JP5055679B2 - Thermosetting resin composition, epoxy resin molding material and semiconductor device using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermosetting resin composition, an epoxy resin molding material using the same, and a semiconductor device. More specifically, a thermosetting resin composition that has good curability, fluidity, and storage stability at room temperature and can be suitably used in the field of electrical and electronic materials, and an epoxy resin molding material using the same, and The present invention relates to a semiconductor device excellent in solder resistance and moisture resistance reliability sealed with a cured product.
[0002]
[Prior art]
In recent years, electrical and electronic materials, especially IC encapsulating materials, have been given more importance to rapid curing for the purpose of improving production efficiency and improvement of preservability to improve handling during distribution and storage. It has become like this.
[0003]
Conventionally, epoxy resins for electronic and electrical fields have various curing compounds such as amines, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, quaternary ammonium, phosphonium or arsonium compounds. Is used.
[0004]
These generally used curing catalysts often exhibit a curing accelerating action even at a relatively low temperature such as room temperature. This is a cause of lowering the quality of the product, such as an increase in viscosity during production and storage of the resin composition, a decrease in fluidity, and a variation in curability.
[0005]
In recent years, in order to solve this problem, research on so-called latent curing accelerators has been actively conducted that suppresses the change in viscosity and fluidity at low temperatures with time and causes a curing reaction only by heating during shaping and molding. Has been made. As a means for this, studies have been made to develop the latent property by protecting the active sites of the curing accelerator with ion pairs. JP-A-8-41290 discloses salt structures of various organic acids and phosphonium ions. Latent cure accelerators having the following are presented: However, this phosphonium salt is easily affected by the external environment because the ion pair is relatively easy to flow in semiconductor encapsulating materials that use molecularly hardeners such as low molecular weight epoxy resins and phenol aralkyl resins in recent years. The problem that property and preservability fall has arisen.
[0006]
[Problems to be solved by the invention]
The present invention relates to a thermosetting resin composition having good curability, fluidity, and storage stability at room temperature and useful in the field of electric / electronic materials, an epoxy resin molding material using the same, and a cured product thereof. It is an object of the present invention to provide a semiconductor device which is excellent in solder resistance and moisture resistance reliability.
[0007]
[Means for Solving the Problems]
The present inventors have excellent curability and fluidity by using a phosphonium compound having a specific structure together with a compound having two or more epoxy groups in one molecule and a compound having two or more phenolic hydroxyl groups in one molecule. As a result, it has been found that a resin composition and an epoxy resin molding material that have good performance and storage stability can be obtained, and that a semiconductor device having high solder resistance and moisture resistance reliability can be obtained, and the present invention has been completed. It was.
[0008]
That is, the present invention relates to the thermosetting resin composition described in items (1) to (6), the epoxy resin molding material described in items (7) to (11), and the item (12). A semiconductor device is provided.
[0009]
(1) Compound (A) having two or more epoxy groups in one molecule, Compound (B) having two or more phenolic hydroxyl groups in one molecule, and a phosphonium compound represented by the general formula (1) ( A thermosetting resin composition comprising C) as an essential component.
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(However, R ₁ , R ₂ , R _3, and R ₄ are substituted or unsubstituted aromatic groups or alkyl groups, P is a phosphorus atom, H is a hydrogen atom, Y is a trivalent or higher proton donor that has 1 proton. (Represents a group formed by individual release, and n represents a value of 0.2 to 2.)
[0010]
(2) The thermosetting resin composition according to (1), wherein the phosphonium compound (C) represented by the general formula (1) is a phosphonium compound represented by the general formula (2).
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(However, R ₁ , R ₂ , R ₃ and R ₄ are substituted or unsubstituted aromatic groups or alkyl groups, P is a phosphorus atom, H is a hydrogen atom, O is an oxygen atom, Ar is an aromatic ring or a heterocyclic ring. P represents an organic group having a valence, p represents an integer of 3 or more, and q represents a value of 0.2 to 2.)
[0011]
(3) The thermosetting resin composition according to (1), wherein the phosphonium compound represented by the general formula (1) is a phosphonium compound represented by the general formula (3).
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(However, R ₁ , R ₂ , R ₃ and R ₄ are substituted or unsubstituted aromatic groups or alkyl groups, P is a phosphorus atom, H is a hydrogen atom, O is an oxygen atom, Ar is an aromatic ring or a heterocyclic ring. And represents an r + 1 valent organic group, r represents an integer of 2 or more, and s represents a value of 0.2 to 2.)
[0012]
(4) The thermosetting resin composition according to item (2), wherein the phosphonium compound (C) represented by the general formula (2) is a phosphonium compound represented by the general formula (4).
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(Wherein P is a phosphorus atom, R ₁ , R ₂ , R ₃ and R ₄ are substituted or unsubstituted aromatic groups or alkyl groups, Ar is a (t + u) -valent aromatic group or heterocyclic group, and X is Represents a hydrogen atom or a monovalent organic group, t represents an integer of 3 to 5, and u represents an integer of 1 to 3.)
[0013]
(5) The thermosetting resin composition according to (4), wherein the phosphonium compound (C) represented by the general formula (4) is a phosphonium compound represented by the general formula (5) or (6). .
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(However, P represents a phosphorus atom, R ₁ , R ₂ , R ₃ and R ₄ represent a substituted or unsubstituted aromatic group or an alkyl group.)
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(Wherein P represents a phosphorus atom, R ₁ , R ₂ , R ₃ and R ₄ represent a substituted or unsubstituted aromatic group or an alkyl group. R ₅ is composed of a hydrogen atom or a C 1-18 carbon atom. Represents a monovalent alkyl group.)
[0014]
(6) The thermosetting resin composition according to item (3), wherein the phosphonium compound (C) represented by the general formula (3) is a phosphonium compound represented by the general formula (7) or (8). .
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Wherein R ₁ , R ₂ , R ₃ and R ₄ are substituted or unsubstituted aromatic groups or alkyl groups, P is a phosphorus atom, H is a hydrogen atom, O is an oxygen atom, and y is 0.2 to Represents a value of 2.)
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(Wherein R ₁ , R ₂ , R ₃ and R ₄ are substituted or unsubstituted aromatic groups or alkyl groups, P is a phosphorus atom, H is a hydrogen atom, O is an oxygen atom, and z is 0.2 to Represents a value of 2.)
[0015]
(7) Compound (A) having two or more epoxy groups in one molecule, Compound (B) having two or more phenolic hydroxyl groups in one molecule, Phosphonium compound (C) represented by the general formula (1) And an epoxy resin molding material characterized by comprising an inorganic filler (D) as an essential component.
(8) The epoxy resin molding material according to (7), wherein the phosphonium compound (C) represented by the general formula (1) is a phosphonium compound represented by the general formula (2) or (3).
(9) The epoxy resin molding material according to (8), wherein the compound represented by the general formula (2) is a phosphonium compound represented by the general formula (4).
(10) The epoxy resin molding material according to item (9), wherein the compound represented by the general formula (4) is a compound represented by the general formula (5) or (6).
(11) The epoxy resin molding material according to item (8), wherein the compound represented by the general formula (3) is a compound represented by the general formula (7) or (8).
[0016]
(12) A semiconductor device sealed with a cured product of the epoxy resin molding material according to any one of (7) to (11).
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The compound (A) having two or more epoxy groups in one molecule used in the present invention is not limited as long as it has two or more epoxy groups in one molecule. For example, biphenyl type epoxy resin, biphenyl Examples include aralkyl-type epoxy resins, novolak-type epoxy resins, naphthalene-type epoxy resins, epoxy resins produced by reacting phenols such as biphenol, phenol resins, and hydroxyl groups such as naphthols with epichlorohydrin. . In addition, an epoxy resin obtained by oxidizing an olefin with a peracid and epoxidizing it, such as an alicyclic epoxy resin, or an epoxy resin obtained by epoxidizing dihydroxybenzenes such as hydroquinone with epichlorohydrin.
[0018]
The compound (B) having two or more phenolic hydroxyl groups in one molecule acts as a curing agent for the compound (A) having two or more epoxy groups in one molecule. Specifically, phenol novolak resins, cresol novolak resins, alkyl-modified novolak resins (including resins obtained by reacting and co-condensing cycloalkene double bonds with Friedel-Crafts-type reactions), phenol aralkyl resins, naphthols Examples include resins obtained by co-condensation of phenols and phenols with carbonyl group-containing compounds, as long as two or more hydrogen atoms bonded to an aromatic ring in one molecule are substituted with hydroxyl groups. .
[0019]
The phosphonium compound (C) functioning as a curing accelerator in the present invention is represented by the general formula (1), the general formulas (2) to (3), and the tetra substitutions represented by the general formulas (4) to (8) It is a complex salt of phosphonium and a polyvalent proton donor. In this phosphonium compound, one tetra-substituted onium cation and an organic anion formed by releasing a proton from a polyvalent proton donor form an ion pair, and the anion molecular part and other proton donor molecules A stable complex salt is formed through intermolecular interactions such as hydrogen bonding.
[0020]
The phosphonium compound (C) used in the present invention is different from the 1: 1 type phosphonium salt which is a conventional phosphonium cation-proton donor anion, in that a trivalent or higher proton donor has a hydroxyl group or a carboxyl group in the molecule. Stable supramolecules that form complex anions with higher-order structures through hydrogen bonds between proton donors via intermolecular hydrogen bonds involving polar groups such as carbonyl, or nitrogen atoms that form heterocycles This is the point of forming a complex salt. This stable supramolecular complex structure suppresses the activity at low temperature and gives good storage stability of the resin composition as compared with the salt of the conventional phosphonium cation-proton donor anion of 1: 1 type. it can. On the other hand, at a high temperature near the molding temperature, the supramolecular complex salt structure formed by hydrogen bonding is rapidly dissociated and activated thermally and accelerates the curing as well as the conventional phosphonium salt. It exhibits curability. Furthermore, compared with the conventional phosphonium salt, since the catalytic activity is further suppressed until reaching the molding temperature, better fluidity can be given during molding. Therefore, by using the specific phosphonium compound (C) of the present invention, good storage stability, curability, fluidity, and resin characteristics and material characteristics are imparted.
[0021]
As the phosphonium cation constituting the phosphonium compound (C) used in the present invention, a tetra-substituted phosphonium ion or a tetra-substituted ammonium ion having a substituted or unsubstituted aryl group or alkyl group as a substituent is suitable for heat and hydrolysis. Preferred from the standpoint of stability. Specifically, tetraarylphosphonium, tetraaryl-substituted phosphonium such as tetratolylphosphonium, triarylphosphine such as ethyltriphenylphosphonium, benzyltriphenylphosphonium, triphenylmethylphosnium, and alkyl halides. Examples include triaryl monoalkylphosphoniums derived from synthesized phosphonium halides, tetraalkyl-substituted phosphonium ions such as tetrabutylphosphonium, and the like.
[0022]
The other component forming the phosphonium compound (C), which is a trivalent or higher proton donor, includes 1,2,3-trihydroxybenzene, 1,3,5-trihydroxybenzene, 2,3 , 4-trihydroxybenzophenone, 2,3,4-trihydroxyacetophenone, 2,4,6-trihydroxypropionphenone, 1,8,9-trihydroxyanthracene, 1,2,4-trihydroxyanthraquinone, 1, 4,9,10-tetrahydroxyanthracene, 2,3,4,4'-tetrahydroxyphenylmethane, gallic acid, methyl gallate, ethyl gallate, n-butyl gallate, n-octyl gallate, gallic acid Trihydroxybenzene derivatives such as acid-n-lauryl, stearyl gallate, trimesic acid, trimellitic acid, pyromellitic acid, citrazic acid, barbituric acid, tannic acid, cyanuric acid, thiocyanuric acid, etc. As shown, from the viewpoint of the balance of stability, curability, fluidity, storage stability, and physical properties of the cured product of the phosphonium compound, 1,2,3-trihydroxybenzene, 1,3,5-trihydroxybenzene, 2, Trihydroxybenzene derivatives such as 3,4-trihydroxybenzophenone, polyhydroxy carboxylic acids such as gallic acid, citrazic acid and tannic acid, methyl gallate, ethyl gallate, gallic acid-n-octyl, gallic acid-n- Gallic acid esters such as dodecyl and stearyl gallate are particularly suitable.
[0023]
On the other hand, Japanese Examined Patent Publication No. 58-39838 describes a tetrahydrocarbylphosphonium phenoxide salt and a compound complexed with 1 mol or more of polyhydric phenol H _m X per mol of the phosphonium phenoxide salt. It is said that it is useful as a catalyst for the reaction of epoxide-containing compounds and polyhydric phenols.
Specific examples of the above phosphonium phenoxide phenoxide and H _m X corresponding to the complexed polyphenol include resorcinol, hydroquinone, phenolphthalein, 2,4 ', 4 "-tris (hydroxyphenyl) methane, etc. And are described in detail in the examples, with unsubstituted or chlorine or bromine substituted bisphenols being particularly preferred.
[0024]
As the trivalent or higher proton donor constituting the anion part of the phosphonium compound used in the present invention, a preferred compound has a total number of hydroxyl groups and carboxyl groups which are hydrogen bonding functional groups substituting the same aromatic nucleus. 3 or more, which is substantially different from polyhydric phenols exemplified in JP-B-58-39838. In polyhydric phenol compounds in which the sum of hydroxyl groups and carboxyl groups substituting the same aromatic nucleus is less than 3, the intermolecular interaction based on hydrogen bonding is weaker, so the stability of the complex anion portion of the phosphonium compound (C) The activity tends to develop at a lower temperature. In the case where a polyhydric phenol as exemplified in JP-B-58-39838 is actually used as a polyvalent proton donor constituting the phosphonium compound (C), a resin which is one of the objects of the present invention The storage stability of the composition cannot be improved. The total number of hydroxyl groups and carboxyl groups, which are hydrogen bonding functional groups in the present invention, is 3 or more, and the larger the number, the stronger the intermolecular hydrogen bond and the more stable complex salt. The storage stability of is improved.
[0025]
In the phosphonium compound (C) represented by the general formula (1) used in the present invention, the molar ratio n of the proton donor YH constituting the complex anion portion to the phosphonium cation is in the range of 0.2 to 2 in the range of phosphonium compound ( C) is preferable in terms of stability. When n is less than 0.2, the stability of the complex salt due to hydrogen bonding is lowered, and it is easy to dissociate and decompose at a low temperature, so that sufficient storage stability cannot be obtained in the resin composition or the molding material. For the same reason, the complex anion portion of the phosphonium compound (C) represented by the general formulas (2) and (3) and the phosphonium compound (C) represented by the general formulas (7) and (8) is constituted. The molar ratios q, s, y, and z of the proton donor YH to the phosphonium cation are preferably in the range of 0.2-2.
[0026]
The phosphonium compound (C) used in the present invention comprises a trivalent or higher proton donor as described above and a base that finally assists dehydrohalogenation, such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Is dissolved in a solvent such as alcohol, followed by addition and reaction of the tetra-substituted phosphonium halide dissolved in a suitable solvent, and finally taken out as a solid content by operations such as recrystallization and reprecipitation, It can be synthesized by a method in which a tetra-substituted phosphonium tetra-substituted borate and a proton donor are heated and reacted in a solvent such as alcohol after the heat reaction.
[0027]
The compounding amount of the phosphonium compound (C) that functions as a curing accelerator used in the present invention is the compound (A) having two or more epoxy groups in one molecule and the phenol in one molecule that functions as a curing agent. When the total weight of the compound (B) having two or more curable hydroxyl groups is 100 parts by weight, about 0.5 to 20 parts by weight is preferable because of a good balance of curability, storage stability and other characteristics. The compounding ratio of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule is 2 or more epoxy groups in one molecule. The total of the phenolic hydroxyl group of the compound (B) having two or more phenolic hydroxyl groups in one molecule and the phenolic hydroxyl group contained in the molecular compound (C) per 1 mol of the epoxy group of the compound (A) having When used in a molar ratio of about 0.5 to 2 mol, preferably about 0.8 to 1.2, the curability, heat resistance, electrical characteristics, etc. are improved.
[0028]
The inorganic filler (D) used in the present invention is not particularly limited as to the type thereof, and those generally used for sealing materials can be used. Examples thereof include fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary agglomerated silica powder, alumina, titanium white, aluminum hydroxide, talc, clay, and glass fiber, with fused spherical silica powder being particularly preferred. The shape is preferably infinitely spherical, and the amount of filling can be increased by mixing particles having different particle sizes.
[0029]
The blending amount of the inorganic filler is about 100 parts by weight of the total amount of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule. 200 to 2400 parts by weight are preferable. If the amount is less than 200 parts by weight, the reinforcing effect of the inorganic filler may not be sufficiently exhibited. If the amount exceeds 2400 parts by weight, the fluidity of the resin composition may be reduced, and there is a risk of poor filling during molding. Absent. In particular, if the blending amount of the inorganic filler is 250 to 1400 parts by weight per 100 parts by weight of the total amount of the components (A) and (B), the moisture absorption rate of the cured material of the molding material becomes low, and solder cracks occur. Since the viscosity of the molding material at the time of melting is lowered, there is no possibility of causing deformation of the gold wire inside the semiconductor device, which is more preferable. Moreover, it is preferable that the inorganic filler is sufficiently mixed in advance.
[0030]
In addition to the components (A) to (D), the epoxy resin molding material of the present invention includes a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and a brominated epoxy as necessary. Various additives such as resin, antimony oxide, flame retardants such as phosphorus compounds, low stress components such as silicone oil and silicone rubber, natural waxes, synthetic waxes, higher fats or their metal salts, release agents such as paraffin, antioxidants, etc. In the present invention, triphenylphosphine and 1,8-diazabicyclo (5,4,0) -7 are used as long as the properties of the phosphonium compound (C) functioning as a curing accelerator in the present invention are not impaired. -There is no problem even if it is used in combination with other known catalysts such as undecene and 2-methylimidazole.
[0031]
In the epoxy resin molding material of the present invention, components (A) to (D) and other additives are mixed at room temperature using a mixer, kneaded with a kneader such as a roll or an extruder, pulverized after cooling. can get.
[0032]
In order to seal an electronic component such as a semiconductor and manufacture a semiconductor device by using the epoxy resin molding material of the present invention, it can be cured and molded by a molding method such as transfer molding, compression molding, or injection molding.
[0033]
A semiconductor device sealed with a cured product of the epoxy resin molding material of the present invention is included in the technical scope of the present invention and exhibits excellent moisture resistance.
[0034]
【Example】
Examples of the present invention will be shown below, but the present invention is not limited thereby.
[0035]
[Synthesis of curing accelerator]
(Synthesis Example 1)
A 1 L separable flask equipped with a stirrer was charged with 25.2 g (0.2 mol) of 1,2,3-trihydroxybenzene and 100 mL of methanol, dissolved by stirring at room temperature, and 4.0 g of sodium hydroxide with further stirring ( 0.1 mol) was previously dissolved in 550 mL of methanol. Next, a solution prepared by previously dissolving 41.9 g (0.1 mol) of tetraphenylphosphonium bromide in 150 mL of methanol was added. After stirring for a while and adding 300 mL of methanol, 500 mL of water was added dropwise to the solution in the flask while stirring to obtain a pale yellow precipitate. The precipitate was filtered and dried to obtain 109.8 g of pale yellow crystals having a melting point of 198 to 200 ° C. This compound is designated as C1. As a result of analyzing C1, by NMR, mass spectrum and elemental analysis, it is represented by the general formula (1) in which one molecule of tetraphenylphosphonium and 1,2,3-trihydroxybenzene are complexed at a molar ratio of 1: 2. It was confirmed to be the target phosphonium compound. The synthesis yield was 93.0%.
[0036]
(Synthesis Examples 2 to 10)
In Synthesis Examples 2 to 8, all basic operations were performed in the same manner as in Synthesis Example 1 under the conditions shown in Table 1, to prepare compounds C2 to C10, respectively. The results are shown in Table 1.
[0037]
[Table 1]
[0038]
[Evaluation of thermosetting resin composition]
The synthesized phosphonium compound (C) is pulverized and mixed in addition to the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule, Furthermore, after melt-kneading on a hot plate at 100 ° C. for 5 minutes, the mixture was cooled and pulverized to prepare a sample of the composition for evaluation. The evaluation method is as follows.
[0039]
(1) Curing torque (curability evaluation)
Using the resin composition produced by the above sample preparation method, the torque after 45 seconds at 175 ° C. was obtained with a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter PS type). The torque in the curast meter is a curability parameter, and a larger value indicates higher curability.
[0040]
(2) Curing heat generation residual rate (preservation evaluation)
Using the resin composition produced by the above sample preparation method, the initial curing calorific value immediately after preparation and the curing calorific value after storage treatment at 40 ° C. for 3 days are measured, and the initial curing calorific value (mJ / mg) is measured. The percentage of the calorific value (mJ / mg) after the storage treatment was calculated. The amount of heat generated by curing was measured by differential thermal analysis under the condition of a temperature increase rate of 10 ° C./min. The larger this value, the smaller the change over time in the amount of heat generated by curing, and the better the storage stability.
[0041]
(Examples 1 to 10 and Comparative Examples 1 to 4)
Samples of the composition were prepared and evaluated by the methods described above according to the formulations shown in Tables 2-3. In Comparative Examples 1 to 4, triphenylphosphine, 1,8-diazabicyclo [5.4.0] -7-undecene, and 2-methylimidazole, which are known curing accelerators, are used instead of the compound (C) in the examples. Tetraphenylphosphonium tetraphenylborate was used. Table 2 shows the evaluation results of the obtained compositions.
[0042]
[Table 2]
[0043]
[Table 3]
[0044]
In Examples 1 to 10 which are the thermosetting resin compositions of the present invention, both curability and storage stability are good, whereas in Comparative Examples 1 and 3, storage stability is poor, and Comparative Examples 2 and 4 Showed poor results in both curability and storage stability.
[0045]
[Evaluation of epoxy resin molding materials]
(Example 11)
YX-4000H (biphenyl type epoxy resin) made of oil-based shell epoxy 52 parts by weight XL225 (phenol aralkyl resin) made by Mitsui Chemicals 48 parts by weight Phosphonium compound C1 3.0 parts by weight fused spherical silica (average particle size 15 μm) 500 parts by weight carbon black 2 2 parts by weight brominated bisphenol A type epoxy resin 2 parts by weight Carnauba wax 2 parts by weight were mixed, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin molding material. The obtained epoxy resin molding material was evaluated by the following methods. The results are shown in Tables 4-5.
[0046]
Evaluation Method (1) The spiral flow was measured using a mold for spiral flow measurement according to EMMI-I-66 at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a curing time of 2 minutes. Spiral flow is a parameter for fluidity, and the larger the value, the better the fluidity.
[0047]
(2) Curing torque was measured using a curast meter (Orientec Co., Ltd., JSR curast meter IVPS type) at 175 ° C. for 45 seconds.
The larger this value, the better the curability.
[0048]
(3) The flow remaining rate was measured by measuring the spiral flow value immediately after preparation and after storing for 1 week at 30 ° C., and expressed as a percentage of the value after storage with respect to the spiral flow value immediately after preparation.
[0049]
(4) Moisture resistance reliability is such that a mold temperature of 175 ° C., a pressure of 6.8 MPa, a curing time of 2 minutes is molded into 16 pDIP, and the molded product is cured at 175 ° C. for 8 hours, and then 125 ° C. and a relative humidity of 100%. In water vapor, a voltage of 20 V was applied to 16 pDIP, and the disconnection failure was examined. The time until a defect appears in eight or more of the 15 packages was defined as a defect time. The unit is time. Note that the measurement time was 500 hours at the longest, and when the number of defective packages was less than 8 at that time, the defective time was 500 hours or more. The longer the defect time, the better the moisture resistance reliability.
[0050]
(Examples 12-18, Comparative Examples 5-8)
About Examples 12-18 and Comparative Examples 5-8, according to the mixing | blending of Table 3, it carried out similarly to Example 9, and prepared and evaluated the epoxy resin molding material. The results are shown in Table 3.
[0051]
[Table 4]
[0052]
[Table 5]
[0053]
The epoxy resin molding materials of Examples 11 to 18 of the present invention have extremely good curability, fluidity, and storage stability. Furthermore, the semiconductor device sealed with a cured product of this epoxy resin molding material has moisture resistance. Is found to be good. In Comparative Examples 5-8, curability, fluidity, storage stability, and reliability could not be satisfied at the same time.
[0054]
【Effect of the invention】
The thermosetting resin composition and the epoxy resin molding material of the present invention have excellent curability, storage stability, and fluidity, and the semiconductor device encapsulated with the cured product of the epoxy resin molding material has moisture resistance reliability. It is excellent and useful.

Claims (5)

A compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a general formula (3), (5) or (6) A thermosetting resin composition comprising a phosphonium compound (C) represented by the phosphonium compound as an essential component, wherein the compounding amount of the phosphonium compound (C) includes an epoxy group in one molecule. The thermosetting resin composition is 0.5 to 20 parts by weight based on 100 parts by weight of the total weight of the compound (A) having two or more and the compound (B) having two or more phenolic hydroxyl groups in one molecule. .
_{(Wherein, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group, P is a phosphorus atom, H is a hydrogen atom O represents an oxygen atom, Ar represents an r + 1 valent organic group composed of a benzene ring or a pyridine ring , r represents an integer of 2 or more, and s represents a value of 0.2 to 2.)
(Where, P is represents a phosphorus _{atom, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group.)
(However, .R ₅ P is representative of the phosphorus _{atom, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group Represents a hydrogen atom or a monovalent alkyl group composed of 1 to 18 carbon atoms.) The thermosetting resin composition according to claim 1, wherein the phosphonium compound represented by the general formula (3) is a phosphonium compound represented by the general formula (7) or (8).
_{(Wherein, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group, P is a phosphorus atom, H is a hydrogen atom , O represents an oxygen atom, and y represents a value of 0.5-2.)
_{(Wherein, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group, P is a phosphorus atom, H is a hydrogen atom , O represents an oxygen atom, and z represents a value of 0.5-2.) A compound having two or more epoxy groups in one molecule (A), a compound having two or more phenolic hydroxyl groups in one molecule (B), represented by the general formula (3), (5) or (6) An epoxy resin molding material comprising phosphonium compound (C) and inorganic filler (D) as essential components, wherein the amount of phosphonium compound (C) contains two epoxy groups in one molecule The epoxy resin molding material which is 0.5-20 weight part with respect to 100 weight part of total weight of the compound (A) which has the above, and the compound (B) which has 2 or more of phenolic hydroxyl groups in 1 molecule.
_{(Wherein, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group, P is a phosphorus atom, H is a hydrogen atom O represents an oxygen atom, Ar represents an r + 1 valent organic group composed of a benzene ring or a pyridine ring , r represents an integer of 2 or more, and s represents a value of 0.2 to 2.)
(Where, P is represents a phosphorus _{atom, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group.)
(However, .R ₅ P is representative of the phosphorus _{atom, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group Represents a hydrogen atom or a monovalent alkyl group composed of 1 to 18 carbon atoms.) The epoxy resin molding material according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the general formula (7) or (8).
_{(Wherein, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group, P is a phosphorus atom, H is a hydrogen atom , O represents an oxygen atom, and y represents a value of 0.5-2.)
_{(Wherein, R 1, R 2, R} 3 and R ₄ are a substituted or unsubstituted A alkyl group in a substituted or unsubstituted phenyl group or a methyl group or a phenyl group with a methyl group, P is a phosphorus atom, H is a hydrogen atom , O represents an oxygen atom, and z represents a value of 0.5-2.)  A semiconductor device sealed with a cured product of the epoxy resin molding material according to claim 3.