysiloxane (G1) having a carboxyl group and / or a reaction product of an organopolysiloxane (G1) having a carboxyl group and an epoxy resin. (G2) may be included.
The semiconductor device of the present invention is characterized in that a semiconductor element is sealed with a cured product of the above-described epoxy resin composition for semiconductor sealing.

  According to the present invention, a brominated epoxy resin and an antimony compound are not used, and the epoxy resin composition for semiconductor encapsulation has excellent flame resistance, low fluidity, good fluidity, continuous moldability, and solder resistance, and low cost. A semiconductor device can be obtained.

The present invention includes (A) an epoxy resin having a structure represented by the general formula (1), (B) a compound containing two or more phenolic hydroxyl groups, (C) an inorganic filler, and (D) curing acceleration. By including an agent and (E) tolylene diisocyanate-modified oxide wax, it is possible to obtain an epoxy resin composition that is excellent in flame resistance, fluidity, continuous moldability, and solder resistance while being low in cost. .
Hereinafter, each component will be described in detail.

  In the present invention, an epoxy resin (A) having a structure represented by the following general formula (1) is used as the epoxy resin. The epoxy resin (A) has many aromatic ring carbons in the molecule, and a cured product of an epoxy resin composition using the epoxy resin is characterized by excellent flame resistance and low water absorption. The ratio m / n between m and n in the epoxy resin (A) having the structure represented by the following general formula (1) is preferably 1/10 to 1/1, and 1/9 to More preferably, it is 1/2. When m / n is within the above range, an effect of improving flame resistance can be obtained. Moreover, if it is in the said range, there is little possibility of causing the fall of the fluidity | liquidity of the resin composition by resin viscosity becoming high.

(In the above general formula (1), Ar is an aromatic group having 6 to 20 carbon atoms, and may be the same or different from each other. R1 is a hydrocarbon group having 1 to 6 carbon atoms. And R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, R3 is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or An aromatic group having 6 to 20 carbon atoms, which may be the same or different from each other, a is an integer of 0 to 10, b is an integer of 1 to 3, m and n are molar ratios; (0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / n is 1/10 to 1/1).

  Although it does not specifically limit as an epoxy resin (A) which has a structure represented by General formula (1) used by this invention, For example, the epoxy resin which has a structure represented by following General formula (4) An epoxy resin having a structure represented by the following general formula (10), an epoxy resin having a structure represented by the following general formula (11), an epoxy resin having a structure represented by the following general formula (12), etc. Can be mentioned. From the viewpoint of flame resistance, an epoxy resin having a structure represented by the following general formula (4) and an epoxy resin having a structure represented by the following general formula (11) are more preferable.

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. C is an integer of 0 to 5 and d is an integer of 0 to 3. m and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / N is 1/10 to 1/1.)

(However, in the said General formula (10), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. D is an integer of 0 to 3. m and n are molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / n is 1/10 to 1/1. .)

(However, in the said General formula (11), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. C is an integer of 0 to 5 and d is an integer of 0 to 3. m and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / N is 1/10 to 1/1.)

(However, in the said General formula (12), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. D is an integer of 0 to 3. m and n are molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / n is 1/10 to 1/1. .)

  The epoxy resin (A) having a structure represented by the general formula (1) used in the present invention comprises a phenolic hydroxyl group-containing aromatic, an aldehyde, and a compound (J) represented by the following general formula (2). The phenol resins obtained by co-condensation can be obtained by glycidyl etherification with epichlorohydrin. Compound (J) represented by the following general formula (2) has an aromatic ring to which a glycidyl ether group is not bonded, W1R2 (W1 is an oxygen atom or a sulfur atom, and R2 is a hydrocarbon group having 1 to 4 carbon atoms. ) Are connected to each other. Since W1R2 is bonded, the compound (J) represented by the following general formula (2) has polarity, and this improves the reactivity. Therefore, a novolak comprising a phenolic hydroxyl group-containing aromatic or aldehyde The structure of the compound (J) can be introduced into the resin structure. The epoxy resin (A) has the advantage that the raw material cost is lower than that of the phenol aralkyl type epoxy resin having a biphenylene skeleton having excellent flame resistance and low water absorption, and the raw material is easily available. It can be manufactured or obtained.

(However, in the said General formula (2), Ar is a C6-C20 aromatic group, R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 Is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, a is an integer of 0 to 10, and b is an integer of 1 to 3).

Although it does not specifically limit as phenolic hydroxyl group containing aromatics used for manufacture of an epoxy resin (A), For example, phenol, catechol, resorcinol, hydroquinone, o-cresol, p-cresol, m-cresol , Phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, t-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, nonylphenol, mesitol, 2,3,5-trimethylphenol, Examples include phenols such as 2,3,6-trimethylphenol, and naphthols such as 1-naphthol, 2-naphthol, and methylnaphthol. Among these, phenol, o-cresol, 1-naphthol and 2-naphthol are preferable, and o-cresol is more preferable. These may be used alone or in combination of two or more.

  Although it does not specifically limit as aldehydes used for manufacture of an epoxy resin (A), For example, aliphatic aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4- Aromatic aldehydes such as dimethylbenzaldehyde, 4-biphenylaldehyde, naphthylaldehyde, salicylaldehyde and the like can be mentioned. Among these, formaldehyde, benzaldehyde, and naphthylaldehyde are preferable, and formaldehyde is more preferable. These may be used alone or in combination of two or more.

  The compound (J) represented by the general formula (2) used for the production of the epoxy resin (A) is not particularly limited as long as it is a structure of the general formula (2). For example, methoxybenzene, Ethoxybenzene, methylphenyl sulfide, ethylphenyl sulfide, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy-2-methylnaphthalene, 1,3,5-trimethyl-2-methoxy Naphthalene, 1-ethoxynaphthalene, 2-ethoxynaphthalene, 1-t-butoxynaphthalene, methyl naphthyl sulfide, ethyl naphthyl sulfide, 1,4-dimethoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1- And methoxyanthracene. Among these, considering flame resistance and low water absorption, a compound represented by the following formula (13) is preferable, and a methoxynaphthalene compound represented by the following formula (14) is more preferable.

(However, in the said General formula (13), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group, W1 is an oxygen atom or a sulfur atom, and c is an integer of 0 to 5.)

(However, in the said General formula (14), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. C is an integer of 0-5.)

  The method for synthesizing the phenol resin that is a precursor of the epoxy resin (A) used in the present invention is not particularly limited. For example, the phenolic hydroxyl group-containing aromatics and aldehydes are represented by the general formula (2). The method of co-condensing a compound (J) using an acidic catalyst in coexistence is mentioned.

  The method for synthesizing the epoxy resin (A) having the structure represented by the general formula (1) used in the present invention is not particularly limited. For example, phenol resins that are precursors of the epoxy resin (A) are excessively added. Examples thereof include a method of reacting at 50 to 150 ° C., preferably 60 to 120 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide after being dissolved in epichlorohydrin. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is removed by distilling off the solvent. Resin (A) can be obtained.

  In this invention, another epoxy resin can be used together in the range by which the effect by using the epoxy resin (A) which has a structure represented by General formula (1) is not impaired. Examples of epoxy resins that can be used in combination include biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenolmethane type epoxy resins, and phenol aralkyl type epoxy resins having a phenylene skeleton. Examples thereof include a resin, a phenol aralkyl type epoxy resin having a biphenylene skeleton, a naphthol type epoxy resin, an alkyl-modified triphenol methane type epoxy resin, a triazine nucleus-containing epoxy resin, and a dicyclopentadiene-modified phenol type epoxy resin. In consideration of moisture resistance reliability as an epoxy resin composition for semiconductor encapsulation, it is preferable that Na ions and Cl ions, which are ionic impurities, be as small as possible. From the viewpoint of curability, the epoxy equivalent is 100 g / eq or more and 500 g / eq. The following is preferred.

  The blending ratio of the epoxy resin (A) having the structure represented by the general formula (1) when other epoxy resins are used in combination is preferably 10% by weight or more, more preferably based on the total epoxy resin. Is 30% by weight or more, particularly preferably 50% by weight or more. The effect which improves a flame resistance, a low water absorption, etc. can be acquired as a compounding ratio exists in the said range.

  In the present invention, a compound (B) containing two or more phenolic hydroxyl groups is used as a curing agent from the viewpoints of flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like. The compound (B) containing two or more phenolic hydroxyl groups is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, phenylene and / or biphenylene skeleton A naphthol aralkyl resin, a bisphenol compound, etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together. Of these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  Moreover, in the compound (B) containing two or more phenolic hydroxyl groups, a compound represented by the following general formula (9) is preferable. Since the compound represented by the following general formula (9) has a large number of phenolic hydroxyl groups, the reactivity of the epoxy resin composition using the same is high, the moldability is excellent, the productivity can be improved, and Very low cost. In addition, the cured product has a high crosslinking density and Tg. Examples of the phenol resin represented by the following general formula (9) include a phenol novolac resin and a cresol novolac resin, but are not particularly limited as long as the structure is the following general formula (9).

(However, in the said General formula (9), R18 represents a C1-C4 hydrocarbon group, and they may mutually be same or different. G is an integer of 0-3. H The average value of is a positive number of 0 or 8 or less.)

  In the present invention, the compounding ratio of the compound represented by the general formula (9) is not particularly limited, but is preferably 10% with respect to the total amount of the compound (B) containing two or more phenolic hydroxyl groups. % Or more, more preferably 30% by weight or more, particularly preferably 50% by weight or more. When the compounding ratio of the compound represented by the general formula (9) is within the above range, good reactivity and productivity can be obtained.

  As the inorganic filler (C) used in the present invention, those generally used for semiconductor sealing resin compositions can be used, for example, fused silica, spherical silica, crystalline silica, alumina, silicon nitride, Examples thereof include aluminum nitride. The particle size of the inorganic filler (C) is preferably 0.01 μm or more and 150 μm or less in consideration of the filling property to the mold. Further, the content of the inorganic filler (C) is preferably 80% by weight or more and 92% by weight or less, more preferably 82% by weight or more and 91% by weight or less, and particularly preferably 84% by weight of the entire epoxy resin composition. % To 90% by weight. When the content of the inorganic filler (C) is within the above range, the amount of moisture absorption of the cured product of the epoxy resin composition increases, and there is little possibility of causing a decrease in solder crack resistance due to a decrease in strength. Further, when the content of the inorganic filler (C) is within the above range, there is little possibility of causing defects on the molding surface due to the loss of fluidity.

  The curing accelerator (D) used in the present invention is not limited as long as it accelerates the reaction between the epoxy group of the epoxy resin and the phenolic hydroxyl group of the compound containing two or more phenolic hydroxyl groups. What is used for the resin composition can be utilized. Specific examples include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphorus atom-containing compounds such as adducts of phosphine compounds and quinone compounds, 1,8-diazabicyclo (5,4,0) undecene-7, benzyl Nitrogen atom-containing compounds such as dimethylamine and 2-methylimidazole are mentioned. Among these, a phosphorus atom-containing compound is preferable, and a tetra-substituted phosphonium compound is particularly preferable in consideration of fluidity, and a phosphobetaine compound and a phosphine compound in consideration of a low elastic modulus when cured of an epoxy resin composition. An adduct of quinone compound and a quinone compound is preferable, and an adduct of a phosphonium compound and a silane compound is preferable in consideration of latent curing property.

  Examples of the organic phosphine that can be used in the present invention include a first phosphine such as ethylphosphine and phenylphosphine, a second phosphine such as dimethylphosphine and diphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine. Tertiary phosphine.

Examples of the adduct of a phosphonium compound and a silane compound that can be used in the present invention include compounds represented by the following general formula (5).
(In the general formula (5), P represents a phosphorus atom and Si represents a silicon atom. R4, R5, R6 and R7 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Wherein X1 is an organic group bonded to the groups Y1 and Y2, and X2 is an organic group bonded to the groups Y3 and Y4. Y2 represents a group formed by releasing a proton from a proton donating group, and groups Y1 and Y2 in the same molecule are combined with a silicon atom to form a chelate structure.Y3 and Y4 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y3 and Y4 in the same molecule are bonded to a silicon atom to form a chelate structure.X1 and X2 may be the same or different from each other, Y1, Y2, Y And Y4 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

  In the general formula (5), as R4, R5, R6 and R7, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like. A substituted aromatic group is more preferred.

  Moreover, in General formula (5), X1 is an organic group couple | bonded with group Y1 and Y2. Similarly, X2 is an organic group bonded to the groups Y3 and Y4. Y1 and Y2 are groups formed by proton-donating groups releasing protons, and groups Y1 and Y2 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y3 and Y4 are groups formed by proton-donating groups releasing protons, and groups Y3 and Y4 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X1 and X2 may be the same or different from each other, and the groups Y1, Y2, Y3, and Y4 may be the same or different from each other. The groups represented by -Y1-X1-Y2- and -Y3-X2-Y4- in general formula (5) are formed by releasing two protons from a bivalent or higher proton donor. Examples of divalent or higher proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1 ′. -Bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2- Propanediol, glycerin, etc. are mentioned, among these, catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene It is more preferable.

Z1 in the general formula (5) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions of aliphatic hydrocarbon groups such as octyl and octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a bivalent or higher proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved. Then, a sodium methoxide-methanol solution is added dropwise with stirring at room temperature. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

  Examples of the tetra-substituted phosphonium compound that can be used in the present invention include compounds represented by the following general formula (6).

(However, in the said General formula (6), P represents a phosphorus atom. R8, R9, R10, and R11 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

  Although the compound represented by General formula (6) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (6) can be precipitated. In the compound represented by the general formula (6), R8, R9, R10 and R11 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the phenol.

Examples of phosphobetaine compounds that can be used in the present invention include compounds represented by the following general formula (7).
(However, in the said General formula (7), X3 represents a C1-C3 alkyl group, Y5 represents a hydroxyl group. E is an integer of 0-5, f is an integer of 0-3.)

  The compound represented by the general formula (7) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

Examples of the adduct of a phosphine compound and a quinone compound that can be used in the present invention include compounds represented by the following general formula (8).
(However, in the said General formula (8), P represents a phosphorus atom. R12, R13, and R14 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R15, R16 and R17 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R15 and R16 are bonded to form a cyclic structure. May be.)

  The phosphine compound used as an adduct of a phosphine compound and a quinone compound has no substitution on aromatic rings such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris (benzyl) phosphine, etc. Or what has substituents, such as an alkyl group and an alkoxyl group, is preferable, and what has 1-6 carbon atoms is mentioned as an organic group of an alkyl group and an alkoxyl group. From the viewpoint of availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

  In the compound represented by the general formula (8), R12, R13 and R14 bonded to the phosphorus atom are phenyl groups, and R15, R16 and R17 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferable in that it reduces the elastic modulus of the cured epoxy resin composition when heated.

  As for the compounding quantity of the hardening accelerator (D) used for this invention, 0.1 to 1 weight% is preferable in all the epoxy resin compositions. There is little possibility of causing curability fall that the compounding quantity of a hardening accelerator (D) exists in the said range. Moreover, there is little possibility of causing a fluid fall as the compounding quantity of a hardening accelerator (D) exists in the said range.

  In the present invention, tolylene diisocyanate-modified oxidized wax (E) is used as a release agent. The tolylene diisocyanate-modified oxidized wax (E) used in the present invention is obtained by modifying an oxidized wax with tolylene diisocyanate, and has excellent releasability. The tolylene diisocyanate modified oxidized wax (E) used in the present invention is not particularly limited, and examples thereof include tolylene diisocyanate modified oxidized polypropylene wax, tolylene diisocyanate modified oxidized polyethylene wax, tolylene diisocyanate modified oxidized paraffin wax. Is mentioned. Among these, tolylene diisocyanate-modified polyethylene oxide wax is more preferable from the viewpoints of releasability and appearance of the cured resin. These tolylene diisocyanate-modified oxidized waxes may be used alone or in combination of two or more.

  The dropping point of the tolylene diisocyanate-modified oxidized wax (E) used in the present invention is preferably 70 ° C. or higher and 120 ° C. or lower, more preferably 80 ° C. or higher and 110 ° C. or lower. The dropping point can be measured by a method based on ASTM D127. Specifically, using a metal nipple, it is measured as the temperature at which molten wax first drops from the metal nipple. In the following examples, it can be measured by the same method. When the dropping point of tolylene diisocyanate-modified oxidized wax (E) is within the above range, tolylene diisocyanate-modified oxidized wax (E) has excellent thermal stability, and tolylene diisocyanate-modified oxidized wax (E) is seized during continuous molding. Hateful. Therefore, it is excellent in the mold release property of the resin cured material from a metal mold | die, and is excellent in continuous moldability. Furthermore, when it is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is sufficiently melted when the resin composition is cured. Thereby, the tolylene diisocyanate-modified oxidized wax (E) is dispersed substantially uniformly in the cured resin. Therefore, segregation of the tolylene diisocyanate-modified oxidized wax (E) on the surface of the cured resin can be suppressed, and deterioration of mold stains and appearance of the cured resin can be reduced.

  The acid value of the tolylene diisocyanate-modified oxidized wax (E) used in the present invention is preferably 10 mgKOH / g or more and 50 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less. The acid value affects the compatibility with the cured resin. The acid value can be measured by a method based on JIS K 3504. Specifically, it is measured as the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of waxes. In the following examples, it can be measured by the same method. When the oxidation value is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the phase separation of tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix does not occur. Therefore, segregation of the tolylene diisocyanate-modified oxidized wax (E) on the surface of the cured resin product is suppressed, and deterioration of mold stains and appearance of the cured resin product can be reduced. Furthermore, since the tolylene diisocyanate-modified oxidized wax (E) is present on the surface of the cured resin, the mold release property of the cured resin from the mold is excellent. On the other hand, if the compatibility between the tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix is too high, the tolylene diisocyanate-modified oxidized wax (E) cannot ooze out on the surface of the cured resin, and sufficient release May not be able to secure the sex.

The number average molecular weight of the tolylene diisocyanate-modified oxidized wax (E) used in the present invention is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less. The number average molecular weight can be calculated by polystyrene conversion using a GPC apparatus such as HLC-8120 manufactured by Tosoh Corporation. In the following examples, it can be measured by the same method. When the number average molecular weight is within the above range, the tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix are in a preferable compatible state. Therefore, the cured resin is excellent in releasability from the mold. On the other hand, if the compatibility between the tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix is high, sufficient releasability may not be obtained. On the other hand, if the compatibility is low, phase separation occurs, which may cause mold stains and deterioration of the appearance of the cured resin.

  The average particle size of the tolylene diisocyanate-modified oxidized wax (E) used in the present invention is preferably 20 μm or more and 70 μm or less, more preferably 30 μm or more and 60 μm or less. The average particle diameter can be measured by using a laser diffraction particle size distribution measuring device such as SALD-7000 manufactured by Shimadzu Corporation as a solvent and water, and a weight-based 50% particle diameter as an average particle diameter. it can. In the following examples, it can be measured by the same method. When the average particle size is in the above range, the tolylene diisocyanate-modified oxidized wax (E) is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the tolylene diisocyanate-modified oxidized wax (E) is present on the surface of the cured resin, and is excellent in releasability of the cured resin from the mold. On the other hand, if the compatibility with the epoxy resin matrix is too high, it cannot be oozed out on the surface of the cured resin and sufficient releasability cannot be ensured. Furthermore, since the tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix are in a preferable compatible state, segregation of the tolylene diisocyanate-modified oxidized wax (E) on the surface of the cured resin is suppressed, and the mold is stained. And deterioration of the appearance of the cured resin can be reduced. Furthermore, when it exists in the said range, when hardening a resin composition, tolylene diisocyanate modified | denatured oxidation wax (E) fully fuse | melts. Therefore, the resin composition is excellent in fluidity. Moreover, it is preferable that the content rate of the particle | grains with a particle size of 106 micrometers or more in all the tolylene diisocyanate modified | denatured oxidation wax (E) is 0.1 weight% or less. If it is said content rate, tolylene diisocyanate modified | denatured oxidation wax (E) will disperse | distribute substantially uniformly, and the deterioration of the external appearance of a mold | die stain | pollution | contamination and a resin cured material can be suppressed. In addition, when the resin composition is cured, the tolylene diisocyanate-modified oxidized wax (E) is sufficiently melted, and thus has excellent fluidity.

  The blending ratio of the tolylene diisocyanate-modified oxidized wax (E) used in the present invention is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.03% by weight or more, 0 in the resin composition. .5% by weight or less. It is excellent in the mold release property of the resin cured material from a metal mold | die as it is said mixture ratio. Moreover, when it exists in the said range, the adhesiveness of resin cured material and a lead frame member is not impaired, and generation | occurrence | production of peeling with the resin cured material and member at the time of a soldering process can be suppressed. Furthermore, when it is within the above range, deterioration of mold stains and appearance of the cured resin can be suppressed.

  The production method of tolylene diisocyanate-modified oxidized wax (E) used in the present invention is not particularly limited. For example, polypropylene wax, polyethylene wax, paraffin wax or the like is used as a raw material compound and oxidized according to a known oxidation method. And the obtained wax oxide and alcohol type wax can be obtained by a method of reacting with tolylene diisocyanate. The tolylene diisocyanate-modified oxide wax (E) used in the present invention is commercially available, and if necessary, a rotating disk mill (pin mill), a screen mill (hammer mill), a centrifugal mill (turbo mill). It can be used after pulverization and particle size adjustment using a pulverizer such as a jet mill.

  Other release agents can be used in combination as long as the effects of using the tolylene diisocyanate-modified oxidized wax (E) used in the present invention are not impaired. Examples of release agents that can be used in combination include natural waxes such as carnauba wax, and metal salts of higher fatty acids such as zinc stearate.

In the present invention, (F) a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and / or a reaction product (F2) of a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and an epoxy resin. Can be used. The butadiene-acrylonitrile copolymer (F1) having a carboxyl group (hereinafter, also simply referred to as “butadiene-acrylonitrile copolymer (F1)”) is a copolymer of butadiene and acrylonitrile, and has an epoxy resin composition for sealing. It has the effect of improving the low stress property of the object. In addition, since the carboxyl group and acrylonitrile group in the butadiene-acrylonitrile copolymer (F1) having a carboxyl group have polarity, the compatibility with the epoxy resin contained as a raw material of the epoxy resin composition for sealing is high. It becomes an appropriate state, and the dispersibility of the butadiene-acrylonitrile copolymer (F1) in the epoxy resin composition for sealing becomes good. For this reason, the butadiene-acrylonitrile copolymer (F1) having a carboxyl group can suppress the progress of dirt on the mold surface and the surface of the cured resin product during molding, and also has an effect of improving continuous moldability. It is what you have.

  Furthermore, by using a reaction product (F2) obtained by previously melting and reacting the whole or a part of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group with an epoxy resin and a curing accelerator, an epoxy for sealing is used. The dispersibility of the butadiene-acrylonitrile copolymer (F1) in the resin composition can be further improved, the mold surface after continuous molding is less likely to be stained, and the continuous moldability is extremely good. Can do. The method for producing the reaction product (F2) of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group and the epoxy resin that can be used in the present invention is not particularly limited. A butadiene-acrylonitrile copolymer (F1) and an epoxy resin can be obtained by melting and reacting in the presence of a curing accelerator. The term “epoxy resin” as used herein refers to monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule. The molecular weight and molecular structure thereof are not particularly limited, and are represented by the general formula (1). As the epoxy resin (A) having a structure or an epoxy resin that can be used in combination with the epoxy resin (A), the same ones as described above can be used. The curing accelerator referred to here may be any accelerator that promotes the curing reaction between the carboxyl group in the butadiene / acrylonitrile copolymer and the epoxy group in the epoxy resin. The same thing as the hardening accelerator which accelerates | stimulates hardening reaction with the phenolic hydroxyl group of the compound containing 2 or more of a functional hydroxyl group can also be used.

The butadiene-acrylonitrile copolymer (F1) having a carboxyl group that can be used in the present invention is not particularly limited, but a compound having a carboxyl group at both ends of the structure is preferred, and the following general formula (15) The compound represented by these is more preferable.
(In the general formula (15), i is a positive number less than 1, j is a positive number less than 1, and i + j = 1. K is an integer of 50 to 80.)

In the general formula (15), i is a positive number less than 1, j is a positive number less than 1, and i + j = 1. k is an integer of 50-80. The acrylonitrile content j in the compound represented by the general formula (15) is preferably 0.05 or more and 0.30 or less, more preferably 0.10 or more and 0.25 or less. The acrylonitrile content j affects the compatibility with the epoxy resin matrix. When the acrylonitrile content j is within the above range, the butadiene-acrylonitrile copolymer (F1) is in an appropriate compatibility state with the epoxy resin matrix, and the mold There is little risk of causing surface contamination or deterioration of the appearance of the cured resin. In addition, when the acrylonitrile content j is within the above range, there is little possibility of causing a defective filling due to a decrease in fluidity, or inconvenience such as a gold wire flow in the electronic component device due to an increase in viscosity.

  The total blending amount of the component (F) that can be used in the present invention is a blending amount as a butadiene-acrylonitrile copolymer (F1) having a carboxyl group, and is 0.01% by weight or more in the total epoxy resin composition. % By weight or less is preferable, 0.05% by weight or more and 0.5% by weight or less is more preferable, and 0.1% by weight or more and 0.3% by weight or less is particularly preferable. By setting it as the said range, generation | occurrence | production of malfunctions, such as generation | occurrence | production of the filling failure at the time of shaping | molding by fall of fluidity | liquidity, and the wire flow by high viscosity can be suppressed.

  The number average molecular weight of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group is preferably 2000 or more and 5000 or less, and more preferably 3000 or more and 4000 or less. By making it within the above range, it is possible to suppress the occurrence of defective filling during molding due to a decrease in fluidity and the occurrence of defects such as gold wire flow due to increased viscosity.

  Further, the carboxyl group equivalent of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group is preferably 1200 or more and 3000 or less, and more preferably 1700 or more and 2500 or less. By making it within the above range, the mold and the cured resin are less likely to be stained without lowering the fluidity and releasability at the time of molding the resin composition, and the effect that the continuous moldability is particularly good. Is obtained.

  The amount of sodium ions and the amount of chlorine ions contained in the component (F) used in the present invention are preferably 10 ppm or less and 450 ppm or less, respectively, with respect to the (F1) equivalent. The amount of sodium ions and the amount of chloride ions can be determined by the following method. Component (F) is subjected to dry decomposition and ashing and then dissolved in acid, and the amount of sodium ions is measured by ICP emission analysis. Chlorine ion content is measured by the combustion tube oxygen method-IC method. When the amount of sodium ions or chlorine ions is within the above range, there is little possibility of causing deterioration of the moisture resistance reliability of the semiconductor device due to the fact that the circuit is easily corroded by sodium ions or chlorine ions.

The butadiene-acrylonitrile copolymer (F1) having a carboxyl group used in the present invention has low heat resistance, and may deteriorate due to heat at the time of molding of a sealing material and reduce the effect as a low stress agent. In order to prevent this, a non-phosphorus antioxidant can be added. Examples of commonly used antioxidants include phosphorus compounds, nitrogen atom-containing compounds, sulfur atom-containing compounds, phenolic compounds including hindered phenols, etc., but when phosphorus compounds are used as antioxidants In this case, the low stress cannot be sufficiently maintained, and the moisture resistance may be lowered. However, when a non-phosphorus antioxidant is used, such problems can be overcome. Among these, in order to further improve the moisture resistance, it is preferable to use an antioxidant that does not contain elements such as nitrogen and sulfur. Examples thereof include, but are not limited to, hindered phenols such as 4,6-di-tertiary-butylphenol (for example, Irganox 129 manufactured by Ciba Geigy Corporation). The antioxidant can be added singly or in plural depending on the purpose. The non-phosphorus antioxidant can be mixed with the component (F) in advance or can be added when the epoxy resin composition is mixed. The addition ratio is preferably 0.01% by weight or more and 10% by weight or less with respect to the butadiene / acrylonitrile copolymer. Within this range, a good antioxidant effect and low stress are exhibited.

In the present invention, (G) a carboxyl group-containing organopolysiloxane (G1) and / or a reaction product (G2) of a carboxyl group-containing organopolysiloxane (G1) and an epoxy resin can be used. . (G) When molding a resin composition by using an organopolysiloxane (G1) having a carboxyl group and / or a reaction product (G2) of an organopolysiloxane (G1) having a carboxyl group and an epoxy resin. Without lowering the fluidity and releasability in the mold, stains on the mold surface and the cured resin surface are less likely to occur, and the effect that the continuous moldability is particularly good is obtained.

  Furthermore, by using a reaction product (G2) obtained by previously melting and reacting all or part of the carboxyl group-containing organopolysiloxane (G1) with an epoxy resin and a curing accelerator, Dirt is less likely to occur and the continuous formability can be made extremely good. The method for producing the reaction product (G2) of the organopolysiloxane (G1) having a carboxyl group and the epoxy resin that can be used in the present invention is not particularly limited. For example, the organopolysiloxane having a carboxyl group is used. (G1) and an epoxy resin can be obtained by melting and reacting in the presence of a curing accelerator. The term “epoxy resin” as used herein refers to monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule. The molecular weight and molecular structure thereof are not particularly limited, and are represented by the general formula (1). As the epoxy resin (A) having a structure or an epoxy resin that can be used in combination with the epoxy resin (A), the same ones as described above can be used. The curing accelerator referred to here may be any accelerator that promotes the curing reaction between the carboxyl group in the organopolysiloxane and the epoxy group in the epoxy resin. The same thing as the hardening accelerator which accelerates | stimulates hardening reaction with the phenolic hydroxyl group of the compound containing 2 or more can also be used.

The organopolysiloxane (G1) having a carboxyl group that can be used in the present invention (hereinafter also simply referred to as “organopolysiloxane (G1)”) is an organopolysiloxane having one or more carboxyl groups in one molecule. Although not particularly limited, organopolysiloxanes represented by the following general formula (16) are desirable.
(However, in the general formula (16), R19 is an organic group having 1 to 40 carbon atoms, at least one of which has a carboxyl group, and the remaining group is a group selected from hydrogen, a phenyl group, or a methyl group. Yes, they may be the same or different, and the average value of l is a positive number between 1 and 50.)

  In the general formula (16), R19 is an organic group having 1 to 40 carbon atoms, at least one of which has a carboxyl group, and the remaining groups are groups selected from hydrogen, a phenyl group, or a methyl group, and are identical to each other. Or different. In addition, carbon number of the organic group which has a carboxyl group of the organopolysiloxane shown by General formula (16) shows what added the carbon number of the hydrocarbon group in an organic group, and a carboxyl group. By making the carbon number of the organic group having a carboxyl group within the above range, deterioration of the appearance of the cured resin surface due to a decrease in compatibility with the resin can be suppressed. Moreover, in General formula (16), the average value of 1 is a positive number of 1 or more and 50 or less. By setting the average value of l within the above range, it is possible to suppress a decrease in fluidity due to an increase in the viscosity of a single oil. When the organopolysiloxane represented by the general formula (16) is used, the fluidity is not lowered and the appearance of the resin cured product surface is particularly good.

  The total blending amount of the component (G) that can be used in the present invention is the blending amount as the organopolysiloxane (G1) having a carboxyl group, and is 0.01% by weight or more and 3% by weight or less in the total epoxy resin composition. It is preferably 0.03% by weight or more and 2% by weight or less, more preferably 0.05% by weight or more and 1% by weight or less. By setting the blending amount in the above range, it is possible to suppress stains on the surface of the cured resin due to the release agent and excess organopolysiloxane and to obtain good continuous moldability.

  Moreover, in this invention, the effect of adding the reaction product (G2) of the organopolysiloxane (G1) which has (G) carboxyl group, and / or the organopolysiloxane (G1) which has a carboxyl group, and an epoxy resin. Other organopolysiloxanes can be used in combination as long as the above is not impaired.

In this invention, in order to improve the adhesiveness of an epoxy resin and an inorganic filler, adhesion assistants, such as a silane coupling agent, can be added. Examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, etc., which react between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler. If it is.
More specifically, examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4 epoxy). (Cyclohexyl) ethyltrimethoxysilane and the like. Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc. In addition, examples of ureidosilane include γ-ureidopropyltriethoxysilane, hexa Methyl disilazane, etc. In addition, mercap Examples of tosilane include γ-mercaptopropyltrimethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.

  As a compounding quantity of the silane coupling agent which can be used for this invention, 0.01 weight% or more and 1 weight% or less are preferable in all the epoxy resin compositions, More preferably, 0.05 weight% or more, 0.8 % By weight or less, particularly preferably 0.1% by weight or more and 0.6% by weight or less. If the blending amount of the silane coupling agent is within the above range, there is little possibility of causing a decrease in solder crack resistance in the semiconductor device due to a decrease in the interface strength between the epoxy resin and the inorganic filler. Moreover, if the compounding quantity of a silane coupling agent exists in the said range, there is little possibility of causing the fall of solder crack resistance by the water absorption of the hardened | cured material of an epoxy resin composition increasing.

  In the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; low stress additives such as silicone oil and silicone rubber; inorganic ion exchangers such as bismuth oxide hydrate; aluminum hydroxide; Additives such as metal hydroxides such as magnesium hydroxide, flame retardants such as zinc borate, zinc molybdate, and phosphazene may be appropriately blended.

  The epoxy resin composition for semiconductor encapsulation of the present invention is obtained by uniformly mixing the components of the present invention and other additives at room temperature using, for example, a mixer, and then heating roll, kneader or extrusion. It is possible to use a material that has been appropriately adjusted in dispersity, fluidity, etc., if necessary, such as melt kneaded using a kneader such as a machine, followed by cooling and pulverization.

  To manufacture a semiconductor device by sealing a semiconductor element with a cured product of the epoxy resin composition for semiconductor sealing of the present invention, for example, a lead frame mounted with a semiconductor element, a circuit board or the like is placed in a mold cavity. Then, what is necessary is just to shape-harden the epoxy resin composition for semiconductor sealing by shaping | molding methods, such as a transfer mold, a compression mold, and an injection mold.

  The semiconductor element that performs sealing in the present invention is not particularly limited, and examples thereof include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.

  The form of the semiconductor device of the present invention is not particularly limited. For example, the dual in-line package (DIP), the plastic lead chip carrier (PLCC), the quad flat package (QFP), the low profile package, and the like. Quad Flat Package (LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Examples include a tape carrier package (TCP), a ball grid array (BGA), and a chip size package (CSP).

  The semiconductor device of the present invention sealed by the molding method such as the transfer mold is completely cured as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours, and then the electronic device Etc.

  FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the epoxy resin composition according to the present invention. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a sealing resin composition.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. Hereinafter, the blending ratio is parts by weight.
The components used in Examples and Comparative Examples are shown below.

Epoxy resin 1: an epoxy resin having a structure represented by the following formula (17) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and 2-methoxynaphthalene with epichlorohydrin) Equivalent 251 and softening point 58 ° C. In the following general formula (17), m / n = 1/4.)
Epoxy resin 2: epoxy resin having a structure represented by the following formula (17) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and 2-methoxynaphthalene with epichlorohydrin) Equivalent 220, softening point 52 ° C. In the following general formula (17), m / n = 1/9.)
Epoxy resin 3: epoxy resin having a structure represented by the following formula (17) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and 2-methoxynaphthalene with epichlorohydrin) Equivalent 270, softening point 63 ° C. In the following general formula (17), m / n = 3/7.)

Epoxy resin 4: an epoxy resin having a structure represented by the following formula (18) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by cocondensation of phenol, formaldehyde and methylphenyl sulfide with epichlorohydrin; epoxy equivalent 196; (Softening point 54 ° C. In the following general formula (18), m / n = 1/4.)

Epoxy resin 5: An epoxy resin having a structure represented by the following formula (19) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by cocondensation of phenol, benzaldehyde and methylphenyl sulfide with epichlorohydrin. Epoxy equivalent 285, (Softening point 74 ° C. In the following general formula (19), m / n = 1/4.)

Epoxy resin 6: An epoxy resin having a structure represented by the following formula (20) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and methylnaphthyl sulfide with epichlorohydrin. Epoxy equivalent) 255, softening point 60 ° C. In the following general formula (20), m / n = 1/4.)

Epoxy resin 7: An epoxy resin having a structure represented by the following formula (21) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by cocondensation of 1-naphthol, formaldehyde and methoxybenzene with epichlorohydrin. Epoxy equivalent 273) The softening point is 68 ° C. In the following general formula (21), m / n = 1/4.)

Epoxy resin 8: biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., jER (registered trademark) YX4000K. Epoxy equivalent 185, melting point 105 ° C.)
Epoxy resin 9: Orthocresol novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON (registered trademark) N-660. Epoxy equivalent 196, softening point 62 ° C.)
Epoxy resin 10: Triphenolmethane type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., jER (registered trademark) 1032H60. Epoxy equivalent 169, softening point 58 ° C.)

Phenol resin 1: Phenol novolak resin represented by general formula (9) (Sumitomo Bakelite Co., Ltd., Sumilite Resin (registered trademark) PR-HF-3. In formula (9), g: 0, average of h Value: 3.0, hydroxyl equivalent weight 104, softening point 80 ° C.)

Phenol resin 2: Phenol aralkyl resin having a phenylene skeleton (Mitsui Chemicals, Millex (registered trademark) XLC-4L. Hydroxyl equivalent 165, softening point 65 ° C.)
Fused spherical silica (average particle size 30μm)

Curing accelerator 1: Curing accelerator represented by the following formula (22)

Curing accelerator 2: Curing accelerator represented by the following formula (23)

Curing accelerator 3: Curing accelerator represented by the following formula (24)

Curing accelerator 4: Curing accelerator represented by the following formula (25)

Curing accelerator 5: Curing accelerator represented by the following formula (26)

Release agent 1: Tolylene diisocyanate-modified polyethylene oxide wax (tolylene diisocyanate-modified polyethylene oxide wax prepared by the above-mentioned method, whose particle size is adjusted by a turbo mill. Drop point 90 ° C., acid value 30 mg KOH / g, number average molecular weight 1800, (The average particle size is 35 μm, the particle size is 106 μm or more, 0.0% by weight.)
Release agent 2: Tolylene diisocyanate-modified oxidized paraffin wax (tolylene diisocyanate-modified oxidized paraffin wax prepared by the above-mentioned method, adjusted in particle size by a hammer mill. Dropping point 85 ° C., acid value 20 mg KOH / g, number average molecular weight 2500 The average particle size is 38 μm, and the particle size is 106 μm or more, 0.0% by weight.)
Release agent 3: Tolylene diisocyanate-modified oxidized polypropylene wax (tolylene diisocyanate-modified oxidized polypropylene wax prepared by the above-mentioned method, whose particle size was adjusted by a jet mill. Drop point: 77 ° C., acid value: 12 mg KOH / g, number average molecular weight: 2300 (The average particle size is 40 μm, the particle size is 106 μm or more, 0.0% by weight.)
Release agent 4: Carnauba wax (manufactured by Nikko Fine Products Co., Ltd., trade name Nikko Carnauba, drop point 83 ° C., acid value 5 mg KOH / g, number average molecular weight 650, average particle size 38 μm, particle size 106 μm or more. 0% by weight.)

F1-1: A butadiene-acrylonitrile copolymer having a carboxyl group at both ends (manufactured by Ube Industries, Ltd., CTBN-1008SP. In the general formula (15), i = 0.82, j = 0.18, k The average value is 62. Number average molecular weight 3550, carboxyl group equivalent 2200 g / eq, sodium ion amount 5 ppm, chlorine ion amount 200 ppm.)

F2-1: Bisphenol A epoxy resin (Japan Epoxy Resin Co., Ltd., jE
65 parts by weight of R (registered trademark) YL-6810 (epoxy equivalent 172 g / eq, melting point 45 ° C.) was heated and melted at 140 ° C., and 33 parts by weight of F1-1 and 0.8 parts by weight of triphenylphosphine were added. And a molten reactant obtained by melting and mixing at 140 ° C. for 30 minutes.

G1-1: Compound represented by the following formula (27) (manufactured by Dow Corning Toray Co., Ltd., BY16-750, molecular weight of about 1500)

  G2-1: 12 parts by weight of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., jER (registered trademark) YL-6810 (epoxy equivalent 172 g / eq, melting point 45 ° C.) at 140 ° C. is heated and melted, and G1 A molten reactant obtained by adding 6 parts by weight of -1 and 0.15 part by weight of triphenylphosphine and melting and mixing at 140 ° C. for 30 minutes.

Silane coupling agent 1: γ-glycidoxypropyltrimethoxysilane carbon black

Example 1
Epoxy resin 1 8.60 parts by weight Phenolic resin 1 3.80 parts by weight Fused spherical silica 86.00 parts by weight Curing accelerator 1 0.20 parts by weight Release agent 1 0.20 parts by weight F2-1 0.30 parts by weight G2-1 0.30 part by weight Silane coupling agent 1 0.30 part by weight Carbon black 0.30 part by weight is mixed at room temperature with a mixer, melt-kneaded with a heating roll at 80 to 100 ° C., cooled and pulverized, An epoxy resin composition was obtained. It evaluated by the following method using the obtained epoxy resin composition. The evaluation results are shown in Table 1.

  Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold according to EMMI-1-66 was applied at 175 ° C., injection pressure 6.9 MPa, holding pressure The epoxy resin composition was injected under the condition of time 120 seconds, and the flow length was measured. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. The unit is cm.

  Metal wire flow rate: epoxy resin composition using a low-pressure transfer automatic molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 70 seconds. A silicon chip or the like is encapsulated with a material, and a 160-pin LQFP (pre-plating frame: nickel / palladium alloy plated with gold, package outer dimensions: 24 mm × 24 mm × 1.4 mm thickness, pad size: 8.5 mm × 8 0.5 mm and a chip size of 7.4 mm × 7.4 mm × 350 μm thickness). The obtained 160-pin LQFP package was observed with a soft X-ray fluoroscope (PRO-TEST100, manufactured by Softex Corporation), and the flow rate of the gold wire was determined as the ratio of (flow rate) / (gold wire length). . The criterion was ○ for less than 5% and x for 5% or more.

Flame resistance: Resin composition using a low pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 175 ° C., an injection time of 15 seconds, a curing time of 120 seconds, and an injection pressure of 9.8 MPa. The product was injection molded to produce a 3.2 mm thick flame resistant test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94. The table shows the flame resistance rank.

  Continuous moldability: epoxy resin composition using a low-pressure transfer automatic molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 70 seconds. A silicon chip or the like is molded by sealing, and 80-pin QFP (preprating frame: nickel / palladium alloy gold-plated, package outer dimension: 14 mm × 20 mm × 2 mm thickness, pad size: 6.5 mm × 6.5 mm, Molding to obtain a chip size of 6.0 mm × 6.0 mm × 350 μm thickness was continuously performed up to 800 shots. Judgment criteria were ◎ for those that could be continuously molded up to 800 shots without any problems such as unfilling or mold release failure, ◯ for those that could be continuously molded up to 500 shots, and × otherwise.

  Package appearance and mold stain resistance: In the evaluation of the continuous moldability, the package and mold after 500 shots and 800 shots were visually evaluated for stains. Judgment criteria for package appearance and mold dirtiness are indicated by x for those in which dirt has occurred up to 500 shots, ◯ for those in which dirt has not been stained up to 500 shots, and ◎ for those not dirty up to 800 shots. Further, in the above-mentioned continuous formability, those that could not be formed without any problem up to 800 shots were judged based on the package appearance and mold contamination status when the continuous forming was abandoned.

  Solder resistance: The package formed in the above-described evaluation of continuous formability is post-cured at 175 ° C. for 8 hours, and the resulting package is humidified at 85 ° C. and 60% relative humidity for 168 hours, followed by IR reflow treatment at 260 ° C. Did. For 20 packages, the adhesion state of the interface between the semiconductor element and the cured product of the epoxy resin composition was observed with an ultrasonic flaw detector, and the peeling occurrence rate [(number of peeling occurrence packages) / (total number of packages) × 100] Calculated. Units%. The criteria for determining solder resistance were ◯ when no peeling occurred, Δ when the peeling rate was less than 20%, and x when the peeling rate was 20% or more.

Examples 2 to 25, Comparative Examples 1 to 5
According to the composition of Table 1, Table 2, Table 3, and Table 4, an epoxy resin composition was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1, Table 2, Table 3, and Table 4.

  In Examples 1 to 25, an epoxy resin (A) having a structure represented by the general formula (1), a compound (B) containing two or more phenolic hydroxyl groups, an inorganic filler (C), a curing accelerator (D ) And tolylene diisocyanate-modified oxidized wax (E), the type and blending amount of epoxy resin (A), the type of compound (B) containing two or more phenolic hydroxyl groups, tolylene diisocyanate-modified oxidized wax ( The butadiene-acrylonitrile copolymer (F1) or carboxyl group having a carboxyl group, including those having different types and blending amounts of E), curing accelerator (D), and inorganic filler (C) A reaction product (F2) of a butadiene-acrylonitrile copolymer (F1) having an epoxy group and an epoxy resin, or an organopolysiloxane (G1) having a carboxyl group , And / or a product obtained by adding a reaction product (G2) of an organopolysiloxane having a carboxyl group (G1) and an epoxy resin. In any case, fluidity (spiral flow), gold wire flow rate Excellent results were obtained in the balance of flame resistance, continuous formability, package appearance and mold stain resistance, and solder resistance.

  According to the present invention, an epoxy resin composition having excellent flame resistance and excellent fluidity, continuous moldability, and solder resistance can be obtained, which is suitable for sealing a semiconductor device.

It is the figure which showed the cross-section about an example of the semiconductor device using the epoxy resin composition which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Gold wire 5 Lead frame 6 Hardening body of resin composition for sealing

Claims (9)

(A) an epoxy resin having a structure represented by the following general formula (1);
(B) a compound containing two or more phenolic hydroxyl groups;
(C) an inorganic filler;
(D) a curing accelerator;
(E) An epoxy resin composition for semiconductor encapsulation containing tolylene diisocyanate-modified oxidized wax, wherein the compound (B) containing two or more phenolic hydroxyl groups is a compound represented by the following general formula (9): 50% by weight or more viewing including,
The (E) of the tolylene diisocyanate-modified oxidized wax, dropping point 70 ° C. or more and 120 ° C. or less, an acid value of 10 mgKOH / g or more and less 50 mg KOH / g, number average molecular weight of 500 or more, 5000 The average particle size is 20 μm or more and 70 μm or less, the content ratio of particles having a particle size of 106 μm or more is 0.1% by weight or less, and the blending ratio is the epoxy resin composition resin composition for all semiconductor encapsulation An epoxy resin composition for encapsulating a semiconductor, wherein the content is 0.01% by weight or more and 1% by weight or less .


(In the above general formula (1), Ar is an aromatic group having 6 to 20 carbon atoms, and may be the same or different from each other. R1 is a hydrocarbon group having 1 to 6 carbon atoms. And R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, R3 is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or An aromatic group having 6 to 20 carbon atoms, which may be the same or different from each other, a is an integer of 0 to 10, b is an integer of 1 to 3, m and n are molar ratios; (0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / n is 1/10 to 1/1).

(However, in the said General formula (9), R18 represents a C1-C4 hydrocarbon group, and they may mutually be same or different. G is an integer of 0-3. H The average value of is a positive number of 0 or 8 or less.) (A) The epoxy resin having the structure represented by the general formula (1) co-condenses the phenolic hydroxyl group-containing aromatics, aldehydes, and the compound (J) represented by the following general formula (2). 2. The epoxy resin composition for semiconductor encapsulation according to claim 1, which is an epoxy resin obtained by glycidyl etherification of the phenol resin obtained in this way with epichlorohydrin.

(However, in the said General formula (2), Ar is a C6-C20 aromatic group, R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 Is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, a is an integer of 0 to 10, and b is an integer of 1 to 3). 3. The semiconductor encapsulation according to claim 2, wherein the epoxy resin having the structure represented by the general formula (1) is an epoxy resin having a structure represented by the following general formula (3). Stopping epoxy resin composition.

(However, in the said General formula (3), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group, W1 is an oxygen atom or a sulfur atom, c is an integer of 0 to 5, d is an integer of 0 to 3, m and n represent a molar ratio, and 0 ≦ m <1, 0 <n ≦ 1 M + n = 1 and m / n is 1/10 to 1/1.) The epoxy resin for semiconductor encapsulation according to claim 3, wherein the epoxy resin having a structure represented by the general formula (3) is an epoxy resin having a structure represented by the following general formula (4). Resin composition.

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. C is an integer of 0 to 5 and d is an integer of 0 to 3. m and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / N is 1/10 to 1/1.) The curing accelerator (D) is a compound represented by the following general formula (5), a compound represented by the following general formula (6), a compound represented by the following general formula (7), and the following general formula (8). The epoxy resin composition for semiconductor encapsulation according to claim 4 , which is at least one selected from compounds represented by

(In the general formula (5), P represents a phosphorus atom and Si represents a silicon atom. R4, R5, R6 and R7 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Wherein X1 is an organic group bonded to the groups Y1 and Y2, and X2 is an organic group bonded to the groups Y3 and Y4. Y2 represents a group formed by releasing a proton from a proton donating group, and groups Y1 and Y2 in the same molecule are combined with a silicon atom to form a chelate structure.Y3 and Y4 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y3 and Y4 in the same molecule are bonded to a silicon atom to form a chelate structure.X1 and X2 may be the same or different from each other, Y1, Y2, Y And Y4 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

(However, in the said General formula (6), P represents a phosphorus atom. R8, R9, R10, and R11 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

(However, in the said General formula (7), X3 represents a C1-C3 alkyl group, Y5 represents a hydroxyl group. E is an integer of 0-5, f is an integer of 0-3.)

(However, in the said General formula (8), P represents a phosphorus atom. R12, R13, and R14 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R15, R16 and R17 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R15 and R16 are bonded to form a cyclic structure. May be.) 6. The epoxy resin composition for semiconductor encapsulation according to claim 5 , wherein the inorganic filler (C) is contained in an amount of 80% by weight or more and 92% by weight or less of the entire resin composition. And (F) a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and / or a reaction product (F2) of a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and an epoxy resin. the epoxy resin composition for semiconductor encapsulation according to any one of claims 4 to 6, characterized. Furthermore (G) organopolysiloxane having a carboxyl group (G1), and / or, claim, characterized in that it comprises the reaction product of a organopolysiloxane (G1) and an epoxy resin having a carboxyl group (G2) 4 The epoxy resin composition for semiconductor sealing in any one of Claim thru | or 7 . Wherein a obtained by encapsulating a semiconductor element with a cured product of the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 8.