JP5573344B2 - Resin composition for sealing and electronic component device - Google Patents

Description

  The present invention relates to a sealing resin composition and an electronic component device.

  The demand for miniaturization, weight reduction, and high performance of electronic equipment has never been stopped, and higher integration and higher density of elements (hereinafter also referred to as “chips”) have progressed year by year. Surface mounting technology has also appeared in the mounting system (hereinafter also referred to as “package”) and is becoming popular. With the advancement of the peripheral technology of such electronic component devices, the demand for a resin composition for sealing an element has also become severe. For example, in the surface mounting process, moisture-absorbing electronic component devices are exposed to high temperatures during solder processing, and cracks and internal delamination occur due to the explosive stress of water vapor that has rapidly vaporized, significantly reducing the operational reliability of electronic component devices. . 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, with the spread of surface mounting technology and switching to lead-free solder, solder resistance has become one of the important technical issues for 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.

  From the above situation, biphenylene skeleton-containing phenol aralkyl epoxy resin, biphenylene skeleton-containing phenol aralkyl type curing as sealing resin composition that can obtain good flame retardancy without adding a flame retardant imparting agent A resin composition using an agent has been proposed (see, for example, Patent Document 3 and Patent Document 4). Although these resin compositions have the advantages of low water absorption, low thermal modulus, high adhesion, excellent flame retardancy, and high reliability electronic component devices, they can be molded after curing. Since the product is soft and highly oleophilic, there may be a problem in continuous formability in the sealing process of the electronic component device, resulting in a decrease in productivity.

  For such a problem, a method of adjusting the molecular weight distribution of the curing agent has been proposed (for example, see Patent Document 5). However, adjustment of the molecular weight distribution described above requires, for example, a step of purifying monomer raw materials in advance of molecular weight classification using a distillation or fractionation column or synthesis after synthesizing a phenol resin. In addition to requiring a large-scale refining facility and a solvent treatment facility, there is a problem that production costs increase due to recovery loss and the like.

  As described above, in the sealing resin composition, it has become an important subject to be excellent in the balance of solder resistance, flame retardancy, and continuous formability.

JP-A-7-130919 JP-A-8-20673 JP-A-11-140277 Japanese Patent No. 362736 International Publication No. 05/088783 Pamphlet

  The present invention provides an economical sealing resin composition having a good balance of solder resistance, flame retardancy, and continuous moldability, and an electronic component device having excellent reliability formed by sealing an element with a cured product thereof. Provided.

  The encapsulating resin composition of the present invention comprises one or more polymers having a structure represented by the following general formula (1), and (d-1) / c = 1 in the following general formula (1) It contains an epoxy resin (A) that also contains different polymers, a phenol resin-based curing agent (B), and an inorganic filler (C).

（上記一般式（１）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のグリシドキシフェニル基であり、構造式の両末端は水素原子である。ｃは１〜２０の整数であり、ｄは１〜２０の整数である。置換もしくは無置換のグリシドキシフェニレン基であるｄ個の繰り返し単位と、置換もしくは無置換のビフェニレン基であるｃ個の繰り返し単位とは、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよいが、それぞれの間には必ず置換もしくは無置換のメチレン基である−Ｃ（Ｒ３）（Ｒ４）−を有する。）

(In the general formula (1), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. A hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, and both ends of the structural formula are hydrogen atoms, c is an integer of 1 to 20 , D is an integer of 1 to 20. Each of d repeating units that are substituted or unsubstituted glycidoxyphenylene groups and c repeating units that are substituted or unsubstituted biphenylene groups are continuous with each other. Or may be alternately or randomly arranged, but each must have a substituted or unsubstituted methylene group -C (R3) (R4)-).

  In the sealing resin composition of the present invention, the epoxy resin (A) is represented by the following general formula (2) as a polymer different from (d-1) / c = 1 in the general formula (1). One or more polymers (A-1) having the structure shown below and / or one or more polymers (A-2) having the structure represented by the following general formula (3) can be included. .

（上記一般式（２）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のグリシドキシフェニル基である。ｅは１〜２０の整数、ｆは１〜１８の整数である。）

(In the above general formula (2), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, e is an integer of 1 to 20, and f is an integer of 1 to 18.)

（上記一般式（３）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のグリシドキシフェニル基である。ｇは１〜１９の整数、ｈは１〜９の整数である。）

(In the above general formula (3), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, g is an integer of 1 to 19, and h is an integer of 1 to 9.)

  The resin composition for sealing of the present invention has a total relative strength of polymers different from (d-1) / c = 1 in the general formula (1) as measured by field desorption mass spectrometry. The total relative strength of the entire resin (A) may be 5% or more and 80% or less.

  The resin composition for sealing of the present invention has a total relative strength of polymers different from (d-1) / c = 1 in the general formula (1) as measured by field desorption mass spectrometry. The total relative strength of the entire resin (A) may be 10% or more and 60% or less.

  In the sealing resin composition of the present invention, the content of the inorganic filler (C) may be 80% by mass or more and 93% by mass or less with respect to the total resin composition.

  In the sealing resin composition of the present invention, the epoxy equivalent of the epoxy resin (A) may be 220 g / eq or more and 300 g / eq or less.

  In the sealing resin composition of the present invention, the amount of the epoxy resin (A) may be 0.5% by mass or more and 10% by mass or less based on the total resin composition.

  The sealing resin composition of the present invention may further contain a curing accelerator (D).

  In the encapsulating resin composition of the present invention, the curing accelerator (D) comprises 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.

  The sealing resin composition of the present invention may further include a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring.

  The sealing resin composition of the present invention may further contain a coupling agent (F).

  In the sealing resin composition of the present invention, the coupling agent (F) may contain a silane coupling agent having a secondary amino group.

  The sealing resin composition of the present invention can further contain an inorganic flame retardant (G).

In the sealing resin composition of the present invention, the inorganic flame retardant (G) may contain a metal hydroxide or a composite metal hydroxide.

  The electronic component device of the present invention is obtained by sealing an element with a cured product obtained by curing the above-described sealing resin composition.

  According to the present invention, a sealing resin composition having an excellent balance of solder resistance, flame retardancy, and continuous moldability, and an electronic component device having excellent reliability formed by sealing an element with a cured product thereof are economical. Can be obtained.

It is the figure which showed the cross-sectional structure about an example of the electronic component apparatus using the resin composition for sealing which concerns on this invention. It is the figure which showed the cross-sectional structure about an example of the electronic component apparatus of the single-sided sealing type using the resin composition for sealing which concerns on this invention. It is a FD-MS chart of the epoxy resin 1 used in the Example. It is a FD-MS chart of the epoxy resin 2 used in the Example. It is a FD-MS chart of the epoxy resin 3 used in the Example. It is a FD-MS chart of the epoxy resin 4 used in the Example.

  The encapsulating resin composition of the present invention comprises one or more polymers having a structure represented by the following general formula (1), and (d-1) / c = 1 in the following general formula (1) It contains an epoxy resin (A) that also contains different polymers, a phenol resin-based curing agent (B), and an inorganic filler (C). Thereby, the resin composition for sealing excellent in balance of solder resistance, a flame retardance, and continuous moldability can be obtained. Moreover, the electronic component device of the present invention is obtained by sealing an element with a cured product of the above-described sealing resin composition. Thereby, the electronic component apparatus excellent in reliability can be obtained economically. Hereinafter, the present invention will be described in detail. In addition, the numerical range represented by “to” in the present specification includes both the upper limit value and the lower limit value.

  First, each component of the resin composition for sealing of this invention is demonstrated in detail.

（上記一般式（１）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のグリシドキシフェニル基であり、構造式の両末端は水素原子である。ｃは１〜２０の整数であり、ｄは１〜２０の整数である。置換もしくは無置換のグリシドキシフェニレン基であるｄ個の繰り返し単位と、置換もしくは無置換のビフェニレン基であるｃ個の繰り返し単位とは、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよいが、それぞれの間には必
ず置換もしくは無置換のメチレン基である−Ｃ（Ｒ３）（Ｒ４）−を有する。） [Epoxy resin (A)]
The epoxy resin (A) is composed of one or more polymers having a structure represented by the following general formula (1), and a polymer different from (d-1) / c = 1 in the following general formula (1). Including.

(In the general formula (1), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. A hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, and both ends of the structural formula are hydrogen atoms, c is an integer of 1 to 20 , D is an integer of 1 to 20. Each of d repeating units that are substituted or unsubstituted glycidoxyphenylene groups and c repeating units that are substituted or unsubstituted biphenylene groups are continuous with each other. Or may be alternately or randomly arranged, but each must have a substituted or unsubstituted methylene group -C (R3) (R4)-).

In the present invention, as shown in the following general formula (X), a part of the bond of the biphenylene structural formula may be represented by a dotted line, but this means that the bonding position is the following general formula (X-1) or the following general formula. It means any one of formula (X-2).

  In the general formula (1), the polymer corresponding to (d-1) / c = 1 includes d repeating units which are substituted or unsubstituted glycidoxyphenylene groups, and substituted or unsubstituted biphenylene groups. A phenol aralkyl type polymer having a biphenylene group, in which c repeating units are alternately arranged via —C (R 3) (R 4) — which is a substituted or unsubstituted methylene group. The resin composition is excellent in properties such as flame resistance, low water absorption, and solder resistance.

  In the general formula (1), the polymer corresponding to (d-1) / c> 1 has a local density of epoxy groups in the polymer as compared with a phenol aralkyl type polymer having a biphenylene group. Therefore, the adhesion with the metal lead frame can be improved, and further the curability with the curing agent component can be improved. As a result, the continuous formability of the resin composition and the solder resistance can be improved. An effect can be obtained.

  In the general formula (1), the polymer corresponding to (d-1) / c <1 has a relative amount of the biphenylene group in the polymer as compared with the phenol aralkyl type polymer having a biphenylene group. Since it increases, as a result, effects, such as an improvement in the flame resistance of a resin composition, a reduction in water absorption, and an improvement in solder resistance, can be obtained. Further, the effect of improving the continuous moldability can be obtained by reducing dirt on the mold surface and clogging of the resin in the air vent portion (air venting) during continuous molding. Although the details of the reason are unknown, it is presumed that a surface-active effect on the release agent component is generated by locally increasing the number of lipophilic biphenyl units in the molecule. An epoxy resin (A) can obtain the resin composition for sealing excellent in balance of solder resistance, a flame retardance, and continuous moldability by including said 3 component.

Among the epoxy resins (A) comprising one or more polymers having a structure represented by the general formula (1), as a polymer different from (d-1) / c = 1, the following general formula (2) One or more polymers (A-1) having a structure represented and / or one or more polymers (A-2) having a structure represented by the following general formula (3) may be included. The one or more polymers (A-1) having a structure represented by the following general formula (2) are included in the epoxy resin (A) comprising one or more polymers having a structure represented by the general formula (1). In the polymer of (d-1) / c = (e + f) / e> 1, one or more polymers (A-2) having a structure represented by the following general formula (3) are represented by the general formula (1). ) Is a polymer corresponding to (d-1) / c = g / (g + h) <1 in the epoxy resin (A) comprising one or more polymers having a structure represented by: The epoxy resin (A) containing these polymers can be obtained by a synthesis method described later.

（上記一般式（２）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のグリシドキシフェニル基である。ｅは１〜２０の整数、ｆは１〜１８の整数である。）

(In the above general formula (2), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, e is an integer of 1 to 20, and f is an integer of 1 to 18.)

（上記一般式（３）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のグリシドキシフェニル基である。ｇは１〜１９の整数、ｈは１〜９の整数である。）

(In the above general formula (3), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, g is an integer of 1 to 19, and h is an integer of 1 to 9.)

  The epoxy resin (A) has a relative strength of a polymer different from (d-1) / c = 1 in the general formula (1) as measured by Field Desorption Mass Spectrometry (FD-MS). The total is preferably from 5% to 80%, more preferably from 10% to 60%, more preferably from 20% to 40%, based on the total relative strength of the epoxy resin (A). It is particularly preferred that When the total relative strength of the polymers different from (d-1) / c = 1 is within the above range, a resin composition having an excellent balance of flame resistance, continuous moldability and solder resistance can be obtained. it can. Here, when the sum of the relative strengths of the polymers corresponding to (d-1) / c> 1 is larger than the above upper limit value, the flame resistance and solder resistance may be lowered. When the sum of the relative strengths of the polymers corresponding to (d-1) / c <1 is larger than the above upper limit value, the continuous moldability may be lowered. When the total ratio of the relative strengths of the polymers different from (d-1) / c = 1 is smaller than the above lower limit value, the resulting resin composition has solder resistance and continuous moldability, or solder resistance and Flame resistance may be reduced. In addition, FD-MS measurement is carried out in a detection mass (m / z) range of 50 to 2000, and for each detected peak, the molecular weight from the detection mass (m / z) and the number of repetitions c, d, and e to The value of h can be obtained.

Next, an example of a method for synthesizing the epoxy resin (A) will be described.
The epoxy resin (A) is prepared by dissolving “precursor phenol resin (P)” described later in excess epihalohydrin, and then in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at 50 to 150 ° C. A method of reacting at 60 to 120 ° C. for 1 to 10 hours is preferable. After completion of the reaction, excess epihalohydrins are distilled off, and the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off. Resin (A) can be obtained. The epihalohydrin used for the synthesis of the epoxy resin (A) of the present invention includes epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiodohydrin. Can be mentioned.

（上記一般式（４）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基であり、構造式の両末端は水素原子である。ｃは１〜２０の整数であり、ｄは１〜２０の整数である。置換もしくは無置換のヒドロキシフェニレン基であるｄ個の繰り返し単位と置換もしくは無置換のビフェニレン基であるｃ個の繰り返し単位は、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよいが、それぞれの間には必ず置換もしくは無置換のメチレン基である−Ｃ（Ｒ３）（Ｒ４）−を有する。） The precursor phenol resin (P) is composed of one or more polymers having a structure represented by the following general formula (4), and is different from (d-1) / c = 1 in the following general formula (4). The precursor phenol resin including a polymer is not particularly limited.

(In the general formula (4), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. A hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, and both ends of the structural formula are hydrogen atoms, c is an integer of 1 to 20, and d Is an integer of 1 to 20. The d repeating units that are substituted or unsubstituted hydroxyphenylene groups and the c repeating units that are substituted or unsubstituted biphenylene groups may be arranged consecutively, (Although they may be alternately or randomly arranged, they always have —C (R3) (R4) — which is a substituted or unsubstituted methylene group.)

  As a polymer different from (d-1) / c = 1 contained in the precursor phenol resin (P) comprising one or more polymers having a structure represented by the general formula (4), the following general formula (5 1) one or more polymers (P-1) having a structure represented by: and / or one or more polymers (P-2) having a structure represented by the following general formula (6): it can. One or more polymers (P-1) having a structure represented by the following general formula (5) are precursor phenol resins (P) composed of one or more polymers having a structure represented by the general formula (4). ) Of (d-1) / c = (e + f) / e> 1, and one or more polymers (P-2) having a structure represented by the following general formula (6): It is a polymer corresponding to (d-1) / c = g / (g + h) <1 of the precursor phenol resin (P) comprising one or more polymers having a structure represented by the general formula (4).

（上記一般式（５）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。ｅは１〜２０の整数、ｆは１〜１８の整数である。）

(In the above general formula (5), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, e is an integer of 1 to 20, and f is an integer of 1 to 18.)

（上記一般式（６）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。ｇは０〜１９の整数、ｈは１〜９の整数である。）

(In the general formula (6), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, and a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, g is an integer of 0 to 19, and h is an integer of 1 to 9.)

As a method for producing a precursor phenol resin (P) composed of one or more polymers having a structure represented by the general formula (4), for example,
(1) After reacting a biphenyl compound represented by the following general formula (7) and an aldehyde represented by the following general formula (8) under a strong acid catalyst to obtain a reaction intermediate (BF), A method obtained by adding a phenol compound represented by the following general formula (9) to the reaction (hereinafter also referred to as “first production method”),
(2) An aldehyde represented by the following general formula (8), a phenol compound represented by the following general formula (9), and a bifunctional biphenyl compound represented by the following general formula (10) under an acidic catalyst A method obtained by co-condensation polymerization (hereinafter also referred to as “second production method”),
(3) A phenol compound represented by the following general formula (9), a bifunctional biphenyl compound represented by the following general formula (10), and a monofunctional biphenyl compound represented by the following general formula (11) A method obtained by co-condensation polymerization under an acidic catalyst (hereinafter also referred to as “third production method”),
However, it is not limited to these. You may synthesize | combine using one of these manufacturing methods independently, or may synthesize | combine combining 2 or more types.

  The method of combining two or more of the above synthesis methods is not particularly limited. For example, the biphenyl-formaldehyde reaction intermediate (B-F) obtained by the first production method described later is used in the second or third method. The method of adding to the reaction system of a manufacturing method, or the method of adding the monofunctional biphenyl compound represented by General formula (11) as a raw material to the reaction system of a 2nd manufacturing method etc. can be mentioned. In addition, two or more precursor phenol resins obtained by different production methods may be mixed to obtain a precursor phenol resin (P), and epoxidized to obtain an epoxy resin (A). Alternatively, the epoxy resin (A) may be obtained by mixing two or more of the precursor phenol resins (P) obtained by different production methods, individually epoxidized.

（上記一般式（７）において、Ｒ２は、互いに独立して、炭素数１〜６の炭化水素基であり、ｂは０〜３の整数である。）

(In the general formula (7), R2 is independently a hydrocarbon group having 1 to 6 carbon atoms, and b is an integer of 0 to 3).

（上記一般式（８）において、Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。）

(In the general formula (8), R3 and R4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group.)

（上記一般式（９）において、Ｒ１は、互いに独立して、炭素数１〜９の炭化水素基であり、ａは０〜３の整数である。）

(In the general formula (9), R1 is independently a hydrocarbon group having 1 to 9 carbon atoms, and a is an integer of 0 to 3).

（上記一般式（１０）において、Ｒ２は、互いに独立して、炭素数１〜６の炭化水素基であり、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。Ｒ５及びＲ６は、互いに独立して、水素原子、炭素数１〜５の炭化水素であり、Ｒ５とＲ６が結合して環状構造となっていてもよい。Ｘは、水酸基、ハロゲン原子、又は炭素数１〜６のアルコキシ基である。）

(In the general formula (10), R2 is independently a hydrocarbon group having 1 to 6 carbon atoms, and b is an integer of 0 to 3. R3 and R4 are independently hydrogen. An atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, and R5 and R6 are each independently a hydrogen atom, a hydrocarbon having 1 to 5 carbon atoms, R6 may be bonded to form a cyclic structure, and X is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms.)

（上記一般式（１１）において、Ｒ２は、互いに独立して、炭素数１〜６の炭化水素基であり、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。Ｒ５及びＲ６は、互いに独立して、水素原子、炭素数１〜５の炭化水素であり、Ｒ５とＲ６が結合して環状構造となっていてもよい。Ｘは、水酸基、ハロゲン原子、又は炭素数１〜６のアルコキシ基である。）

(In the general formula (11), R2 is independently a hydrocarbon group having 1 to 6 carbon atoms, and b is an integer of 0 to 3. R3 and R4 are independently hydrogen. An atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, and R5 and R6 are each independently a hydrogen atom, a hydrocarbon having 1 to 5 carbon atoms, R6 may be bonded to form a cyclic structure, and X is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms.)

The biphenyl compound used as a raw material for the precursor phenol resin (P) is not particularly limited as long as it has a chemical structure represented by the general formula (7). For example, biphenyl, 1,1′-dimethylbiphenyl, 2,2′-dimethylbiphenyl, 3,3′-dimethylbiphenyl, 4,4′-dimethylbiphenyl, 1,1′-diethylbiphenyl, 2,2′-diethyl Biphenyl, 3,3′-diethylbiphenyl, 4,4′-diethylbiphenyl and the like can be mentioned, but are not limited thereto. These may be used alone or in combination of two or more. Among these, biphenyl is preferable from the viewpoint that it is relatively inexpensive and can be synthesized at a low temperature.

  The aldehydes used for the production of the precursor phenol resin (P) are not particularly limited as long as the chemical structure is represented by the general formula (8). Examples include, but are not limited to, formaldehyde, paraformaldehyde, acetaldehyde, salicylaldehyde, benzaldehyde and the like. These may be used alone or in combination of two or more. Among these, formaldehyde and paraformaldehyde are preferable from the viewpoints of curability of the resin composition and raw material costs.

  The phenol compound used for the production of the precursor phenol resin (P) is not particularly limited as long as it has a chemical structure represented by the general formula (9). For example, phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, Nonylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol and the like are exemplified, but not limited thereto. These may be used alone or in combination of two or more. 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 precursor phenol resin (P), these phenol compounds may be used alone or in combination of two or more.

  = C (R5) (R6) (alkylidene group) in the biphenylene compound represented by the general formulas (10) and (11) used for the production of the precursor phenol resin (P) includes a methylidene group, an 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 Group, 2-methylpentylidene group, 3-methylpentylidene group, 4-methylpentylidene group, 2,2-dimethylbutylidene group, 2,3-dimethylbutylidene group, 2,4-dimethylbutylidene group, 3,3-dimethylbutylidene group, 3,4-dimethylbutylidene group, 4,4-dimethylbutylidene group, 2-ethylbutylidene group, 1 Ethyl butylidene group and cyclohexylidene group and the like.

  In X in the compounds represented by the general formulas (10) and (11) used for the production of the precursor phenol resin (P), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It is done. 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, and 1-ethyl And a butoxy group.

The bifunctional biphenyl compound used for the production of the precursor phenol resin (P) is not particularly limited as long as it has a chemical structure represented by the general formula (10). For example, 4,4′-bischloromethylbiphenyl, 3,5-bischloromethylbiphenyl, 4,4′-bisbromomethylbiphenyl, 3,5-bisbromomethylbiphenyl, 4,4′-bisiodomethylbiphenyl, 3 , 5-bisiodomethylbiphenyl, 4,4'-bishydroxymethylbiphenyl, 3,5-bishydroxymethylbiphenyl, 4,4'-bismethoxymethylbiphenyl, 3,5-bismethoxymethylbiphenyl, 3,3 ' , 5,5′-tetramethyl-4,4′-bischloromethylbiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bisbromomethylbiphenyl, 3,3 ′, 5,5 '-Tetramethyl-4,4'-bisiodomethylbiphenyl, 3,3', 5,5'-tetramethyl-4,4'-bishydroxymethylbiphenyl, 3,3 ', , 5'-tetramethyl-4,4'-bis although methoxymethyl biphenyl, but is not limited thereto. These may be used alone or in combination of two or more. Among these, 4,4′-bismethoxymethylbiphenyl is preferable from the viewpoint that the synthesis is possible at a relatively low temperature, and the reaction by-product is easily distilled off and handled, which is caused by the presence of a small amount of moisture. Thus, 4,4′-bischloromethylbiphenyl is preferable in that the hydrogen halide generated can be used as an acid catalyst.

  The monofunctional biphenyl compound used for the production of the precursor phenol resin (P) is not particularly limited as long as it has a chemical structure represented by the general formula (11). For example, 4-chloromethylbiphenyl, 3-chloromethylbiphenyl, 2-chloromethylbiphenyl, 4-bromomethylbiphenyl, 4-iodomethylbiphenyl, 4-hydroxymethylbiphenyl, 4-methoxymethylbiphenyl, 3,3 ′, 5 Examples thereof include, but are not limited to, 5′-tetramethyl-4-chloromethylbiphenyl and 3,3′-dimethyl-4-chloromethylbiphenyl. These may be used alone or in combination of two or more. Among these, 4-methoxymethylbiphenyl is preferable from the viewpoint that synthesis is possible at a relatively low temperature, and that reaction by-products are easily distilled off and handled, and is generated due to the presence of a small amount of moisture. 4-chloromethylbiphenyl is preferred in that hydrogen halide can be used as an acid catalyst.

  The acidic catalyst used for the synthesis of the precursor phenol resin (P) is not particularly limited, but the strong acidic catalyst used in the first production method includes oxalic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and the like. Examples of the acidic catalyst used in the second and third production methods include formic acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and Lewis acid. In the second and third production methods, when X in the general formula (10) or the general formula (11) is a halogen atom, hydrogen halide produced as a by-product during the reaction acts as an acidic catalyst. Therefore, it is not necessary to add an acidic catalyst to the reaction system, and the reaction can be started quickly by adding a small amount of water.

  Among the methods for synthesizing the precursor phenol resin (P), in the case of the first production method, 1 to 2.5 mol of an aldehyde is used per 1 mol of the biphenyl compound represented by the general formula (7), and the catalyst. A strong acid such as paratoluenesulfonic acid, xylenesulfonic acid, sulfuric acid, etc. is added as 0.1 to 2.5 mol and reacted at a temperature of 100 to 150 ° C. for 0.5 to 5 hours to give a biphenyl-formaldehyde reaction intermediate ( BF) is obtained. Subsequently, 1 to 20 mol of phenol compound, 0 to 2.5 mol of aldehydes, acidic catalyst 0.005 to oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid, etc. While adding 0.05 mol and discharging the generated gas out of the system by nitrogen flow at a temperature of 50 to 200 ° C., a co-condensation reaction is carried out for 2 to 20 hours. It can be obtained by distilling off by a method such as distillation.

（ただし、上記一般式（１２）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。ｉは１〜２０の整数であり、ｊは０〜２０の整数である。置換もしくは無置換のヒドロキシフェニレン基を有するｊ個の繰り返し単位と、ビフェニレン基を有するi個
の繰り返し単位とは、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよい。） The precursor phenol resin obtained by the first production method (hereinafter also referred to as “precursor phenol resin (P-0)”) is composed of one or more polymers having a structure represented by the following general formula (12). In the following general formula (12), a polymer different from j / i = 1 is included. The relationship between i and j in the following general formula (12) and c and d in the general formula (4) is i = c, j = d−1, and j / i in the following general formula (12). The polymer of = 1 corresponds to the polymer of (d-1) / c = 1 in the general formula (4).

(However, in the said General formula (12), R1 and R2 are a C1-C9 hydrocarbon group mutually independently, a and b are integers of 0-3. R3 and R4 are Independently of each other, they are a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, i is an integer of 1 to 20, and j is an integer of 0 to 20. The j repeating units having a substituted or unsubstituted hydroxyphenylene group and the i repeating units having a biphenylene group may be arranged continuously or may be arranged alternately or randomly. )

  Examples of the hydrocarbon group having 1 to 9 carbon atoms in R1 and R2 in the general formula (12) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and 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, 4,4-dimethylbutyl group, 2 -Ethylbutyl group, 1-ethylbutyl group, nonyl group, cyclohexyl group, phenyl group and the like. These may be the same as or different from each other.

  Examples of the hydrocarbon group having 1 to 6 carbon atoms in R3 and R4 in the general formula (12) include methyl group, ethyl group, n-propyl group, isopropyl 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-methyl Pentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4,4-dimethylbutyl group , 2-ethylbutyl group, 1-ethylbutyl group, cyclohexyl group, phenyl group and the like. These may be the same as or different from each other.

When the values of i and j in the precursor phenol resin (P-0) comprising one or more polymers having a structure represented by the general formula (12) obtained by the first production method are described as average values, i The average value of is preferably 0.25 to 8, more preferably 0.5 to 4, and still more preferably 0.8 to 2, and the average value of j is preferably 0.4 to 12, more preferably 0.8. It is 6-6, More preferably, it is 0.8-3. The average value of i + j is preferably 0.8 to 20, and more preferably 1.7 to 10. When the above preferable range is rewritten as the average value of c and d in the general formula (1), the average value of c is preferably 0.25 to 8, more preferably 0.5 to 4, and still more preferably 0.8. The average value of d is preferably 1.4 to 13, more preferably 1.6 to 7, and still more preferably 1.8 to 4. The average value of c + d is preferably 1.8 to 21, and more preferably 2.7 to 11. When the average value of i is smaller than the above lower limit value, the flame resistance and solder resistance of the resin composition obtained after the epoxidation of the precursor phenol resin P-0 may be lowered. When the average value of i is larger than the above upper limit, the fluidity of the resin composition prepared after epoxidation of the precursor phenol resin P-0 may be lowered. Moreover, when the average value of j is smaller than the said lower limit, there exists a possibility that the continuous moldability and solder crack resistance of the resin composition obtained by preparing after epoxidation of precursor phenol resin P-0 may fall. When the average value of j is larger than the above upper limit value, the fluidity of the resin composition prepared after epoxidation of the precursor phenol resin 1 may be lowered. Moreover, when the average value of i + j is smaller than the said lower limit, sclerosis | hardenability and intensity | strength may fall. When the average value of i + j is larger than the above upper limit value, the fluidity of the resin composition prepared after epoxidation of the precursor phenol resin 1 may be lowered. The values of i and j are the hydrogen atom in the hydroxyl group contained in the skeleton by H-NMR or C-NMR measurement or the signal derived from the carbon atom bonded to the hydrogen atom, the hydrogen directly bonded to the benzene ring. It can be calculated by the intensity ratio of the signal derived from the carbon atom constituting the atom or benzene ring and the signal derived from the hydrogen atom or carbon atom contained in -C (R3) (R4)-. Similarly, the values corresponding to i and j in the epoxy resin obtained by epoxidizing the precursor phenol resin P-0 composed of one or more polymers having the structure represented by the general formula (12) The signal intensity ratio can be calculated by H-NMR or C-NMR measurement.

Here, as a method of adjusting the average value of j in the first manufacturing method,
(I) In the reaction of the biphenyl compound represented by the general formula (7) and the aldehyde, the amount of the aldehyde is increased to such an extent that gelation does not occur, the reaction temperature is increased, and the amount of the catalyst is increased.
(Ii) In the reaction of the reaction intermediate (BF) obtained by the reaction of the biphenyl compound represented by the general formula (7) and the aldehyde and the phenol compound, the compounding amount of the aldehyde is increased.
The average value of j can be increased by such a method.
In addition, as a method of adjusting the average value of i in the first manufacturing method,
(Iii) In the reaction of the intermediate (BF) obtained by the reaction of the biphenyl compound represented by the general formula (7) and aldehydes with the phenol compound, the phenol compound / reaction intermediate (BF) The average value of i can be increased by methods such as lowering the compounding ratio, increasing the reaction temperature, and increasing the amount of catalyst.
As a method of adjusting the average value of i + j, it can be adjusted by appropriately combining the methods (i) to (iii) described above.

  In the precursor phenol resin P-0 obtained by the first production method, a phenol novolak that is a polymer corresponding to i = 0 among one or more polymers having a structure represented by the general formula (12) Ingredients may be included. About these content rates, the sum total of the relative intensity | strength of the phenol novolak component calculated | required by the measurement by field desorption mass spectrometry (FD-MS) is 50% or less with respect to the sum total of the relative strength of the precursor phenol resin P-0 whole. Is preferable, more preferably 30% or less, still more preferably 15% or less. If the content of the phenol novolak (corresponding to i = 0 in the general formula (12)) component is larger than the above upper limit, the solder resistance and flame resistance of the resin composition prepared after epoxidation may be lowered. There is. As a method for adjusting the content ratio of the above-described phenol novolac (corresponding to i = 0 in the general formula (12)), an intermediate obtained by the reaction between the biphenyl compound represented by the general formula (7) and aldehydes is used. Formaldehyde (BF) is subjected to steam distillation under strong acid conditions to remove and remove the formaldehyde component, and then reacted with the phenol compound, thereby corresponding to phenol novolak (i = 0 in the general formula (12)) ) Component can be reduced.

Moreover, in the case of the 2nd manufacturing method among the synthesis methods of precursor phenol resin (P), the aldehydes represented by General formula (8) and the bifunctional biphenyl compound represented by General formula (10) 3 to 5 mol of the phenol compound represented by the general formula (9), formic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid Monomer remaining after completion of the reaction by reacting 0.005-0.05 mol of an acidic catalyst such as, etc. at a temperature of 50-200 ° C. while discharging the generated gas and moisture out of the system by nitrogen flow. Can be obtained by distilling off by a method such as vacuum distillation or steam distillation.

  The precursor phenol resin (P) obtained by the second production method is (d-1) / c = (e + f) / e ≧ out of one or more polymers having a structure represented by the general formula (4). 1 and includes at least one polymer having a structure represented by the following general formula (5) (hereinafter also referred to as precursor phenol resin (P-1 ′)). In addition, the ratio of the average value of e and f in the precursor phenol resin (P-1 ′) as a whole almost reflects the ratio of the bifunctional biphenyl compound represented by the general formula (10) and the aldehyde. A preferable range of the blending ratio is aldehydes: bifunctional biphenyl compound = 5: 95 to 70:30, more preferably 10:90 to 50:50 in terms of molar ratio. In the reaction, in addition to the method in which raw materials are charged all at once as described above, the reaction is started by adding phenols and a bifunctional biphenyl compound in advance, and then sequentially adding aldehydes, or in advance After adding the phenol compound and the aldehyde and starting the reaction, the order of addition such as sequentially adding the bifunctional biphenyl compound can be changed.

（上記一般式（５）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。ｅは１〜２０の整数、ｆは１〜１８の整数である。）

(In the above general formula (5), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, e is an integer of 1 to 20, and f is an integer of 1 to 18.)

The precursor phenol resin (P-1 ′) obtained by the second production method may contain a phenol novolak (a component corresponding to e = 0 in the general formula (5)) as a by-product. About these content rates, when the relative strength of the precursor phenol resin (P) and the epoxidized epoxy resin (A) is 100%, it is preferably 50% or less, more preferably 30% or less, and still more preferably Is 15% or less. When the component corresponding to e = 0 in the general formula (5) is larger than the upper limit, solder resistance and flame resistance may be lowered. As a method for reducing these, a phenol novolak (general formula) can be used by batch reaction in the second production method, or by adding aldehydes sequentially after reacting phenols with a bifunctional biphenyl compound in advance. Among the components (corresponding to e = 0 in (5)), the generation of components corresponding to e = 0 and f ≧ 3 in the general formula (5) can be suppressed. Further, when the precursor phenol resin (P-1 ′) obtained is subjected to steam distillation or vacuum distillation, the phenol novolak (e in the general formula (5) is increased by increasing the degree of vacuum or increasing the distillation treatment time. Among the components), the components corresponding to e = 0 and f ≦ 2 in the general formula (5) can be reduced. Alternatively, the components corresponding to e = 0 and f ≦ 2 in the general formula (5) can be removed by performing classification using a column for the precursor phenol resin (P-1).

Among the synthesis methods of the precursor phenol resin (P), in the case of the third production method, the bifunctional biphenyl compound represented by the general formula (10) and the monofunctional biphenyl represented by the general formula (11) 3 to 5 mol of the phenol compound represented by the general formula (9) with respect to 1 mol in total of the compound,
0.005 to 0.05 mol of an acidic catalyst such as formic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid, etc. at a temperature of 50 to 200 ° C. by nitrogen flow It can be obtained by reacting for 2 to 20 hours while discharging the generated gas and water out of the system, and distilling off the monomer remaining after the reaction by a method such as vacuum distillation or steam distillation.

  The precursor phenol resin (P) obtained by the third production method is (d-1) / c = g / (g + h) ≦ of one or more polymers having a structure represented by the general formula (4). 1 and includes one or more polymers having a structure represented by the following general formula (6) (hereinafter also referred to as precursor phenol resin (P-2 ′)). In addition, the ratio of the average value of g and h in the precursor phenol resin (P-2 ′) as a whole is represented by the bifunctional biphenyl compound represented by the general formula (10) used and the general formula (11). The ratio with the monofunctional biphenyl compound is almost reflected, and a preferable range of the blending ratio includes monofunctional biphenyl compound: bifunctional biphenyl compound = 5: 95 to 70:30 in terms of molar ratio, More preferably, it is 10: 90-50: 50.

（上記一般式（６）において、Ｒ１及びＲ２は、互いに独立して、炭素数１〜９の炭化水素基であり、ａ、ｂは０〜３の整数である。Ｒ３及びＲ４は、互いに独立して、水素原子、炭素数１〜６の炭化水素基、又は置換もしくは無置換のヒドロキシフェニル基である。ｇは０〜１９の整数、ｈは１〜９の整数である。）

(In the general formula (6), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, and a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted hydroxyphenyl group, g is an integer of 0 to 19, and h is an integer of 1 to 9.)

  Here, in order to obtain a precursor phenol resin (P) having a lower viscosity, the blending amount of the phenol compound is increased, the blending amount of the acid catalyst is decreased, and when hydrogen halide gas is generated, this is treated 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 reaction temperature can be used. In this case, the reaction proceeds by the generation of water by-produced by the reaction of aldehydes and phenol, hydrogen halide by-produced by the reaction of general formula (10) or general formula (11) and phenol, and alcohol gas. The situation or the product in the middle of the reaction can be sampled and confirmed by molecular weight by gel permeation chromatography.

  The precursor phenol resin (P) of the epoxy resin (A) used in the present invention is one or more polymers having a structure represented by the general formula (4). Precursor phenol resin (P-0) composed of one or more polymers having a structure represented by formula (5), and a precursor phenol resin (P) comprising one or more polymers having a structure represented by formula (5) -1 ′), a precursor phenol resin (P-2 ′) containing one or more polymers having a structure represented by the general formula (6) can be obtained. In the first production method and the second production method, May contain a component of a phenol novolac type resin.

Although there is no restriction | limiting in particular in the lower limit of the epoxy equivalent of an epoxy resin (A), 220 g / eq or more is preferable, More preferably, it is 230 g / eq or more, More preferably, it is 240 g / eq or more. When the lower limit is within the above range, the resulting resin composition has good flame resistance and solder resistance. The upper limit of the epoxy equivalent of the epoxy resin (A) is preferably 300 g / eq or less, more preferably 290 g / eq or less, still more preferably 280 g / eq or less.
When the upper limit is within the above range, the resulting resin composition has good fluidity and moldability.

  An epoxy resin (A) obtained by epoxidizing a precursor phenol resin (P) containing a polymer having a plurality of structures as described above is used to provide a sealing resin composition having an excellent balance of solder resistance, flame retardancy and continuous moldability. Can be obtained.

  The lower limit of the compounding amount of the epoxy resin (A) in the sealing resin composition of the present invention is preferably 0.5% by mass or more, more preferably relative to the total mass of the sealing resin composition. It is 1 mass% or more, More preferably, it is 1.5 mass% or more. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the upper limit of the compounding quantity of the epoxy resin (A) in the resin composition for sealing is preferably 12% by mass or less, more preferably 10% by mass or less, with respect to the total mass of the sealing resin composition. Yes, and more preferably 8% by mass or less. When the upper limit is within the above range, the resulting resin composition has good solder resistance and curability.

  In the sealing resin composition of the present invention, other epoxy resins can be used as long as the effects of using the epoxy resin (A) are not impaired.

Other epoxy resins that can be used in combination are not particularly limited. For example, crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, dihydroanthracene diol type epoxy resins; phenol novolac type epoxies Resin, novolak type epoxy resin such as cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin; aralkyl type epoxy such as phenol aralkyl type epoxy resin having phenylene skeleton Resin: Epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene-type epoxy resin, hydroxynaphthalene and / or dihydroxynaphthalene dimer, phenylene skeleton Epoxidizing a novolak naphthol resin obtained by reacting naphthols such as naphthol aralkyl type epoxy resin, hydroxynaphthalene or dihydroxynaphthalene with aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde and salicylaldehyde in the presence of an acid catalyst Naphthol type epoxy resins such as obtained resins; modified novolak type epoxy resins having a methoxynaphthalene skeleton; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene modified phenol type epoxy resins Examples thereof include, but are not limited to, a bridged cyclic hydrocarbon compound-modified phenol type epoxy resin. These epoxy resins preferably do not contain Na ⁺ ions and Cl ⁻ ions, which are ionic impurities, as much as possible from the viewpoint of moisture resistance reliability of the resulting sealing resin composition. From the viewpoint of curability of the resin composition, the epoxy equivalent of the epoxy resin is preferably 100 g / eq or more and 500 g / eq or less.

  Among them, biphenyl type epoxy resins and bisphenol type epoxy resins are preferable from the viewpoint of fluidity, and phenol aralkyl type epoxy resins having a phenylene skeleton and modified novolak type epoxy resins having a methoxynaphthalene skeleton from the viewpoint of solder resistance. preferable. Also, from the viewpoint of low warpage in a single-side sealed electronic component device, a triphenolmethane type epoxy resin, a naphthol aralkyl type epoxy resin having a phenylene skeleton, a resin obtained by epoxidizing a novolac type naphthol resin, a dihydroanthracenediol type Epoxy resins and the like are preferable.

In the case where such other epoxy is used in combination, the lower limit of the blending ratio of the epoxy resin (A) is preferably 30% by mass or more, and 50% by mass or more with respect to the total epoxy resin. Is more preferable, and 70% by mass or more is particularly preferable. When the blending ratio is within the above range, it is possible to obtain an effect of improving the balance of solder resistance, flame retardancy and continuous moldability of the resin composition.

  In addition, the phenol resin as a hardening | curing agent mentioned later and an epoxy resin are equivalent ratio (EP) / (OH) of the number of epoxy groups (EP) of all the epoxy resins, and the number of phenolic hydroxyl groups (OH) of all the phenol resins. However, it is preferable to mix | blend so that it may become 0.8 or more and 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.

[Phenolic resin curing agent (B)]
Next, the phenol resin curing agent (B) will be described. The phenol resin-based curing agent (B) 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, a phenol novolak resin , Novolak resins such as cresol novolac resin and naphthol novolak resin; polyfunctional phenol resins such as triphenolmethane phenol resin; modified phenol resins such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton and / or Aralkyl resins such as phenol aralkyl resins having a biphenylene skeleton, phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F; Zen, formaldehyde and a phenol of the resin obtained by polymerization and paraxylylene compounds modified with obtained phenol-modified alkyl-substituted aromatic hydrocarbon resins, and the like. Moreover, the above-mentioned precursor phenol resin (P) can be used as a curing agent. These may be used alone or in combination of two or more. Such a phenol resin curing agent (B) provides a good balance of flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like. Particularly, from the viewpoint of curability, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less.

  In the present invention, other curing agents can be used in combination. 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 the polyaddition type curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diamino. In addition to aromatic polyamines such as diphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydralazide, and the like; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) , Acid anhydrides including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); novolac-type phenolic resin, phenol poly Polyphenol compounds such as chromatography; 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 BF3 complexes.

  Examples of the condensation type curing agent include urea resins such as methylol group-containing urea resins; melamine resins such as methylol group-containing melamine resins.

  In the case where such other curing agents are used in combination, the lower limit of the blending ratio of the phenol resin curing agent (B) is preferably 20% by mass or more, and 30% by mass with respect to the total curing agent. More preferably, it is more preferably 50% by 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.

[Inorganic filler (C)]
As the inorganic filler (C) used in the sealing resin composition of the present invention, inorganic fillers generally used in the 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 (C) is desirably 0.01 μm or more and 150 μm or less from the viewpoint of filling properties in the mold cavity.

  The lower limit of the amount of the inorganic filler (C) in the sealing resin composition is preferably 78% by mass or more, more preferably 80% by mass or more, with respect to the total mass of the sealing resin composition. More preferably, it is 86 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. In addition, there is little risk of causing molding defects due to resin clogging on the mold gate side during continuous molding. Moreover, the upper limit of the amount of the inorganic filler (C) in the sealing resin composition is preferably 93% by mass or less, more preferably 91% by mass with respect to the total mass of the sealing resin composition. % Or less, and more preferably 90% by 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.

[Other ingredients]
The stopping resin composition of the present invention may contain a curing accelerator (D). The curing accelerator (D) may be any accelerator that promotes the reaction between the epoxy group of the epoxy resin and the hydroxyl group of the phenol resin-based curing agent (B), and a generally used curing accelerator can be used.

Specific examples of the curing accelerator (D) include phosphorus atom-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; Examples thereof include nitrogen atom-containing compounds such as 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, and 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 sealing resin composition of the present invention include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, and tributylphosphine. And a third phosphine such as triphenylphosphine.

  Examples of the tetra-substituted phosphonium compound that can be used in the sealing resin composition of the present invention include compounds represented by the following general formula (13).

（ただし、上記一般式（１３）において、Ｐはリン原子を表す。Ｒ７、Ｒ８、Ｒ９及びＲ１０は芳香族基又はアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の整数、ｚは０〜３の整数であり、かつｘ＝ｙである。）

(However, in the said General formula (13), P represents a phosphorus atom. R7, R8, R9, and R10 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

  Although the compound represented by General formula (13) 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 (13) can be precipitated. In the compound represented by the general formula (13), R7, R8, R9 and R10 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the phenol.

（ただし、上記一般式（１４）において、Ｘ１は炭素数１〜３のアルキル基、Ｙ１はヒドロキシル基を表す。ｋは０〜５の整数であり、ｌは０〜３の整数である。） Examples of the phosphobetaine compound that can be used in the encapsulating resin composition of the present invention include compounds represented by the following general formula (14).

(However, in the said General formula (14), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. K is an integer of 0-5, and l is an integer of 0-3.)

  The compound represented by the general formula (14) 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.

（ただし、上記一般式（１５）において、Ｐはリン原子を表す。Ｒ１１、Ｒ１２及びＲ１３は炭素数１〜１２のアルキル基又は炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ１４、Ｒ１５及びＲ１６は水素原子又は炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ１４とＲ１５が結合して環状構造となっていてもよい。） Examples of the adduct of a phosphine compound and a quinone compound that can be used in the sealing resin composition of the present invention include compounds represented by the following general formula (15).

(However, in the said General formula (15), P represents a phosphorus atom. R11, R12, and R13 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R14, R15 and R16 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R14 and R15 are bonded to form a cyclic structure. May be.)

  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 (15), R11, R12 and R13 bonded to the phosphorus atom are phenyl groups, and R14, R15 and R16 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 modulus of the cured product of the encapsulating resin composition.

（ただし、上記一般式（１６）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ１７、Ｒ１８、Ｒ１９及びＲ２０は、それぞれ、芳香環又は複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ２は、基Ｙ２及びＹ３と結合する有機基である。式中Ｘ３は、基Ｙ４及びＹ５と結合する有機基である
。Ｙ２及びＹ３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ２及びＹ３が珪素原子と結合してキレート構造を形成するものである。Ｙ４及びＹ５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ４及びＹ５が珪素原子と結合してキレート構造を形成するものである。Ｘ２、及びＸ３は互いに同一であっても異なっていてもよく、Ｙ２、Ｙ３、Ｙ４、及びＹ５は互いに同一であっても異なっていてもよい。Ｚ１は芳香環又は複素環を有する有機基、あるいは脂肪族基である。） Examples of the adduct of a phosphonium compound and a silane compound that can be used in the sealing resin composition of the present invention include compounds represented by the following general formula (16).

(However, in the said General formula (16), P represents a phosphorus atom and Si represents a silicon atom. R17, R18, R19, and R20 are respectively an organic group or an aliphatic group which has an aromatic ring or a heterocyclic ring. X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5. 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, and Y4 and Y5 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure.X2 and X3 are the same or different from each other. Well Y2, Y3, Y4, and Y5 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

  In the general formula (16), examples of R17, R18, R19, and R20 include 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 (16), 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 (16) 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, and salicylic acid. 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

  Z1 in the general formula (16) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions 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 blending ratio of the curing accelerator (D) that can be used in the sealing resin composition of the present invention is more preferably 0.1% by mass or more and 1% by mass or less in the total resin composition. When the blending ratio of the curing accelerator (D) is within the above range, sufficient curability can be obtained. Moreover, sufficient fluidity | liquidity can be obtained as the mixture ratio of a hardening accelerator (D) exists in the said range.

  In the present invention, a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. A compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter also referred to as “compound (E)”) can be used in the general formula (1). Even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator that promotes the crosslinking reaction between the epoxy resin (A) having the structure represented and the curing agent (B), the resin Reaction during melt kneading of the composition can be suppressed, and a sealing resin composition can be obtained stably. The compound (E) also has an effect of lowering the melt viscosity of the sealing resin composition and improving fluidity. As the compound (E), a monocyclic compound represented by the following general formula (17) or a polycyclic compound represented by the following general formula (18) can be used. It may have a substituent.

（ただし、上記一般式（１７）において、Ｒ２１、Ｒ２５はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基又は水酸基以外の置換基である。Ｒ２２、Ｒ２３及びＲ２４は水素原子、水酸基又は水酸基以外の置換基である。）

(However, in the general formula (17), one of R21 and R25 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R22, R23 and R24 are hydrogen atoms. An atom, a hydroxyl group or a substituent other than a hydroxyl group.)

（ただし、上記一般式（１８）において、Ｒ２６、Ｒ３２はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基又は水酸基以外の置換基である。Ｒ２７、Ｒ２８、Ｒ２９、Ｒ３０及びＲ３１は水素原子、水酸基又は水酸基以外の置換基である。）

(However, in the general formula (18), when one of R26 and R32 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. R27, R28, R29, R30) And R31 is 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 (17) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (18) 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 (E) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (E) may be used individually by 1 type, or may use 2 or more types together.

The compounding ratio of the compound (E) is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more and 0.8% by mass in the total sealing resin composition. % Or less, particularly preferably 0.05% by mass or more and 0.5% by mass or less. When the lower limit value of the compounding ratio of the compound (E) is within the above range, a sufficient viscosity reduction and fluidity improving effect of the sealing resin composition can be obtained. Moreover, there is little possibility of causing the fall of sclerosis | hardenability of a resin composition for sealing, and the fall of physical property of hardened | cured material as the upper limit of the compounding ratio of a compound (E) is in the said range.

  In the sealing resin composition of the present invention, a coupling agent (F) such as a silane coupling agent may be added in order to improve the adhesion between the epoxy resin (A) and the inorganic filler (C). it can. Examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, and the like, and may include a silane coupling agent having a secondary amino group. What is necessary is just to react between an epoxy resin (A) and an inorganic filler (C), and to improve the interface strength of an epoxy resin (A) and an inorganic filler (C). Moreover, a silane coupling agent can also raise the effect of the compound (E) of reducing the melt viscosity of a resin composition and improving fluidity | liquidity by using together with the above-mentioned compound (E).

  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 It may be used as a latent aminosilane coupling agent in which a primary amino moiety is 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 formability, 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 (F) such as a silane coupling agent that can be used in the sealing resin composition of the present invention is preferably 0.01% by mass or more in the total resin composition. 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 (F) such as a silane coupling agent is within the above range, the interface strength between the epoxy resin (A) and the inorganic filler (C) does not decrease, and the electron Good solder crack resistance in the component device can be obtained. Moreover, as an upper limit of the mixture ratio of coupling agents (F), 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 (F) such as a silane coupling agent is within the above range, the interface strength between the epoxy resin (A) and the inorganic filler (C) does not decrease, and the apparatus Good solder crack resistance can be obtained. Moreover, if the blending ratio of the coupling agent (F) such as a silane coupling agent is within the above range, the water absorption of the cured product of the resin composition will not increase, and good solder crack resistance in the electronic component device Sex can be obtained.

  In the sealing resin composition of the present invention, an inorganic flame retardant (G) 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 easily available on the market. Of these, aluminum hydroxide and magnesium hydroxide / zinc solid solution are preferable from the viewpoint of the balance between solder resistance and continuous moldability. An inorganic flame retardant (G) may be used independently or may be used 2 or more types. Further, for the purpose of reducing the influence on the 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 sealing resin composition of the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; natural wax such as carnauba wax; synthetic wax such as polyethylene wax; stearic acid and zinc stearate; A higher fatty acid and a metal salt thereof or a mold release agent such as paraffin; a low stress additive such as silicone oil or silicone rubber may be appropriately blended.

  The sealing resin composition of the present invention uses an epoxy resin (A), a phenol resin-based curing agent (B), an inorganic filler (C), and other additives as described above, for example, using a mixer or the like. Mix uniformly at room temperature, and then melt-knead using a kneader such as a heating roll, kneader or extruder, if necessary, and then cool and pulverize as necessary. It can be adjusted to fluidity.

[Electronic component equipment]
Next, the electronic component device of the present invention will be described. As a method for producing an electronic component device using the sealing resin composition of the present invention, for example, after a lead frame or a circuit board on which an element is mounted is placed in a mold cavity, the sealing resin composition There is a method of sealing this element by molding and curing by a molding method such as transfer molding, compression molding, injection molding or the like.

  Examples of the 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.

  The material of the lead frame is not particularly limited, and copper, copper alloy, 42 alloy (Fe-42% Ni alloy) or the like can be used. The surface of the lead frame is plated with, for example, pure copper strike plating, silver plating (mainly the wire joint at the tip of the inner lead), or nickel / palladium / gold multi-layer plating (PPF (Palladium Pre-Plated Frame)). May be. As a result, copper, copper alloy, gold or 42 alloy exists on the surface of the lead frame where adhesion is a problem.

  As a form of the obtained electronic component 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 Is packages and the like, but not limited thereto.

  Moreover, the epoxy resin (A) of the resin composition for sealing is composed of one or more polymers having a structure represented by the general formula (1). In the general formula (1), (d-1) / c = Since it has a polymer different from 1, it has sufficient air vent at the time of molding, hardness of the cured product of the gate part, or strength, and can improve the continuous moldability. Therefore, the continuous formability when an organic substrate such as BGA is used can be improved as well.

  An electronic component device in which an element is sealed by a molding method such as transfer molding of a sealing resin composition is used as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. After completely curing the resin composition, it is mounted on an electronic device or the like.

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

  FIG. 2 is a diagram showing a cross-sectional structure of a single-side sealed semiconductor device which is an example of an electronic component device using the sealing resin composition according to the present invention. The semiconductor element 1 is fixed on the substrate 8 via the solder resist 7 and 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 semiconductor sealing which concerns on this invention. 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. Such a semiconductor device is economically obtained because the semiconductor element 1 is encapsulated with the resin composition for encapsulating a semiconductor according to the present invention, so that the semiconductor device is excellent in reliability and productivity.

  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.

Each component used for the resin composition for sealing obtained by the Example and comparative example which are mentioned later is demonstrated. Unless otherwise specified, the amount of each component is part by mass.
The ICI viscosity at 150 ° C. of various epoxy resins and phenol resin curing agents is S. tea. It was measured by Engineering Co., Ltd., high temperature ICI type cone plate type rotational viscometer (plate temperature set at 150 ° C., using 5P cone).

(Synthesis of precursor phenol resin 1)
A separable flask was equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet, and biphenyl (special grade reagent manufactured by Wako Pure Chemical Industries, biphenyl, boiling point 70 ° C., molecular weight 154, purity 98.4%
) 150 parts by mass, 155 parts by mass of a 37% aqueous solution of formaldehyde (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) and 43 parts by mass of sulfuric acid (concentration 98%), and then heating was started while replacing with nitrogen. The system was stirred for 8 hours while maintaining a temperature range of 90 to 100 ° C., cooled to room temperature, added with 200 parts by mass of toluene, dissolved uniformly, transferred to a separatory funnel, and distilled water 150 After adding mass parts and shaking, after repeating the operation of discarding the aqueous layer (washing) until the washing water becomes neutral, the oil layer is treated at a reduced pressure of 125 ° C., and the viscous biphenyl-formaldehyde reaction intermediate The body (BF) was obtained. Next, a separable flask is equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, and 70 parts by mass of the above-mentioned reaction intermediate (BF), 2 parts by mass of a 37% aqueous formaldehyde solution, are granulated in advance. Crushed 4,4′-bischloromethylbiphenyl (manufactured by Wako Pure Chemical Industries, Ltd., purity 95%, molecular weight 251) 147 parts by mass, phenol (Kanto Chemical Co., Ltd. special grade reagent, phenol, melting point 40.9 ° C. , Molecular weight 94, purity 99.3%) 400 parts by mass were added, heated while performing nitrogen substitution and stirring, and reacted for 5 hours while maintaining the system temperature in the range of 110 to 120 ° C. 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. After repeating the process until the oil layer is obtained, the oil layer is treated at a reduced pressure of 125 ° C. to distill off volatile components such as toluene and residual unreacted components, and consists of one or more polymers having a structure represented by the following formula (19). Precursor phenol resin 1 (hydroxyl equivalent 186, softening point 60 ° C., both ends of the structural formula were hydrogen atoms) was obtained.

(Synthesis of epoxy resin 1)
A separable flask was equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, and 300 parts by mass of the above precursor phenol resin 1, 900 parts by mass of epichlorohydrin, and 180 parts by mass of dimethyl sulfoxide were added. After heating to 45 ° C. to dissolve, 65 parts by mass of sodium hydroxide (solid fine granular, 99% purity reagent) is added over 2 hours, the temperature is raised to 50 ° C., 2 hours, and further raised to 70 ° C. The reaction was allowed to warm for 2 hours. After the reaction, after adding 150 parts by mass of distilled water and shaking, the operation of discarding the aqueous layer (washing) was repeated until the washing water became neutral, and then the oil layer was subjected to epichlorohydrin and reduced pressure conditions at 125 ° C. and 2 mmHg. Dimethyl sulfoxide was distilled off. After 750 parts by mass of methyl isobutyl ketone was added to the obtained solid and dissolved, the mixture was heated to 70 ° C., 21 parts by mass of a 30% by mass aqueous sodium hydroxide solution was added over 1 hour, and the reaction was further continued for 1 hour. The water layer was discarded. After adding 150 parts by mass of distilled water to the oil layer and performing a water washing operation, the same water washing operation was repeated until the washing water became neutral, and then methyl isobutyl ketone was distilled off by heating under reduced pressure. An epoxy resin 1 (epoxy equivalent 265, softening point 55 ° C., ICI viscosity 1.0 dPa · s at 150 ° C. at both ends of the structural formula, hydrogen atoms) having one or more polymers having the structure represented was obtained.

  An FD-MS chart of the epoxy resin 1 is shown in FIG. For example, m / z = 478 in the FD-MS analysis of FIG. 3 corresponds to a polymer in which i = 1 and j = 1 in formula (20) (c = 1 and d = 2 in general formula (1)) And a polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer having j / i = 1 in the formula (20)). M / z = 644 is a polymer in which i = 2 and j = 1 in the general formula (20) (a polymer corresponding to c = 2 and d = 2 in the general formula (1)). In the formula (1), it is a polymer corresponding to (d-1) / c <1 (a polymer in which j / i <1 in the formula (20)), and m / z = 640 is represented by the general formula (20) In which i = 1 and j = 2 (a polymer corresponding to c = 1 and d = 3 in the general formula (1)), and (d-1) / c> 1 in the general formula (1) (A polymer satisfying j / i> 1 in the formula (20)). That is, the epoxy resin 1 is composed of one or more polymers having a structure represented by the general formula (1), and includes a polymer different from (d-1) / c = 1 in the general formula (1). It was confirmed that the epoxy resin corresponds to the epoxy resin (A).

  Further, in the relative intensity ratio of FD-MS analysis, a polymer corresponding to (d-1) / c = 1 in the general formula (1) in the epoxy resin 1 (j / i = 1 in the general formula (20)) The total amount of the polymer is 70.0%, a polymer corresponding to (d-1) / c> 1 in the general formula (1) (a polymer in which j / i> 1 in the formula (20)) The total amount of the polymer corresponding to (d-1) / c <1 in the general formula (1) (the polymer satisfying j / i <1 in the formula (20)) is 14%. .1%, the total amount of the polymer corresponding to c = 0 in the general formula (1) contained as a by-product (the polymer corresponding to i = 0 in the formula (20), the polymer corresponding to the phenol novolac type epoxy resin) Was 5.3%. Moreover, the average values of c and d in the general formula (1) obtained by calculating the relative intensity ratio of the FD-MS analysis as a mass ratio are 1.1, 2.0, and in the formula (20), respectively. The average values of i and j were 1.1 and 1.0, respectively. In the components other than the polymer corresponding to c = 0 in the general formula (1) which is a by-product (the polymer corresponding to i = 0 in the formula (20), the polymer corresponding to the phenol novolac epoxy resin), A polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer in which j / i = 1 in the general formula (20)), (d-1) / in the general formula (1) Polymer corresponding to c> 1 (polymer having j / i> 1 in formula (20)), polymer corresponding to (d-1) / c <1 in general formula (1) (formula (20)) In this case, the average value of c and d in the general formula (1) is 73.9%, 11.2%, and 14.9%, respectively. Are 1.2 and 2.0, respectively, and the average values of i and j in Equation (20) are 1.2 and 1.0, respectively. It is calculated. Here, the FD-MS measurement of the epoxy resin 1 was performed under the following conditions. After adding 1 g of the solvent dimethyl sulfoxide (DMSO) to 10 mg of the epoxy resin 1 sample and dissolving it sufficiently, it was applied to the FD emitter and subjected to measurement. The FD-MS system uses an MS-FD15A manufactured by JEOL Ltd. as the ionization unit and an MS-700 model name double-focusing mass spectrometer manufactured by JEOL Ltd. as the detector. Measurement was performed at a detection mass range (m / z) of 50 to 2,000.

(Synthesis of precursor phenol resin 2)
A separable flask was equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, and 400 parts by mass of phenol, 4,4′-bischloromethylbiphenyl 211 previously crushed into granules
A mass part was weighed into a separable flask and heated while substituting with nitrogen, and stirring was started in conjunction with the start of melting of phenol. From the time when the temperature in the system reached 95 ° C., 12 parts by mass of a 37% aqueous formaldehyde solution was gradually added to the system over 3 hours, and further reacted for 3 hours. During the reaction, the inside of the system was maintained at a temperature range of 95 ° C. to 105 ° C., and hydrochloric acid gas generated in the system by the reaction was discharged out of the system by a nitrogen stream. After completion of the reaction, after completion of the reaction, unreacted components and the like are distilled off under reduced pressure conditions of 160 ° C. and 2 mmHg, and then 200 parts by mass of toluene is added and dissolved uniformly, then transferred to a separatory funnel and 150 parts by mass of distilled water. After shaking and adding water, the water layer is discarded (washing) repeatedly until the washing water becomes neutral, and then the oil layer is treated under reduced pressure at 125 ° C. to remove volatile components such as toluene and residual unreacted components. Was distilled off to obtain a precursor phenol resin 2 (hydroxyl equivalent 189, softening point 63 ° C.) composed of one or more polymers having a structure represented by the following formula (21).

（エポキシ樹脂２の合成）
エポキシ樹脂１の合成において、前駆体フェノール樹脂１のかわりに、前駆体フェノール樹脂２を３００質量部に変更した以外は、エポキシ樹脂１と同様の合成操作を行い、式（２２）で表される構造を有する１以上の重合体からなるエポキシ樹脂２（エポキシ当量２７０、軟化点５９℃、１５０℃におけるＩＣＩ粘度１．２ｄＰａ・ｓ。）を得た。

(Synthesis of epoxy resin 2)
In the synthesis of the epoxy resin 1, a synthetic operation similar to that of the epoxy resin 1 is performed except that the precursor phenol resin 2 is changed to 300 parts by mass instead of the precursor phenol resin 1, and is represented by the formula (22). An epoxy resin 2 (epoxy equivalent 270, softening point 59 ° C., ICI viscosity 1.2 dPa · s at 150 ° C.) made of one or more polymers having a structure was obtained.

  The FD-MS chart of the epoxy resin 2 is shown in FIG. For example, m / z = 478 in the FD-MS analysis of FIG. 4 corresponds to a polymer in which e = 1 and f = 0 in formula (22) (c = 1 and d = 2 in general formula (1)) A polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer having (e + f) / e = 1 in the formula (22)). M / z = 640 is a polymer in which e = 1 and f = 1 in the formula (22) (a polymer corresponding to c = 1 and d = 3 in the general formula (1)), m / z = 968 is a polymer in which e = 2 and f = 1 in the formula (22) (a polymer corresponding to c = 2 and d = 4 in the general formula (1)), both of which are represented by the general formula (1) (D-1) / c> 1 (a polymer having (e + f) / e> 1 in formula (22)), and an epoxy resin represented by general formula (2) (A- It is a polymer corresponding to 1). That is, the epoxy resin 2 includes one or more polymers having a structure represented by the general formula (1), and includes a polymer different from (d-1) / c = 1 in the general formula (1). It was confirmed that the epoxy resin corresponds to the epoxy resin (A).

Further, in the relative intensity ratio of FD-MS analysis, a polymer corresponding to (d-1) / c = 1 in the general formula (1) in the epoxy resin 2 ((e + f) / e = in the formula (22)) 1) is a polymer corresponding to (d-1) / c> 1 in the general formula (1) ((e + f) / e> 1 in the formula (22)). The total amount of the polymer) is 19.5%, a polymer corresponding to c = 0 in the general formula (1) contained as a by-product (a polymer in which e = 0 in the formula (22), a phenol novolak type) The total amount of the polymer corresponding to the epoxy resin was 2.7%. In addition, the average values of c and d in the general formula (1) obtained by calculating the relative intensity ratio of the FD-MS analysis as a mass ratio are 1.4 and 2.6, respectively. ) Average values of e and f were 1.4 and 0.2, respectively. In addition, in the component excluding the polymer corresponding to c = 0 in the general formula (1) which is a by-product (the polymer corresponding to e = 0 in the formula (22), the polymer corresponding to the phenol novolac type epoxy resin), A polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer in which (e + f) / e = 1 in the formula (22)), (d-1) in the general formula (1) The total amount of the polymer corresponding to / c> 1 (the polymer satisfying (e + f) / e> 1 in the formula (22)) is 80.0% and 20.0%, respectively. The average values of c and d in the general formula (1) obtained by calculating the relative intensity ratio of the MS analysis as a mass ratio are 1.4 and 2.6, respectively, and e in the formula (22) , F are calculated as 1.4 and 0.2, respectively.

(Synthesis of precursor phenol resin 3)
In the synthesis of the precursor phenol resin 2, the same synthetic operation as that of the precursor phenol resin 2 was performed except that 4,4′-bischloromethylbiphenyl was changed to 162 parts by mass and the 37% aqueous formaldehyde solution was changed to 28 parts by mass. Thus, a precursor phenol resin 2A (hydroxyl equivalent 172, softening point 59 ° C.) composed of one or more polymers having a structure represented by the formula (21) was obtained.

(Synthesis of epoxy resin 3)
In the synthesis of the epoxy resin 1, instead of the precursor phenol resin 1, the precursor phenol resin 3 was changed to 300 parts by mass, epichlorohydrin was changed to 968 parts by mass, and dimethyl sulfoxide was changed to 192 parts by mass. The same synthetic operation was performed, and an epoxy resin 2 composed of one or more polymers having a structure represented by the formula (22) (epoxy equivalent 243, softening point 53 ° C., ICI viscosity 1.0 dPa · s at 150 ° C.) Got.

  An FD-MS chart of the epoxy resin 3 is shown in FIG. For example, m / z = 478 in the FD-MS analysis of FIG. 5 corresponds to a polymer in which e = 1 and f = 0 in formula (22) (c = 1 and d = 2 in general formula (1)) A polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer having (e + f) / e = 1 in the formula (22)). M / z = 640 is a polymer in which e = 1 and f = 1 in the formula (22) (a polymer corresponding to c = 1 and d = 3 in the general formula (1)), m / z = 968 is a polymer in which e = 2 and f = 1 in the formula (22) (a polymer corresponding to c = 2 and d = 4 in the general formula (1)), both of which are represented by the general formula (1) (D-1) / c> 1 (a polymer having (e + f) / e> 1 in formula (22)), and an epoxy resin represented by general formula (2) (A- It is a polymer corresponding to 1). That is, the epoxy resin 3 is composed of one or more polymers having a structure represented by the general formula (1), and includes a polymer different from (d-1) / c = 1 in the general formula (1). It was confirmed that the epoxy resin corresponds to the epoxy resin (A).

Further, in the relative intensity ratio of FD-MS analysis, a polymer corresponding to (d-1) / c = 1 in the general formula (1) in the epoxy resin 3 ((e + f) / e = in the formula (22)) 1) is a polymer corresponding to (d-1) / c> 1 in the general formula (1) ((e + f) / e> 1 in the formula (22)). The total amount of the polymer) is 45.6%, a polymer corresponding to c = 0 in the general formula (1) contained as a by-product (a polymer in which e = 0 in the formula (22), a phenol novolak type) The total amount of the polymer corresponding to the epoxy resin was 8.3%. Moreover, the average values of c and d in the general formula (1) obtained by calculating the relative intensity ratio of the FD-MS analysis as a mass ratio are 1.2 and 2.8, respectively. The average values of e and f in 22) were 1.2 and 0.6, respectively. In addition, in the component excluding the polymer corresponding to c = 0 in the general formula (1) which is a by-product (the polymer corresponding to e = 0 in the formula (22), the polymer corresponding to the phenol novolac type epoxy resin), A polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer in which (e + f) / e = 1 in the formula (22)), (d-1) in the general formula (1) The total amount of the polymer corresponding to / c> 1 (the polymer satisfying (e + f) / e> 1 in the formula (22)) is 50.3% and 49.7%, respectively. The average values of c and d in formula (1) are 1.3 and 2.8, respectively, and the average values of e and f in general formula (22) are calculated as 1.3 and 0.5, respectively.

(Synthesis of precursor phenol resin 4)
In the synthesis of the precursor phenol resin 2, instead of blending 211 parts by mass of 4,4′-bischloromethylbiphenyl, 186.5 parts by mass of 4,4′-bischloromethylbiphenyl and 4-phenylbenzyl chloride (Wako Pure Chemical Industries, Ltd.) Yakuhin Kogyo Co., Ltd., purity 96%, molecular weight 202.5) 50 parts by mass, except that the formaldehyde 37% aqueous solution was changed to 0 parts by mass, the same synthetic operation as the precursor phenol resin 1 was performed, Precursor phenol resin 4 (hydroxyl equivalent 214, softening point 64 ° C.) composed of one or more polymers having a structure represented by the following formula (23) was obtained.

(Synthesis of epoxy resin 4)
In the synthesis of epoxy resin 1, 300 parts by mass of precursor phenol resin 1, 600 parts by mass of precursor phenol resin 2, 90 parts by mass of precursor phenol resin 3, and precursor phenol resin 4 As a blending amount of 150 parts by mass, the same synthetic operation as that of the epoxy resin 1 is performed, one or more polymers having a structure represented by the general formula (20), and a structure represented by the general formula (22) Epoxy resin 4 (epoxy equivalent 272, softening point 56 ° C., ICI viscosity 1.1 dPa · s at 150 ° C.) which is a mixture of the above polymer and one or more polymers having a structure represented by the general formula (24). )

The FD-MS chart of the epoxy resin 4 is shown in FIG. For example, m / z = 478 in the FD-MS analysis of FIG. 6 is a polymer in which i = 1 and j = 1 in the formula (20), and a polymer in which e = 1 and f = 0 in the formula (22). Or a polymer in which g = 1 and h = 0 in the formula (24) (a polymer corresponding to c = 1 and d = 2 in the general formula (1)), and (d−1 in the general formula (1)) ) / C = 1 (a polymer in which j / i = 1 in formula (20), a polymer in which (e + f) / e = 1 in formula (22), or g / in formula (24)) (G + h) = 1 polymer). M / z = 640 is a polymer in which i = 1 and j = 2 in the general formula (20), or a polymer in which e = 1 and f = 1 in the formula (22) (in the general formula (1)). c = 1, a polymer corresponding to d = 3), which is a polymer corresponding to (d-1) / c> 1 in the general formula (1) (j / i> 1 in the formula (20)). A polymer or a polymer in which (e + f) / e> 1 in the formula (22)), and a polymer corresponding to the epoxy resin (A-1) represented by the general formula (2). M / z = 644 is a polymer in which i = 2 and j = 1 in the general formula (20) or a polymer in which g = 1 and h = 1 in the formula (24) (in the general formula (1) c = 2, a polymer corresponding to d = 2). This is a polymer corresponding to (d-1) / c <1 in the general formula (1) (j / i <1 in the formula (20)). A polymer or a polymer satisfying g / (g + h) <1 in the formula (24), and a polymer corresponding to the epoxy resin (A-2) represented by the general formula (3). That is, the epoxy resin 4 is composed of one or more polymers having a structure represented by the general formula (1), and includes a polymer different from (d-1) / c = 1 in the general formula (1). It was confirmed that the epoxy resin corresponds to the epoxy resin (A).

  Further, in the relative intensity ratio of FD-MS analysis, a polymer corresponding to (d-1) / c = 1 in the general formula (1) in the epoxy resin 4 (j / i = 1 in the formula (20)) The total amount of a certain polymer, (e + f) / e = 1 in the formula (22) or g / (g + h) = 1 in the formula (24)) is 60.9%, 1) a polymer corresponding to (d-1) / c> 1 (a polymer having j / i> 1 in formula (20) or a polymer having (e + f) / e> 1 in formula (22)) Is a polymer corresponding to (d-1) / c <1 in the general formula (1) (a polymer in which j / i <1 in the formula (20) or in the formula (24)). The total amount of the polymer (g / (g + h) <1) is 9.6%, and is included in the general formula (1) contained as a by-product. Polymers corresponding to c = 0 the total amount of (polymer falls phenol novolak type epoxy resin) was 3.2%. Moreover, the average values of c and d in the general formula (1) obtained by calculating the relative intensity ratio of FD-MS analysis as a mass ratio were 1.4 and 2.5, respectively. In addition, a polymer corresponding to c = 0 in the general formula (1) which is a byproduct (a polymer in which i = 0 in the formula (20) or a polymer in which e = 0 in the formula (22), a phenol novolak In the component excluding the polymer corresponding to the type epoxy resin), a polymer corresponding to (d-1) / c = 1 in the general formula (1) (a polymer having j / i = 1 in the general formula (20), (E + f) / e = 1 in the formula (22) or g / (g + h) = 1 in the formula (24)), (d-1) / c> 1 in the general formula (1) (A polymer in which j / i> 1 in formula (20) or a polymer in which (e + f) / e> 1 in formula (22)), (d-1) in general formula (1) Polymer corresponding to / c <1 (polymerization where j / i <1 in formula (20)) Or the total amount of g / (g + h) <1 in the formula (24) is 62.9%, 27.2%, and 9.9%, respectively. In this case, the FD-MS analysis The average values of c and d in the general formula (1) obtained by calculating the relative intensity ratio as a mass ratio are calculated as 1.5 and 2.5, respectively.

(Other epoxy resins)
Epoxy resin 5: biphenyl type epoxy resin (Mitsubishi Chemical Corporation, YX4000K. Epoxy equivalent 185, melting point 107 ° C., ICI viscosity 0.1 dPa · s at 150 ° C.)

  Epoxy resin 6: bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, YL6810. Epoxy equivalent 172, melting point 45 ° C., ICI viscosity 0.03 dPa · s at 150 ° C.)

Epoxy resin 7: Bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., YSLV-80XY. Epoxy equivalent 190, melting point 80 ° C., ICI viscosity 0.03 dPa at 150 ° C.
・ S. )

  Epoxy resin 8: Orthocresol novolak type epoxy resin (manufactured by DIC Corporation, N-660. Epoxy equivalent 210, softening point 62 ° C., ICI viscosity 2.3 dPa · s at 150 ° C.)

  Epoxy resin 9: phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC3000, epoxy equivalent 276, softening point 58 ° C., ICI viscosity 1.1 dPa · s at 150 ° C.)

(Curing agent)
Hardener 1: Phenol aralkyl resin having a biphenylene skeleton (Maywa Kasei Co., Ltd., MEH-7851SS. Hydroxyl equivalent 203, softening point 67 ° C., ICI viscosity 1.1 dPa · s at 150 ° C.)

Curing agent 2: A separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 116.3 parts by mass of a 37% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, 37% formalin), 37.7 sulfuric acid After weighing 100 parts by mass of m-xylene (manufactured by Kanto Chemical Co., Ltd., special grade reagent, m-xylene, boiling point 139 ° C., molecular weight 106, purity 99.4%), 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. In this reaction system, 839 parts by mass of phenol, α, α′-dichloro-
338 parts by mass of p-xylene was added and heated while performing nitrogen substitution and stirring, and the reaction was carried out for 5 hours while maintaining the system temperature in the range of 110 to 120 ° C. 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. After repeating repeatedly until the oil layer, the volatile components such as toluene and residual unreacted components are distilled off under reduced pressure conditions of 125 ° C. and 2 mmHg, and the oil layer is composed of one or more polymers having a structure represented by the following formula (25). Phenol resin curing agent 3 (hydroxyl equivalent 180, softening point 67 ° C., ICI viscosity 0.6 dPa · s at 150 ° C. p in formula (25) is an integer of 0-20, q is an integer of 0-20, r is 0 The average value of p, q and r is 1.8, 0.3 and 0.6, respectively, in the polymer mixture which is an integer of ˜20. The terminal is a hydrogen atom and the right terminal is a phenol structure or key. Was obtained, which is a lens structure.).

  Curing agent 3: Phenol aralkyl resin having a phenylene skeleton (Maywa Kasei Co., Ltd., MEH-7800SS. Hydroxyl equivalent 170, softening point 65 ° C., ICI viscosity 0.9 dPa · s at 150 ° C.)

  Curing agent 4: Phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3. Hydroxyl equivalent weight 104, softening point 80 ° C., ICI viscosity 0.7 dPa · s at 150 ° C.)

  Curing agent 5: Naphthol aralkyl resin having a phenylene skeleton (manufactured by Tohto Kasei Co., Ltd., SN-170L, hydroxyl equivalent 182; softening point 70 ° C .; ICI viscosity 0.8 dPa · s at 150 ° C.)

(Inorganic filler)
Inorganic filler 1: manufactured by Denki Kagaku Kogyo Co., Ltd., 100 parts by mass of fused spherical silica FB560 (average particle size 30 μm), manufactured by Admatechs Co., Ltd., synthetic spherical silica SO-C2 (average particle size 0.5 μm) Mixture of 5 parts by mass, manufactured by Admatechs Co., Ltd., 7.5 parts by mass of synthetic spherical silica SO-C5 (average particle size 1.5 μm)

(Curing accelerator)
Curing accelerator 1: Curing accelerator represented by the following formula (26)

  Curing accelerator 2: Curing accelerator represented by the following formula (27)

  Curing accelerator 3: Curing accelerator represented by the following formula (28)

Curing accelerator 4: Curing accelerator represented by the following formula (29)

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

(Compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring)
Compound E1: Compound represented by the following formula (30) (manufactured by Tokyo Chemical Industry Co., Ltd., 2,3-naphthalenediol, purity 98%)

(Silane coupling agent)
Silane coupling agent 1: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
Silane coupling agent 2: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
Silane coupling agent 3: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573).

(Inorganic flame retardant)
Inorganic flame retardant 1: Aluminum hydroxide (Sumitomo Chemical Co., Ltd., CL310)
Inorganic flame retardant 2: Magnesium hydroxide / zinc hydroxide solid solution composite metal hydroxide (Echo Mug Z-10, manufactured by Tateho Chemical Co., Ltd.)

(Coloring agent)
Colorant 1: Carbon black (MA600) manufactured by Mitsubishi Chemical Corporation

(Release agent)
Mold release agent 1: Carnauba wax (Nikko Carnauba, melting point 83 ° C) manufactured by Nikko Rica Co., Ltd.

About the resin composition for sealing obtained by the Example and comparative example which are mentioned later, the following measurements and evaluation were performed.
(Evaluation item)
Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold conforming to ANSI / ASTM D 3123-72, 175 ° C., injection pressure 6.9 MPa, The resin composition was injected under the condition of a holding time of 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: Resin composition using a low pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 175 ° C., an injection time of 15 seconds, a curing time of 120 seconds, and an injection pressure of 9.8 MPa. The product was injection molded to produce a 3.2 mm thick flame resistant test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method. The table shows ΣF, Fmax and the fire resistance rank (class) after determination.

Continuous moldability: The obtained resin composition was subjected to powder molding press machine (Samagawa Machinery Co., Ltd., S-
20-A), the weight was adjusted to 15 g, size φ18 mm × height about 30 mm, and tableting was performed at a tableting pressure of 600 Pa to obtain a tablet. A tablet supply magazine loaded with the obtained tablet was set in the molding apparatus. For molding, a low pressure transfer automatic molding machine (GP-ELF, manufactured by Daiichi Seiko Co., Ltd.) is used as a molding device, under conditions of a mold temperature of 175 ° C., a molding pressure of 9.8 MPa, and a curing time of 120 seconds. A silicon chip or the like is sealed with the composition, and an 80-pin QFP (Cu lead frame, package outer dimension: 14 mm × 20 mm × 2.0 mm thickness, pad size: 8.0 mm × 8.0 mm, chip size 7.0 mm × 7.0 mm × 0.35 mm thickness) was continuously performed up to 450 shots. At this time, the state of the mold surface and the package molding state (whether or not unfilled) are checked every 25 shots, and the number of shots in which the mold has been confirmed for the first time, and no mold contamination has occurred. If there is no filling, mark the ○ mark in the “Mould stain” section of the table, the number of shots that were initially unfilled, or if no filling occurred, Each is described in the section. It should be noted that the mold surface contamination may transfer to the surface of the molded semiconductor device or may be an unfilled precursor, and it is not preferable that the mold contamination occurs in less than 400 shots. In addition, when the mold contamination occurs after 400 shots or more, it is determined that there is no effect on the continuous productivity. Further, the tablets to be used were in a standby state in the magazine of the molding apparatus until they were actually used for molding, and were in a state in which a maximum of 13 tablets were stacked vertically at a surface temperature of about 30 ° C. The tablet is fed and transported in the molding device by raising the push-up pin from the bottom of the magazine, so that the top tablet is pushed out from the top of the magazine and lifted by the mechanical arm to the transfer molding pot. Be transported. At this time, if the tablet sticks up and down during standby in the magazine, a conveyance failure occurs. In the section of “conveyance failure” in the table, the number of shots in which the conveyance failure was first confirmed, or a circle mark when no conveyance failure occurred.

  Solder resistance test 1: Resin composition using a low-pressure transfer molding machine (GP-ELF, manufactured by Daiichi Seiko Co., Ltd.) under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. The lead frame on which the semiconductor element (silicon chip) is mounted is sealed and molded, and 80-pin QFP (Cu lead frame with Cu strike plating on the surface, size is 14 × 20 mm × thickness 2. Six semiconductor devices having a size of 00 mm, a semiconductor element of 7 × 7 mm × thickness of 0.35 mm, and a semiconductor element and an inner lead portion of a lead frame are bonded with a gold wire with a diameter of 25 μm) were manufactured. Six semiconductor devices heat treated at 175 ° C. for 4 hours as post-cure were humidified for 120 hours at 85 ° C. and 85% relative humidity, and then subjected to IR reflow treatment (260 ° C. condition). The presence or absence of peeling and cracks inside these semiconductor devices was observed with an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope 10), and the occurrence of either peeling or cracking was regarded as defective. . When the number of defective semiconductor devices is n, n / 6 is displayed. The resin composition obtained in Example 1 showed a good reliability of 0/6.

  Solder resistance test 2: In the solder resistance test 1 described above, a copper lead frame subjected to nickel / palladium / gold plating treatment was used instead of the Cu lead frame, and the humidification conditions were 60 ° C., relative humidity 60%, 96 hours. The test was carried out in the same manner as the solder resistance test 1 except that. The resin composition obtained in Example 1 showed a good reliability of 0/6.

  About an Example and a comparative example, according to the compounding quantity shown in Table 1, Table 2, and Table 3, each component is mixed at room temperature using a mixer, melt-kneaded with a heating roll of 80 ° C-100 ° C, and then cooled, Subsequently, it was pulverized to obtain a sealing resin composition. Said measurement and evaluation were performed using the obtained resin composition for sealing. The results are shown in Table 1, Table 2 and Table 3.

Examples 1-18 consist of one or more polymers which have a structure represented by General formula (1), and also include a polymer different from (d-1) / c = 1 in General formula (1). A sealing resin composition comprising an epoxy resin (A), a phenol resin-based curing agent (B), and an inorganic filler (C). In any of Examples 1 to 18, fluidity (spiral) Flow), flame resistance, continuous formability (mold dirt, filling property, transportability) and solder resistance were excellent. On the other hand, in Comparative Example 1 using the epoxy resin 8 which is an ortho-cresol novolak type epoxy resin instead of the epoxy resin (A), the fluidity, flame resistance and solder resistance were inferior. Moreover, in the comparative example 2 using the epoxy resin 9 which is a phenol aralkyl type epoxy resin having a biphenylene skeleton instead of the epoxy resin (A), the result was inferior in continuous moldability. Further, in Comparative Example 3 in which the epoxy resin 8 which is an orthocresol novolac type epoxy resin and the epoxy resin 9 which is a phenol aralkyl type epoxy resin having a biphenylene skeleton are used in combination instead of the epoxy resin (A), the flame resistance is inferior and continuous. As a result, the moldability also decreased.

  According to the present invention, a sealing resin composition having an excellent balance of solder resistance, flame resistance and continuous moldability, and an electronic component device having excellent reliability formed by sealing an element with a cured product thereof are economical. Therefore, it can be suitably used for manufacturing an industrial resin-sealed electronic component device, particularly a resin-sealed electronic component device for surface mounting.

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 (13)

The following general formula (1):

(In the general formula (1), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. A hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, and both ends of the structural formula are hydrogen atoms, c is an integer of 1 to 20 , D is an integer of 1 to 20. Each of d repeating units that are substituted or unsubstituted glycidoxyphenylene groups and c repeating units that are substituted or unsubstituted biphenylene groups are continuous with each other. Or may be alternately or randomly arranged, but each must have a substituted or unsubstituted methylene group -C (R3) (R4)-).
An epoxy resin (A) comprising one or more polymers having a structure represented by formula (1), including a polymer different from (d-1) / c = 1 in the general formula (1),
A phenolic resin-based curing agent (B);
An inorganic filler (C);
Only including,
In the measurement by field desorption mass spectrometry, the sum of the relative intensities of the polymers different from (d-1) / c = 1 in the general formula (1) is the sum of the relative intensities of the entire epoxy resin (A). A sealing resin composition characterized by being 10% or more and 60% or less .
The sealing resin composition according to claim 1, wherein the epoxy resin (A) is a polymer different from (d-1) / c = 1 in the general formula (1).
The following general formula (2):

(In the above general formula (2), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, e is an integer of 1 to 20, and f is an integer of 1 to 18.)
One or more polymers (A-1) having a structure represented by: and / or
The following general formula (3):

(In the above general formula (3), R1 and R2 are each independently a hydrocarbon group having 1 to 9 carbon atoms, a and b are integers of 0 to 3. R3 and R4 are independent of each other. And a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a substituted or unsubstituted glycidoxyphenyl group, g is an integer of 1 to 19, and h is an integer of 1 to 9. One or more polymers (A-2) having the structure represented;
The sealing resin composition characterized by including. 3. The sealing resin composition according to claim 1, wherein the content of the inorganic filler (C) is 80% by mass or more and 93% by mass or less with respect to the total resin composition. Resin composition for sealing. The sealing resin composition according to any one of claims 1 to 3 , wherein the epoxy equivalent of the epoxy resin (A) is 220 g / eq or more and 300 g / eq or less. Resin composition. In encapsulating resin composition according to any one of claims 1 to 4, wherein the amount of the epoxy resin (A) is 0.5 wt% or more based on the total resin composition, 10 mass% or less There is a resin composition for sealing. The sealing resin composition according to any one of claims 1 to 5 , further comprising a curing accelerator (D). 7. The sealing resin composition according to claim 6 , wherein the curing accelerator (D) is a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, or an addition of a phosphonium compound and a silane compound. A sealing resin composition comprising at least one curing accelerator selected from the group consisting of products. The sealing resin composition according to any one of claims 1 to 7 , further comprising a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring. A sealing resin composition. The sealing resin composition according to any one of claims 1 to 8 , further comprising a coupling agent (F). The sealing resin composition according to claim 9 , wherein the coupling agent (F) includes a silane coupling agent having a secondary amino group. The resin composition for sealing according to any one of claims 1 to 10 , further comprising an inorganic flame retardant (G). The sealing resin composition according to claim 11 , wherein the inorganic flame retardant (G) contains a metal hydroxide or a composite metal hydroxide. An electronic component device obtained by sealing an element with a cured product obtained by curing the sealing resin composition according to any one of claims 1 to 12 .

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