WO2018025850A1 - Resin composition - Google Patents

Abstract

Provided is a resin composition which is in a liquid state before curing, and a cured product of which maintains high elastic modulus in the actual working temperature range of a semiconductor device and is not susceptible to cracks or separation even if used for a long period of time. A thermosetting resin composition which contains a thermosetting resin and a curing catalyst, and which is characterized in that: the viscosity as measured at 25°C at a shear rate of 0.009 s^-1 is 1,500 Pa·s or less; the storage elastic moduli of a cured product of this thermosetting resin composition at 25°C and at 180°C are 1.0 × 10⁸ Pa or more; and the ratio of the volume resistivity a at 25°C to the volume resistivity b at 200°C of a cured product of this thermosetting resin composition, namely a/b is 8,500 or less.

Description

Resin composition

The present invention relates to a resin composition suitably used as a sealing material for semiconductor devices and the like.

In addition to insulation and thermal reliability, sealing materials such as semiconductor devices are required to have a low coefficient of linear expansion. This is to prevent the sealing resin from being cracked or peeled off due to expansion due to heat generated from the semiconductor device. In general, a filler (filler) is added to the sealing material in order to reduce the linear expansion coefficient (for example, Patent Documents 1 and 2).

Further, in order to seal the device, the sealing material needs to have a high elastic modulus. A sealing material having a high elastic modulus is generally preferable from the viewpoint of protecting chips, wires, and their connection portions inside the device, because deformation with respect to external force is small.
Moreover, as an evaluation method of the sealing material, a power cycle test in which the circuit is actually sealed and the reliability of the heat generated from the inside is evaluated by repeating energization, and a heating furnace without energization, etc. A thermal cycle test is performed in which reliability is evaluated by repeating rapid heating and cooling in a container.

JP 2004-27005 A JP 2009-67890 A

However, if a sealing material with a high elastic modulus is used to seal a semiconductor device that generates a large amount of heat, such as a power device, even if a sealing material with a linear expansion coefficient as small as possible is used, the internal stress is reduced due to thermal expansion during use. Increases and cracks and peeling occur in the encapsulant resin. Furthermore, there is a problem that the chip, the wire, and their connection part inside the device are damaged.

Therefore, as a sealing material, a resin that is moderately soft, that is, having a low elastic modulus has been used. However, when a resin having a low elastic modulus is used, a device in a reliability test such as a power cycle test is used. The problem is that the internal chips, wires, and their connections cannot be adequately protected. Furthermore, even when a resin having a low elastic modulus is used, the occurrence of cracks and peeling may not be suppressed.

Transfer using a solid encapsulant as a material that sufficiently protects the chip, wires, and their connection parts inside the device in reliability tests such as power cycle tests, and does not cause cracks or peeling in the encapsulant resin Although there is sealing by molding or the like, a mold is required for the molding process. Further, when the semiconductor device is increased in size, there is a problem that a larger mold is required and the process cost is increased.

The present invention is a liquid before curing, and the cured product maintains a high elastic modulus in the operating temperature range of the semiconductor device, and does not easily crack or peel off even when used for a long period of time. It is an object of the present invention to provide a resin composition in which cracking and peeling do not occur in a sealing material resin even in a thermal cooling test.

As a result of various studies to solve the above problems, the present inventors have found that a liquid resin having fluidity before curing, and the cured product has a high elastic modulus in the working temperature region of the semiconductor device. However, by further keeping the volume resistivity ratio of the cured product at 25 ° C. and 200 ° C. within a certain range, a resin composition is obtained in which cracks and peeling are unlikely to occur in a rapid cooling test such as a thermal cycle test. I found out that And it was conceived that by using the resin composition as a sealing material, high reliability can be obtained even when it is generally applied to a power device having a large size. The present invention has been accomplished based on these findings. That is, the gist of the present invention is as follows.
(1) A thermosetting resin composition comprising a thermosetting resin and a curing catalyst, wherein the viscosity at 25 ° C. and a shear rate of 0.009 s ⁻¹ is 1500 Pa · s or less, and the thermosetting resin composition The storage elastic modulus of the cured product at 25 ° C. and 180 ° C. is 1.0 × 10 ⁸ Pa or more, respectively, and the ratio of the volume resistivity a at 25 ° C. and the volume resistivity b at 200 ° C. is 8500. The resin composition characterized by the following.
(2) The resin composition according to (1), wherein the thermosetting resin includes an epoxy resin.
(3) The resin composition according to (2), wherein the epoxy resin contains an alicyclic epoxy group.
(4) The resin composition according to (2) or (3), wherein the epoxy resin contains a glycidyl group.
(5) The resin composition according to (4), wherein the epoxy resin contains an epoxy resin containing two or more glycidyl groups.
(6) The resin composition according to any one of (2) to (5), wherein the epoxy resin contains an epoxy group-containing silicon compound.
(7) The resin composition according to (6), wherein the epoxy group-containing silicon compound contains an alicyclic epoxy group.
(8) The resin composition according to any one of (1) to (7), further containing 50% by mass or more of a filler.
(9) The resin composition according to (8), wherein the filler contains silica.
(10) The resin composition according to any one of (1) to (9), further comprising an acid anhydride.
(11) The resin composition according to any one of (1) to (10), wherein the resin composition is cured by accompanying ring-opening polymerization of an epoxy group.
(12) The resin composition according to (11), wherein the ring-opening polymerization is cationic polymerization.
(13) The resin composition according to any one of (1) to (12), wherein the curing catalyst includes a metal catalyst.
(14) The resin composition according to (13), wherein the metal catalyst is a gallium compound.
(15) A molded product obtained by curing the resin composition according to any one of (1) to (14).
(16) A semiconductor device encapsulated with the resin composition according to any one of (1) to (14).

According to the present invention, it is a liquid resin that is fluid before curing, and the cured product retains a high elastic modulus in the working temperature region of the semiconductor device, and further the volume of the cured product at 25 ° C. and 200 ° C. By providing a resistivity ratio within a certain range, a resin composition that does not easily crack or peel off even when used for a long period of time, that is, does not easily crack or peel off in a rapid thermal cooling test such as a thermal cycle test. be able to.

In rapid thermal testing such as thermal cycle testing, the cause of cracks and peeling in the encapsulant resin is that the encapsulant resin undergoes a local structural change when the semiconductor device is exposed to the rapid thermal cooling environment. This is considered to be a factor. As a result, stress concentration locally occurs, and the degree of charge of the resin is also sparse and dense, which is considered to damage the resin. In the present invention, it has been found that the change appears as a large change in the volume resistivity of the encapsulant resin. In other words, by setting the ratio of the volume resistivity of the encapsulant resin at 25 ° C., which is room temperature, to 200 ° C., which is the practical upper limit of the practical temperature, within a certain range, the reliability in rapid thermal testing such as thermal cycle testing In addition, the high elastic modulus can be maintained in the working temperature region of the semiconductor device, so that high performance can be expected in a reliability test such as a power cycle test.

Hereinafter, the present invention will be described in detail according to embodiments. However, the present invention is not limited to the embodiments described explicitly or implicitly in the present specification. In addition, each embodiment described in the present specification can be variously modified without departing from the gist of the invention, and features described by other embodiments within a feasible range. Can be combined.

1. Thermosetting resin composition The resin composition which is one embodiment of the present invention is a thermosetting resin composition containing a thermosetting resin and a curing catalyst (hereinafter sometimes abbreviated as "resin composition"). It is. The resin composition before thermosetting is liquid and fluid, and has a viscosity at 25 ° C. and a shear rate of 0.009 s ⁻¹ of 1500 Pa · s or less. The cured product of the resin composition has a storage elastic modulus at 25 ° C. and 180 ° C. of 1.0 × 10 ⁸ Pa or more, and the cured product of the resin composition has a volume resistivity a at 25 ° C. The ratio a / b of the volume resistivity b at 200 ° C. is 8500 or less. In this resin composition, as long as the viscosity of the resin composition before thermosetting, and the storage elastic modulus and volume resistivity ratio a / b of the cured product satisfy the above values, a thermosetting resin is used as necessary. Components other than the curing catalyst, for example, epoxy compounds, reactive or non-reactive silicones, fillers, epoxy resin curing agents, and the like can be contained.

1-1. Thermosetting resin composition containing thermosetting resin and curing catalyst and physical properties of cured product of resin composition As described above, 25 ° C. and shear rate of the resin composition before thermosetting. The viscosity at 009 s ⁻¹ is 1500 Pa · s or less, the storage modulus of the cured product of the resin composition at 25 ° C. and 180 ° C. is 1.0 × 10 ⁸ Pa or more, and the resin composition is cured. The ratio a / b of the volume resistivity a at 25 ° C. to the volume resistivity b at 200 ° C. is 8500 or less. In addition, the measuring method of a viscosity, a storage elastic modulus, and a volume resistivity is demonstrated in the item of [Example]. The method for curing (crosslinking) the resin composition will be described later.

1-1-1. Viscosity The resin composition has a viscosity at 25 ° C. at a shear rate of 0.009 s ⁻¹ of 1500 Pa · s or less, preferably 1200 Pa · s or less, more preferably 1000 Pa · s or less, and even more preferably. Is 900 Pa · s or less, particularly preferably 800 Pa · s or less. By satisfying the physical properties in this range, not only is it easy to handle, especially when sealing by potting, but also leveling without applying share after potting, the resin tends to get wet to the entire area and details inside the semiconductor package. . Moreover, although a lower limit is not specifically limited, Usually, it is 1 Pa.s or more.

1-1-2. Storage Elastic Modulus In this specification, the storage elastic modulus is a value obtained by solid viscoelasticity measurement at a frequency of 1 Hz.
The storage elastic modulus at 25 ° C. of the cured product of the resin composition is 1.0 × 10 ⁸ Pa or more, preferably 2.0 × 10 ⁸ Pa or more, more preferably 3.0 × 10 ⁸ Pa or more, Preferably it is 4.0 × 10 ⁸ Pa or more, more preferably 5.0 × 10 ⁸ Pa or more, and the upper limit is usually 1.0 × 10 ¹⁵ Pa or less, preferably 1.0 × 10 ¹⁴ Pa or less, more preferably Is 1.0 × 10 ¹³ Pa or less, more preferably 1.0 × 10 ¹² Pa or less.
The storage elastic modulus at 180 ° C. of the cured product of the resin composition is 1.0 × 10 ⁸ Pa or more, preferably 1.5 × 10 ⁸ Pa or more, more preferably 2.0 × 10 ⁸ Pa or more, Preferably it is 3.0 × 10 ⁸ Pa or more, more preferably 4.0 × 10 ⁸ Pa or more, and the upper limit is usually 1.0 × 10 ¹⁵ Pa or less, preferably 1.0 × 10 ¹⁴ Pa or less, more preferably Is 1.0 × 10 ¹³ Pa or less, more preferably 1.0 × 10 ¹² Pa or less.
By satisfying the physical properties in this range, it can be expected that the chip, wires, and their connection portions inside the device can be sufficiently protected particularly in a reliability test such as a power cycle test.

As a method for controlling the storage elastic modulus at 25 ° C. and 180 ° C. to a high elastic modulus, in addition to selection of each component such as a thermosetting resin and a curing agent described later, for example, an alicyclic epoxy group or glycidyl group as a reactive group For example, a method of increasing the cross-linking density by adding an epoxy resin having 2 or more can be used. Moreover, it can control by selection of a hardening | curing agent, a hardening catalyst, etc.

1-1-3. Volume Resistivity Ratio In this specification, the volume resistivity ratio is the ratio of the volume resistivity a at 25 ° C. and the volume resistivity b at 200 ° C. of the cured resin composition a / b, which is an index for determining whether or not there is a reliability problem in a rapid cooling test such as a thermal cycle test.
The ratio a / b of the volume resistivity a at 25 ° C. and the volume resistivity b at 200 ° C. is 8500 or less, preferably 8000 or less, more preferably 7000 or less, and further preferably 6000 or less. More preferably, it is 5000 or less, More preferably, it is 4000 or less, More preferably, it is 3000 or less, More preferably, it is 2000 or less, More preferably, it is 1000 or less, More preferably, it is 500 or less. Further, a / b is usually 1 or more.
The volume resistivity a at 25 ° C. of the cured product of the resin composition of one embodiment of the present invention is 1.0 × 10 ¹⁴ Ω · cm or more, preferably 1.0 × 10 ¹⁵ Ω · cm or more. is there. The volume resistivity b at 200 ° C. of the cured product of the resin composition is 1.0 × 10 ¹¹ Ω · cm or more, preferably 1.0 × 10 ¹² Ω · cm or more.

As a method for controlling the ratio a / b of the volume resistivity a at 25 ° C. and the volume resistivity b at 200 ° C. of the cured product of the resin composition to be low, each component such as a thermosetting resin and a curing agent to be described later In addition to the above selection, for example, a method of suppressing the transfer of electrons and ions, such as filling with a low linear expansion coefficient filler, increasing the reactive group density in the resin and suppressing the molecular motion of the cured product, etc. . Furthermore, a method of making the crosslink density in the resin uniform and reducing the density structure is also effective.

1-1-4. Average linear expansion coefficient In this specification, the average linear expansion coefficient is obtained using thermomechanical analysis (TMA) based on JIS K7197, and is between a certain temperature T1 and T2. The rate at which the length of the object expands as the temperature rises is shown per 1 K (° C.).
The average linear expansion coefficient at −30 ° C. to 200 ° C. of the cured product of the resin composition is usually 100 ppm / K or less, preferably 90 ppm / K or less, more preferably 80 ppm / K or less, and even more preferably 70 ppm / K. Hereinafter, it is more preferably 60 ppm / K or less, further preferably 50 ppm / K or less, and further preferably 40 ppm / K or less. The lower limit of the average linear expansion coefficient is not particularly limited, and is preferably as low as possible. For example, the lower limit is a value similar to the linear expansion coefficient of a member adjacent to the cured product of the resin composition (a metal such as aluminum or copper used for patterns or wires, a ceramic used for a substrate, or the like).

The resin composition of one embodiment of the present invention can form a cured product with a low average linear expansion coefficient. When the value of the average linear expansion coefficient of the cured product obtained by curing the resin composition is too large, cracks during curing tend to occur. If the average linear expansion coefficient of the cured product obtained by curing the resin composition exceeds the upper limit, the internal stress generated by the temperature change during curing and during use increases, which may lead to the generation of cracks.

As will be described later, the average linear expansion coefficient can be kept low by increasing the crosslinking density of a thermosetting resin such as an epoxy resin and other organic components, filling with a low linear expansion coefficient filler, and the like. The crosslinking density of the cured resin can be controlled in the same manner as when controlling the storage elastic modulus. For example, when an epoxy resin is used as the thermosetting resin, it can be controlled by selecting a curing agent, a curing catalyst, and the like in addition to the epoxy value of the epoxy resin and the number of epoxy groups per molecule.

1-2. Thermosetting resin In the present specification, the thermosetting resin is cured in the presence of a curing catalyst, and the resin composition before thermosetting has a predetermined viscosity, and also has a predetermined storage elastic modulus and volume resistance. It will not specifically limit if it can become the hardened | cured material which satisfy | fills a rate ratio. Specifically, an epoxy resin, a phenol resin, a polycarbonate resin, an unsaturated polyester resin, a urethane resin, a melamine resin, a urea resin, etc. are mentioned, for example. Among these, an epoxy resin is preferable. Examples of the epoxy resin include an epoxy group-containing silicon compound, an aliphatic epoxy resin, a bisphenol A or F epoxy resin, a novolac epoxy resin, an alicyclic epoxy resin, and a glycidyl ester. Type epoxy resin, polyfunctional type epoxy resin, polymer type epoxy resin and the like.
Of these, epoxy group-containing silicon compounds and polyfunctional epoxy resins are particularly preferred. Since the epoxy group-containing silicon compound has a siloxane bond as a main skeleton, it is excellent in heat resistance and insulation and is suitable as a sealing material. In addition, since one molecule contains an epoxy part, which is an organic component, and a siloxane part, which is an inorganic component, it has high affinity with organic substances such as resins and curing agents and inorganic fillers, and high uniformity including crosslinking density. A sealing layer can be produced. In addition, it greatly contributes to adhesion with adjacent members. Since the polyfunctional epoxy resin contains many reactive groups, it is excellent in elasticity, heat resistance and insulation and is suitable as a sealing material. Moreover, the resin is effectively cross-linked by reacting more epoxy groups, and the effect is greater. The resin composition may contain an epoxy group-containing silicon compound or an epoxy resin different from that alone, or a mixture of an epoxy group-containing silicon compound and a known epoxy resin.
Further, the thermosetting resin is usually contained in an amount of 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more in the thermosetting resin composition according to the present invention. The upper limit of the content of the thermosetting resin in the thermosetting resin composition is usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

1-2-1. Epoxy resin Epoxy resin is a general term for compounds having one or more oxirane rings (epoxy groups) in the molecule. In this invention, the epoxy group containing silicon compound mentioned later is also contained in an epoxy resin.
From the viewpoint of increasing the storage elastic modulus of the cured product after thermosetting, especially the high storage modulus at high temperatures, which is important when the calorific value is high, such as a power device, two or more oxirane rings ( An epoxy resin having an epoxy group) is preferable, and an epoxy resin having three or more oxirane rings (epoxy groups) in the molecule is more preferable. By having a plurality of oxirane rings (epoxy groups) in the molecule, the polarity of the matrix resin can be adjusted, and the composition viscosity due to the attractive force between the hydrophilic fillers can be controlled. Further, the oxirane ring (epoxy group) possessed may be either an alicyclic epoxy group or a glycidyl group.
Specifically, for example, the epoxy resin may be an aromatic oxirane ring (epoxy group) -containing compound. Examples include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrafluorobisphenol A, etc. as shown in formula (12). Bisphenol-type epoxy resins obtained by glycidylation of bisphenols, biphenyl-type epoxy resins represented by the formula (13), dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene and other divalent phenols are glycidylated. Epoxy resin, epoxy resin obtained by glycidylation of trisphenols such as 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) Tetrakis phenols glycidylated epoxy resins such as Tan, phenol novolac, cresol novolac, bisphenol A, novolak, such as novolaks the glycidylated novolak type epoxy resins such as brominated bisphenol A novolak and the like.

[R independently represents an optionally substituted hydrocarbon group or halogen having 1 to 12 carbon atoms]
The aromatic oxirane ring (epoxy group) -containing compound may be hydrogenated as an epoxy resin and an oxetane resin having an alicyclic structure.
The epoxy resin may be a non-aromatic oxirane ring (epoxy group) -containing resin. Examples include Denacol (registered trademark) EX-211L EX-216L EX-722P EX-810P (manufactured by Nagase ChemteX Corporation) Celoxide 2021P (manufactured by Daicel Corporation) YED216 (manufactured by Mitsubishi Chemical Corporation). In addition, from the viewpoint of increasing the storage elastic modulus of a cured product after heat curing, in particular, increasing the storage elastic modulus at a high temperature, an epoxy resin having three or more oxirane rings (epoxy groups) is preferable. For example, Denacol (registered trademark) EX321-L, DLC-301, DLC-402 (manufactured by Nagase ChemteX Corporation). By using these polyfunctional epoxy resins, the linear expansion coefficient of the cured product can be kept low. These may be used alone or in combination of two or more.

1-2-2. Epoxy group-containing silicon compound The epoxy group-containing silicon compound is a compound having a structure containing silicon in the molecule and further having an epoxy group. The epoxy group may be a glycidyl group or an alicyclic epoxy group, and is preferably an alicyclic epoxy group represented by a cyclohexyl epoxy group. As the thermosetting resin contained in the resin composition, those containing an epoxy group-containing silicon compound are particularly preferable.

The molecular weight of the epoxy group-containing silicon compound is 100 or more in terms of weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) from the viewpoints of handleability, wettability to the filler surface, and viscosity reduction of the resin composition. Preferably, it is 500 or more, more preferably 700 or more. Moreover, it is preferable that it is 4000 or less, and it is more preferable that it is 3500 or less.
Further, from the viewpoint of increasing the storage elastic modulus of the cured product after thermosetting, the weight average molecular weight (Mw) measured by GPC is preferably 100 or more, more preferably 200 or more, and 300 or more. More preferably. Moreover, it is preferable that it is 4000 or less, and it is more preferable that it is 3000 or less.
The content of the epoxy group-containing silicon compound is 0.1% by mass or more, preferably 1% by mass or more, more preferably, when the total amount of the resin composition is 100% by mass from the viewpoint of reducing the viscosity of the resin composition. Is 2% by mass or more. Further, the content of the epoxy group-containing silicon compound is preferably 20% by mass or less, and more preferably 15% by mass or less, when the total amount of the resin composition is 100% by mass.
Hereinafter, the epoxy group-containing silicon compound will be described.
The epoxy group-containing silicon compound is a compound having a structure containing silicon in the molecule and further having an epoxy group.

Epoxy group-containing silicon compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) diethoxysilane , (Γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexylethyl) (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) Dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl (Methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxypropyl) ( Methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) dimethyl Silane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4-epoxycyclohexyl) ) Ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) L) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,3,3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, 3 -Epoxypropyl (phenyl) dimethoxysilane and the like.

Moreover, the organopolysiloxane represented by Formula (1) is also contained in the silicon compound containing an epoxy group.
(R ¹¹ ₃ SiO _1/2 ) _a1 (R ¹² ₂ SiO _2/2 ) _b1 (R ¹³ SiO _3/2 ) _c1 (SiO _4/2 ) _d1 (O _1/2 H) _e1 (1)
In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a monovalent organic group, and at least one in each molecule is an organic group containing an epoxy group.

In the formula (1), R ¹¹ ₃ SiO _1/2 represents an M unit, R ¹² ₂ SiO _2/2 represents a D unit, R ¹³ SiO _3/2 represents a T unit, and SiO _4/2 represents a Q unit. Yes. a1, b1, c1, and d1 are each integers of 0 or more, and a1 + b1 + c1 + d1 ≧ 2. E1 is an integer of 0 or more.
Although it does not specifically limit as an upper limit, It is preferable that it is 200> = a1 + b1 + c1 + d1, and it is preferable that e1 is an integer of 200 or less. This value corresponds to a value when the weight average molecular weight is about 15000 or less.
In the formula (1), R ¹¹ , R ¹² and R ¹³ are preferably hydrocarbon groups having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Alkyl groups such as hexyl and heptyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; aryl groups such as phenyl, tolyl and xylyl; benzyl and phenethyl And substituted alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, and nonafluorobutylethyl group.

In the formula (1), the organic group containing an epoxy group includes an epoxyalkyl group such as 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group; 2-glycidoxyethyl Groups, glycidoxyalkyl groups such as 3-glycidoxypropyl group, 4-glycidoxybutyl group; β- (or 2-) (3,4-epoxycyclohexyl) ethyl group, γ- (or 3-) Examples include epoxycyclohexylalkyl groups such as (3,4-epoxycyclohexyl) propyl group.

In the formula (1), e1 is an integer of 0 or more, and represents the number of hydroxyl groups (silanol) directly bonded to the silicon atom.
The epoxy resin has a hydrolyzable group bonded to a silicon atom. When the hydrolyzable group is hydrolyzed, the organopolysiloxane represented by the formula (1) (where e1 ≧ 1) The compound which produces | generates may be sufficient. In other words, in the organopolysiloxane represented by the formula (1) (however, e1 ≧ 1), it may be a compound in which all or part of the hydroxyl groups directly bonded to the silicon atom are replaced with hydrolyzable groups. .

Here, the hydrolyzable group is a group that generates a hydroxyl group (silanol) bonded to a silicon atom by hydrolysis. Specific examples include a hydroxy group, an alkoxy group, hydrogen, an acetoxy group, an enoxy group, an oxime group, A halogen group is mentioned. A preferred hydrolyzable group is an alkoxy group, particularly an alkoxy group having 1 to 3 carbon atoms, that is, a methoxy group, an ethoxy group, or a propoxy group.

The organopolysiloxane type epoxy resin represented by the above formula (1) can be produced, for example, by the following method.
(Method 1) A method of cohydrolyzing and polycondensing a silane compound having an epoxy group and a silane compound having no epoxy group and / or an oligomer thereof.
(Method 2) A method of adding an organic compound having an epoxy group and a carbon-carbon double bond group to a polysiloxane having a hydrosilyl group.
(Method 3) A method in which the double bond portion of the polysiloxane having an organic group containing a carbon-carbon double bond is oxidized and converted to an epoxy group.

The raw materials that can be used when the polysiloxane type epoxy resin is produced by the method 1 are as follows.
Examples of the raw material for introducing the M unit include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylsilanol.

As raw materials for introducing D unit, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, and their hydrolysis condensates (oligomers) Illustrated.
As dialkylsiloxane oligomers having hydroxyl groups at both ends, compounds having silanol-modified compounds at both ends such as polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, and polydiphenylsiloxane are commercially available.

Raw materials for introducing T unit include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyl Examples include trimethoxysilane and hydrolytic condensates thereof.
Examples of the raw material for introducing the Q unit include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and hydrolytic condensates thereof.

As raw materials for introducing the epoxy group, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) Diethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl ] (Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ) Ethyl] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxy) (Propyl) (methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] ( Methoxy) dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4 -Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxysilane) Chlohexyl) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,3,3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, 3 -Epoxypropyl (phenyl) dimethoxysilane and the like are exemplified.

The epoxy value of the epoxy group-containing silicon compound is usually 100 g / eq or more, preferably 200 g / eq or more, more preferably 250 g / eq or more, further preferably 300 g / eq or more, and particularly preferably 400 g / eq or more. It is 4000 g / eq or less, preferably 3500 g / eq or less, more preferably 3000 g / eq or less, and further preferably 2500 g / eq or less. In particular, from the viewpoint of increasing the storage elastic modulus of the cured product after heat curing, the epoxy value is preferably slightly lower, 100 g / eq or more, preferably 150 g / eq or more, and 4000 g / eq or less, Preferably it is 3000 g / eq or less, More preferably, it is 2000 g / eq or less, More preferably, it is 1000 g / eq or less.
By making the epoxy value below these upper limits (this corresponds to the fact that the polarity is not too low and the epoxy density is sufficient), the resin can easily stay on the filler surface and can be sufficiently cured. It becomes easy and it can prevent that hardened | cured material becomes weak. Moreover, by setting it to the lower limit value or more (this corresponds to the fact that the polarity does not become too high and the epoxy density does not become excessive), the resin can easily stay on the surface of the filler, and the elastic modulus of the cured product increases. It is easy to prevent cracks from occurring due to internal stress caused by temperature changes during curing or in use.

In this specification, the epoxy value is the mass (g) of an epoxy group-containing compound (including a polymer) containing 1 equivalent (eq) of an epoxy group.

As the thermosetting resin in the resin composition, one kind of the above-described resins may be used alone, or two or more kinds may be used in combination. Moreover, it is preferable that an epoxy group containing silicon compound is included from a wettability viewpoint to the filler surface.

1-3. Curing catalyst The resin composition which is one Embodiment of this invention contains a curing catalyst. The curing catalyst may be appropriately selected depending on the type of resin used, and the curing catalyst is not particularly limited as long as it is a compound that can cure the thermosetting resin. Hereinafter, examples of the curing catalyst for the epoxy resin will be shown.

(1) Curing catalyst of epoxy resin When using an epoxy resin, the catalyst used for normal epoxy resin hardening can be used. For example, tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n- Undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) ) -2-Ethyl-4-methylimidazo 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5-di [( 2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- ( 2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2,4-diamino- 6- (2′-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- ( ')] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1')] ethyl Imidazoles such as isocyanuric acid adduct of s-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphospho Nitrobromide, Methyltriphenylphosphonium bromide, Ethyltriphenylphosphonium bromide, n-Butyltriphenylphosphonium bromide, Tetraphenylphosphonium bromide, Ethyltriphenylphosphonium iodide, Et Tiltriphenylphosphonium acetate, methyltributylphosphonium dimethyl phosphate, tetrabutylphosphonium diethylphosphodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n Quaternary phosphonium salts such as butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate; diaza such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts Bicycloalkenes; Organometallic compounds such as zinc octylate, tin actylate, aluminum acetylacetone complex, gallium compounds, indium compounds; tetraethylammonium bromide, tetra-n-butyl Quaternary ammonium salts such as ruammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride, additions of dicyandiamide, amines and epoxy resins, etc. High melting point dispersion type latent curing accelerators such as amine addition type accelerators; Microcapsule type latents in which the surface of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts are coated with a polymer Curing accelerator; amine salt type latent curing agent accelerator; latent curing accelerator such as high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt other than gallium compound, Bronsted acid salt, etc. Can be mentioned.

Among these, since strong catalytic activity is required, an organometallic compound is preferable, a gallium compound and an indium compound are more preferable, and a gallium compound is more preferable.
Of these, gallium acetylacetonate and gallium acetate are particularly preferred.

The gallium compound is a component that acts as a catalyst for the self-polymerization reaction of the epoxy resin in combination with silanol supplied from a silanol source compound described in detail later. The gallium compound is not particularly limited as long as it is a compound containing gallium as a metal atom, and various forms such as an oxide, a salt, and a chelate complex can be used. Gallium complex having chelate ligand, gallium acetate, gallium oxyacetate, triethoxygallium, tris (8-quinolinolato) gallium, gallium oxalate, gallium ethylxanthate, diethylethoxygallium, gallium maleate, n-octylic acid, Examples thereof include gallium salts of long chain carboxylic acids such as 2-ethylhexanoic acid and naphthenic acid.
Examples of the chelate ligand include β-diketone type compounds and o-ketophenol type compounds. Some β-diketone type compounds have structures represented by the following formulas (15) to (17).

In formulas (15) to (17), R ₅ independently represents an alkyl group or a halogen-substituted alkyl group.
Specific examples of the compound of the formula (15) include acetylacetone, trifluoroacetylacetone, pentafluoroacetylacetone, hexafluoroacetylacetone and the like, and specific examples of the compound of the formula (16) include ethylacetoacetate and the compound of the formula (17). Specific examples of such include diethyl malonate.
The o-ketophenol type compound is a compound represented by the following formula (18).

In the formula (18), R ′ represents a hydrogen atom, an alkyl group, a halogen-substituted alkyl group or an alkoxy group.
Specific examples of the compound of formula (18) include salicylaldehyde, ethyl-o-hydroxyphenyl ketone and the like.
A gallium complex having a chelate ligand is a preferred example of a gallium compound, and among them, gallium acetylacetonate can be particularly preferably used. Two or more kinds of gallium compounds can be used in any combination.

When a gallium compound is used, the weight loss when the cured product is exposed to a high temperature is less than that of an Al catalyst. A great effect is obtained particularly when the cured product contains a siloxane structure.
Specifically, the weight loss when the temperature is maintained at 150 to 200 ° C. for 500 hours is preferably 20% by mass or less of the mass before heating, and more preferably 10% by mass or less.
When the epoxy resin-containing composition containing a gallium compound and an epoxy resin is cured, the content of the gallium compound is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, based on 100 parts by mass of the epoxy resin. Usually, 5.0 parts by mass or less, preferably 1.0 parts by mass or less.

(2) Silanol source compound The silanol source compound is a compound that is a supply source of silanol. Silanol, in combination with the aforementioned gallium compound, acts as a catalyst for the self-polymerization reaction of the epoxy resin.
The role of silanol is considered to be a cation source necessary for the initiation of the self-polymerization reaction of the epoxy resin. When an aromatic group such as a phenyl group is bonded to the silicon atom of the silanol source compound, the aromatic group functions to increase the acidity of the silanol hydroxyl group, that is, to enhance the action of silanol as a cation source. it seems to do.

The silanol source compound may be a potential silanol source. For example, it is a compound which has a silicon atom to which a hydrolyzable group is bonded and which produces silanol when the hydrolyzable group is hydrolyzed. Specific examples of the hydrolyzable group include a hydroxy group, an alkoxy group, hydrogen, an acetoxy group, an enoxy group, an oxime group, and a halogen group. A preferred hydrolyzable group is an alkoxy group, particularly an alkoxy group having 1 to 3 carbon atoms, that is, a methoxy group, an ethoxy group, or a propoxy group.

An example of a silanol source compound is a silicon atom to which hydroxyl groups such as phenyldimethylsilanol, diphenylmethylsilanol, triphenylsilanol, dihydroxydiphenylsilane (diphenyldisilanol), trimethylsilanol, triethylsilanol, dihydroxydimethylsilane, and trihydroxymethylsilane are bonded. It is a monosilane compound having

Another example of the silanol source compound is an organopolysiloxane represented by the formula (19) having a silicon atom to which a hydroxyl group is bonded.
(R ²¹ ₃ SiO _1/2 ) a ₂ (R ²² ₂ SiO _2/2 ) _{b 2} (R ²³ SiO _3/2 ) _{c 2} (SiO _4/2 ) _{d 2} (O _1/2 H) _{e 2} (19)
In the formula (19), R ²¹ , R ²² and R ²³ each independently represent a monovalent organic group.

In the formula (19), R ²¹ ₃ SiO _1/2 represents an M unit, R ²² ₂ SiO _2/2 represents a D unit, R ²³ SiO _3/2 represents a T unit, and SiO _4/2 represents a Q unit. Yes. Each of a2, b2, c2, and d2 is an integer of 0 or more, and a2 + b2 + c2 + d2 ≧ 1. e2 is a natural number of 1 or more, and represents the number of hydroxyl groups (silanol) directly bonded to the silicon atom.

R ²¹ , R ²² and R ²³ in the formula (19) are usually hydrocarbon groups having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Alkyl groups such as hexyl and heptyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; aryl groups such as phenyl, tolyl and xylyl; aralkyls such as benzyl and phenethyl Groups; substituted alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutylethyl group and the like.

The silanol source compound has a hydrolyzable group bonded to a silicon atom, and produces a organopolysiloxane represented by the formula (19) when the hydrolyzable group is hydrolyzed. Also good. In other words, the organopolysiloxane represented by the formula (19) may be a compound in which all or a part of hydroxyl groups directly bonded to silicon atoms are replaced with hydrolyzable groups.

When the silanol source compound is an organopolysiloxane and is used together with an epoxy resin that does not contain a siloxane structure, the organopolysiloxane is silicon from the viewpoint of ensuring compatibility between the organopolysiloxane and the epoxy resin. It preferably has an aromatic group bonded to an atom.
When the silanol source compound is an organopolysiloxane, the weight average molecular weight is preferably 500 or more and more preferably 700 or more so that it does not volatilize during or after curing of the thermosetting resin composition. preferable. On the other hand, if the degree of polymerization is too high, the viscosity becomes high and the handleability deteriorates, so that the weight average molecular weight is preferably 20,000 or less, more preferably 15,000 or less.

In a preferred embodiment, the silanol source compound may be an organopolysiloxane or a silane compound having two or more silicon atoms bonded to a hydroxyl group or a hydrolyzable group in one molecule. Such a silanol source compound is polycondensed by the action of the gallium compound to increase the molecular weight when heated, so that it does not bleed out after curing.
Examples of the organopolysiloxane that can be suitably used as the silanol source compound include those having structures represented by the following formulas (20) to (23).

The organopolysiloxane represented by the formula (22) includes a compound represented by the formula (20) and a compound represented by the formula (24) (dihydroxydimethylsilane or polydimethylsiloxane having hydroxyl groups at both ends), It can be obtained by polycondensation. As the polycondensation catalyst, a metal catalyst can be used in addition to an acid and a base, and a gallium compound such as gallium acetylacetonate can also be used.
The organopolysiloxane represented by the formula (23) can be obtained by polycondensing the compound represented by the formula (21) and the compound represented by the formula (24). As the polycondensation catalyst, a metal catalyst can be used in addition to an acid and a base, and a gallium compound such as gallium acetylacetonate can also be used.

In the expressions (20) to (24), m, n, M, N, m1, and m2 are each an integer of 1 or more. When these numbers are increased too much, that is, when the degree of polymerization of the polysiloxane is increased too much, the viscosity becomes too high and handling becomes difficult, and the catalytic performance tends to decrease due to a decrease in the content of silanol. Note that occurs. From the viewpoint of handling properties, the viscosity of the organopolysiloxane or the viscosity of the resin composition obtained using the organopolysiloxane is 50,000 cp or less, preferably 40,000 cp or less, more preferably at 30 ° C. and 1 atm. Is preferably set to 30,000 cp or less, more preferably 20,000 cp or less, particularly preferably 15,000 cp or less, and most preferably 10,000 cp or less.

An organopolysiloxane obtained by polycondensation of one or more selected from the organopolysiloxanes represented by formulas (20) to (23) together with a trifunctional silane compound such as methyltrimethoxysilane or phenyltrimethoxysilane This is a preferred example of a silanol source compound. As the polycondensation catalyst, a metal catalyst can be used in addition to an acid and a base, and a gallium compound such as gallium acetylacetonate can also be used. Such organopolysiloxanes have the property of being cured by the action of a condensation catalyst such as an acid, a base or a metal compound such as a gallium compound. As the silanol source, a monosilane compound and an organopolysiloxane may be used in combination.

A silanol source compound is 0.05 mass part or more normally with respect to 100 mass parts of epoxy resins, Preferably it is 0.1 mass part or more, and is 500 mass parts or less, Preferably it is 200 mass parts or less.
Further, the content ratio of the gallium compound and the silanol source compound is preferably 1: 0.05 to 0.001: 100, more preferably 1:10 to 0.01: 100 in terms of mass ratio.
The content of the curing catalyst in the thermosetting resin composition is preferably adjusted to be 0.001% by mass to 0.3% by mass with respect to 100% by mass of the thermosetting resin composition.

In the epoxy group-containing silicon compound, either one or both of the epoxy resin and the silanol source compound may have an organopolysiloxane structure portion. In that case, when silanol is introduced into the organopolysiloxane structure, the gallium compound acts as a dehydration condensation catalyst between silanols, so that both the self-polymerization reaction and silanol condensation reaction of epoxy resin are involved in curing A good thermosetting resin composition is obtained. Since the gallium compound also serves as a catalyst for the dealcoholization condensation reaction between silanol and alkoxy group, the same effect can be obtained when silanol and alkoxy group are introduced into the organopolysiloxane structure. When the thermosetting resin has a silanol group, the gallium compound is preferable because it also serves as a catalyst for siloxane condensation and the crosslinking system proceeds simultaneously. Further, it has good compatibility with siloxane and silica and contributes to silica dispersion. Furthermore, when an epoxy group-containing silicon compound is reacted with a gallium compound, the linear expansion coefficient of the resulting cured product becomes constant over a wide range.

In another example, a hydrosilyl group is introduced into one of the organopolysiloxane structure part of the epoxy resin and the organopolysiloxane structure part of the silanol source compound, and a vinylsilyl group is introduced into the other, and a hydrosilylation reaction catalyst such as a platinum compound is used. By adding, a thermosetting resin composition with good curability in which both the self-polymerization reaction and hydrosilylation reaction of the epoxy resin are involved in the curing can be obtained.

Alternatively, by introducing a hydrosilyl group into the organopolysiloxane structure part of either or both of the epoxy resin and the silanol source compound, and adding an organopolysiloxane having a vinylsilyl group and a hydrosilylation reaction catalyst, the epoxy resin Thus, a thermosetting resin composition in which both the self-polymerization reaction and hydrosilylation reaction are involved in curing is obtained. This example may be modified so that a vinylsilyl group is introduced into the organopolysiloxane structure part of either one or both of the epoxy resin and the silanol source compound, and the organopolysiloxane to be added is introduced with a hydrosilyl group.

1-4. Curing agent for epoxy resin Examples of the curing agent that forms a cross-linked product by reaction with an epoxy group include amines, polyamide resins, acid anhydrides, and phenols. From the viewpoints of reducing the linear expansion coefficient, controlling the polymerization rate, and reducing the viscosity, it is preferable to use an acid anhydride. Examples of the acid anhydride include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, halogen acid anhydrides, and acyclic carboxylic acid anhydrides. When using this resin composition for an optical semiconductor device, it is preferable to use an alicyclic carboxylic acid anhydride from the viewpoint of increasing the light resistance and the elastic modulus of the cured product.
Although there is no restriction | limiting in particular as content of an acid anhydride, when too much, Tg of an acid anhydride may affect the linear expansion coefficient of the hardened | cured material obtained.

Examples of the alicyclic carboxylic acid anhydride include compounds represented by formulas (25) to (31), 4-methyltetrahydrophthalic acid anhydride, methylnadic acid anhydride, dodecenyl succinic acid anhydride, Examples thereof include Diels-Alder reaction products of alicyclic compounds having a conjugated double bond such as α-terpinene and alloocimene and maleic anhydride, and hydrogenated products thereof.

In addition, arbitrary structural isomers and arbitrary geometrical isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.
In addition, the alicyclic carboxylic acid anhydride can be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.
By containing an acid anhydride, effects such as control of the epoxy reaction rate, handling, improvement in leveling, and prevention of coloring may be obtained. Although there is no restriction | limiting in particular as content of an acid anhydride, It is preferable that it is 1.5 equivalent or less with respect to the amount of epoxy. More preferably, it is 1 equivalent or less, More preferably, it is 0.8 equivalent or less, More preferably, it is 0.6 equivalent or less.
Examples of the acyclic carboxylic acid anhydride include those represented by the formula (32).

(In the formula (32), R ₆ and R ₇ are not connected, and R ₆ and R ₇ are the same or each independently represent an optionally substituted hydrocarbon group.)
The hydrocarbon group may be any aliphatic, alicyclic or aromatic hydrocarbon group. The aliphatic hydrocarbon group is a linear or branched saturated hydrocarbon or unsaturated hydrocarbon, and examples thereof include an aliphatic hydrocarbon group having 2 to 18 carbon atoms. More specifically, a compound represented by the formula (33) can be given.

(N ′ represents an integer of 0 to 18)
In the formula (33), n ′ is preferably 0 or more, more preferably 2 or more, and still more preferably 4 or more in terms of low volatility. In view of solubility, n ′ is preferably 15 or less, and more preferably 12 or less.
Aliphatic hydrocarbon groups include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, etc. An alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.

Examples of the aromatic hydrocarbon group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, Aryl groups such as biphenyl-2-yl, anthryl, and phenanthryl; benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl, and β-naphthylethyl An aralkyl group is mentioned.

Examples of the substituent that may be substituted on the hydrocarbon group include a hydroxyl group, an alkyl group, a nitro group, an amino group, a mercapto group, an acetyl group, and a halogen (Cl, Br, F).

Moreover, the storage stability of a resin composition can be improved at the point which can control the reaction rate of an epoxy group by containing a non-cyclic carboxylic acid anhydride.
Furthermore, by containing a non-cyclic carboxylic acid anhydride, effects such as improved handling, leveling, and prevention of coloring may be obtained. Specifically, the ester bond portion of the acyclic carboxylic acid anhydride is a highly polar site, or R ₆ and R _{7 in} the formula (32) are nonpolar sites, thereby eliminating the phase separation structure in the resin composition. May function as an activator.

Although there is no restriction | limiting in particular as content of an acyclic carboxylic acid anhydride, The minimum of content is 0.015 equivalent or more with respect to the amount of epoxy, Preferably it is 0.1 equivalent or more, More preferably, it is 0.12 equivalent or more. More preferably, it is 0.15 equivalent or more. Moreover, the upper limit is 1.5 equivalent or less with respect to the amount of epoxy, Preferably it is 1.0 equivalent or less, More preferably, it is 0.8 equivalent or less, More preferably, it is 0.6 equivalent or less.

1-5. Silicone resin curing catalyst When a silicone resin is used, examples of the curing catalyst include metal compounds. As the metal compound, a chelate complex, an organic acid salt, an inorganic salt, or an alkoxide of zirconium, hafnium, yttrium, tin, zinc, titanium, or gallium can be used. From the viewpoint of the linear expansion coefficient of the cured product, the above-described gallium compound is preferably used.

1-6. Organic group-containing silicon compounds other than epoxy group-containing silicon compounds Organic group-containing silicon compounds other than epoxy group-containing silicon compounds (hereinafter also simply referred to as “organic group-containing silicon compounds”) are organic groups other than epoxy groups in the molecule. It is a silicon compound having Examples of the organic group include an alcohol group, a carboxyl group, an acrylic group, a methacryl group, a thiol group, an ether group, an aralkyl group, an amino group, and an alkyl group. As the organic group-containing silicon compound, it is preferable to use at least one silicon compound modified with an alcohol group or a carboxyl group.

By including the organic group-containing silicon compound as described above in the resin composition, they are likely to stay on the filler surface, and are easily adsorbed to the filler because they have an appropriately polar organic group. Furthermore, since it has an appropriate weight average molecular weight, it is easy to stay on the filler surface, and the structural viscosity of the filler can be destroyed.

In addition, by including the organic group-containing silicon compound in the resin composition, there are cases where effects such as handling, improvement in leveling, and prevention of coloring can be obtained. Specifically, the surfactant that eliminates the phase separation structure in the resin composition by contacting the silicon compound portion of the organic group-containing silicon compound with the low polarity portion of the filler and the organic group portion with the polar portion of the filler. May function as.

Moreover, the effect of controlling the elastic modulus of the cured product of the resin composition may be obtained by containing the organic group-containing silicon compound in the resin composition. Specifically, the organic group-containing silicon compound chemically reacts with other resins to form a cross-linked structure, the cured product is made highly elastic, or when the organic group-containing silicon compound has a flexible skeleton, Lower elasticity.

Next, the alcohol group-containing silicon compound and the carboxyl group-containing silicon compound will be described. For these organic group-containing silicon compounds, the molecular weight is preferably 100 or more in terms of weight average molecular weight (Mw) measured by GPC from the viewpoints of handleability, filler wettability, and viscosity reduction. It is more preferably 1000 or more, further preferably 2000 or more, and preferably 10,000 or less, more preferably 5000 or less. The content of these organic group-containing silicon compounds is 0.01% by mass or more, preferably 0 when the total amount of the resin composition is 100% by mass from the viewpoint of viscosity reduction and storage modulus control of the cured product. 0.05% by mass or more, more preferably 0.1% by mass or more. Moreover, 20 mass% or less is preferable and 10 mass% or less is more preferable.

The alcohol group-containing silicon compound has one or a plurality of primary alcohols, secondary alcohols, tertiary alcohols in the molecule, and preferably contains primary alcohols. Examples of such a silicon compound include those represented by formula (2).

(N represents an integer from 1 to 120, a represents an integer from 1 to 10, and b represents an integer from 1 to 10.)
In the formula (2), R ₁ and R ₂ independently represent a divalent organic group. Examples of R ₁ and R ₂ are an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrocarbon group that may contain an aromatic group. Further, R ₁ and R ₂ are not linked, and R ₁ and R ₂ may be the same or different and may have a substituent. Ra and Rb represent a hydrogen atom or a hydroxyl group.

In view of low volatility, n is preferably 1 or more, more preferably 5 or more, and still more preferably 10 or more. In view of solubility, n is preferably 120 or less, more preferably 100 or less. About a and b, 1 or more are preferable and 10 or less are preferable.

The alcohol group-containing silicon compound is not limited to the form of the formula (2), and the silicone part may have a branched structure via a T unit and a Q unit. Moreover, you may have M unit. The number of alcohol groups contained in one molecule is not limited, but more preferably is 2. For example, the following formula (2 ') is exemplified.

(In the formula (2 ′), x represents an integer of 1 to 120, y represents an integer of 1 to 120, and R represents an organic group.)
In formula (2 ′), examples of the organic group represented by R include an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrocarbon group that may contain an aromatic group.

Examples of alcohol group-containing silicon compounds include BY-16-201 (Toray Dow Corning), SF8427 (Toray Dow Corning), SF8428 (Toray Dow Corning), KF-6000 (Shin-Etsu Chemical). KF6001 (manufactured by Shin-Etsu Chemical) KF6002 (manufactured by Shin-Etsu Chemical) KF6003 (manufactured by Shin-Etsu Chemical) and the like.

Examples of the carboxyl group-containing silicon compound include those represented by the formula (3).

(M ′ represents an integer of 1 to 120.)
In the formula (3), R ₃ and R ₄ independently represent a divalent organic group. Examples of R ₃ and R ₄ are an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrocarbon group that may contain an aromatic group. R ₃ and R ₄ are not linked, and R ₃ and R ₄ may be the same or different, and may have a substituent. In view of low volatility, m ′ is preferably 1 or more, more preferably 5 or more, and still more preferably 10 or more. In view of solubility, m ′ is preferably 120 or less, and more preferably 100 or less.

The carboxyl group-containing silicon compound is not limited to the form of the formula (3), and the silicone part may have a branched structure via a T unit and a Q unit. Moreover, you may have M unit. The number of carboxyl groups contained in one molecule is not limited, but more preferably is 2.
Examples of the carboxyl group-containing silicon compound include Magnassoft 800L (Momentive), BY16-880 (Toray Dow Corning), X-22-3710 (Shin-Etsu Chemical).

1-7. Filler The resin composition may contain a filler, and the content thereof is not particularly limited, but usually contains 50% by mass or more of filler with respect to the total amount of the resin composition. As the filler, both general organic fillers and inorganic fillers can be used. Organic fillers include styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, polyamide polymer particles, synthetic polymer particles such as polynylon polymer particles, natural products such as starch and wood flour, Examples thereof include cellulose which may be modified and various organic pigments. The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine powder amorphous silica. Silica-based inorganic fillers such as alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black , Ferrite, graphite, diatomaceous earth, clay, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, silver powder, etc. Can do. These may be used alone or in combination of two or more. Moreover, you may perform a surface treatment suitably. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

The content of the filler with respect to the total amount of the resin composition is usually 50% by mass or more. From the viewpoint of reducing the linear expansion coefficient of the cured product of the resin composition, it is preferably 75% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more.

By using a filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectivity, flame retardancy, fire resistance, thixotropy of the resulting molded product (cured product) Properties (characteristics of the composition, not the molded body), and various physical properties such as gas barrier properties can be improved.
Among the fillers, a silica filler is preferably contained. Hereinafter, the silica filler will be described in detail.

In the present specification, the silica filler refers to a filler such as silica-based inorganic filler such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica.
In a normal resin composition, when the amount of filler added increases, the viscosity of the composition increases significantly.

From the viewpoint of viscosity control, the shape is preferably spherical rather than fibrous or irregular. Here, the spherical shape may be a true spherical shape, an elliptical shape, or a substantially spherical shape including an oval shape. Specifically, the aspect ratio (ratio of major axis to minor axis) is usually 1. .3 or less, preferably 1.2 or less, more preferably 1.1 or less.

Furthermore, it is preferable to have a hydroxyl group on the filler surface from the viewpoint of formulation. Since the polarity of the filler surface can be improved by having a hydroxyl group, an organic polymer having a higher polarity than an inorganic substance can be easily mixed.
It is also possible to increase the amount of filler added by controlling the particle size distribution. That is, a higher filling rate can be obtained by mixing fillers having different particle sizes.

The average particle diameter of the filler is measured using (Particle Size Analyzer CILAS 1064), preferably 0.1 μm or more, and more preferably 1 μm or more. Moreover, 100 micrometers or less are preferable and 50 micrometers or less are more preferable.

Further, the silica filler may be appropriately surface-treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited. By the surface treatment, the type of particle surface functional group can be controlled. From the viewpoint of reducing the viscosity, it is preferable to use (glycidylated) treated filler.
A silica filler may use 1 type and may use 2 or more types together.

Increasing the amount of filler may decrease the viscosity at low shear while increasing the viscosity at high shear. The viscosity at the time of low shear is the viscosity when the viscosity is measured by the method described later, that is, at 25 ° C. and a shear rate of 0.09 s ⁻¹ or less. The viscosity at high shear is the viscosity at a shear rate of 1 s ^-1 or higher. This is presumably because the filler mobility is hindered by increasing the amount of filler, and it becomes difficult for the filler to form a secondary structure at low shear.

Also, when an effect of improving flame retardancy is expected, it is effective to add a hydrated metal compound filler such as aluminum hydroxide or magnesium hydroxide.

1-8. Thermoplastic resin The resin composition of this invention may contain the thermoplastic resin as needed. The thermoplastic resin is not particularly limited, but vinyl polymers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, (meth) acrylic resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polylactic acid resin, Polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon and polyamidoamine; polyvinyl acetal resins such as polyvinyl acetoacetal, polyvinyl benzal and polyvinyl butyral resin; ionomer resins; polyphenylene ether; polyphenylene sulfide; polycarbonate; Polyacetal, ABS resin, LCP (liquid crystal polymer), fluorine resin, urethane resin, elastomer, or these Including resin modified products and the like.

The thermoplastic resin is preferably stretchable. The elongation can relieve stress and suppress cracks.
The maximum elongation of the thermoplastic resin is preferably 5% or more, and more preferably 10% or more. The maximum elongation of the thermoplastic resin is a value measured by a measuring method based on JIS K7113 or ASTM D638.

Further, the thermoplastic resin may be soluble in at least one component of the thermosetting resin in the resin composition.

Among the thermoplastic resins, polyvinyl acetals such as polyvinyl butyral and vinyl resins such as (meth) acrylic resins are preferable, and polyvinyl acetals such as polyvinyl butyral are particularly preferable. Polyvinyl acetal has a hydroxyl group and is excellent in dispersibility. In addition, when the curing agent is reactive with a hydroxyl group (such as an acid anhydride), a part of the acetal is taken in, making it difficult to separate from the thermosetting resin. . It is also possible to positively introduce a reactive group by modification with an acid anhydride in advance.

The thermoplastic resin is preferably insoluble in the thermosetting resin in the resin composition.
Insoluble in the thermosetting resin means that the component soluble in the thermosetting resin component in the resin composition is less than 10%, preferably less than 5%, more preferably less than 3%, still more preferably less than 1%. Say something.
When the thermoplastic resin is insoluble in the thermosetting resin, it is possible to prevent the viscosity of the liquid resin composition from increasing and improve the leveling property.
Also, by mixing a thermoplastic resin that is insoluble in a thermosetting resin simultaneously with a large amount of fillers, that is, in combination, a component phase that is thermoplastic and has good elongation can be efficiently dispersed in the resin composition, and stress is relieved. It's easy to do.
Furthermore, when the dispersed thermoplastic resin is insoluble in the thermosetting resin, cracks can be suppressed without lowering the elastic modulus of the cured product of the resin composition.

Of these, polyamide resins such as nylon and cellulose resins are particularly preferable, and polyamide resins such as nylon are particularly preferable.
The thermoplastic resin is preferably stretchable. The elongation can relieve stress and suppress cracks.

In order to efficiently disperse the thermoplastic resin phase in the resin composition, it is preferable that the particle diameter of the thermoplastic resin is small. The average particle size of the thermoplastic resin is preferably 500 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less.

The content of the thermoplastic resin in the resin composition is preferably 0.001% or more, more preferably 0.003% or more, and further preferably 0.005% or more, as a lower limit value in the resin composition. Moreover, as an upper limit, Preferably it is 10% or less, More preferably, it is 5% or less, More preferably, it is 2% or less.

1-9. Others In addition to the above-mentioned components, the resin composition according to the embodiment of the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, and a leveling agent from the viewpoint of improving physical properties and imparting functions. Further, additives such as a light diffusing agent, a thermal conductivity, a flame retardant, a reactive or non-reactive diluent, an adhesive, and an adhesion improver may be further contained.

(1) Antioxidant The resin composition according to one embodiment of the present invention may contain an antioxidant in order to suppress yellowing under the use environment. Phenol-based antioxidants, phosphorus-based antioxidants, hindered amines, and the like are preferably used. Among n, hindered phenol-based antioxidants having an alkyl group at one or both ortho positions of the phenol hydroxyl group are particularly suitable. Used.

(2) Silane coupling agent A silane coupling agent can be contained in the resin composition in order to improve the adhesion to metal parts and fillers. Specific examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Examples include aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

(3) Flame retardant In addition, in order to improve the flame retardancy, organic flame retardants such as halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and their composite types, antimony compounds, metals An inorganic flame retardant such as hydroxide can be contained. They may be additive or reactive.

2. Method for Producing Resin Composition The resin composition can be produced by mixing a thermosetting resin and a curing catalyst with other components such as the filler, resin, and antioxidant described above as necessary. The order of mixing is not particularly limited. For example, when an epoxy group-containing silicon compound is used, it must be mixed with an epoxy resin in the absence of a gallium compound, a silanol source compound, and a catalyst used for curing the epoxy resin in order to prevent the curing reaction from proceeding due to heat generation during mixing. Is desirable.

The means for mixing the filler is not particularly limited, but specifically, for example, a two-roll or three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, etc., a plast mill And a melt kneader. Mixing may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.
This resin composition may be a one-component curable type or a two-component curable type in consideration of storage stability.

3. Sealing Method The resin composition of the present invention is preferably used as a sealing material for semiconductor devices, but the sealing method may be performed by a commonly performed method.
Examples of the sealing method include transfer molding and potting. Since the resin composition of the present invention is a resin composition having fluidity at room temperature, it is preferably used for potting. Specifically, a liquid containing a resin composition and a liquid containing a curing catalyst are respectively prepared and then mixed to prepare a mixed liquid that can be used for potting. A part is placed in the housing, and the above-mentioned mixed liquid is poured into it. Then it is cured. Depending on the resin composition used, room temperature curing or heat curing may be used. For heat curing, conventionally known methods such as hot air circulation heating, infrared heating, and high-frequency heating can be employed.

The resin composition of the present invention contains a thermosetting resin. The heat treatment conditions may be determined according to the resin composition, the catalyst concentration, the thickness of the member to be formed with the composition, and the like as long as the resin composition can be brought into a desired cured state. By setting the curing temperature to about 100 ° C. at first and then to 120 to 180 ° C., foaming due to residual solvent or dissolved water vapor in the composition can be prevented. Moreover, since the difference in the curing rate between the deep portion and the surface of the resin composition can be reduced, a cured product having a smooth surface and no wrinkles and a good appearance can be obtained. If the difference in cure speed between the deep part and the surface of the resin composition is small, the cured state becomes uniform, so that the generation of internal stress in the cured product is suppressed, and the occurrence of cracks can be prevented.

4). Use of Resin Composition The use of the resin composition according to the embodiment of the present invention is not particularly limited, and can be used as a sealing material for various semiconductor devices including light emitting devices such as LED devices. Further, the molded body obtained by curing the resin composition according to one embodiment of the present invention contains 50% by mass or more of silica filler, so that it has a low coefficient of thermal expansion even at a high temperature, and cracks are generated by relaxing the stress. It is difficult to use and excellent in reliability, so it is particularly suitable for power devices. Examples of the power device include those used as rectification, frequency conversion, a regulator, an inverter, and the like. The resin composition of the present invention has fluidity as a composition, can be suitably used for sealing by potting, and has a very low linear expansion coefficient of a cured product, so it is suitable for a wide range of power devices. Can be used for It can also be used for power devices such as home appliances and computers, and can also be used for large power devices for controlling automobiles, railway vehicles, and substations.

Hereinafter, the present invention will be described in more detail with reference to experimental examples (Examples and Comparative Examples), but the present invention is not limited to the following Examples as long as it does not exceed the gist thereof. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit. It may be a range defined by a combination of values of the following examples or values of the examples.

First, materials and reagents used in Examples and Comparative Examples will be described.
Synthetic resins A and B, which are epoxy group-containing silicon compounds, were synthesized as in Synthesis Examples 1 and 2, respectively. In the following synthesis examples, the weight average molecular weight (Mw) and the epoxy value were measured as follows.
-Weight average molecular weight (Mw)
The weight average molecular weight (Mw) of the curable composition was measured by gel permeation chromatography under the following conditions and indicated as a standard polystyrene equivalent value. Moreover, what prepared the 1 mass% tetrahydrofuran solution of polysiloxane, and filtered with the filter of 0.45 micrometer after that was used as the measurement sample solution.
Apparatus: Waters 2690 (manufactured by Waters)
Column: KF-G, KF-602.5, KF-603, KF-604 (manufactured by Showa Denko)
Eluent: THF, flow rate 0.7 mL / min, sample concentration 1%, injection volume 10 μL
-Epoxy value It implemented according to JISK7236: 2001. The precisely weighed sample was dissolved in chloroform, and acetic acid and tetraethylammonium bromide acetic acid solution were added, followed by titration with a 0.1 mol / L perchloric acid acetic acid standard solution. The end point was determined using a crystal violet indicator.

<Synthesis Example 1: Synthesis Method of Synthetic Resin A>
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 13.0 g, double-ended silanol-type dimethylsiloxane (XC96-723 manufactured by Momentive) 55.4 g, trimethylmethoxysilane 3.67 g, isopropyl alcohol 34.6 g, toluene 34.6 g and a 0.37% KOH aqueous solution 6.99 g were mixed, stirred at room temperature for 2 hours, and further heated and stirred for 6 hours under reflux conditions (internal temperature of about 73 ° C.). Thereafter, the reaction solution is neutralized with an aqueous sodium dihydrogen phosphate solution (10% by mass), washed with water until the washed water becomes neutral, volatile components are removed under reduced pressure, and Mw = 3300 epoxy. A polysiloxane synthetic resin A having a value of 1160 g / eq was obtained.

<Synthesis Example 2: Synthesis Method of Synthetic Resin B>
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (64.9 g), trimethylethoxysilane (40.1 g), isopropyl alcohol (45 g) and 1N hydrochloric acid (24.2 g) were mixed and stirred at room temperature for 3 hours. .45 g and 50.2 g of isopropyl alcohol were added, and the mixture was heated and stirred for 4 hours under reflux conditions of isopropyl alcohol. Thereafter, the reaction solution is neutralized with an aqueous solution of sodium dihydrogen phosphate (10% by mass), washed with water until the washed water becomes neutral, volatile components are removed under reduced pressure, and Mw = 1100 epoxy. A polysiloxane synthetic resin B having a value of 290 g / eq was obtained.

<Evaluation of viscosity and fluidity of the composition>
In this embodiment, the viscosity at 25 ° C. and a shear rate of 0.009 s ⁻¹ is defined as follows. The viscosity of the resin composition was measured with a rheometer VISCOANALYSER (Reologica Inst. AB). Measurement conditions are 25 ° C for temperature, Φ30 parallel plate for use plate, gap of 0.800 mm, preshear condition of 0.1 (1 / s) for 60 seconds, and equilibration time (wait time before measurement) of 25.0 seconds. Delay time (time when data is not acquired) 40 seconds, integration time (time when data is acquired) 80 seconds, measurement shear rate range: 0.001 to 600 (1 / s). As a measurement procedure, the viscosity at 0.009 s ⁻¹ was calculated by placing an appropriate amount of the resin composition on the sample stage, lowering the jig, and measuring the viscosity when the shear rate was increased under the above conditions. .

<Measurement of physical properties of cured product>
The physical properties of the cured products obtained in the following examples and comparative examples were measured as follows.
Measurement of average linear expansion coefficient From a plate-like cured product having a thickness of 1 to 2 mm, it was cut into 3 × 3 mm and used as a measurement sample.
The average linear expansion coefficient is EXSTAR as a thermomechanical analyzer in accordance with JIS K7197.
Using TMA / SS6100 (manufactured by SII Nanotechnology Inc.), measurement was performed in a compression mode with a temperature program shown in Table 1, and an average linear expansion coefficient in Program 3 was calculated.

-Storage elastic modulus (E ') measurement From a plate-like cured product having a thickness of 1 to 2 mm, it was cut into a strip shape having a width of 5 mm and used as a measurement sample.
The storage elastic modulus is based on JIS K7244, using EXSTAR DMS / 6100 (manufactured by SII NanoTechnology) as a thermomechanical analyzer, in a tensile mode, with a chuck distance (effective length) of 15 mm. The frequency was measured by a temperature program shown in Table 2 below at a frequency of 1 Hz, and the storage elastic modulus at 25 ° C. and 180 ° C. in Program 1 was calculated.

-Volume resistivity measurement A cured product of a disk having a thickness of 1 to 2 mm and a diameter of 7 cm was used as a measurement sample. The volume resistivity measurement was performed under the following conditions using a resiliency chamber 12708 and a digital ultrahigh resistance / microammeter 5451 (manufactured by ADC Corporation).
Voltage: 500V
Charge time: 4 minutes Electrode size: Conforms to ASTM D257

Calculation formula: (volume resistivity) = (π * (main electrode diameter) ² ) / (4 * (sample thickness)) * (volume resistance (measured value))

<Thermal cycle test>
An evaluation case was prepared by combining a nickel-plated copper plate on the bottom surface of a module case (34 PM case manufactured by Kojin Co., Ltd.) having a PPS wall. About 44 g of the resin composition was poured into the case, and the resin composition was sequentially heated and cured under predetermined curing conditions to produce a thermal cycle test sample.
Using a thermal shock device TSA-41LA (manufactured by ESPEC), a thermal cycle test was performed with 70 cycles of 175 ° C high temperature exposure for 30 minutes, normal temperature exposure for 1 minute, and -40 ° C low temperature exposure for 30 minutes. A sample was taken out later, and it was visually confirmed whether the cured product was cracked or peeled off from the PPS wall. The case where no crack was generated was marked as ◯, and the case where a crack was generated was marked as x.

[Example 1]
2.0 g of modified silicone oil X-22-169 (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.54 g of trimethylolpropane triglycidyl ether Denacol (registered trademark) EX-321L (manufactured by Nagase ChemteX), nylon fine particle SP500 (Toray Industries, Inc.) 0.10 g) and 30 g of true spherical filler HL-3100 (manufactured by Tatsumori) were stirred and mixed using Planetary Vacuum Mixer ARV-300 manufactured by THIKY. To this mixture, 0.58 g of Ricacid MH700 (manufactured by Shin Nippon Rika Co., Ltd.), 0.075 g of both-end hydroxy group polymethylphenylsiloxane YF3804 (manufactured by Momentive), gallium acetylacetonate (manufactured by Strem Chemicals, Inc.) 0.0032 g and 0.0078 g of diphenylsilane diol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and further stirred and mixed to obtain a resin composition.
The viscosity of the obtained resin composition at 25 ° C. and a shear rate of 0.009 s ⁻¹ was measured. Further, the obtained resin composition was cured at 80 ° C. for 0.5 hour, 120 ° C. for 1 hour, and 180 ° C. for 5 hours to obtain a cured product, and the physical properties of the cured product were measured by the above method. The results are shown in Table 4. In Table 4, WPE is an epoxy value (g / eq).

[Example 2]
In accordance with the method of Example 1, a resin composition was obtained with the composition shown in Table 4.
In Table 4, X22-169A is a modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.), Magnasoft (registered trademark) 800L is an organic group-containing silicon compound (manufactured by Momentive), and TSL9906 is an epoxy group-containing silicon compound (manufactured by Momentive). .
The viscosity of the obtained resin composition at 25 ° C. and a shear rate of 0.009 s ⁻¹ was measured. Moreover, the obtained resin composition was hardened on the same conditions as Example 1, the hardened | cured material was obtained, and the physical property of the hardened | cured material was measured by said method. The results are shown in Table 4.

[Example 3]
In accordance with the method of Example 1, a resin composition was obtained with the composition shown in Table 4.
In Table 4, DLC-402 is a liquid epoxy resin, Denacol (registered trademark) DLC-402 (manufactured by Nagase ChemteX Corporation).
The viscosity of the obtained resin composition at 25 ° C. and a shear rate of 0.009 s ⁻¹ was measured. Moreover, the obtained resin composition was hardened on the same conditions as Example 1, the hardened | cured material was obtained, and the physical property of the hardened | cured material was measured by said method. The results are shown in Table 4.

[Comparative Example 1]
In accordance with the method of Example 1, a resin composition was obtained with the composition shown in Table 4.
In Table 4, E-PO is an epoxy resin (manufactured by Shin Nippon Chemical Co., Ltd.), JER871 is an epoxy resin (manufactured by Mitsubishi Chemical Corporation), EX-216L is an epoxy resin (manufactured by Nagase ChemteX), FLD516 is a silanol source compound (BLUESTARS) SILICONES).
The viscosity of the obtained resin composition at 25 ° C. and a shear rate of 0.009 s ⁻¹ was measured. Moreover, the obtained resin composition was cured at 80 ° C. for 0.5 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 3 hours to obtain a cured product. Physical properties were measured. The results are shown in Table 4.

[Comparative Example 2]
In accordance with the method of Example 1, a resin composition was obtained with the composition shown in Table 4.
In Table 4, YED216D is an epoxy resin (manufactured by Mitsubishi Chemical Corporation).
The viscosity of the obtained resin composition at 25 ° C. and a shear rate of 0.009 s ⁻¹ was measured. Moreover, the obtained resin composition was cured at 80 ° C. for 1 hour, 120 ° C. for 2 hours, 150 ° C. for 1 hour, and 200 ° C. for 1 hour to obtain a cured product. It was measured. The results are shown in Table 4.

As shown in Table 4, in Examples 1 to 3, the viscosity of the resin composition before curing was low, and the cured product exhibited high storage elastic modulus at 25 ° C and 180 ° C. The volume resistivity ratio a / b was within a predetermined range, and no cracks or peeling from the PPS wall was observed after 70 cycles of the thermal cycle test.
On the other hand, the cured product of Comparative Example 1 had a low storage elastic modulus at 180 ° C., indicating that the temperature dependency of the storage elastic modulus was large, and cracks were observed after 70 cycles of the thermal cycle test. Comparative Example 2 exhibited high storage modulus at 25 ° C. and 180 ° C., but the volume resistivity ratio a / b was outside the predetermined range, and cracks were observed after 70 cycles of the thermal cycle test.

Claims (16)

1. A thermosetting resin composition comprising a thermosetting resin and a curing catalyst,
   The viscosity at 25 ° C. and a shear rate of 0.009 s ⁻¹ is 1500 Pa · s or less,
   The cured product of the thermosetting resin composition has a storage elastic modulus at 25 ° C. and 180 ° C. of 1.0 × 10 ⁸ Pa or more, and a volume resistivity a at 25 ° C. and a volume resistivity at 200 ° C. A resin composition, wherein the ratio a / b of b is 8500 or less.
2. The resin composition according to claim 1, wherein the thermosetting resin contains an epoxy resin.
3. The resin composition according to claim 2, wherein the epoxy resin contains an alicyclic epoxy group.
4. The resin composition according to claim 2 or 3, wherein the epoxy resin contains a glycidyl group.
5. The resin composition according to claim 4, wherein the epoxy resin contains an epoxy resin containing two or more glycidyl groups.
6. The resin composition according to any one of claims 2 to 5, wherein the epoxy resin contains an epoxy group-containing silicon compound.
7. The resin composition according to claim 6, wherein the epoxy group-containing silicon compound contains an alicyclic epoxy group.
8. The resin composition according to any one of claims 1 to 7, further comprising 50% by mass or more of a filler.
9. The resin composition according to claim 8, wherein the filler contains silica.
10. The resin composition according to any one of claims 1 to 9, further comprising an acid anhydride.
11. The resin composition according to any one of claims 1 to 10, wherein the resin composition is cured by accompanying ring-opening polymerization of an epoxy group.
12. The resin composition according to claim 11, wherein the ring-opening polymerization is cationic polymerization.
13. The resin composition according to any one of claims 1 to 12, wherein the curing catalyst contains a metal catalyst.
14. The resin composition according to claim 13, wherein the metal catalyst is a gallium compound.
15. A molded product obtained by curing the resin composition according to any one of claims 1 to 14.
16. A semiconductor device encapsulated with the resin composition according to any one of claims 1 to 14.