JPH11343323A - Modified phenolic resin, production of the same, epoxy resin composition containing the same, and cured product of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin having low-stress properties, excellent hydrophobicity, and an excellent ability to wet a filter by modifying with an organic protonic acid a phenolic resin being an alternating copolymer of a phenolic compound with a compound having a bivalent bonding group. SOLUTION: This resin is a modified phenolic resin obtained by adding 0.1-10,000 ppm of an organic protonic acid such as p-toluenesulfonic acid to a phenolic resin being an alternating copolymer of a phenolic compound with a xylylene compound having a divalent bonding group and reacting the obtained mixture at 50-200 deg.C. A bifunctional epoxy resin is mixed with the modified phenolic resin as a curing agent, a cure accelerator, and an organic or inorganic filler to obtain an epoxy resin composition. The phenolic resins used are a phenol aralkyl resin, a naphthol aralkyl resin, a novolac resin, and a phenol dicyclopentadiene resin represented by formulae I to IV. In the formulae, R1 , R2 , and R5 are each hydrogen, a halogen, or the like; R3 and R4 are each hydrogen, a 1-6C alkyl, or the like; (l) is 1-3; (m) is 0-50; and (n) is 0-15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol resin used in various industrial fields such as casting, laminating, bonding, molding, friction material, etc., and particularly to IC, LS.
The present invention relates to a phenol resin which is a curing agent useful as an epoxy resin composition for encapsulating semiconductor integrated circuits such as I and VLSI, and an epoxy resin composition using the same. More specifically, the present invention relates to a phenol resin modified with an organic protonic acid having excellent wettability with a filler.

[0002]

2. Description of the Related Art Semiconductor integrated circuit sealing techniques include hermetic sealing with a metal case or ceramic, and resin sealing with methods such as potting, casting, low-pressure transfer, and powder coating. Resin sealing by a molding method has become mainstream. For resin encapsulation, reliability such as moisture resistance, heat stress resistance, and electrical stability is required. Encapsulation with an epoxy resin cured product is required based on the balance between these cured physical properties, cost, and moldability. Stop is the mainstream.

With the recent trend toward higher densities and higher integration of semiconductor integrated circuits, downsizing of final products, and thinning of packages with the trend toward lighter weight, the performance required for sealing materials has become more severe. . In particular, there is a great demand for solder heat resistance. As a countermeasure, many studies have been made to make the resin hydrophobic and reduce the stress.

On the other hand, apart from the basic performance of a resin, when viewed as a sealing material, the degree of adhesion between the resin and the filler greatly contributes to physical properties, particularly mechanical bending strength and moisture absorption. Is obvious. That is, when the adhesiveness between the resin and the filler is not sufficient, the strength as a whole is naturally lost, and the moisture enters the part where the resin is peeled off, so that the moisture absorption rate increases. Therefore, this causes a reduction in solder heat resistance and crack resistance. That is, in order to sufficiently bring out the basic physical properties of the resin, it is ideal that the resin and the filler are in close contact with each other. Thus, with respect to the resin, along with the improvement of the basic physical properties, to sufficiently adhere to the filler, that is, regarding the wetting property,
Further improvements are desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a phenolic resin having improved wetting property with respect to a filler and an epoxy resin composition using the same as a curing agent, whereby the resin in the encapsulant is filled with the resin. An object of the present invention is to provide a sealing resin for a semiconductor integrated circuit, which has improved adhesiveness to an agent and has excellent mechanical strength and moisture resistance, that is, excellent solder heat resistance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a curing agent having low stress, excellent hydrophobicity, and excellent wettability with a filler, and as a result, have completed the present invention. Was. That is, the present invention provides a phenol resin, which is an alternating copolymer of a phenol compound and a compound having a divalent linking group, wherein the phenol resin is modified with an organic protonic acid. A phenolic resin having an amount of 0.1 to 10,000 ppm (weight ratio) relative to the phenolic resin, wherein the phenolic resin is a phenol aralkyl resin represented by the general formula (1) A naphthol aralkyl resin represented by the formula (2) (formula 4), a novolak resin represented by the formula (3) (formula 4), or a phenol-diamine represented by the formula (4) (formula 4) After adding an organic protonic acid to the modified phenolic resin or phenolic resin described or described in any of cyclopentadiene resins, the temperature is changed from room temperature to 200 ° C. The method for producing a modified phenolic resin according to any one of the above-mentioned, characterized in that the modified phenolic resin comprises a bifunctional or higher functional epoxy resin, and the modified phenolic resin according to any one of the above-mentioned as a curing agent An epoxy resin composition, characterized by further comprising a curing accelerator, an organic and / or inorganic filler, wherein the epoxy resin composition is cured by curing the epoxy resin composition described in or above. The present invention relates to a cured product obtained, and a semiconductor device obtained by sealing a semiconductor integrated circuit using the epoxy resin composition described above.

[0007]

Embedded image (In the above _{formulas, R 1, R 2, R} 5 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group or an aryl,, R _3, R ₄ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, which may be the same or different, and l is an integer of 1 to 3 And m indicating the number of repeating units is an integer in the range of 0 to 50, and n is an integer in the range of 0 to 15)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. TECHNICAL FIELD The present invention relates to a phenol resin characterized by being modified with an organic protonic acid and an epoxy resin composition using the same as a curing agent. The phenol resin used in the present invention refers to a resin in a form in which a phenol compound and a compound having a divalent linking group are alternately copolymerized. As preferred resins, for example, a phenol aralkyl resin represented by the general formula (1), a naphthol aralkyl resin represented by the general formula (2), a novolak type resin represented by the general formula (3), a general formula ( And phenol-dicyclopentadiene resin represented by 4).

The phenol aralkyl resin represented by the general formula (1) or the naphthol aralkyl resin represented by the general formula (2) is a compound having a divalent linking group with a phenol compound or a naphthol compound, respectively. It can be obtained by reacting a certain xylylene compound with or without a catalyst or in the presence of a catalyst. Examples of the phenol compound used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, on-propylphenol, min-propylphenol, and pn -Propylphenol, o-isopropylphenol, m-
Isopropylphenol, p-isopropylphenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, octylphenol, nonylphenol,
2,4-xylenol, 2,6-xylenol, 3,
5, -xylenol, 2,4,6-trimethylphenol, resorcinol, catechol, hydroquinone, 4-methoxyphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, p-cyclohexylphenol, o-allylphenol, p-allylphenol, o-benzylphenol, p-benzylphenol, o-chlorophenol, p-chlorophenol, o-bromophenol, p-bromophenol,
o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol, p-fluorophenol and the like. These phenols may be used alone or in combination of two or more.
Preferred are phenol, o-cresol, m-cresol, p-cresol and the like. The naphthol compounds include α-naphthol and β-naphthol.

As a xylylene compound which is a compound having a divalent linking group, xylylene dihalide, xylylene diglycol and derivatives thereof are used. For example, α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dibromo-p-xylene, α, α ′ −
Dibromo-m-xylene, α, α′-dibromo-o-xylene, α, α′-diiodo-p-xylene, α, α ′
-Diiodo-m-xylene, α, α'-diiodo-o-
Xylene, α, α′-dihydroxy-p-xylene,
α, α′-dihydroxy-m-xylene, α, α′-dihydroxy-o-xylene, α, α′-dimethoxy-p
-Xylene, α, α′-dimethoxy-m-xylene,
α, α′-dimethoxy-o-xylene, α, α′-diethoxy-p-xylene, α, α′-diethoxy-m-xylene, α, α′-diethoxy-o-xylene, α, α
α'-di-n-propoxy-p-xylene, α, α'-
n-propoxy-m-xylene, α, α′-di-n-propoxy-o-xylene, α, α′-di-isopropoxy-p-xylene, α, α′-di-isopropoxy-m
-Xylene, α, α′-di-isopropoxy-o-xylene, α, α′-di-n-butoxy-p-xylene,
α, α′-di-n-butoxy-m-xylene, α, α ′
-Di-n-butoxy-o-xylene, α, α'-di-isobutoxy-p-xylene, α, α'-di-isobutoxy-m-xylene, α, α'-di-isobutoxy-o-
Xylene, α, α′-di-tert-butoxy-p-xylene, α, α′-tert-butoxy-m-xylene, α, α′-di-tert-butoxy-o-xylene and the like can be mentioned. These are used alone or in combination of two or more.

Preferably, α, α'-dichloro-p-
Xylene, α, α′-dichloro-m-xylene, α,
α′-dichloro-o-xylene, α, α′-dihydroxy-p-xylene, α, α′-dihydroxy-m-xylene, α, α′-dihydroxy-o-xylene, α,
α′-dimethoxy-p-xylene, α, α′-dimethoxy-m-xylene and α, α′-dimethoxy-o-xylene.

In the reaction of the above-mentioned phenol compound or naphthol compound (hereinafter referred to as phenol compound) with a xylylene compound, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid and polyphosphoric acid, dimethyl sulfate, diethyl sulfate, p-
Organic carboxylic acids such as toluenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, super strong acids such as trifluoromethanesulfonic acid, strongly acidic ion exchange resins such as alkanesulfonic acid type ion exchange resins, perfluoroalkane sulfone Ultra-strong acidic ion exchange resins such as acid type ion exchange resins (trade names: Nafion, Nafion, D
u'Pont), natural and synthetic zeolites, activated clay (acid clay), etc.
At 0 ° C., the reaction is carried out until the xylylene compound as the raw material substantially disappears and the reaction composition becomes constant. The reaction time depends on the raw materials and the reaction temperature, but is generally from 1 hour to
It is about 15 hours, and in practice, it may be determined while tracking the reaction composition by GPC (gel permeation chromatography) or the like. After the reaction, an unreacted phenol compound is recovered.

In the case of a halogenoxyxylene derivative such as α, α′-P-xylene, the reaction proceeds in the absence of a catalyst while generating a corresponding hydrogen halide gas. do not do. In other cases, the reaction proceeds in the presence of an acid catalyst to yield the corresponding water or alcohol. The reaction molar ratio between the phenol compound and the xylylene compound usually uses an excess amount of the phenol compound. In this reaction, the average molecular weight is determined by the amount of the phenolic compound, and a phenol aralkyl resin having a lower average molecular weight is obtained as the amount of the phenolic compound increases in excess.

A typical phenol aralkyl resin produced in this manner is, for example, MILEX XLC-3L manufactured by Mitsui Chemicals, Inc. This is a condensate of phenol and a p-xylylene compound. In the case of a phenol aralkyl resin in which the phenol compound portion is allyl phenol, the phenol aralkyl resin can be obtained by reacting an unallylated phenol aralkyl resin with an allyl halide, passing through an allyl ether, and allylating by Claisen rearrangement. is there.

The novolak type phenolic resin represented by the general formula (3) is produced by a known and commonly used method, that is, by reacting a phenol compound with an aldehyde or a ketone in the presence of an acid catalyst. The phenol compound used is the same as in the case of the phenol aralkyl resin described above. Compounds used as the compound having a divalent linking group are aldehydes and ketones,
For example, formaldehyde (formalin),
Paraformaldehyde, acetaldehyde, cyclohexylaldehyde, acetone, acetophenone, benzophenone and the like.

The two are reacted in the presence of hydrochloric acid, oxalic acid, or any of the various acid catalysts mentioned above, and if neutralization of the catalyst acid is necessary, neutralization and washing are performed. When a phenol compound is present, it can be recovered to obtain the desired novolak resin. still,
The molar ratio of the phenol compound to the aldehydes and ketones is usually such that the phenol compound is used in excess, and after the reaction, the unreacted phenol compound is recovered.

As a representative example, Showa High Polymer Co., Ltd.
Manufactured by: BRG # 556, manufactured by Mitsui Chemicals, Inc .: VR83
There are 10 magnitudes. The former is a condensate of phenol and formalin (formaldehyde), and the latter is a residue obtained by cutting a bisphenol compound from the same condensate by distillation.

The phenol-dicyclopentadiene resin represented by the general formula (4) is, for example, a phenol compound and a divalent linking group, dicyclopentadiene.
It is obtained by reacting in the presence of an acid catalyst. The phenol compound used in this case is the same as the above-mentioned phenol compound. To this phenol compound, add dicyclopentadiene to an organic acid such as methanesulfonic acid,
The reaction is performed in the presence of an acid catalyst such as a super strong acid such as trifluoromethanesulfonic acid, a strongly acidic ion exchange resin, a super strong acid ion exchange resin, and a Lewis acid such as boron trifluoride (ether complex).

This reaction is a two-step reaction of etherification by addition of dicyclopentadiene to a phenolic hydroxyl group and regeneration of the hydroxyl group by transfer of an ether form. This reaction is also carried out in excess of phenol, and after the reaction, unreacted phenol is removed to obtain the desired product. If necessary,
A neutralization and removal process of the acid catalyst may be performed. A typical example is DPR # 5000 manufactured by Mitsui Chemicals, Inc.

The modified phenolic resin of the present invention is obtained by modifying the above phenolic resin with an organic protonic acid. The production method is a method characterized by reacting a phenolic resin with an organic protonic acid in the presence or absence of an organic solvent in the range of room temperature to 200 ° C. Considering production efficiency, workability, etc., the following method is desirable. That is, the phenol resin is melted at a temperature equal to or higher than the softening point, preferably 50 ° C to 200 ° C, more preferably 80 ° C to 180 ° C, particularly preferably 90 ° C to 150 ° C, and sufficiently stirred. This is a method in which a desired organic protonic acid is added as a state and reacted. In addition, it is also possible to use an organic solvent that does not react with the hydroxyl group of the phenol resin or the organic protonic acid, and to perform the reaction in the state of a solution in which the phenol resin is dissolved.

Examples of the organic solvent used at this time include aromatic hydrocarbons such as benzene, toluene and xylene, aromatic halogenated hydrocarbons such as chlorobenzene and o-dichlorobenzene, dichloromethane, 1,2-dichloroethane. , 1,1,2-trichloroethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride and the like, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like Proton polar solvents, dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and the like, among which toluene and chlorobenzene are preferable.

The amount of the organic solvent used is not particularly limited, but may be 0.5 parts by weight based on the phenol resin.
10 to 10 times, preferably the same amount to 5 times,
After completion of the reaction, distillation may be performed by any method such as distillation under reduced pressure.
The time required for the reaction depends on the temperature, but is generally about 10 minutes to 5 minutes.
In consideration of time and realistic production, stirring for about 1 to 5 hours is sufficient. The organic protonic acid used in the present invention is represented by the general formula (5) or (6), and represents a compound containing at least one sulfonic acid group or carboxylic acid group in one molecule. R _6- [SO ₃ H] _p (5) R _6- [COOH] _p (6) (wherein, R ₆ represents an alkyl group, an aralkyl group or an aryl group, and p represents an integer of 1 to 3)

As R ₆ , for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, tert-butyl group, n-pentyl group,
Isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, cyclohexylmethyl group, n-heptyl group, n-octyl group, ter
alkyl groups such as t-octyl group and 2-ethylcyclohexyl group; aralkyl groups such as benzyl group, phenethyl group and 3-phenylpropyl group; phenyl group, 4-methylphenyl group, 3-methylphenyl group and 2-methylphenyl Group, 4-ethylphenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 1-naphthyl group, 2-
And an aryl group such as a naphthyl group.

Specifically, preferred organic protonic acids include methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, n-heptanesulfonic acid, cyclohexylsulfone, benzenesulfonic acid, p-toluenesulfonic acid, -Hydroxybenzenesulfonic acid, 1-naphthylsulfonic acid, 2-naphthylsulfonic acid, phenylacetic acid, salicylic acid, benzoic acid, p-hydroxybenzoic acid and the like, particularly preferably p-toluenesulfonic acid, salicylic acid and benzoic acid. .

The amount of the organic protonic acid used is 0.1 ppm to 1000 parts by weight based on the phenol resin to be modified.
The range is 0 ppm, preferably 1 ppm to 1000 ppm, and more preferably 5 ppm to 500 ppm.

The added organic protonic acid is uniformly dispersed in the resin, and in the case of an organic sulfonic acid, a part thereof may sulfonate the phenol aromatic ring of the phenol resin.

The epoxy resin composition of the present invention is obtained by adding the modified phenol resin of the present invention as a curing agent to a bifunctional or higher epoxy resin. The epoxy resin composition of the present invention preferably contains a curing accelerator and an organic and / or inorganic filler in addition to the modified phenol resin of the present invention and a bifunctional or higher epoxy resin. further,
The epoxy resin composition of the present invention may contain a coupling agent, a release agent, a flame retardant, and the like.

The bifunctional or higher functional epoxy resin used in the epoxy resin composition of the present invention includes all those having two or more epoxy groups in one molecule. Specifically, it has an epoxy group obtained by oxidation of olefins, glycidyl etherification of hydroxyl groups, glycidyl amination of 1,2 primary amines, glycidyl esterification of carboxylic acid, and the like. These raw materials that can be epoxidized include dihydroxybenzenes such as catechol, resorcin, and hydroquinone; 2,6-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2- (3 -Hydroxyphenyl) -2- (4 '
-Hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane (bisphenol F), bis (4-hydroxyphenyl) sulfone (bisphenol S), bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methylcyclohexane , Bis (4-hydroxyphenyl) methylbenzene, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-2,2 ', 6,6'-tetramethylbiphenyl, 4,4'-dihydroxydiphenyl ether, 6, 6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1
Bisphenols such as spirobiindane and 1,3,3-trimethyl-1- (4-hydroxyphenyl) -1-indan-6-ol; oligophenols such as tetraphenylolethane and naphthol-cresol resol condensate; phenol Novolaks, cresol novolaks; and phenol aralkyl resins and phenol-dicyclopentadiene alternating copolymer resins, which are raw materials that can be modified in the present invention.

As the filler used in the epoxy resin composition of the present invention, fillers of various shapes such as powder, plate, fiber and the like, reinforcing materials and the like are used. Preferred fillers and reinforcing materials include metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, aluminum silicate, magnesium silicate, and silica. Natural and synthetic silicates such as calcium silicate, natural and synthetic silicates, graphite, carbon black, wood flour,
Nut shell powder, fluorine resin powder, molybdenum disulfide, antimony trioxide, mica, asbestos, glass fiber, rock wool, mineral fiber, ceramic fiber, cellulose fiber, alumina fiber, potassium titanate fiber, carbon fiber, polyamide fiber, Organic fillers and the like can be mentioned. Examples of the curing accelerator include an amine compound, an organic phosphorus compound, and a modified product thereof.

Examples of the coupling agent include a silane coupling agent and the like, examples of the release agent include waxes and oils, and examples of the flame retardant include a brominated epoxy resin and antimony oxide. Further, additives such as dyes and pigments may be added to the epoxy resin composition of the present invention, and if necessary, organic solvents such as methanol and ethanol may be added. Further, a curing agent other than the resin of the present invention, for example, a cross-linked methylene source such as hexamethylenetetramine, paraformaldehyde or trioxane, or a phenol novolak resin may be used in combination as long as the effects of the present invention are not impaired.

The cured product of the present invention is an epoxy resin composition obtained by adding the modified phenol resin of the present invention as a curing agent to the above-mentioned bifunctional or higher epoxy resin, or a curing accelerator, an organic and It is obtained by thermally curing an epoxy resin composition obtained by containing an inorganic filler. Further, the semiconductor device of the present invention is a semiconductor device comprising an epoxy resin composition containing the above-mentioned bifunctional or higher functional epoxy resin, the modified phenol resin of the present invention as a curing agent, and a curing accelerator, an organic and / or inorganic filler. It is obtained by sealing an integrated circuit.

[0032]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. In the examples, “parts” indicates “parts by weight”. In addition, the measuring method of the physical property value in an Example is shown below. <Bending strength measurement method> After transfer molding at a mold temperature of 165 ° C and a transfer pressure of 7 MPa,
Heat treatment was performed at 65 ° C. for 6 hours. After that, JIS K-6
The bending strength of the molded article was measured in accordance with 991. <Breaking Section Observation Method> The bending fracture section of the molded product subjected to the bending strength measurement was observed with a scanning electron microscope.

Example 1 A glass reactor equipped with a thermometer and a stirrer was charged with 156 g (1.7 mol) of phenol, and the temperature was raised while stirring to raise the internal temperature to 100 to 110 ° C. Kept. Next, while maintaining the same temperature, 175 g (1 mol) of α, α′-dichloro-p-xylene was added in portions over 2 hours. On the way, the generated hydrogen chloride gas was collected by an aspirator by suction using an aspirator. After the addition was completed, the internal temperature was raised to 150 ° C. over 3 hours. Thereafter, aging was performed at a temperature of 150 to 160 ° C. for 6 hours to complete the reaction. Next, unreacted phenol was recovered from the reaction solution under vacuum. During this treatment, the internal temperature was set to 170 ° C., and the vacuum pressure was set to 2 mmHg. The viscous reaction liquid from which the unreacted phenol was recovered was immediately discharged to a magnetic dish, and allowed to cool to obtain 198 g of a phenol aralkyl resin. This is a phenolic polymer represented by the above formula (1) and has a softening point of 73.
° C (according to JIS K-2207), number average molecular weight (M
w) 950 (in terms of polystyrene), hydroxyl equivalent 176 g /
eq) (hereinafter referred to as Resin-1). This resin
1 was heated in advance at 115 ° C. to 120 ° C. for 40 minutes to obtain a melt, and then 0.01 part with respect to 100 parts of the resin.
P-Toluenesulfonic acid was added in parts and stirred at this temperature for 60 minutes. At this time, p-toluenesulfonic acid was immediately melted and mixed, and the inside of the flask became uniform. Thereafter, the resin was discharged, cooled and pulverized to obtain an acid-modified resin of the present invention.

To 100 parts of this resin, 112 parts of YX-4000H manufactured by Yuka Shell Epoxy Co., 1440 parts of silica subjected to silane coupling treatment, 2 parts of catalyst triphenylphosphine (TPP), and carbana wax Was mixed in a ratio of 4.5 parts and roll-kneaded at 80 ° C. for 5 minutes. After cooling, it was pulverized to obtain Compound-1. When transfer molding was performed using Compound-1 and the bending strength was measured, it was 150 MPa. Further, the form of the bending fracture surface was as shown in FIG. 1, and it was found that the resin was stuck to the silica surface and the base material was broken. The length of the scale bar in the figure is 10 μm. Further, 3 parts of carbon black and 10 parts of antimony oxide were added to the above compound-1, and a compound 1 ′ for a sealing material was obtained in the same manner. Using this compound-1 ′, a test element (10 mm) was mounted on the element mounting portion of a flat package type semiconductor device lead frame.
(× 10 mm square), and transfer molding was performed to obtain a test semiconductor device. When a solder bath test (crack generation test) was performed using this test semiconductor device, no crack was observed in any one of the 20 samples, and the effect of the present invention was remarkably exhibited.

Comparative Example 1 Compound-2 was obtained in the same manner as in Example 1 except that resin-1 was used without acid modification. Transfer molding was performed using this compound-2, and the bending strength was measured to be 95 MPa. Also,
The form of the bending fracture surface was as shown in FIG. 2, and it was presumed that the silica surface was smooth and the interface was broken. In addition,
The length of the scale bar in the figure is 10 μm. Further, the compound-2 was mixed with carbon black 3
And 10 parts of antimony oxide, and a compound 2 ′ for a sealing material was obtained in the same manner. This compound-2 '
A transfer semiconductor device was used to obtain a test semiconductor device. When a solder bath test (crack occurrence test) was performed using this test semiconductor device, cracks were observed in three out of the 20 semiconductor devices.

Example 2 A glass reactor equipped with a thermometer and a stirrer was charged with 200 g of a phenol novolak resin (trade name: BRG # 55).
8, number average molecular weight (Mw) 750 (in terms of polystyrene), hydroxyl equivalent 104 g / eq, manufactured by Showa Polymer Co., Ltd.]
(Hereinafter, referred to as resin-2). This resin-2
Was heated in advance at 115 ° C. to 120 ° C. for 40 minutes to obtain a melt, and then 0.01 part with respect to 100 parts of the resin.
P-Toluenesulfonic acid was added in parts and stirred at this temperature for 60 minutes. At this time, p-toluenesulfonic acid was immediately melted and mixed, and the inside of the flask became uniform. Thereafter, the resin was discharged, cooled and pulverized to obtain an acid-modified resin of the present invention.

To 100 parts of this resin, 112 parts of YX-4000H manufactured by Yuka Shell Epoxy Co., 1440 parts of silica subjected to silane coupling treatment, 2 parts of catalyst triphenylphosphine (TPP), and carbana wax Was mixed in a ratio of 4.5 parts and roll-kneaded at 80 ° C. for 5 minutes. After cooling, it was pulverized to obtain Compound-3. Transfer molding was performed using Compound-3, and the bending strength was measured to be 155 MPa. Further, 3 parts of carbon black and 10 parts of antimony oxide were added to the above compound-3, and a compound 3 ′ for a sealing material was obtained in the same manner. Using this compound-3 ',
After a test element (10 mm × 10 mm square) was mounted on the element mounting portion of the flat package type semiconductor device lead frame, transfer molding was performed to obtain a test semiconductor device. A solder bath test (crack generation test) was performed using this test semiconductor device.
No one out of 0 was observed, and the effect of the present invention was remarkably exhibited.

Comparative Example 2 Compound 4 was obtained in the same manner as in Example 2 except that resin-2 was used without acid modification. Transfer molding was performed using this compound-4, and the bending strength was measured to be 95 MPa. Further, carbon black 3 was added to the compound-4.
And 10 parts of antimony oxide, and a compound 4 ′ for a sealing material was obtained in the same manner. This compound-4 '
A transfer semiconductor device was used to obtain a test semiconductor device. When a solder bath test (crack occurrence test) was performed using this test semiconductor device, cracks were observed in three out of the 20 semiconductor devices.

Example 3 A glass reactor equipped with a thermometer and a stirrer was charged with 200 g of phenol-dicyclopentadiene resin [trade name: DP
R # 3000, number average molecular weight (Mw) 810 (polystyrene equivalent), hydroxyl equivalent 185 g / eq, manufactured by Mitsui Chemicals, Inc.] (hereinafter referred to as Resin-3). This resin-3 was previously heated at 115 ° C. to 120 ° C. for 40 minutes to form a melt.
One part of p-toluenesulfonic acid was added and stirred at this temperature for 60 minutes. At this time, p-toluenesulfonic acid was immediately melted and mixed, and the inside of the flask became uniform. Thereafter, the resin was discharged, cooled and pulverized to obtain an acid-modified resin of the present invention.

Based on 100 parts of this resin, 112 parts of YX-4000H manufactured by Yuka Shell Epoxy, 1440 parts of silica subjected to silane coupling treatment, 2 parts of catalyst triphenylphosphine (TPP), and carbana wax Was mixed in a ratio of 4.5 parts, and roll-kneaded at 80 ° C. for 5 minutes. After cooling, it was pulverized to obtain Compound-5.
Transfer molding using this compound-5,
When the bending strength was measured, it was 160 MPa. Further, 3 parts of carbon black and 10 parts of antimony oxide were added to the above compound-5, and a sealing compound 5 ′ was obtained in the same manner. This compound-5 '
A test element (10 mm × 10 mm) is mounted on the element mounting portion of the lead frame for a flat package type semiconductor device by using
After mounting, the semiconductor device for test was obtained by transfer molding. When a solder bath test (crack generation test) was performed using this test semiconductor device, no crack was observed in any one of the 20 samples, and the effect of the present invention was remarkably exhibited.

Comparative Example 3 Compound 6 was obtained in the same manner as in Example 3, except that resin-3 was used without acid modification. Transfer molding was performed using this compound-6, and the bending strength was measured to be 100 MPa. Further, carbon black 3 was added to the compound-6.
And 10 parts of antimony oxide, and a compound 6 ′ for a sealing material was obtained in the same manner. This compound-6 '
A transfer semiconductor device was used to obtain a test semiconductor device. When a solder bath test (crack occurrence test) was performed using this test semiconductor device, cracks were observed in four out of the 20 semiconductor devices.

Example 4 Compound 7 was obtained in the same manner as in Example 1, except that the amount of p-toluenesulfonic acid was reduced to 0.004 part. Transfer molding was performed using this compound-7, and the bending strength was measured.
Pa. Further, 3 parts of carbon black and 10 parts of antimony oxide were added to the compound-7,
Similarly, a compound 7 ′ for a sealing material was obtained. Transfer molding was performed using this compound-7 'to obtain a test semiconductor device. Using this test semiconductor device, a solder bath test (crack occurrence test) was performed. As a result, no crack was observed in any one of the 20 cracks, and the effect of the present invention was remarkably exhibited.

Example 5 Compound-8 was obtained in the same manner as in Example 1, except that the amount of p-toluenesulfonic acid was reduced to 0.001 part. Transfer molding was performed using this compound-8, and the bending strength was measured.
Pa. Further, the form of the bending fracture surface was very similar to that of Example 1, and the base material was broken. Further, 3 parts of carbon black and 10 parts of antimony oxide were added to the above compound-8 to obtain a sealing compound-8 'in the same manner. Transfer molding was performed using this compound-8 'to obtain a test semiconductor device. Using this test semiconductor device, a solder bath test (crack occurrence test) was performed. As a result, no crack was observed in any one of the 20 cracks, and the effect of the present invention was remarkably exhibited.

Example 6 In Example 1, p-toluenesulfonic acid was used in an amount of 0.0
Compound-9 was obtained in the same manner except that the benzoic acid was replaced with 05 parts of benzoic acid. Transfer molding was performed using this compound-9, and the bending strength was measured.
Pa. Further, the form of the bending fracture surface was very similar to that of Example 1, and the base material was broken. Further, 3 parts of carbon black and 10 parts of antimony oxide were added to the compound 9 and the sealing was performed in the same manner. A compound for stopping material-9 'was obtained. Transfer molding was performed using this compound-9 'to obtain a test semiconductor device. Using this test semiconductor device, a solder bath test (crack occurrence test) was performed. As a result, no crack was observed in any one of the 20 cracks, and the effect of the present invention was remarkably exhibited.

Example 7 In Example 1, p-toluenesulfonic acid was used in an amount of 0.0
Compound-10 was obtained in the same manner except that 1 part of phenylacetic acid was used. Transfer molding was performed using this compound-10, and the bending strength was measured.
It was 60 MPa. Further, the above compound-10
Was mixed with 3 parts of carbon black and 10 parts of antimony oxide to obtain a sealing compound 10 'in the same manner. Transfer molding was performed using this compound-10 'to obtain a test semiconductor device. Using this test semiconductor device, a solder bath test (crack occurrence test) was performed. As a result, no crack was observed in any one of the 20 cracks, and the effect of the present invention was remarkably exhibited.

Example 8 In Example 1, p-toluenesulfonic acid was used in an amount of 0.0
Compound-11 was obtained in the same manner except that salicylic acid was changed to 1 part. Transfer molding was performed using this compound-11, and the bending strength was measured.
It was 0 MPa. Furthermore, 3 parts of carbon black and 10 parts of antimony oxide were added to the compounding of the above-mentioned compound 11, and a compound 11 ′ for a sealing material was obtained in the same manner. Transfer molding was performed using this compound-11 'to obtain a test semiconductor device. Using this test semiconductor device, a solder bath test (crack occurrence test) was performed. As a result, no crack was observed in any one of the 20 cracks, and the effect of the present invention was remarkably exhibited.

[0047]

By using the modified phenolic resin of the present invention as a curing agent, the epoxy resin composition of the present invention makes it possible to remarkably improve the wetting property between the resin and the filler. The reliability of the sealing could be improved.

[Brief description of the drawings]

FIG. 1 is a scanning electron microscope image of a bending fracture surface of a molded article (Example 1) obtained using the modified phenolic resin of the present invention [(a) 1000 times, (b) 5000 times]

FIG. 2 is a scanning electron microscope image of a bending fracture surface of a molded product (Comparative Example 1) obtained using a resin that has not been acid-modified [(a) × 1000, (b) × 5,000]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takuo Tajima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref. (72) Inventor Nao Maeda 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals ( 72) Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals, Inc.

Claims (10)

[Claims] 1. A modified phenol resin, wherein the phenol resin, which is an alternating copolymer of a phenol compound and a compound having a divalent linking group, is modified with an organic protonic acid. 2. The modified phenolic resin according to claim 1, wherein the content of the organic protonic acid is 0.1 to 10,000 ppm (weight ratio) based on the phenolic resin. 3. The phenol resin according to claim 1, wherein the phenol resin is a phenol aralkyl resin represented by the general formula (1) or a naphthol aralkyl resin represented by the general formula (2). The modified phenolic resin of the above. Embedded image (In the above formula, R ₁ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, or an aryl; l represents an integer of 1 to 3; M represents an integer in the range of 0 to 50) 4. The modified phenolic resin according to claim 1, wherein the phenolic resin is a novolak resin represented by the general formula (3). Embedded image (Wherein, R ₂ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, or an aryl group, and R ₃ and R ₄ each independently represent a hydrogen atom, A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, which may be the same or different, 1 represents an integer of 1 to 3, and n represents the number of repeating units. (Shows an integer in the range of 0 to 15) 5. A phenolic resin represented by the general formula (4):
The modified phenolic resin according to claim 1, which is a phenol-dicyclopentadiene resin represented by the formula: Embedded image (Wherein, R ₅ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, or an aryl group; l represents an integer of 1 to 3; Represents an integer in the range of 0 to 15) 6. The method for producing a modified phenolic resin according to claim 1, wherein an organic protonic acid is added to the phenolic resin, and the phenolic resin is reacted at room temperature to 200 ° C. . 7. An epoxy resin composition comprising a bifunctional or higher-functional epoxy resin and the modified phenol resin according to claim 1 as a curing agent. 8. The epoxy resin composition according to claim 7, further comprising a curing accelerator and an organic and / or inorganic filler. 9. A cured product obtained by thermally curing the epoxy resin composition according to claim 7 or 8. 10. A semiconductor device obtained by sealing a semiconductor integrated circuit using the epoxy resin composition according to claim 8.