JP2018123194A - Thermosetting resin composition, cured product, electronic component sealing material, and electronic component package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition for electronic component sealing, which can achieve both of high Tg and low water absorption, and provide a cured product, an electronic component sealing material, and an electronic component package using the same.SOLUTION: A thermosetting resin composition contains a bismaleimide compound represented by the formula (1) (A) and a curing accelerator (B).SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition, a cured product, an electronic component sealing material, and an electronic component package.

  The electronic component sealing material is required to have a viscosity suitable for casting, a high storage stability, and a sufficient curing rate. Moreover, what hardened | cured after casting was requested | required that it is heat resistance, low hygroscopicity.

  However, as semiconductor elements and other electronic components become denser and smaller, the driving temperature of the elements increases, and as a sealing resin (cured product), it has superior long-term heat resistance and is suitable for heating. Along with this, it is required that the amount of thermal expansion is low. In addition, recently, it has become an important issue to suppress warpage of a semiconductor and a package including the semiconductor (to achieve low warpage), and as a sealing resin (cured product), a high glass transition temperature (high Tg). What uses the resin composition which has this is also requested | required. In response to this, a sealing resin composition using a maleimide resin, which is a thermosetting resin superior in heat resistance to an epoxy resin, instead of an epoxy resin relatively inferior in heat resistance has been proposed (for example, Patent Document 1).

Japanese Patent Laid-Open No. 7-138483

  However, in general, a cured product obtained by using an aromatic maleimide resin has a problem of high water absorption although it has better heat resistance than an epoxy resin.

  The present invention has been made in view of such problems, and is capable of realizing both high Tg and low water absorption, a thermosetting resin composition for electronic component sealing, a cured product, and electronic component sealing. It is an object to provide a material and an electronic component package using the same.

  As a result of intensive studies to solve the above problems, the present inventors can increase the glass transition temperature (Tg) of the cured product by using a thermosetting resin composition containing a specific bismaleimide compound. In addition, the inventors have found that the water absorption rate can be lowered, that is, that both high Tg and low water absorption can be realized, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A bismaleimide compound (A) represented by the following formula (1);
A curing accelerator (B);
Containing thermosetting resin composition.

[2]
Further containing a filler (C),
[1] The thermosetting resin composition according to [1].

[3]
A cured product obtained by curing the thermosetting resin composition according to [1] or [2].

[4]
An electronic component encapsulating material comprising the thermosetting resin composition according to [1] or [2].

[5]
Electronic components,
An electronic component package comprising: the cured product according to [3] or the electronic component sealing material according to [4] that seals the electronic component.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition for electronic component sealing which can implement | achieve both high Tg and low water absorption, hardened | cured material, an electronic component sealing material, and an electronic component package using them Can be provided.

  Hereinafter, embodiments of the present invention (hereinafter referred to as “present embodiments”) will be described in detail. However, the present invention is not limited thereto, and various modifications can be made without departing from the scope of the present invention. is there. In the present embodiment, “resin solid content” means a component excluding the filler (C) in the thermosetting resin composition unless otherwise specified, and “resin solid content 100 parts by mass”. The sum of the components excluding the filler (C) in the thermosetting resin composition is 100 parts by mass.

[Thermosetting resin composition]
The thermosetting resin composition of this embodiment contains a bismaleimide compound (A) and a curing accelerator (B).

[Bismaleimide compound (A)]
The bismaleimide compound (A) used in this embodiment is a bismaleimide of 1,3-bis (aminomethyl) cyclohexane represented by the following formula (1).

  This bismaleimide compound (A) can be synthesized, for example, by the method described in JP-A-9-249645. Specifically, such bismaleimide compound (A) can be produced by reacting 1,3-bis (aminomethyl) cyclohexane and maleic anhydride.

  In this reaction, generally, maleic anhydride is used in an amount twice as much as 1,3-bis (aminomethyl) cyclohexane, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, or aprotic such as dimethylformamide and dimethylacetamide are used. A first stage reaction performed at a reaction temperature of about 0 to 15 ° C. using a polar solvent as a reaction solvent is first performed to obtain a predetermined bis-maleamic acid as an intermediate.

  In the second stage reaction, generally, the formed bis-maleamic acid is not particularly separated, and a basic catalyst such as triethylamine is added to the reaction mixture at about 0.01 to 0.1 with respect to the bis-maleamic acid. Further, a dehydrating agent such as acetic anhydride is added at a molar ratio of about 1 to 3 with respect to the bis-maleamic acid, and the reaction is performed at a reaction temperature of about 15 to 50 ° C. for about 1 to 3 hours. The bismaleimide compound (A) represented by the above formula (1) as a cyclization reaction product is obtained.

[Curing accelerator (B)]
The curing accelerator (B) is not particularly limited, and examples thereof include amine compounds including imidazoles (amine curing accelerators); acid anhydrides; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachloro Organic peroxides such as benzoyl peroxide, di-tert-butyl-di-perphthalate; azo compounds such as azobisnitrile; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, lead stearate Organic metal salts such as zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; these organic metal salts are dissolved in hydroxyl-containing compounds such as phenol and bisphenol. Become; tin chloride, zinc chloride, salt Inorganic metal salts such as aluminum; dioctyltin oxide, other alkyltin, organotin compounds such as alkyl tin oxide.

  Among these, amine-based curing accelerators are more preferable. It does not specifically limit as an amine type hardening accelerator, For example, C2-C20 linear aliphatic diamine, such as ethylenediamine; Metaphenylenediamine, paraphenylenediamine, paraxylenediamine, metaxylenediamine, 1, 3- Diaminomethylcyclohexane, 1,4-diaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodicyclohexane, bis (4- Aminos such as aminophenyl) phenylmethane, 1,5-diaminonaphthalene, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide; 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1 -Benzyl-2-phenyl Imidazoles such as midazole and 2,4,5-triphenylimidazole; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethyl Tertiary amines such as anilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N-methylpiperidine and the like can be mentioned. Among these, imidazoles are particularly preferable from the viewpoint of storage stability.

[Filler (C)]
The thermosetting resin composition of the present embodiment may further include a filler (C). It does not specifically limit as a filler (C), For example, an inorganic filler and an organic filler are mentioned. A filler (C) may be used individually by 1 type, or may use 2 or more types together.

  The inorganic filler is not particularly limited, and examples thereof include silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; nitrides such as boron nitride, aggregated boron nitride, silicon nitride and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide and aluminum hydroxide heat-treated products (heat treatment of aluminum hydroxide) In addition, metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina, Clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, ma F, E glass, A glass, NE glass, C glass, L glass, D glass, S glass, M glass G20, short glass fibers (glass fine powder such as E glass, T glass, D glass, S glass, Q glass, etc. Etc.), hollow glass, spherical glass and the like.

  The organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; It is done.

  Among these, silicas are preferable from the viewpoint of thermal expansion coefficient and heat resistance.

  The content of the filler (C) is preferably 50 to 1600 parts by mass, more preferably 60 to 1200 parts by mass, and still more preferably 70 to 1000 parts by mass with respect to 100 parts by mass of the resin solid content. Yes, particularly preferably 80 to 800 parts by mass. When the content of the filler (C) is 50 parts by mass or more, the thermal expansion coefficient tends to be further reduced.

〔Silane coupling agent〕
The thermosetting resin composition of this embodiment may further contain a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a silane coupling agent that is generally used for inorganic surface treatment. For example, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ. Aminosilane compounds such as aminopropyltrimethoxysilane; Epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; Acrylic silane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds and the like.

  A silane coupling agent may be used individually by 1 type, or may use 2 or more types together. Further, the amount of the silane coupling agent used for the surface treatment and the surface treatment method are not particularly limited. By using such a silane coupling agent, the bond between the filler (C) and the bismaleimide compound (A) and / or other components can be further strengthened.

[Other ingredients]
The thermosetting resin composition of the present embodiment may contain other components as necessary in addition to the above components. Other components are not particularly limited, and examples include additives such as pigments including carbon black.

[Method for producing thermosetting resin composition]
The manufacturing method of the thermosetting resin composition of this embodiment is not specifically limited, It can manufacture by mixing each above-mentioned component by a well-known means. Specifically, it can be produced, for example, by mixing with a mixer such as a dissolver and melt-kneading with a kneader such as a roll, kneader or extruder. Moreover, you may mix with mixers, such as a dissolver, heating as needed. In this case, heating temperature should just be a temperature which can mix a bismaleimide compound (A) and a hardening accelerator (B), for example, 60-100 degreeC is preferable. The obtained thermosetting resin composition can be used as a sealing resin composition.

[Usage: Cured product, electronic component sealing material, and electronic component package]
The thermosetting resin composition of this embodiment can be used suitably as a hardened | cured material for electronic component sealing, or an electronic component sealing material.

  When producing the cured product of the thermosetting resin composition of the present embodiment, molding methods such as transfer molding, sheet molding, compression molding, and press molding can be used. The curing and molding conditions of the thermosetting resin composition in this case are preferably performed under conditions of, for example, a temperature of 100 to 240 ° C. and a reaction time of 1 to 240 minutes. Moreover, it can also post-cure as needed and it is preferable to perform the post-cure on the conditions of temperature 100-260 degreeC, and reaction time 1-240 minutes.

  Moreover, an electronic component sealing material is obtained by mixing by a well-known means with the composition containing the thermosetting resin composition of this embodiment. Specifically, for example, a melt mixing process is performed using a hot roll, a kneader, etc., solidified by cooling, pulverized to an appropriate size, and then molded by the above-described method of molding a cured product. Can be used as As a sealing method, it can carry out by well-known methods, such as transfer molding.

  The electronic component package of the present embodiment can be manufactured by sealing the electronic component such as a semiconductor element fixedly arranged on the substrate using the cured product or the electronic component sealing material thus obtained. The sealing molding conditions are not particularly limited, but can be performed by, for example, compression molding. In this case, in order to achieve a high Tg, the compression molding is more preferably performed under a temperature condition of 100 ° C. or higher and 180 ° C. or lower, and the pressure is not particularly limited as long as casting is possible.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

(Synthesis Example 1) 1,3-bis (aminomethyl) cyclohexane bismaleimide compound A 100 ml three-necked flask was charged with maleic anhydride (8.26 g) and dimethylformamide (30 g), and then cooled in an ice bath. Then, a solution of 1,3-bis (aminomethyl) cyclohexane (5.67 g) and dimethylformamide (30 g) was added dropwise. After completion of the dropwise addition, the solution obtained by dropping the stirred solution at 80 ° C./3 hr into a solution of water / methanol = 1/1 (1 L) was recovered and recrystallized with methanol to obtain the above formula. A bismaleimide compound (A) of 1,3-bis (aminomethyl) cyclohexane represented by (1) was obtained.

Example 1
100 parts by mass of the bismaleimide compound (A) (maleimide equivalent 151 g / eq.) Of 1,3-bis (aminomethyl) cyclohexane represented by the above formula (1) obtained in Synthesis Example 1 was dissolved by heating. What added 1.0 mass part of 2-ethyl-4-methylimidazole (made by Wako Pure Chemical Industries Ltd.) as a hardening accelerator (B) was cast in the metal mold | die of length 10cm x width 10cm x thickness 1mm. And heated at 200 ° C. for 1 hour to obtain a cured product. Further, the cured product was subjected to a post-cure treatment for additional heating at 240 ° C. for 2 hours to obtain an evaluation sample.

(Comparative Example 1)
Instead of the bismaleimide compound (A) of 1,3-bis (aminomethyl) cyclohexane, the aromatic maleimide compound bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (Kay-Ii Kasei) An evaluation sample was obtained in the same manner as in Example 1 except that BMI-70, maleimide equivalent 179 g / eq.) Was used.

(Comparative Example 2)
In place of the bismaleimide compound (A) of 1,3-bis (aminomethyl) cyclohexane, 35.7 parts by mass of a phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., PS4271), and a bisphenol A epoxy resin (Epicoat 828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 189 g / eq.) 64.3 parts by mass, and 2-ethyl-4-methylimidazole (Wako Pure Chemical) as a curing accelerator (B) An evaluation sample was obtained in the same manner as in Example 1 except that the blending amount of Kogyo Co., Ltd. was 0.2 parts by mass.

(Characteristic evaluation)
Using the evaluation samples obtained in Example 1 and Comparative Examples 1 and 2, the glass transition temperature (Tg) and the water absorption rate were measured by the following methods. The results are summarized in Table 1.

(Glass transition temperature (Tg))
For the evaluation samples obtained in Example 1 and Comparative Examples 1 and 2, the glass transition temperature (Tg) was determined by the DMA method using a dynamic viscoelasticity analyzer (manufactured by TA Instruments, Discovery HR-2 rheometer system). Measured (average value of n = 3). As measurement temperature conditions at this time, the temperature was raised from room temperature to 200 ° C. at a rate of 10 ° C./min, and the measurement frequency was set to 10 Hz.

(Water absorption rate)
The evaluation samples obtained in Example 1 and Comparative Examples 1 and 2 were molded into a length of 1 cm × width of 2 cm × thickness of 1 mm, and the processed samples were heat-dried at a temperature of 110 ° C. for 12 hours by heating vacuum drying, The weight was measured to obtain the initial weight (W1). Next, the processed sample was subjected to a heat absorption treatment for 5 hours at a temperature of 121 ° C. and a humidity of 100% RH using a PCT device (Capachy) manufactured by Hirayama Seisakusho, and the weight (W2) after the moisture absorption was It was measured. The water absorption (wt%) was calculated from the numerical values using the following formula.
Water absorption (wt%) = (W2−W1) / W1 × 100

  The thermosetting resin composition of the present invention has industrial applicability as a material such as a cured product for encapsulating electronic components and an electronic component encapsulating material.

Claims (5)

A bismaleimide compound (A) represented by the following formula (1);
A curing accelerator (B);
Containing thermosetting resin composition.
Further containing a filler (C),
The thermosetting resin composition according to claim 1.   A cured product obtained by curing the thermosetting resin composition according to claim 1.   The electronic component sealing material which uses the thermosetting resin composition of Claim 1 or 2. Electronic components,
The cured product according to claim 3 or the electronic component sealing material according to claim 4, wherein the electronic component is sealed.
Electronic component package comprising.