JP5651968B2 - Semiconductor sealing resin composition and semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor sealing resin composition and a semiconductor device.

  The demand for miniaturization, weight reduction, and high performance of electronic devices is not limited, and the integration and density of semiconductor elements (hereinafter, also referred to as “elements” and “chips”) have progressed year by year. Furthermore, surface mounting technology has appeared and is becoming popular in the mounting method of semiconductor devices (hereinafter also referred to as “packages”). Due to such advances in peripheral technology of semiconductor devices, demands for resin compositions for sealing semiconductor elements have become severe. For example, in the surface mounting process, a semiconductor device that has absorbed moisture is exposed to a high temperature during the soldering process, and cracks and internal delamination occur due to explosive stress of water vapor that is rapidly vaporized, thereby significantly reducing the operational reliability of the semiconductor device. Furthermore, the lead-free use of the lead is switched to lead-free solder having a higher melting point than before, and the mounting temperature is about 20 ° C. higher than that of the conventional one, so that the stress during the soldering process becomes more serious. Thus, due to the spread of surface mounting technology and switching to lead-free soldering, solder resistance has become one of the important technical issues for semiconductor sealing resin compositions.

  Also, against the background of environmental problems in recent years, there has been an increasing social demand to eliminate the use of flame retardants such as brominated epoxy resins and antimony oxide, which have been used in the past, without using these flame retardants. Therefore, a technology for imparting the same flame retardance as that of the prior art has become necessary. As such an alternative flame-retarding technique, for example, a technique of applying a low-viscosity crystalline epoxy resin and blending more inorganic fillers has been proposed (see, for example, Patent Document 1 and Patent Document 2). . However, it cannot be said that these methods also sufficiently satisfy solder resistance and flame retardancy.

  Further, in recent years, a structure in which chips are stacked in one package or a semiconductor device in which the wire diameter is smaller than that in the past has appeared. In such a semiconductor device, the thickness of the resin-encapsulated portion is thinner than before, so that unfilling is likely to occur or wire flow during molding is likely to occur, which may reduce the yield of the sealing process. There is. Therefore, in order to improve the flow characteristics of the resin composition, a method using a low molecular weight epoxy resin or a phenol resin curing agent is easily conceived, but by this method, molding is performed by fixing resin compositions (tablets) to each other. In some cases, defects such as poor conveyance during the process, equipment stoppage easily (decrease in handling properties), and deterioration in curability may impair any of the properties of solder resistance, flame resistance, and moldability. As described above, by thinning and thinning the semiconductor device, the resin composition can ensure and balance handling properties, solder resistance, flame resistance, and moldability while improving fluidity more than before. It has become an important issue.

JP-A-7-130919 JP-A-8-20673

  The present invention provides a resin composition for encapsulating a semiconductor having a good balance of handling properties, solder resistance, flame resistance and continuous moldability, and encapsulating a semiconductor element with its cured product while improving fluidity more than before. The present invention provides an economical semiconductor device with excellent reliability.

The resin composition for semiconductor encapsulation of the present invention is a phenol resin composed of one or two or more components, and is represented by the following general formula (1):
(In the general formula (1), R1 is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is an integer of 0 to 3. R2, R3, R4 and R5 are independent of each other. A hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) and the following general formula (2):
(In the above general formula (2), R1 is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is an integer of 0 to 3. R6 is independently 1 each having 1 carbon atom. And b is an integer of 1 to 4. R7, R8, R9 and R10 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) A phenol resin (A) containing a component (A1) made of a polymer containing a structural unit represented by:
Epoxy resin (B);
An inorganic filler (C);
A curing accelerator (D);
Glycerin trifatty acid ester (E),
It is characterized by including.

  The resin composition for encapsulating a semiconductor of the present invention has a total relative strength of the polymer corresponding to the component (A1) as measured by field desorption mass spectrometry based on the total relative strength of the phenol resin (A). 10% or more and 80% or less.

  In the semiconductor sealing resin composition of the present invention, the phenol resin (A) includes a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). It may further contain a component (A2) comprising no polymer.

  In the resin composition for encapsulating a semiconductor of the present invention, the phenol resin (A) includes a structural unit represented by the general formula (2) and does not include a structural unit represented by the general formula (1). It may further include a component (A3) made of a polymer.

  The resin composition for encapsulating a semiconductor of the present invention is the total number of structural units represented by the general formula (1) in the entire phenol resin (A) and the structural units represented by the general formula (2). The ratio with respect to the total number can be 30/70 to 95/5.

  In the resin composition for semiconductor encapsulation of the present invention, R6 in the structural unit represented by the general formula (2) may be a methyl group, and b may be 1 to 3.

  In the resin composition for encapsulating a semiconductor of the present invention, the phenol resin (A) can be contained in an amount of 20% by mass or more and 100% by mass or less in the total curing agent.

  In the resin composition for semiconductor encapsulation of the present invention, the epoxy resin (B) is a biphenyl type epoxy resin, a bisphenol type epoxy resin, a stilbene type epoxy resin, an anthracene diol type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type. Epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, phenol aralkyl type epoxy resin having phenylene skeleton, phenol aralkyl type epoxy resin having biphenylene skeleton, naphthol aralkyl type epoxy resin having phenylene skeleton, dihydroxy Naphthalene-type epoxy resin, epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer, novolak with methoxynaphthalene skeleton Epoxy resins, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, can be made at least one epoxy resin selected from the group consisting of dicyclopentadiene-modified phenol type epoxy resins.

  In the resin composition for semiconductor encapsulation of the present invention, the content of the inorganic filler (C) may be 80% by mass or more and 93% by mass or less.

  In the resin composition for encapsulating a semiconductor according to the present invention, the curing accelerator (D) is composed of a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, or an adduct of a phosphonium compound and a silane compound. It may contain at least one curing accelerator selected from the group consisting of:

  In the semiconductor sealing resin composition of the present invention, the semiconductor sealing resin composition further includes a compound (F) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring. Can do.

  In the semiconductor sealing resin composition of the present invention, the semiconductor sealing resin composition may further contain a coupling agent (G).

  The resin composition for semiconductor encapsulation of the present invention may contain a silane coupling agent in which the coupling agent (G) has a secondary amino group.

  The semiconductor device of the present invention is obtained by sealing a semiconductor element with a cured product of the above-described resin composition for encapsulating a semiconductor.

  According to the present invention, a resin composition for encapsulating a semiconductor having a good balance of handling properties, solder resistance, flame resistance and continuous moldability while improving fluidity more than before, and a semiconductor element using the cured product thereof A highly reliable semiconductor device that is sealed can be obtained economically.

It is the figure which showed the cross-sectional structure about an example of the semiconductor device using the resin composition for semiconductor sealing which concerns on this invention. It is the figure which showed the cross-sectional structure about an example of the single-side sealing type semiconductor device using the resin composition for semiconductor sealing which concerns on this invention. It is a GPC chart of the phenol resin 1 used in the Example. It is a GPC chart of the phenol resin 2 used in the Example. It is a GPC chart of the phenol resin 3 used in the Example. It is a GPC chart of the phenol resin 4 used in the Example. It is a FD-MS chart of the phenol resin 1 used in the Example. It is an FD-MS chart of the phenol resin 2 used in the Example. It is a FD-MS chart of the phenol resin 3 used in the Example. It is a FD-MS chart of the phenol resin 4 used in the Example.

  The resin composition for semiconductor encapsulation of the present invention is a phenol resin composed of one or more components, and a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) A phenol resin (A) containing a component (A1) comprising a polymer containing, an epoxy resin (B), an inorganic filler (C), a curing accelerator (D), and a glycerin trifatty acid ester (E) , Including. Thereby, the resin composition for semiconductor sealing which is excellent in balance of handling property, solder resistance, flame resistance, and continuous moldability can be obtained while improving fluidity more than before. Moreover, the semiconductor device of the present invention is obtained by sealing a semiconductor element with a cured product of the above-described resin composition for encapsulating a semiconductor. Thereby, a highly reliable semiconductor device can be obtained economically. Hereinafter, the present invention will be described in detail.

  First, the resin composition for semiconductor encapsulation will be described. The resin composition for encapsulating a semiconductor of the present invention is a phenol resin composed of one or more components as a curing agent for an epoxy resin, and a structural unit represented by the following general formula (1) and the following general formula ( A phenol resin (A) containing a component (A1) made of a polymer containing the structural unit represented by 2) is used.

Here, in General formula (1), R1 is a C1-C6 hydrocarbon group mutually independently, and a is an integer of 0-3. R2, R3, R4 and R5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

Here, in General formula (2), R1 is a C1-C6 hydrocarbon group mutually independently, and a is an integer of 0-3. R6 is independently a hydrocarbon group having 1 to 6 carbon atoms, and b is an integer of 1 to 4. R7, R8, R9 and R10 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

  The component (A1) in the phenol resin (A) has a skeleton structure similar to that of the phenol aralkyl type phenol resin having a phenylene skeleton, thereby exhibiting good curability and solder resistance. Further, in the general formula (2) Since the substituent R6 of the structural unit represented is hydrophobic, good moisture resistance can be exhibited. Furthermore, the component (A1) in the phenol resin (A) has a feature that it is less likely to be fixed and exhibits good handling properties as compared with a phenol aralkyl resin having a phenylene skeleton having the same molecular weight. The details of the reason why the sticking is difficult to occur are unknown, but by including the substituent R6 partially, the intermolecular force (van der Waals force) is locally strong, thereby restricting the movement of the molecule. It is assumed that the softening point is relatively increased. The resin composition using the phenol resin (A) can exhibit excellent fluidity and curability without impairing handling properties, and the cured product has excellent flame resistance, low water absorption, and solder resistance. It has the characteristic that crack property improves.

  The phenol resin (A) includes a component (A1) composed of a polymer including the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). Although the structural unit represented by formula (2) is included, the component (A2) composed of a polymer not containing the structural unit represented by the general formula (2) or the structural unit represented by the general formula (2) is included. The component (A3) which consists of a polymer which does not contain the structural unit represented by (1) can further be included. The ratio of the total number of structural units represented by the general formula (1) and the total number of structural units represented by the general formula (2) in the entire phenol resin (A) is 30 / It is preferably 70 to 95/5, more preferably 40/60 to 90/10, and particularly preferably 50/50 to 85/15. Here, “to” in this specification includes all the upper and lower ends. When the ratio of the average number of repetitions of both structural units is in the above range, a resin composition having an excellent balance of flame resistance, handling properties, continuous moldability and solder resistance can be obtained. The ratio of the total number of structural units represented by general formula (1) to the total number of structural units represented by general formula (2) in the entire phenol resin (A) is the field desorption mass. It can obtain | require by analysis (FD-MS) measurement. For each peak detected by FD-MS analysis measured in a detected mass (m / z) range of 50 to 2000, the molecular weight and the number of repetitions can be obtained from the detected mass (m / z). The content ratio of each structural unit of the general formula (1) and the general formula (2) can be obtained by arithmetically calculating the intensity ratio of the above as the content ratio (mass).

  Such a polymerization method of the phenol resin (A) is not particularly limited. For example, the phenol resin, the compound represented by the following general formula (3), and the following general formula (4) are represented. A method obtained by co-condensation polymerization of a compound (hereinafter also referred to as “first production method”), an alkyl-substituted aromatic compound represented by the following general formula (5) and aldehydes are reacted, Examples thereof include a method obtained by adding a compound represented by the general formula (3) and a phenol compound and performing copolymerization (hereinafter, also referred to as “second production method”), and the like. You may superpose | polymerize combining. Among these, the 2nd manufacturing method is preferable at the point that a raw material can be obtained cheaply.

Here, in General formula (3), R2, R3, R4, and R5 are a hydrogen atom or a C1-C6 hydrocarbon group mutually independently. X is a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms. R11 and R12 are each independently a hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom.

Here, in General formula (4), R6 is a C1-C6 hydrocarbon group mutually independently, and b is an integer of 1-4. R7, R8, R9 and R10 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X is a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms. R13 and R14 are each independently a hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom.

Here, in General formula (5), R6 is mutually independently a C1-C6 hydrocarbon group, b is an integer of 1-4.

  Examples of the phenol compound used in the production of the phenol resin (A) include phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, and t-butylphenol. Xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, nonylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, etc. is not. Among these, phenol and o-cresol are preferable, and phenol is more preferable from the viewpoint of reactivity with the epoxy resin. In the production of the phenol resin (A), these phenol compounds may be used alone or in combination of two or more.

  Examples of the hydrocarbon group having 1 to 6 carbon atoms in R2, R3, R4 and R5 in the compound represented by the general formula (3) used for the production of the phenol resin (A) include a methyl group, an ethyl group, Propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methyl Pentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4 -A dimethylbutyl group, 4, 4- dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, a cyclohexyl group, a phenyl group, etc. are mentioned.

  = CR11R12 (alkylidene group) in the compound represented by the general formula (3) used for the production of the phenol resin (A) includes methylidene group, ethylidene group, propylidene group, n-butylidene group, isobutylidene group, t- Butylidene group, n-pentylidene group, 2-methylbutylidene group, 3-methylbutylidene group, t-pentylidene group, n-hexylidene group, 1-methylpentylidene group, 2-methylpentylidene group, 3-methylpentylidene group Group, 4-methylpentylidene group, 2,2-dimethylbutylidene group, 2,3-dimethylbutylidene group, 2,4-dimethylbutylidene group, 3,3-dimethylbutylidene group, 3,4-dimethyl Butylidene group, 4,4-dimethylbutylidene group, 2-ethylbutylidene group, 1-ethylbutylidene group, and cyclohexyl Den group and the like.

  Examples of the halogen atom in X in the compound represented by the general formula (3) used for the production of the phenol resin (A) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a C1-C6 alkoxy group in X in the compound represented by General formula (3) used for manufacture of a phenol resin (A), a methoxy group, an ethoxy group, a propoxy group, n-butoxy group , Isobutoxy group, t-butoxy group, n-pentoxy group, 2-methylbutoxy group, 3-methylbutoxy group, t-pentoxy group, n-hexoxy group, 1-methylpentoxy group, 2-methylpentoxy group, 3-methylpentoxy group, 4-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 2,4-dimethylbutoxy group, 3,3-dimethylbutoxy group, 3,4- Examples thereof include dimethylbutoxy group, 4,4-dimethylbutoxy group, 2-ethylbutoxy group, and 1-ethylbutoxy group.

  In manufacture of a phenol resin (A), the compound represented by General formula (3) may be used individually by 1 type, or 2 or more types may be mixed and used for it. Among these, p-xylylene glycol is preferable because it can be synthesized at a relatively low temperature and the reaction by-product can be easily distilled off and handled. When X is a halogen atom, hydrogen halide generated due to the presence of a small amount of moisture can be used as an acid catalyst.

  Examples of the hydrocarbon group having 1 to 6 carbon atoms in R7, R8, R9, R10 and R6 in the compound represented by the general formula (4) used for the production of the phenol resin (A) include a methyl group, Ethyl group, propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, Examples include 3,4-dimethylbutyl group, 4,4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, cyclohexyl group, and phenyl group.

  = CR13R14 (alkylidene group) in the compound represented by the general formula (4) used for the production of the phenol resin (A) includes methylidene group, ethylidene group, propylidene group, n-butylidene group, isobutylidene group, t- Butylidene group, n-pentylidene group, 2-methylbutylidene group, 3-methylbutylidene group, t-pentylidene group, n-hexylidene group, 1-methylpentylidene group, 2-methylpentylidene group, 3-methylpentylidene group Group, 4-methylpentylidene group, 2,2-dimethylbutylidene group, 2,3-dimethylbutylidene group, 2,4-dimethylbutylidene group, 3,3-dimethylbutylidene group, 3,4-dimethyl Butylidene group, 4,4-dimethylbutylidene group, 2-ethylbutylidene group, 1-ethylbutylidene group, and cyclohexyl Den group and the like.

  In X in the compound represented by the general formula (4) used for the production of the phenol resin (A), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentoxy group, 2-methylbutoxy group, 3-methylbutoxy group, t-pentoxy group, n-hexoxy group, 1-methylpentoxy group, 2-methylpentoxy group, 3-methylpentoxy group, 4-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3- Dimethylbutoxy group, 2,4-dimethylbutoxy group, 3,3-dimethylbutoxy group, 3,4-dimethylbutoxy group, 4,4-dimethylbutoxy group, 2-ethylbutoxy group, 1-ethylbutoxy group, etc. Can be mentioned.

  In manufacture of a phenol resin (A), the compound represented by General formula (4) may be used individually by 1 type, or 2 or more types may be mixed and used for it. Among these, from the viewpoint of a balance between the flame resistance and moisture resistance of the resin composition, R6 is preferably a methyl group and b is preferably 1 to 3. When X is methoxy, it is preferable because the reaction by-product can be easily distilled off and handled. When X is a halogen atom, hydrogen halide generated due to the presence of a small amount of moisture is used as an acid catalyst. Can be used.

  In R6 in the compound represented by the general formula (5) used for the production of the phenol resin (A), the hydrocarbon group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, a propyl group, and an n-butyl group. , Isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4, Examples include 4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, cyclohexyl group, and phenyl group. Examples of such alkyl-substituted aromatic compounds include toluene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene, 1,2,3-trimethylbenzene, 1,2,4. -Trimethylbenzene, ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,3,5-triethylbenzene, 1,2,3-triethylbenzene, n-1,2,4-triethylbenzene, cumene, o -Cymene, m-cymene, p-cymene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, pentylbenzene, dipentylbenzene and the like. Among these, toluene, dimethylbenzene, trimethylbenzene, and tetramethylbenzene are preferable from the viewpoint of the raw material price and the balance between the flame resistance and moisture resistance of the resin composition. In manufacture of a phenol resin (A), the compound represented by General formula (5) may be used individually by 1 type, or may use 2 or more types together.

  Examples of aldehydes used in the production of the phenol resin (A) include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. Among these, formaldehyde and paraformaldehyde are preferable from the viewpoints of curability of the resin composition and raw material costs.

  The method for synthesizing the phenol resin (A) is not particularly limited. For example, in the case of the first production method, the compound represented by the general formula (3) is generally used with respect to 1 mol of the phenol compound. 0.1 to 0.6 mol in total with the compound represented by the formula (4), formic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid, etc. The catalyst is reacted at a temperature of 50 to 200 ° C. at a temperature of 50 to 200 ° C. for 2 to 20 hours while discharging the generated gas and moisture out of the system by nitrogen flow, and the monomer remaining after the reaction is distilled under reduced pressure. It can be obtained by distilling off by a method such as steam distillation. The total number of structural units represented by general formula (1) and the total number and ratio of structural units represented by general formula (2) in the entire phenol resin (A) are the ratios of the raw materials used. As a preferred range of the compounding ratio, which is almost reflected, the compound represented by the general formula (3) by molar ratio: the general formula (4) = 20: 80 to 80:20 can be mentioned.

  The phenol resin (A) obtained by the first production method is a polymer mixture represented by the following general formula (6), wherein m is an integer of 0 to 20 and n is an integer of 0 to 20.

Here, R1 is a C1-C6 hydrocarbon group mutually independently, and a is an integer of 0-3. R6 is independently a hydrocarbon group having 1 to 6 carbon atoms, and b is an integer of 1 to 4. R2, R3, R4, R5, R7, R8, R9 and R10 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The terminal of the molecule is a hydrogen atom or a substituted or unsubstituted hydroxyphenyl group.

  When the values of m and n in the polymer mixture represented by the general formula (6), m is an integer of 0 to 20, and n is an integer of 0 to 20 are described as average values, the average value of m is It is 1-7, More preferably, it is 1.2-2.5, The average value of n is 0.2-2, More preferably, it is 0.4-1. When the average value of m is less than the above lower limit value, the handleability of the resulting resin composition and the curability of the resin composition may be reduced. Moreover, when the average value of m exceeds the said upper limit, since the viscosity of phenol resin itself is high, there exists a possibility that the fluidity | liquidity of the resin composition obtained may fall. Moreover, when the average value of n is less than the said lower limit, there exists a possibility that the solder resistance and conveyance property of the resin composition obtained may fall. Moreover, when the average value of n exceeds the said upper limit, the fluidity | liquidity and sclerosis | hardenability of a resin composition will fall, and there exists a possibility that a moldability may fall. In addition, the value of m and n can be calculated | required by the FD-MS analysis method. The molecular weight of the compound of the general formula (6) measured by the FD-MS analysis method is 300 or more and 1500 or less, preferably 500 or more and 900 or less. In consideration of the ease of handling of the phenol resin (A) itself, the balance of fluidity, curability, flame resistance and solder resistance as a resin composition, the structural unit and the general formula represented by the general formula (1) Component (A1) consisting of a polymer containing the structural unit represented by (2) is 10% by mass or more and 80% by mass or less, based on the total amount of phenol resin (A) obtained by the first production method. Preferably they are 15 mass% or more and 70 mass% or less, Most preferably, they are 20 mass% or more and 50 mass% or less.

  As a method of adjusting the component (A1) contained in the phenol resin (A) obtained by the first production method, for example, the amount of the compound represented by the general formula (4) is increased, or the general formula (3 ), The content ratio of the component (A1) can be increased.

  Moreover, among the synthesis methods of a phenol resin (A), in the case of the 2nd manufacturing method, aldehydes are 1-2.5 with respect to 1 mol of alkyl substituted aromatic compounds represented by General formula (5). In the case of an alkali metal catalyst, 0.1 to 2.5 mol of an alkali metal catalyst such as sodium hydroxide or potassium hydroxide or a strong acid such as paratoluenesulfonic acid, xylenesulfonic acid or sulfuric acid is added as a catalyst. A reaction intermediate is obtained by reacting at a temperature of 5 to 80 ° C., in the case of an acidic catalyst, at a temperature of 100 to 150 ° C. for 0.5 to 5 hours. Next, 0.2 to 5 mol of the compound represented by the general formula (3) and 1 to 20 mol of the phenol compound, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid, etc. Monomer remaining after the completion of the reaction by adding 0.005 to 0.05 mol of the acidic catalyst and co-condensation reaction for 2 to 20 hours while discharging the generated gas out of the system by nitrogen flow at a temperature of 50 to 200 ° C. And water can be obtained by distilling off by a method such as vacuum distillation or steam distillation. In the general formula (3), when X is a halogen atom, hydrogen halide generated due to the presence of a small amount of moisture can be used as the acid catalyst.

  The phenol resin (A) obtained by the second production method is represented by the following general formula (7), i is an integer of 0-20, j is an integer of 0-20, and k is 0-20. It is a mixture of polymers that are integers.

Here, R1 is a C1-C6 hydrocarbon group mutually independently, and a is an integer of 0-3. R6 is independently a hydrocarbon group having 1 to 6 carbon atoms, and b is an integer of 1 to 4. R2, R3, R4, R5, R7, R8, R9, R10, R15 and R16 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The terminal of the molecule is a hydrogen atom, a substituted or unsubstituted hydroxyphenyl group, or a phenyl group substituted with 1 to 4 hydrocarbon groups having 1 to 6 carbon atoms.

  Values of i, j, and k in the polymer mixture represented by the general formula (7), i is an integer of 0 to 20, j is an integer of 0 to 20, and k is an integer of 0 to 20. Is an average value, the average value of i is 0.5 to 7, more preferably 1 to 4, the average value of j is 0.2 to 3, more preferably 0.4 to 2, and k Is 0 or more and 5 or less, more preferably 0 or more and 3 or less. When i is less than the lower limit, the curability of the resulting resin composition may be reduced. When i exceeds the above upper limit, the viscosity of the phenol resin itself is high, so that the fluidity of the resulting resin composition may be lowered. Moreover, when j is less than the said lower limit, the obtained phenol resin tends to adhere, and there exists a possibility that the solder crack resistance of the obtained resin composition may fall. When j exceeds the upper limit, the fluidity and curability of the resin composition may be reduced. Moreover, when k exceeds the said upper limit, there exists a possibility that the flame resistance of a resin composition may fall. Note that the values of i, j, and k can be obtained by an FD-MS analysis method. The molecular weight of the compound of the general formula (7) measured by FD-MS analysis is 350 or more and 1200 or less, preferably 400 or more and 900 or less. In consideration of the ease of handling of the phenol resin (A) itself, the balance of fluidity, curability, flame resistance and solder resistance as a resin composition, the structural unit and the general formula represented by the general formula (1) The component (A1) composed of a polymer containing the structural unit represented by (2) is 10% by mass or more and 80% by mass or less based on the total amount of the phenol resin (A) obtained by the second production method. Preferably they are 15 mass% or more and 70 mass% or less, Most preferably, they are 20 mass% or more and 50 mass% or less.

  Here, in the phenol resin (A) obtained by the second production method, a component comprising a polymer containing a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) ( Examples of the method for increasing the content ratio of A1) include a method of reducing the compounding amount or gradually adding the compound represented by the general formula (3) to the reaction system.

  The phenol resin (A) obtained by the second production method does not contain the structural unit represented by the general formula (1) and does not contain the structural unit represented by the general formula (2) (general Ingredients where i = 0 and j = 0 in formula (7) may be included as by-products, but the handling properties as phenol resin (A) and the curability, fluidity and flame resistance of the resin composition are not impaired. A range of these by-products may be included. In addition, as a method of reducing the content of the above-mentioned by-product, a method of reducing the amount of formaldehyde, or removing unreacted aldehydes remaining in the reaction intermediate by a known method such as recrystallization or reduced pressure , Etc.

  In the phenol resin (A) obtained by the second production method, a binuclear component (a dinuclear phenol aralkyl having a phenylene skeleton, a part of hydrogen atoms of the phenylene skeleton is a hydrocarbon group having 1 to 6 carbon atoms. A phenol aralkyl dinuclear having a substituted phenylene skeleton, or a phenol novolac dinuclear). About these content rates, the content calculated | required by the area method of a gel permeation chromatograph (GPC) has preferable 20% or less, More preferably, it is 15% or less. When the binuclear amount exceeds the above upper limit, the phenol resin is likely to be blocked, and the curability of the resin composition is lowered. As a method of reducing the above-mentioned dinuclear body, the binuclear component can be reduced by increasing the degree of vacuum or extending the treatment time in steam distillation or vacuum distillation after the reaction of phenol.

  Here, in order to obtain a phenol resin with a lower viscosity, increase the compounding amount of the phenol compound, reduce the formaldehyde component, decrease the compounding amount of the acid catalyst, and if hydrogen halide gas is generated, this is removed with a nitrogen stream. For example, a method of reducing the production of a high molecular weight component by a method such as quickly discharging out of the system or lowering the cocondensation temperature can be used. In this case, the progress of the reaction is represented by the general formulas (3) and (4), the generation of water, hydrogen halide, and alcohol gas by-produced by the reaction between the reaction intermediate and phenol, or the product during the reaction And the molecular weight can be confirmed by gel permeation chromatography.

The phenol resin (A) used in the present invention is a phenol resin composed of one or more components, and a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) A phenol resin containing a component (A1) comprising a polymer containing, specifically, the following component 1) or 2) is an essential component, and the following components 3) to 6) can be included.
1) Copolymer of a phenol aralkyl resin having a phenylene skeleton and a phenol aralkyl resin having a phenylene skeleton in which some of the hydrogen atoms of the phenylene skeleton are substituted with a hydrocarbon group having 1 to 6 carbon atoms 2) having a phenylene skeleton Copolymer of phenol aralkyl resin and phenol novolac resin having a phenylene skeleton in which a part of hydrogen atoms of the phenylene skeleton is substituted with a hydrocarbon group having 1 to 6 carbon atoms 3) Phenol aralkyl having a phenylene skeleton Resin or phenol aralkyl resin having a phenylene skeleton in which a part of hydrogen atoms of the phenylene skeleton is substituted with a hydrocarbon group having 1 to 6 carbon atoms 4) Phenol novolac resin 5) Phenol aralkyl resin having a phenylene skeleton or phenylene skeleton Part of hydrogen atom A copolymer of a phenol aralkyl resin having a phenylene skeleton and a phenol novolac resin having a phenylene skeleton substituted with a hydrocarbon group having 1 to 6 carbon atoms. 6) In the phenol resin of the above 1) to 5), the terminal of the molecule or hydroxy Polymer in which phenyl group substituted with 1 to 4 hydrocarbon groups having 1 to 6 carbon atoms is bonded directly or via a paraxylylene group to a phenyl group substituent

  By including a polymer having a plurality of structures as described above, the phenol aralkyl resin having a phenylene skeleton has a low viscosity but is difficult to be fixed, so that the handling property is good and the curability is not impaired. It has excellent solderability and flame resistance, and can exhibit good continuous formability. In particular, in the case of the second production method, the raw material cost is lower than that of the phenol aralkyl resin having a phenylene skeleton, and it can be produced at a low cost.

  The values of m and n in the general formula (6) and the values of i, j, and k in the general formula (7) can be obtained by FD-MS measurement. For each peak detected by FD-MS analysis measured in a detected mass (m / z) range of 50 to 2000, the molecular weight and the number of repetitions (m, n and i, j) are determined from the detected mass (m / z). K), and by calculating the intensity ratio of each peak as a content ratio (mass), the average values of m and n and the average values of i, j, and k can be obtained. it can.

  When the phenol resin (A) contains a phenol novolac resin, the content of the phenol novolac resin in the phenol resin (A) is 5 to 20% by mass, more preferably 5%, based on the total amount of the phenol resin (A). ˜15 mass%. By setting it as the above range, good curability and flame resistance can be obtained.

  The compounding amount of the phenol resin (A) in the resin composition for semiconductor encapsulation of the present invention is preferably 0.5% by mass or more, more preferably 1% with respect to the total mass of the resin composition for semiconductor encapsulation. It is at least mass%, more preferably at least 1.5 mass%. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the amount of the phenol resin in the resin composition for semiconductor encapsulation is preferably 10% by mass or less, more preferably 9% by mass, and still more preferably 8% with respect to the total mass of the semiconductor encapsulation resin composition. It is below mass%. When the upper limit is within the above range, the resulting resin composition has good solder resistance and curability.

  In the resin composition for semiconductor encapsulation of this invention, another hardening | curing agent can be used together in the range by which the effect by using the said phenol resin (A) is not impaired. Examples of the curing agent that can be used in combination include a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent. Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA). In addition to aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, etc .; alicyclics such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides, including acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic anhydrides such as benzophenone tetracarboxylic acid (BTDA), etc .; novolac-type phenolic resin, phenol Polyphenol compounds such as Rimmer; polysulfide, thioester, polymercaptan compounds such as thioethers; isocyanate prepolymer, isocyanate compounds such as blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resins.

Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF ₃ complexes.

  Examples of the condensation type curing agent include phenolic resin-based curing agents such as novolak type phenolic resin and resol type phenolic resin; urea resin such as methylol group-containing urea resin; melamine resin such as methylol group-containing melamine resin; Can be mentioned.

  Among these, a phenol resin-based curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. The phenol resin-based curing agent 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, novolak resin such as naphthol novolak resin; polyfunctional phenol resin such as triphenolmethane phenol resin; modified phenol resin such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton and / or biphenylene skeleton Aralkyl type resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, etc. Type may be used in combination of two or more be used alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  In the case where such other curing agents are used in combination, the lower limit value of the blending ratio of the phenol resin (A) is preferably 20% by mass or more and 30% by mass or more with respect to the total curing agent. It is more preferable, and it is especially preferable that it is 50 mass% or more. When the blending ratio is within the above range, good fluidity can be exhibited while maintaining flame resistance and solder resistance.

  The lower limit of the blending ratio of the entire curing agent is not particularly limited, but is preferably 0.8% by mass or more and more preferably 1.5% by mass or more in the total resin composition. preferable. When the lower limit value of the blending ratio is within the above range, sufficient fluidity can be obtained. Further, the upper limit of the blending ratio of the entire curing agent is not particularly limited, but is preferably 10% by mass or less and more preferably 8% by mass or less in the entire resin composition. . When the upper limit of the blending ratio is within the above range, good solder resistance can be obtained.

Examples of the epoxy resin (B) used in the resin composition for semiconductor encapsulation of the present invention include crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, anthracene diol type epoxy resins; Novolak type epoxy resins such as phenol novolac type epoxy resins and cresol novolak type epoxy resins; polyfunctional epoxy resins such as triphenolmethane type epoxy resins and alkyl-modified triphenolmethane type epoxy resins; phenol aralkyl type epoxy resins having a phenylene skeleton; Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a biphenylene skeleton, naphthol aralkyl type epoxy resins having a phenylene skeleton, dihydroxynaphthalene type epoxy resins, A naphthol type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a dimer of hydroxynaphthalene; a novolac type epoxy resin having a methoxynaphthalene skeleton; a triazine nucleus-containing epoxy resin such as triglycidyl isocyanurate or monoallyl diglycidyl isocyanurate Bridged cyclic hydrocarbon compound-modified phenolic epoxy resins such as dicyclopentadiene-modified phenolic epoxy resins, but are not limited thereto. These epoxy resins preferably do not contain Na ⁺ ions or Cl ⁻ ions, which are ionic impurities, as much as possible from the viewpoint of moisture resistance reliability of the obtained resin composition for semiconductor encapsulation. Moreover, it is preferable that the epoxy equivalent of an epoxy resin is 100 g / eq or more and 500 g / eq or less from a sclerosing | hardenable viewpoint of a semiconductor resin composition.

  Among them, biphenyl type epoxy resins and bisphenol type epoxy resins are preferable from the viewpoint of fluidity, and from the viewpoint of solder resistance, phenol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having a biphenylene skeleton, and methoxynaphthalene. A novolac type epoxy resin having a skeleton is preferable. From the viewpoint of low warpage in a single-side sealed semiconductor device, a triphenolmethane type epoxy resin, a naphthol aralkyl type epoxy resin having a phenylene skeleton, an anthracenediol type epoxy resin, and the like are preferable. If it is such an epoxy resin, as shown in the examples described later, by using it in combination with the phenol resin (A) of the present invention, while improving the fluidity, handling, solder resistance, flame resistance and The effect that the balance of continuous formability is stably improved is obtained.

  The amount of the epoxy resin (B) in the resin composition for semiconductor encapsulation is preferably 2% by mass or more, more preferably 4% by mass or more, based on the total mass of the resin composition for semiconductor encapsulation. . When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the amount of the epoxy resin in the resin composition for semiconductor encapsulation is preferably 15% by mass or less, more preferably 13% by mass or less, with respect to the total mass of the resin composition for semiconductor encapsulation. When the lower limit is in the above range, the resulting resin composition has good solder resistance.

  The phenol resin and the epoxy resin have an equivalent ratio (EP) / (OH) between the number of epoxy groups (EP) of all epoxy resins and the number of phenolic hydroxyl groups (OH) of all phenol resins, of 0.8 or more, It is preferable to mix | blend so that it may become 1.3 or less. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when the resulting resin composition is molded.

  As an inorganic filler (C) used for the resin composition for semiconductor encapsulation of the present invention, an inorganic filler generally used in this field can be used. Examples thereof include fused silica, spherical silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. The particle size of the inorganic filler is desirably 0.01 μm or more and 150 μm or less from the viewpoint of filling properties in the mold cavity.

  The amount of the inorganic filler (C) in the resin composition for semiconductor encapsulation is preferably 80% by mass or more, more preferably 83% by mass or more, based on the total mass of the resin composition for semiconductor encapsulation. Yes, more preferably 86% by mass or more. When the lower limit value is within the above range, an increase in moisture absorption and a decrease in strength due to curing of the resulting resin composition can be reduced, and therefore a cured product having good solder crack resistance can be obtained. Moreover, the amount of the inorganic filler in the resin composition for semiconductor encapsulation is preferably 93% by mass or less, more preferably 91% by mass or less, with respect to the total mass of the resin composition for semiconductor encapsulation. More preferably, it is 90 mass% or less. When the upper limit is within the above range, the resulting resin composition has good fluidity and good moldability.

  In addition, when using inorganic flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc molybdate and antimony trioxide described later, these inorganic flame retardants and the above It is desirable that the total amount of the inorganic filler is within the above range.

  The resin composition for semiconductor encapsulation of the present invention contains a curing accelerator (D). The curing accelerator (D) is not particularly limited as long as it accelerates the reaction between the epoxy group of the epoxy resin and the hydroxyl group of the phenol resin, and a generally used curing accelerator (D) can be used. Specific examples include phosphorus-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo (5 , 4, 0) Undecene-7, benzyldimethylamine, nitrogen atom-containing compounds such as 2-methylimidazole. Among these, a phosphorus atom-containing compound is preferable from the viewpoint of curability, and from the viewpoint of balance between fluidity and curability, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, a phosphonium compound A catalyst having latency such as an adduct of silane compound and silane compound is more preferable. In view of fluidity, tetra-substituted phosphonium compounds are particularly preferable. From the viewpoint of solder resistance, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds are particularly preferable, and in view of latent curability. An adduct of a phosphonium compound and a silane compound is particularly preferable. Further, from the viewpoint of continuous moldability, a tetra-substituted phosphonium compound is preferable.

  Examples of the organic phosphine that can be used in the resin composition for encapsulating a semiconductor of the present invention include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, and tributyl. Third phosphine such as phosphine and triphenylphosphine can be used.

  Examples of the tetra-substituted phosphonium compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following general formula (8).

In the general formula (8), P represents a phosphorus atom, R17, R18, R19 and R20 each independently represents an aromatic group or an alkyl group, and A represents a functional group selected 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 groups in the aromatic ring, and AH is an aromatic organic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring Represents an acid, 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 (8) 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. Subsequently, when water is added, the compound represented by the general formula (8) can be precipitated. In the compound represented by the general formula (8), R17, R18, R19, and R20 bonded to the phosphorus atom are phenyl groups and AH is bonded to the phosphorus atom from the viewpoint of excellent balance between the yield at the time of synthesis and the curing acceleration effect. A compound having a hydroxyl group in an aromatic ring, that is, a phenol compound, and A is preferably an anion of the phenol compound.

  Examples of the phosphobetaine compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following general formula (9).

In General formula (9), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group, f is an integer of 0-5, g is an integer of 0-4.

  The compound represented by the general formula (9) 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 resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (10).

In General Formula (10), P represents a phosphorus atom, R21, R22, and R23 each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R24, R25, and R26 independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R24 and R25 may be bonded to each other to form a ring.

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent such as a substituent or an alkyl group or an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. 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 (10), R21, R22 and R23 bonded to the phosphorus atom are phenyl groups, and R24, R25 and R26 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferred in that it reduces the thermal elastic modulus of the cured product of the resin composition.

  Examples of the adduct of a phosphonium compound and a silane compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following formula (11).

In the general formula (11), P represents a phosphorus atom, and Si represents a silicon atom. R27, R28, R29 and R30 each independently represent an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group, and X2 is an organic group bonded to the groups Y2 and Y3. X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 represent a group formed by releasing a proton from a proton donating group, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure. Y4 and Y5 represent a group formed by releasing a proton from a proton donating group, and groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4, and Y5 may be the same or different from each other. Z1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.

  In the general formula (11), as R27, R28, R29 and R30, 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 (11), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other. The groups represented by -Y2-X2-Y3- and Y4-X3-Y5- in the general formula (11) are composed of groups in which a proton donor releases two protons. Examples of proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, Examples include 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable from the viewpoint of easy availability of raw materials and a curing acceleration effect.

  Z1 in the general formula (11) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions such as aliphatic hydrocarbon groups such as octyl group and aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group 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 proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then room temperature. Sodium methoxide-methanol solution is added dropwise with stirring. 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.

  The lower limit of the blending ratio of the curing accelerator (D) used for the resin composition for semiconductor encapsulation of the present invention is preferably 0.1% by mass or more in the total resin composition. Sufficient curability can be obtained when the lower limit of the blending ratio of the curing accelerator (D) is within the above range. Moreover, it is preferable that the upper limit of the mixture ratio of a hardening accelerator (D) is 1 mass% or less in all the resin compositions. Sufficient fluidity | liquidity can be obtained as the upper limit of the mixture ratio of a hardening accelerator (D) is in the said range.

The glycerin trifatty acid ester (E) used in the present invention is a triester obtained from glycerin and saturated fatty acid, and acts as a release agent. The glycerin trifatty acid ester (E) used in the present invention is not particularly limited. For example, glycerin tricaproic acid ester, glycerin tricaprylic acid ester, glycerin tricapric acid ester, glycerin trilauric acid ester, glycerin. Trimyristic acid ester, glycerin tripalmitic acid ester, glycerin tristearic acid ester, glycerin triraquinic acid ester, glycerin tribehenic acid ester, glycerin trilignoceric acid ester, glycerin triserotinoic acid ester, glycerin trimontanic acid ester, glycerin Trimellisin ester and the like can be mentioned. Of these, glycerin trifatty acid esters with saturated fatty acids having 22 to 36 carbon atoms are preferred. Furthermore, glycerin trimontanate is more preferable. These glycerin trifatty acid esters may be used alone or in combination of two or more. In addition, the carbon number of the saturated fatty acid in the present invention refers to the sum of the carbon number of the alkyl group and the carboxyl group in the saturated fatty acid.

  The dropping point of the glycerin trifatty acid ester (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 the glycerin trifatty acid ester (E) is within the above range, the glycerin trifatty acid ester (E) is excellent in thermal stability, and the glycerin trifatty acid ester (E) is not easily seized during continuous molding. Therefore, it is excellent in the mold release property of the resin cured material from a metal mold | die, and is excellent also in continuous moldability. Furthermore, when it hardens | cures a resin composition as it is in the said range, glycerol tri-fatty acid ester (E) fully fuse | melts. Thereby, glycerol tri fatty acid ester (E) disperse | distributes substantially uniformly in resin cured | curing material. Therefore, segregation of the glycerin trifatty acid ester (E) to the surface of the cured resin can be suppressed, and deterioration of the mold stain and the appearance of the cured resin can be reduced.

  The acid value of the glycerin trifatty acid ester (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 acid value is within the above range, the glycerin trifatty acid ester (E) is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, phase separation does not raise | generate a glycerol tri fatty acid ester (E) and an epoxy resin matrix. Therefore, segregation of glycerin trifatty acid ester (E) on the surface of the cured resin product is suppressed, and deterioration of the appearance of the mold and the cured resin product can be reduced. Furthermore, since the glycerin trifatty acid ester (E) exists 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 with the epoxy resin matrix is too high, the glycerin trifatty acid ester (E) cannot ooze out on the surface of the cured resin, and sufficient releasability may not be ensured.

  The blending ratio of glycerin trifatty acid ester (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 and 0.5% by weight in the resin composition. % Or less. It is excellent in the mold release property of the resin cured material from a metal mold | die within the said range. Moreover, when it is within the above range, adhesion between the cured resin and the lead frame member is not impaired, and peeling between the cured resin and the lead frame member during the soldering process can be suppressed. Moreover, when it is in the above-mentioned range, it is also possible to suppress deterioration of mold stains and resin cured product appearance.

  Although it does not specifically limit about the manufacturing method of the glycerol tri fatty acid ester (E) used by this invention, For example, it can obtain by the method etc. which carry out an ester reaction according to a well-known method, using glycerol and a fatty acid as a raw material compound. . The glycerin trifatty acid ester (E) used in the present invention is commercially available, such as Clariant Japan Co., Ltd., Recolve WE4, and, if necessary, a rotating disk mill (pin mill), screen mill (hammer mill). ), Using a crusher such as a centrifugal mill (turbo mill), a jet mill or the like, and pulverizing and adjusting the particle size.

  Other mold release agents can be used in combination as long as the effects of using the glycerin trifatty acid ester (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, a compound (F) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter also simply referred to as “compound (F)”) can be used. The compound (F) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring is used as a curing accelerator (D) that promotes a crosslinking reaction between a phenol resin and an epoxy resin. Even when a phosphorus atom-containing curing accelerator having no latency is used, the reaction during melt-kneading of the resin composition can be suppressed, and the resin composition can be obtained stably. The compound (F) also has the effect of lowering the melt viscosity of the resin composition and improving the fluidity. As the compound (F), a monocyclic compound represented by the following general formula (12) or a polycyclic compound represented by the following general formula (13) can be used. You may have the substituent of.

In General Formula (12), when one of R31 and R35 is a hydroxyl group and one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R32, R33, and R34 are a hydrogen atom, It is a hydroxyl group or a substituent other than a hydroxyl group.

In General Formula (13), when one of R36 and R42 is a hydroxyl group and one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R37, R38, R39, R40, and R41 are , A hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.

  Specific examples of the monocyclic compound represented by the general formula (12) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (13) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (F) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (F) may be used individually by 1 type, or may use 2 or more types together.

  The lower limit of the compounding ratio of the compound (F) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and particularly preferably 0.05% by mass or more in the total resin composition. It is. When the lower limit value of the compounding ratio of the compound (F) is within the above range, the resin composition can be sufficiently reduced in viscosity and improved in fluidity. In addition, the upper limit of the compounding ratio of the compound (F) is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less in the total resin composition. is there. When the upper limit of the compounding ratio of the compound (F) is within the above range, there is little possibility of causing a decrease in the curability of the resin composition and a decrease in the physical properties of the cured product.

  In the resin composition for semiconductor encapsulation of the present invention, a coupling agent (G) such as a silane coupling agent can be added in order to improve the adhesion between the epoxy resin and the inorganic filler. Examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, etc., reacting between epoxy resin and inorganic filler, and interfacial strength between epoxy resin and inorganic filler. What is necessary is just to improve. Moreover, a silane coupling agent can also raise the effect of the compound (F) of reducing the melt viscosity of a resin composition and improving fluidity | liquidity by using together with the above-mentioned compound (F).

  Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Etc. 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. of aminosilane The primary amino moiety may be used as a latent aminosilane coupling agent protected by reacting with a ketone or aldehyde, and examples of mercaptosilane include γ-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. In addition to silane coupling agents that exhibit the same functions as mercaptosilane coupling agents by thermal decomposition such as bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide These silane coupling agents may be pre-hydrolyzed, and these silane coupling agents may be used alone or in combination of two or more. Good.

  In the case of the present invention, mercaptosilane is preferable from the viewpoint of the balance between solder resistance and continuous moldability, and aminosilane is preferable from the viewpoint of fluidity, and is suitable for organic members such as polyimide on the silicon chip surface and solder resist on the substrate surface. Epoxysilane is preferable from the viewpoint of adhesion.

  The lower limit of the blending ratio of the coupling agent (G) such as a silane coupling agent that can be used in the resin composition for semiconductor encapsulation of the present invention is preferably 0.01% by mass or more in the total resin composition, More preferably, it is 0.05 mass% or more, Most preferably, it is 0.1 mass% or more. If the lower limit of the blending ratio of the coupling agent (G) such as a silane coupling agent is within the above range, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good solder resistance in a semiconductor device Cracking properties can be obtained. Moreover, as an upper limit of the mixture ratio of coupling agents (G), such as a silane coupling agent, 1 mass% or less is preferable in all the resin compositions, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.8. 6% by mass or less. If the upper limit of the blending ratio of the coupling agent (G) such as a silane coupling agent is within the above range, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good solder resistance in a semiconductor device Cracking properties can be obtained. Further, when the blending ratio of the coupling agent (G) such as a silane coupling agent is within the above range, the water absorption of the cured product of the resin composition does not increase, and good solder crack resistance in the semiconductor device. Can be obtained.

  In the resin composition for semiconductor encapsulation of the present invention, a flame retardant can be added in order to improve flame retardancy. Among these, a metal hydroxide or a composite metal hydroxide that inhibits the combustion reaction by dehydrating and absorbing heat during combustion is preferable in that the combustion time can be shortened. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconia hydroxide. The composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, wherein at least one metal element is magnesium, and the other metal elements are calcium, aluminum, tin, titanium, iron Any metal element selected from cobalt, nickel, copper, or zinc may be used, and as such a composite metal hydroxide, a magnesium hydroxide / zinc solid solution is commercially available. Of these, aluminum hydroxide and magnesium hydroxide / zinc solid solution are preferable from the viewpoint of the balance between solder resistance and continuous moldability. Said flame retardant may be used independently or may be used 2 or more types. Further, for the purpose of reducing the influence on continuous moldability, a surface treatment may be performed with a silicon compound such as a silane coupling agent or an aliphatic compound such as wax.

  In the semiconductor sealing resin composition of the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; stearic acid and zinc stearate Release agents such as higher fatty acids and their metal salts or paraffin; low-stress additives such as silicone oil and silicone rubber may be appropriately blended.

  The resin composition for encapsulating a semiconductor of the present invention is obtained by mixing a phenol resin, an epoxy resin, an inorganic filler, and the above-mentioned other additives, for example, uniformly at room temperature using a mixer or the like. Accordingly, it is possible to adjust to a desired degree of dispersion, fluidity, and the like by melt-kneading using a kneader such as a heating roll, a kneader, or an extruder, followed by cooling and pulverization as necessary.

  Next, the semiconductor device of the present invention will be described. As a method for producing a semiconductor device using the resin composition for semiconductor encapsulation of the present invention, for example, after a lead frame or a circuit board on which a semiconductor element is mounted is placed in a mold cavity, the resin for semiconductor encapsulation is used. The method of sealing this semiconductor element by shape | molding and hardening a composition with shaping | molding methods, such as a transfer mold, a compression mold, and an injection mold, is mentioned.

  Examples of the semiconductor element to be sealed include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.

  As a form of the obtained semiconductor device, for example, dual in-line package (DIP), chip carrier with plastic lead (PLCC), quad flat package (QFP), low profile quad flat package ( LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package ( TCP), ball grid array (BGA), chip size package (CSP), matrix array package ball grid array (MAPBGA), chip stacked chip support 'S package and the like, but not limited thereto.

  A semiconductor device in which a semiconductor element is encapsulated by a molding method such as transfer molding of a resin composition for encapsulating a semiconductor is used as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. After this resin composition is completely cured, it is mounted on an electronic device or the like.

  FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the resin composition for encapsulating a semiconductor 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 wire 4. The semiconductor element 1 is sealed with a cured body 6 of a semiconductor sealing resin composition.

  FIG. 2 is a view showing a cross-sectional structure of an example of a single-side sealed semiconductor device using the resin composition according to the present invention. The semiconductor element 1 is fixed on the substrate 8 through the die bond material cured body 2. The electrode pads of the semiconductor element 1 and the electrode pads on the substrate 8 are connected by wires 4. Only the single side | surface side in which the semiconductor element 1 of the board | substrate 8 was mounted is sealed by the hardening body 6 of the resin composition for sealing. The electrode pads on the substrate 8 are bonded to the solder balls 9 on the non-sealing surface side on the substrate 8 inside.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples at all. Unless otherwise specified, the amount of each component described below is part by mass.

(Curing agent)
The following phenol resins 1 to 7 were used as curing agents.
Phenol resin 1: A separable flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, m-xylene (special grade reagent manufactured by Kanto Chemical Co., Inc., m-xylene, boiling point 139 ° C., molecular weight 106, purity 99.4%) After weighing 100 parts by mass and 198 parts by mass of 20% by mass sodium hydroxide, heating was started while replacing with nitrogen. The system was stirred for 30 minutes while maintaining a temperature range of 50 to 60 ° C. and cooled to 10 ° C., then paraformaldehyde (special grade reagent manufactured by Kanto Chemical Co., Inc., paraformaldehyde, molecular weight 106, purity 90%, After adding 47.2 parts by mass and reacting for 2 hours with stirring, the system was neutralized by gradually adding 100 parts by mass of 38% by mass hydrochloric acid aqueous solution. An intermediate containing was obtained. In addition, temperature control operation was performed from the reaction start to the completion | finish of neutralization so that the temperature in a system might be the range of 10-15 degreeC. To this intermediate, 847 parts by mass of phenol (special grade reagent manufactured by Kanto Chemical Co., Inc., phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%), α, α′-dichloro-p-xylene (Tokyo) 343 parts by mass of a reagent manufactured by Kasei Kogyo Co., Ltd., melting point 100 ° C., molecular weight 175, purity 98%) was heated while performing nitrogen substitution and stirring, while maintaining the system temperature in the range of 110 to 120 ° C. Reacted for hours. The hydrochloric acid gas generated in the system by the above reaction was discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components and water were distilled off under reduced pressure conditions at 150 ° C. and 2 mmHg. Next, after adding 200 parts by mass of toluene and dissolving it uniformly, it was transferred to a separatory funnel, and after adding 150 parts by mass of distilled water and shaking, the operation of rinsing the aqueous layer (washing) was carried out to neutralize the washing water. Then, the oil layer is subjected to a vacuum treatment at 125 ° C. to distill off volatile components such as toluene and residual unreacted components, and phenol resin 1 represented by the following formula (14) (p in formula (14)) Is an integer from 0 to 20, q is an integer from 0 to 20, and r is an integer from 0 to 20, and the average values of p, q, and r are 1.7, 0.3, respectively. A hydroxyl group equivalent of 175, an ICI viscosity of 0.47 dPa · s at a softening point of 64 ° C. and 150 ° C. was obtained. The GPC chart of the obtained phenol resin 1 is shown in FIG. 3, and the FD-MS chart is shown in FIG. For example, m / z = 514 in the FD-MS analysis in FIG. 7 is (p, q, r) = (1, 1, 0) in formula (14), the left end is a hydrogen atom, and the right end is a hydroxyphenyl group. M / z = 526 is the component (p, q, r) = (1, 1, 0) in the formula (14), the left end is a hydrogen atom, and the right end is m-xylene. Correspondingly, it was confirmed that the phenol resin 1 contains the component (A1) composed of a polymer containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). In addition, as measured by gel permeation chromatographic area method, the amount of dinuclear body is 6.8%, and as measured by the relative intensity ratio of FD-MS, the total amount of polymer corresponding to component (A1), component ( The total amount of the polymer corresponding to A2) and the total amount of the polymer corresponding to component (A3) were 28%, 66% and 6%, respectively, in relative strength ratio. Moreover, ratio of the total number of the structural unit represented by General formula (1) in the phenol resin 1 whole and the total number of the structural unit represented by General formula (2) was 85/15. .

  Phenol resin 2: A separable flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, 116.3 parts by weight of formaldehyde 37% aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.), 98% by weight sulfuric acid 37 0.7 parts by mass and 100 parts by mass of m-xylene (special grade reagent manufactured by Kanto Chemical Co., Ltd., m-xylene, boiling point 139 ° C., molecular weight 106, purity 99.4%) were weighed, and then heating was started while replacing with nitrogen. The system was stirred for 6 hours while maintaining a temperature range of 90 to 100 ° C., cooled to room temperature, and then neutralized by gradually adding 150 parts by weight of 20 mass% sodium hydroxide. This reaction system, 839 parts by mass of phenol, and 338 parts by mass of α, α′-dichloro-p-xylene were added, heated while performing nitrogen substitution and stirring, and the system temperature was maintained within the range of 110 to 120 ° C. Reacted for hours. The hydrochloric acid gas generated in the system by the above reaction was discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components and water were distilled off under reduced pressure conditions at 150 ° C. and 2 mmHg. Next, after adding 200 parts by mass of toluene and dissolving it uniformly, it was transferred to a separatory funnel, and after adding 150 parts by mass of distilled water and shaking, the operation of rinsing the aqueous layer (washing) was carried out to neutralize the washing water. Then, the oil layer is subjected to vacuum treatment at 125 ° C. to distill off volatile components such as toluene and residual unreacted components, and phenol resin 2 represented by the following formula (14) (p in formula (14)). Is an integer of 0-20, q is an integer of 0-20, r is an integer of 0-20, and the average values of p, q, r are 1.8, 0.3, respectively. A hydroxyl equivalent of 180, a softening point of 67 ° C., and an ICI viscosity of 0.60 dPa · s at 150 ° C. was obtained. The GPC chart of the obtained phenol resin 2 is shown in FIG. 4, and the FD-MS chart is shown in FIG. For example, m / z = 514 in the FD-MS analysis of FIG. 8 is (p, q, r) = (1, 1, 0) in formula (14), the left end is a hydrogen atom, and the right end is a hydroxyphenyl group. M / z = 526 corresponds to the component (p, q, r) = (1,1,0) in the formula (14), the hydrogen atom at the left end and m-xylene at the right end And it has confirmed that the phenol resin 2 was a thing containing the component (A1) which consists of a polymer containing the structural unit represented by General formula (1), and the structural unit represented by General formula (2). In addition, the amount of dinuclear body is 6.6% as measured by gel permeation chromatographic area method, and the total amount of the polymer corresponding to component (A1) is measured according to the relative intensity ratio of FD-MS. The total amount of the polymer corresponding to A2) and the total amount of the polymer corresponding to component (A3) were 30%, 64% and 6%, respectively, in relative strength ratio. Moreover, ratio of the total number of the structural unit represented by General formula (1) in the phenol resin 1 whole and the total number of the structural unit represented by General formula (2) was 85/15. .

  Phenol resin 3: phenol (special grade reagent manufactured by Kanto Chemical Co., Inc., phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) 100 parts by mass, α, α′-dichloro-p-xylene (Tokyo Chemical Industry) Reagents, Inc., melting point 100 ° C., molecular weight 175, purity 98%) 65.2 parts by mass, 2,5-bis- (chloromethyl) -p-xylene (Sigma Aldrich reagent, melting point 133 ° C., molecular weight) 203, purity 98%) 32.4 parts by mass in a separable flask, equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, heated while bubbling nitrogen, and stirred at the start of melting The reaction was continued for 5 hours while maintaining the temperature in the system in the range of 110 ° C to 120 ° C. From the start to the end of the reaction, hydrogen chloride gas generated in the system by the reaction was quickly discharged out of the system by a nitrogen stream. The operation after completion of the reaction is the same as that of the phenol resin 1, and the phenol resin 3 represented by the following formula (15) (in the formula (15), s is an integer of 0 to 20, and t is an integer of 0 to 20). (The average value of s and t is 1.6 and 0.6, respectively. Hydroxyl equivalent weight 174, softening point 68 ° C., ICI viscosity 0.65 dPa · s at 150 ° C.) Obtained. A GPC chart is shown in FIG. 5, and an FD-MS chart is shown in FIG. For example, m / z = 514 in the FD-MS analysis of FIG. 9 is a component in which (s, t) = (1, 1) in formula (15), the left end is a hydrogen atom, and the right end is a hydroxyphenyl group. Correspondingly, it was confirmed that the phenol resin 3 includes a component (A1) composed of a polymer including the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). In addition, in the measurement by the gel permeation chromatograph area method, no binuclear substance is detected, and the total amount of the polymer corresponding to the component (A1), measured by the relative intensity ratio of FD-MS, the component (A2) The total amount of the polymer corresponding to 1 and the total amount of the polymer corresponding to the component (A3) were 36.5%, 48.5%, and 15.0% in relative strength ratio, respectively. The ratio of the total number of structural units represented by general formula (1) to the total number of structural units represented by general formula (2) in the entire phenol resin 2 was 72/28. .

  Phenol resin 4: In the synthesis of phenol resin 1, 1,3,5-trimethylbenzene (Tokyo Kasei Kogyo deer special grade reagent, boiling point 165 ° C., molecular weight 120, purity 99%) 100 weight instead of m-xylene Part, 20% by weight of sodium hydroxide, 175 parts by weight, paraformaldehyde, 66.7 parts, phenol, 1372 parts, α, α'-dichloro-p-xylene Except for changing to 620 parts by mass, the same synthetic operation as that of phenol resin 1 was performed, and phenol resin 4 represented by the following formula (16) (u in formula (16) was an integer of 0 to 20, v was 0. A polymer mixture in which an integer of ˜20 and w is an integer of 0 to 20, and the average values of u, v, and w are 1.9, 0.1, and 0.9, respectively. , Softening point 68 ICI viscosity at 150 ° C. and 0.65 dPa · s) was obtained. The GPC chart of the obtained phenol resin 2 is shown in FIG. 6, and the FD-MS chart is shown in FIG. For example, m / z = 528 in the FD-MS analysis of FIG. 10 is (u, v, w) = (1, 1, 0) in formula (14), the left end is a hydrogen atom, and the right end is a hydroxyphenyl group. The phenol resin 4 includes a component (A1) composed of a polymer including the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). It could be confirmed. In addition, the measurement by the gel permeation chromatograph area method has a binuclear amount of 11%, the measurement by the relative intensity ratio of FD-MS, the total amount of the polymer corresponding to the component (A1), the component (A2) The total amount of the polymer corresponding to the component (A3), the total amount of the polymer corresponding to the component (A3), and the total amount of the components not corresponding to (A1 to A3) (u = v = 0) are 12 in terms of relative intensity ratio. %, 86%, 1%, 1%. The ratio of the total number of structural units represented by general formula (1) to the total number of structural units represented by general formula (2) in the entire phenol resin 2 was 94/6. .

  Phenol resin 5: Phenol aralkyl resin having a phenylene skeleton (manufactured by Mitsui Chemicals, Inc., XLC-4L. Hydroxyl equivalent 168, softening point 62 ° C., ICI viscosity 0.76 dPa · s at 150 ° C.)

  Phenol resin 6: Phenol (special grade reagent manufactured by Kanto Chemical Co., Inc., phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) 100 parts by mass, xylene formaldehyde resin (manufactured by Fudou Co., Ltd., Nikanol LLL, average Molecular weight molecular weight 340) 67.7 parts by mass, p-toluenesulfonic acid monohydrate (Wako Pure Chemical Industries, Ltd., p-toluenesulfonic acid, molecular weight 190, purity 99%) 0.03 parts by mass is separable. The flask is weighed and heated while substituting with nitrogen, and stirring is started at the start of melting. After making it react for 1 hour after confirming that the system reached 110 ° C., 48.8 parts by mass of 37% formaldehyde aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts by mass of oxalic acid Was added over 30 minutes. Next, the reaction was carried out for 120 minutes while maintaining the temperature in the system in the range of 100 ° C to 110 ° C. Until the end of the reaction, water generated in the system by the reaction or mixed into the system with the addition of formalin was discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components were distilled off under reduced pressure conditions of 160 ° C. and 2 mmHg, and then 200 parts by mass of toluene was added and dissolved uniformly, then transferred to a separatory funnel, and 150 parts by mass of distilled water was added and shaken. After repeating the operation of rinsing the water layer (washing) until the wash water becomes neutral, volatile components such as toluene and residual unreacted components are distilled off by subjecting the oil layer to 125 ° C. under reduced pressure, Phenol resin 6 (hydroxyl equivalent 167, softening point 86 ° C., ICI viscosity 2.1 dPa · s at 150 ° C.) represented by the following formula (17) was obtained.

(X is an integer from 1 to 10, y is an integer from 0 to 10)
Phenol resin 7: Phenol resin represented by the following formula (18) (manufactured by FUDO Co., Ltd., Zystar GP-90, hydroxyl group equivalent 197, softening point 86 ° C., ICI viscosity 3.1 dPa · s at 150 ° C.)

  The softening points and ICI viscosities of phenol resins 1 to 7 are summarized in Table 1 below. Furthermore, the blocking of these phenol resins was evaluated. The results are listed in Table 1.

  In addition, blocking evaluation of the phenol resin was performed as follows. In a cylindrical cylindrical container made of polypropylene having an inner diameter of 29 mm and a height of 10 cm, 20 g of granular phenol resin previously cooled to 5 ° C. was put, and a piston with an outer diameter of 29 mm and a mass of 200 g was inserted into the cylindrical container, and set to a predetermined temperature. When the phenolic resin was loaded in a state where it stood vertically in the thermostat for a predetermined time, and then the phenolic resin was taken out by turning the cylindrical container upside down, it was easily removed from the container in its original granular form ◎, ◯ when the internal shape of the piston is maintained but easily unraveled by hand, x when the internal shape of the piston cannot be unraveled by hand, and xx when the resin cannot be melted and taken out.

  Phenol resins 1 to 4 corresponding to the phenol resin (A) containing the component (A1) composed of a polymer containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are: Phenol resin 5 containing only the structural unit represented by the general formula (1) (XLC-4L manufactured by Mitsui Chemicals, Inc.) and phenol resins 6 and 7 containing only the structural unit represented by the general formula (2) As a result, the viscosity was low and the blocking property was excellent.

(Epoxy resin)
The following epoxy resins 1 to 4 were used.

  Epoxy resin 1: phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC3000P. Epoxy equivalent 275, softening point 60 ° C., ICI viscosity 1.1 dPa · s at 150 ° C.)

  Epoxy resin 2: Biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd., YX-4000HK. Epoxy equivalent 191, softening point 105 ° C., ICI viscosity 0.03 dPa · s at 150 ° C.)

  Epoxy resin 3: bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., YSLV-80XY. Epoxy equivalent 190, softening point 80 ° C., ICI viscosity 0.03 dPa · s at 150 ° C.)

  Epoxy resin 4: Phenol aralkyl type epoxy resin having a phenylene skeleton (Mitsui Chemicals Co., Ltd., E-XLC-3L. Epoxy equivalent 238, softening point 52 ° C., ICI viscosity 1.2 dPa · s at 150 ° C.)

(Inorganic filler)
As the inorganic filler, 80 parts by mass of fused spherical silica FB560 (average particle size 30 μm) manufactured by Denki Kagaku Kogyo Co., Ltd., 10 parts by mass of synthetic spherical silica SO-C2 (average particle size 0.5 μm) manufactured by Admatex, Admatex A blend of 10 parts by weight of synthetic spherical silica SO-C5 (average particle size 1.5 μm) was used.

(Curing accelerator (D))
The following curing accelerators 1-5 were used.

  Curing accelerator 1: Curing accelerator represented by the following formula (20)

  Curing accelerator 2: Curing accelerator represented by the following formula (21)

  Curing accelerator 3: Curing accelerator represented by the following formula (22)

  Curing accelerator 4: Curing accelerator represented by the following formula (23)

  Curing accelerator 5: triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd., TPP)

As the release agent, the following release agents 1 to 5 were used.
Mold release agent 1: Glycerin trimontanic acid ester (manufactured by Clariant Japan Co., Ltd., Ricorub (registered trademark) WE4, dropping point 82 ° C., acid value 25 mgKOH / g)
Release agent 2: Glycerin trimellisin ester prepared by the method described above (drop point 95 ° C., acid value 30 mg KOH / g)
Release agent 3: Glycerin tribehenate prepared by the above-mentioned method (drop point 80 ° C., acid value 15 mgKOH / g)
Release agent 4: Glycerin monostearate (Riken Vitamin Co., Ltd., Riquemar (registered trademark) S-100, dropping point 65 ° C., acid value 2 mgKOH / g.)
Mold release agent 5: Carnauba wax (Nikko Fine Co., Ltd., Nikko Carnauba, melting point 83 ° C., acid value 7 mg KOH / g)

(Compound F)
As the compound F, a compound represented by the following formula (24) (manufactured by Tokyo Chemical Industry Co., Ltd., 2,3-naphthalenediol, purity 98%) was used.

(Silane coupling agent)
The following silane coupling agents 1 to 3 were used.
Silane coupling agent 1: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803).
Silane coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)

(Coloring agent)
Carbon black (MA600) manufactured by Mitsubishi Chemical Industries, Ltd. was used as a colorant.

Example 1
The following components were mixed at room temperature using a mixer, melted and kneaded with a heating roll at 80 ° C. to 100 ° C., then cooled, and then pulverized to obtain a resin composition for semiconductor encapsulation.
Phenolic resin 1 4.58 parts by weight Epoxy resin 1 7.92 parts by weight Inorganic filler 1 86.5 parts by weight Curing accelerator 1 0.4 parts by weight Release agent 1 0.2 parts by weight Silane coupling agent 1 1 part by mass Silane coupling agent 2 0.1 part by mass Colorant 0.2 part by mass The following resin sealing resin compositions were evaluated for the following items. The evaluation results are shown in Table 2.

(Evaluation item)
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 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.

  Flame resistance: Epoxy resin 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 composition was injection molded to produce a 3.2 mm thick flame proof test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method. 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 500 shots. Judgment criteria were ◎ for those that could be continuously molded up to 500 shots without any problems such as unfilling or mold release failure, ◯ for those that could be continuously molded up to 300 shots, and × otherwise.

  Package appearance and mold stain resistance: In the evaluation of the continuous moldability, the package and mold after 300 shots and after 500 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 300 shots, ◯ for those that have not been soiled up to 300 shots, and ◎ that are not dirty up to 500 shots. Further, in the above-mentioned continuous formability, those that could not be formed without any problem up to 500 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 15 and Comparative Examples 1 to 6
According to the formulation in Table 2, a 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 2.

  Examples 1-15 are the phenol resin (A) containing the component (A1) which consists of a polymer containing the structural unit represented by Formula (1), and the structural unit represented by Formula (2), and an epoxy resin. (B), an inorganic filler (C), a curing accelerator (D), and a glycerin trifatty acid ester (E), and the blending ratio of the structural unit of the phenol resin (A) was changed. , A modified type of epoxy resin (B), a modified type of curing accelerator (D), or a modified type of glycerin trifatty acid ester (E). Excellent results were obtained in the balance of fluidity (spiral flow), flame resistance, continuous formability, package appearance, mold stain resistance, and solder resistance.

  On the other hand, in Comparative Examples 1 to 6, any of the items of fluidity (spiral flow), flame resistance, continuous formability, package appearance, mold stain resistance, and solder resistance is not sufficient, and the balance is poor. became.

  According to the present invention, it is possible to obtain a resin composition for encapsulating a semiconductor having excellent flame resistance and solder resistance, excellent fluidity and curability, and further excellent continuous moldability. It is suitable for sealing a semiconductor device having a structure in which chips are stacked in one package or a wire wire diameter smaller than that of a conventional device.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Wire 5 Lead frame 6 Hardening body of sealing resin composition 7 Solder resist 8 Substrate 9 Solder ball

Claims (12)

A phenol resin comprising one or more components, the following general formula (1):
(In the general formula (1), R1 is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is an integer of 0 to 3. R2, R3, R4 and R5 are independent of each other. And a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
And the following general formula (2):
(In the above general formula (2), R1 is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is an integer of 0 to 3. R6 is independently 1 each having 1 carbon atom. And b is an integer of 1 to 4. R7, R8, R9 and R10 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
A phenol resin (A) containing a component (A1) made of a polymer containing a structural unit represented by:
Epoxy resin (B);
An inorganic filler (C);
A curing accelerator (D);
A semiconductor sealing resin composition comprising glycerin trifatty acid ester (E),
The dropping point of the glycerin trifatty acid ester (E) is 80 to 95 ° C., the acid value is 15 to 30 mg KOH / g,
The curing accelerator (D) is at least one curing accelerator selected from the group consisting of tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. agent only contains,
The epoxy resin (B) is at least one epoxy resin selected from the group consisting of biphenyl type epoxy resins, bisphenol type epoxy resins, phenol aralkyl type epoxy resins having a phenylene skeleton, and phenol aralkyl type epoxy resins having a biphenylene skeleton. And
And a butadiene-acrylonitrile copolymer having a carboxyl group, a reaction product of a butadiene-acrylonitrile copolymer having a carboxyl group and an epoxy resin, an organopolysiloxane having a carboxyl group, an organopolysiloxane having a carboxyl group and an epoxy resin A reaction product of, and an organopolysiloxane having a polycaprolactone group, and a reaction product of an organopolysiloxane having a polycaprolactone group and an epoxy resin,
A resin composition for encapsulating a semiconductor.   The total relative strength of the polymer corresponding to the component (A1) is 10% or more and 80% or less with respect to the total relative strength of the phenol resin (A) as measured by field desorption mass spectrometry. The resin composition for semiconductor encapsulation according to claim 1, which is characterized by:   The phenol resin (A) further includes a component (A2) comprising a polymer containing the structural unit represented by the general formula (1) and not containing the structural unit represented by the general formula (2). The resin composition for semiconductor encapsulation according to claim 1 or 2, wherein the resin composition is for semiconductor encapsulation.   The phenol resin (A) further includes a component (A3) comprising a polymer containing the structural unit represented by the general formula (2) and not containing the structural unit represented by the general formula (1). The resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein:   The ratio of the total number of structural units represented by the general formula (1) and the total number of structural units represented by the general formula (2) in the phenol resin (A) as a whole is 30/70 to It is 95/5, The resin composition for semiconductor sealing of any one of Claim 1 thru | or 4 characterized by the above-mentioned.   6. The semiconductor encapsulation according to claim 1, wherein R6 in the structural unit represented by the general formula (2) is a methyl group, and b is 1 to 3. Resin composition.   7. The resin composition for encapsulating a semiconductor according to claim 1, wherein the phenol resin (A) is contained in a total curing agent in an amount of 20% by mass to 100% by mass. . Wherein the inorganic filler (C) content is 80 mass% or more, the resin composition for semiconductor encapsulation according to any one of claims 1 to 7, characterized in that at most 93 mass%. Any of the semiconductor encapsulating resin composition of claim 1 to claim 8 and further comprising a compound in which a hydroxyl group each carbon atom is bonded to adjacent two or more constituting the aromatic ring (F) The resin composition for semiconductor encapsulation according to item 1. The said resin composition for semiconductor sealing further contains a coupling agent (G), The resin composition for semiconductor sealing of any one of Claim 1 thru | or 9 characterized by the above-mentioned. The resin composition for semiconductor encapsulation according to claim 10 , wherein the coupling agent (G) contains a silane coupling agent having a secondary amino group. The semiconductor device obtained by sealing a semiconductor element with the hardened | cured material of the resin composition for semiconductor sealing of any one of Claim 1 thru | or 11 .