JPH0687933A - Thermosetting resin composition and its use - Google Patents

Abstract

PURPOSE:To provide a thermosetting resin composition containing a specific imide compound and a cure accelerator as essential components, having excellent moisture resistance, processability, adhesiveness and heat-resistance and useful as a sealing material for electronic parts, etc. CONSTITUTION:The composition contains (A) an imide compound of formula (R1 to R5 are H, halogen or 1-6C (halogenated) hydrocarbon group; R7 and R8 are H or 1-6C (halogenated) hydrocarbon group; R9 and R10 are halogen or l-6C (halogenated) hydrocarbon group; a and b are 0-4; D is 2-24C bivalent organic group having ethylenic unsaturated bond), (B) preferably 1-3 pts.wt. (based on 100 pts.wt. of the component A) of a cure accelerator such as triphenylphosphine and preferably further (C) an epoxy resin such as novolak epoxy resin and (D) an epoxy resin hardener such as polyphenol compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition which is particularly useful as a sealing material for electronic parts and an electronic part which is sealed with the composition.

[0002]

2. Description of the Related Art Conventionally, electrical and electronic parts such as semiconductors, which are molded and sealed with epoxy resin, have been widely used. This epoxy resin has been widely put into practical use because it is economically advantageous as compared with the hermetic sealing method using glass, metal, or ceramic. However,
In recent years, the usage conditions of electronic parts have tended to become severe. For example, as the mounting method shifts from conventional insertion mounting to surface mounting, the sealing material itself is exposed to the solder bath temperature. As a result, the heat resistance of the sealing material has become an important characteristic. Recently, thermosetting polyimide resin encapsulation has been proposed for the purpose of obtaining high heat resistance.

[0003]

However, although the electronic encapsulation component molded and encapsulated with a polyimide resin has excellent heat resistance, it has a major drawback in terms of moisture resistance, which is a characteristic of a thermosetting polyimide resin. have. From such a background, the present inventors have diligently studied a resin composition that gives a cured product having excellent moisture resistance, processability, adhesiveness and heat resistance, and as a result, a resin composition containing a specific imide compound is They have found that they are suitable for their purposes and have completed the present invention.

[0004]

The present invention comprises the following inventions. (1) (A) The following general formula [I]

[Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogenated carbon atom having 1 to 6 carbon atoms. Hydrogen radical, R
₇ , R ₈ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group having 1 to 6 carbon atoms,
R ₉ and R ₁₀ are each independently a halogen atom and a carbon number of 1 to
It represents a hydrocarbon group of 6 or a halogenated hydrocarbon group of 1 to 6 carbon atoms, and a and b each represent an integer of 0 or more and 4 or less. R ₉
Alternatively, when a plurality of R _10's are present, they may be the same or different. The bond position of the imide group is ortho, meta or para to the bond position of the oxygen atom.
D represents a divalent organic group having 2 to 24 carbon atoms and having an ethylenically unsaturated bond. The thermosetting resin composition which has an imide compound and the (B) hardening accelerator which are represented by these as an essential component.

(2) A thermosetting resin containing (A) the imide compound represented by the general formula [I], (B) a curing accelerator, (C) an epoxy resin and (D) an epoxy curing agent as essential components. Composition.

(3) An electronic component sealed with the thermosetting resin composition according to (1) or (2) above.

The present invention will be described in detail below. In the compound represented by the general formula [I] used as the component (A) in the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Specific examples thereof include a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, but from the viewpoint of moisture resistance, a methyl group, an ethyl group, a propyl group and a butyl group are preferable, Of these, a butyl group is particularly preferable. Specific examples of R ₇ and R ₈ include a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group, but a butyl group is preferable from the viewpoint of moisture resistance. Specific examples of R ₉ and R ₁₀ include a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group and a butyl group, but a hydrogen atom and a methyl group are preferable from the viewpoint of reactivity.

The imide compound represented by the general formula [I] is
General formula [II]

[Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
_{R 8, R 9, R 10} , a, b are the same meaning as that of general formula (I). ) And an amino compound represented by the general formula [I
II]

[0009]

[Chemical 4] (In the formula, D has the same meaning as that of the general formula [I].) It is obtained by reacting with an ethylenically unsaturated dicarboxylic acid anhydride represented by the known method.

The amino compound represented by the general formula [II] is represented by the general formula [IV] in the presence of a basic substance in a solvent.

[Chemical 5] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , and R ₈ have the same meanings as those in the general formula [I].) V]

[0011]

[Chemical 6] (In the formula, R ₉ and a have the same meanings as those in formula [I], X represents a halogen atom or a nitro group, and —NO
The bonding position of ₂ is ortho, meta or para to the bonding position of X. ) It reacts with the nitrobenzene derivative represented by, and it can manufacture by reducing the aromatic nitro compound obtained.

Examples of the phenolic compound represented by the general formula [IV] include bis (2-methyl-4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) ethane and bis (2-methyl-). 4-hydroxyphenyl) propane, bis (2-methyl-4-hydroxyphenyl) butane, bis (3-t-butyl-6-methyl-)
4-hydroxyphenyl) methane, bis (3-t-butyl-6-methyl-4-hydroxyphenyl) ethane, bis (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, bis (3-t -Butyl-6-methyl-
4-hydroxyphenyl) butane, bis (2,3,5-
Trimethyl-4-hydroxyphenyl) methane, bis (2,3,5-trimethyl-4-hydroxyphenyl) ethane, bis (2,3,5-trimethyl-4-hydroxyphenyl) propane, bis (2 , 3,5-Trimethyl-4-hydroxyphenyl) butane, bis (2,2
3,6-Trimethyl-4-hydroxyphenyl) methane, bis (2,3,6-trimethyl-4-hydroxyphenyl) ethane, bis (2,3,6-trimethyl-4-)
Examples thereof include hydroxyphenyl) propane and bis (2,3,6-trimethyl-4-hydroxyphenyl) butane. These compounds may be used alone or in combination of two or more.

Examples of the nitrobenzene derivative represented by the general formula [V] include chloronitrobenzene, bromonitrobenzene, chloronitrotoluene, bromonitrotoluene, chloronitroxylene, bromonitroxylene, chlorophenylnitrobenzene, chloronitroanisole, bromonitroanisole and dinitrobenzene. And various isomers and derivatives. These may be used alone or in combination of two or more.

Methods for reacting a phenolic compound with a nitrobenzene derivative in the presence of a basic compound are known, and specific examples of the literature are Org. Synt
h. , 445, (VolI), US Pat. No. 453800.
No. 6, J. Org. Chem. , 50 (20) ,
3717 (1985), J. Org. Chem. , 50
(17) , 3091 (1985), JP-A-61-194.
055 publication, JP-A-62-70347 publication, Macro
molecules, 25 , 64 (1992) and the like.

Examples of the ethylenically unsaturated dicarboxylic acid anhydride represented by the general formula [III] include maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, pyrocinchonic anhydride, and tetrahydrophthalic anhydride. Or a Diels-Alder reaction product of these unsaturated carboxylic acid anhydrides and dienes, such as at least one of cyclopentadiene, furan, cycloaddition reaction product of terpinene and maleic anhydride, and the like.

As the curing accelerator used as the component (B) in the resin composition of the present invention, known curing accelerators can be used. Examples of such curing accelerators include organic phosphine compounds such as triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, and triphosphine compounds. Tertiary amines such as butylamine, triethylamine, 1,8-diazabicyclo (5,4,0) undecene-7, triamylamine, and quaternary ammonium such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, and triethylammonium tetraphenylborate. Salts, imidazoles, boron trifluoride complexes, transition metal acetylacetonates, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetone Peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t- butyl hydroperoxide, although radical initiator such as azobisisobutyronitrile are exemplified, but not limited thereto. Among these, organic phosphine compounds, 1,8-diazabicyclo (5,4,0)
Undecene-7 and triethylammonium tetraphenylborate are particularly preferable from the viewpoint of moisture resistance and curability.

It is also possible to use a known polymerization inhibitor together in order to adjust the curing speed. For example,
2,6-di-t-butyl-4-methylphenol, 2,
2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-)
Butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), phenols such as hydroquinone monomethyl ether, hydroquinone, catechol, pt-butylcatechol, 2,5-di-t-
Butylhydroquinone, methylhydroquinone, t-butylhydroquinone, polyhydric phenols such as pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine and acetamidophenothiazine, N-
There are N-nitrosamine compounds such as nitrosodiphenylamine and N-nitrosodimethylamine.

As the epoxy resin of the component (C) used in the present invention, known epoxy resins can be used. To specifically exemplify these, a novolac-based epoxy resin derived from a novolac resin which is a reaction product of phenols such as phenol and o-cresol and formaldehyde; phloroglysin, tris- (4-hydroxyphenyl) -methane, Glycidyl ether compounds derived from trivalent or higher phenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; bisphenol A, bisphenol F, hydroquinone,
Glycidyl ether compounds derived from dihydric phenols such as resorcin, 1,1′-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, tetramethylbiphenol; tetrabromobisphenol A
Diglycidyl ether compounds derived from halogenated bisphenols such as; glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds;

P-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,
3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 1,
3-bis (3-aminophenoxy) benzene, 2,2-
Bis (4-aminophenoxyphenyl) propane, p-
Phenylenediamine, m-phenylenediamine, 2,4
-Toluenediamine, 2,6-toluenediamine, p-
Xylylenediamine, m-xylylenediamine, 1,4
-Amine-based epoxy resin derived from cyclohexanebis (methylamine), 1,3-cyclohexanebis (methylamine), etc .;

Glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, 5,5-
Hydantoin-based epoxy compounds derived from dimethylhydantoin, 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-
Epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; N, N-diglycidylaniline, etc. One type or two or more types of resins are used. Among them, an o-cresol novolac epoxy resin and a polyhydric phenol glycidyl ether compound obtained by a condensation reaction of a phenol and an aromatic carbonyl compound are preferable from the viewpoint of curability and heat resistance.

As the epoxy curing agent of the component (D) used in the present invention, known ones can be used. Examples of these are bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, bis (4-hydroxyphenyl) cyclohexane,
Bis (4-hydroxyphenyl) ethane, 1,3,3-
Trimethyl-1-m-hydroxyphenylindan-5
Or 7-ol, 1,3,3-trimethyl-1-p-
Hydroxyphenylindan-6-ol, resorcin, hydroquinone, catechol and phenol, o
-Phenols, which are reaction products of phenols such as cresol and formaldehyde, polyphenol compounds such as novolac, polycarboxylic acids such as maleic acid, phthalic acid, nadic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and their anhydrides, diamino Diphenylmethane,
Polyamine compounds such as diaminodiphenyl sulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (each containing isomers), ethylenediamine, hexamethylenediamine,
Furthermore, active hydrogen-containing compounds capable of reacting with an epoxy group such as dicyandiamide and tetramethylguanidine can be exemplified. Of these, phenol novolac resins are preferably used from the viewpoint of curability and moisture resistance.

In the thermoplastic resin composition of the present invention,
The proportion of the curing accelerator used as the component (B) varies depending on the degree of curing speed required. This degree depends on the application. For example, in the case of the encapsulating material, the curing accelerator is usually 1 to 3 parts by weight with respect to 100 parts by weight of the resin. In the composition of the present invention, the use ratio of each of the components (A), (C) and (D) can be appropriately selected according to the application, desired heat resistance and the like. However, generally, the weight content of the imide compound {(A) /
It is preferable that [(A) + (C) + (D)]} is selected to be 90% to 10%. More preferably, it is 70 to 30%. If the blending ratio of the imide compound deviates from the above range, the moisture resistance and the heat resistance decrease, which is not preferable.

The epoxy resin as the component (C) and the epoxy curing agent as the component (D) are preferably mixed in equal amounts. If the blending amount of the component (C) and the component (D) deviates from the equimolar blending amount, moisture resistance, curability and the like are deteriorated, which is not preferable.

A filler is often added to the thermosetting resin composition (1) or (2) of the present invention. Examples of the filler used include fused silica, crystalline silica, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, and glass fiber. Among them, fused silica, crystalline silica, and alumina are preferably used. To be The blending ratio of the filler can be appropriately determined according to the purpose, but when used for semiconductor encapsulation, it is preferably 30 to 90% by weight, more preferably 60 to 85% by weight based on the total amount of the resin composition. %. If the amount of the filler is less than 30% by weight, the moisture resistance is inferior, and if it exceeds 90% by weight, there is a problem in moldability.

In the present invention, a natural wax, a synthetic wax, a higher fatty acid and its metal salt, a release agent such as paraffin or a colorant such as carbon black, and a surface of a silane coupling agent or the like, if necessary. A treating agent or the like may be added. Further, a flame retardant such as antimony trioxide, a phosphorus compound and a brominated epoxy resin may be added. A brominated epoxy resin is particularly preferable for producing a flame retardant effect. Further, for example, in order to reduce the stress, various elastomers may be added or reacted in advance and used. Specific examples thereof include addition-type or reaction-type elastomers such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber, and silicone oil. The thermosetting resin composition thus obtained can be compounded by melt-mixing with a general kneader such as a roll or a co-kneader.

In order to seal electronic parts such as semiconductors using the thermosetting resin composition according to the present invention, molding and curing may be carried out by a conventionally known molding method such as transfer molding, compression molding, injection molding or the like. .

[0027]

The thermosetting resin composition of the present invention is
It is superior to the conventionally known heat-resistant resin in moisture resistance of the cured product, and is also excellent in processability and heat resistance of the cured product, particularly strength and adhesiveness when heated. The electronic component sealed with the thermosetting resin composition of the present invention has excellent solder cracking property.

[0028]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The evaluation of the kneaded product and the cured molded product is as follows. Gel time: 1 for the kneaded product obtained in Examples and Comparative Examples
0.5 g was taken in the concave portion of the hot plate at 80 ° C., and the time until gelation was measured.・ Glass transition temperature: Thermomechanical analyzer (SHIMAZU
It was measured using DT-30). Barcol hardness: 93 according to ASTM D-648
It was measured with a type 5 under the condition of 175 ° C./3 minutes. Bending strength and flexural modulus: Instron universal material testing machine (SHIMAZU I) according to JIS K-6911.
S-10T). Moisture absorption rate: A weight change was measured under the conditions of 85 ° C./85% RH using a constant temperature and constant humidity chamber (TABAI PR-2).・ Spiral flow: 17 according to EMMI-1-66
It was carried out under the conditions of 5 ° C./70 kg / cm ² . -Adhesive strength (aluminum peel): A molded product was transfer-molded on a commercially available aluminum foil, and the peel strength was evaluated.・ Solder cracking property: Simulated IC (52-pin QFP package: package thickness 2.05 mm) at 85 ° C / 85%
Immediately after absorbing moisture under the condition of RH / 72 hours, 240 ° C
With cracks after dipping in the solder bath for 30 seconds
C population. 10 test individuals.

Reference Example 1 [Synthesis of N, N'-1,1'-bis [4- (4-aminophenoxy) -2-methyl-5-t-butylphenyl] butane bismaleimide] 2 liter four-neck 97.1 g of maleic anhydride in a flask
And 226.5 g of acetone were charged, and they were dissolved by stirring under a nitrogen stream. 1,1 'while keeping the temperature between room temperature and 35 ℃
-Bis [4- (4-aminophenoxy) -2-methyl-
5-t-butylphenyl] butane (Sumitomo Chemical Co., Ltd.
(Manufactured by K.K.), 256.5 g of which was dissolved in 598.5 g of acetone was added dropwise for 2 hours. Stirring was continued for another 3 hours. After adding 27.3 g of triethylamine and stirring at room temperature for half an hour, 0.95 g of nickel acetate was added and the temperature was raised to 40 ° C. After adding 119.9 g of acetic anhydride dropwise over 1 hour, the reaction was continued at the same temperature. After the reaction is completed, the reaction mixture is mixed with water 2.5.
It was discharged to kg and the crystals were collected by filtration. The crystals were washed with water and then with methanol, heated under reduced pressure and dried to obtain 306.1 g of yellow crystals (yield 93.9%) (M
BM-M). The product was recrystallized from a mixed solvent of methyl cellosolve / isopropyl alcohol and had a melting point of 127 to 130 ° C.

Examples 1 to 3 MBM-M obtained in Reference Example 1 above, glycidyl ether of o-cresol novolac as epoxy resin:
Product name Sumiepoxy ESCN-195XL (Sumitomo Chemical Co., Ltd., epoxy equivalent 201 g / equivalent, hydrolyzable chlorine content 330 ppm) and polyphenol glycidyl ether (PHG, epoxy equivalent, obtained by condensation of phenols and hydroxybenzaldehyde) 213 g / equivalent, hydrolyzable chlorine 200 ppm, phenol novolac as an epoxy curing agent (manufactured by Arakawa Chemical Co., Ltd., trade name Tamanol 759, OH equivalent = 106 g)
/ Eq), triphenylphosphine and triethylammonium tetraphenylborate as curing accelerators,
Fractured fused silica (brand name FS-891 manufactured by Denki Kagaku Kogyo KK) and spherical fused silica (brand name FB-)
74 Denki Kagaku Kogyo Co., Ltd., carnauba wax as a release agent, coupling agent (trade name SH-6040, manufactured by Toray Dow Corning Silicone and trade name KBM-573).
Shin-Etsu Chemical Co., Ltd.) was blended in the amount (g) shown in Table 1, and the mixture was heated and kneaded with a roll to perform transfer molding. Further, post-curing was performed at 200 ° C. for 5 hours to obtain a cured molded product. Table 1 shows the compounding recipe, the physical properties of the resulting thermosetting resin composition and the physical properties of the cured moldings thereof.
Shown in.

Comparative Examples 1 and 2 Comparative Example 1 uses N, N '-(4,4'- as an imide compound.
Diaminodiphenylmethane) bismaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-18
0), ESCN-195XL as an epoxy resin, Tamanor 759 as an epoxy curing agent, and Comparative Example 2 is the same as Example 1 except that an imide compound is not used among the three.
A cured molded product was obtained in the same manner as in 3. Regarding post cure, Comparative Example 1 was conducted at 200 ° C. for 5 hours, and Comparative Example 2 was used.
Was carried out at 180 ° C. for 5 hours. Table 1 shows the compounding formulation, the physical properties of the resulting thermosetting resin composition, and the physical properties of the cured moldings thereof.

[0032]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Takebe 6 Kitahara, Tsukuba City, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Shinichiro Kitayama 6 Kitahara, Tsukuba City, Ibaraki Sumitomo Chemical Co., Ltd. (72) Inventor Mitsuhiro Shibata 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Shuichi Kanagawa 6, Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. (A) General formula [I]: (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogenated carbon atom having 1 to 6 carbon atoms. Hydrogen radical, R
₇ , R ₈ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group having 1 to 6 carbon atoms,
R ₉ and R ₁₀ are each independently a halogen atom and a carbon number of 1.
To a hydrocarbon group of 6 or a halogenated hydrocarbon group of 1 to 6 carbon atoms, and a and b each represent an integer of 0 or more and 4 or less. R
_{When 9} or R ₁₀ are present in plural, they may be the same or different from each other. The bond position of the imide group is ortho, meta or para to the bond position of the oxygen atom. D represents a divalent organic group having 2 to 24 carbon atoms and having an ethylenically unsaturated bond. The thermosetting resin composition which has an imide compound and the (B) hardening accelerator which are represented by these as an essential component. 2. A heat containing (A) an imide compound represented by the general formula [I] according to claim 1, (B) a curing accelerator, (C) an epoxy resin and (D) an epoxy curing agent as essential components. Curable resin composition. 3. An electronic component sealed with the thermosetting resin composition according to claim 1.