JPH07173237A - Allylnaphthol cocondensate and epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide an allylnaphthol cocondensate which has low m.p. and melt viscosity, is useful as a curative for an epoxy resin, and gives a cured item excellent in heat resistance, moisture resistance, flexibility, etc., by selecting a specific allylnaphthol cocondensate. CONSTITUTION:An allylnaphthol cocondensate is selected which has a wt. average mol.wt. of 300-2,000 and is represented by formula I (wherein A is an allylnaphthol compd. of formula II; B is a phenol compd. of formula I; D is a naphthol compd. of formula IV; E is A or B provided the molar ratio of A to the sum of A, B, D, and E is 0.1-0.5; R<1>, R<2>, and R<3> are each H, alkyl, allyl, or OH; R<4> is H or CH3; R<5> is an aldehyde residue; and k, It, m, and n are each 0-10 provided that when k=l=0, then at least one of E's contains allyl group, that when k=m=0, then at least one of E's is the phenol compd., and that when k=l=m=n=0, then one of E' s is the allylnaphthol compd. and the other is the phenol compd.).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel allylnaphthol cocondensate and an epoxy resin composition containing the cocondensate.

[0002]

2. Description of the Related Art Conventionally, in the field of electric / electronic parts, particularly semiconductor encapsulating materials, a method of encapsulating a semiconductor element with an epoxy resin composition has been widely used in order to protect it from the external environment. Has been adopted. This composition
It is composed of epoxy resin, curing agent, curing accelerator, filler and other additives. As an epoxy resin,
A resin obtained by epoxidizing a novolac resin obtained by the reaction of phenols and formaldehyde, in particular, a cresol novolac type epoxy resin is widely used, and a phenol-formaldehyde novolac resin is used as a curing agent.

However, the recent trend toward higher density and higher integration in semiconductor devices requires the encapsulant to be further improved in various properties such as heat resistance, moisture resistance and adhesion.

Particularly, in the case of mounting the semiconductor element by the surface mounting method, the package of the semiconductor element is 200
It is placed in an oven at a high temperature of about 260 ° C. and exposed to severe temperature conditions. Therefore, even if the above-mentioned epoxy resin composition is used, there is still a problem that cracks occur in the package of the semiconductor device, and the demand for high heat resistance, low water absorption and high adhesion to the cured product is becoming stronger. .

Novolak resins obtained by reacting naphthol and aldehyde have been proposed as those satisfying these requirements. This resin is intended to improve physical properties such as heat resistance and moisture resistance of a cured product by introducing a naphthol skeleton. In fact, these properties give excellent properties, but on the other hand, it has a high viscosity. Therefore, there are problems such as poor molding workability and poor adhesion.

The object of the present invention is that it is useful as a curing agent for epoxy resins and has excellent workability due to its low melting point and melt viscosity, and also has a high glass transition temperature, heat resistance, moisture resistance, adhesion and flexibility. A novel allylnaphthol co-condensate capable of providing a cured product having properties and free from cracks is provided.

Another object of the present invention is a novel epoxy resin composition having a high glass transition temperature, excellent heat resistance, moisture resistance, adhesiveness and flexibility, and capable of preventing cracks from being generated in a package. Is provided.

[0008]

The allylnaphthol cocondensate of the present invention is a compound represented by the following general formula (I) and having a weight average molecular weight of 300 to 2000.

[0009]

[Chemical 3]

The allylnaphthol cocondensate of the present invention has a weight average molecular weight of 3 represented by the following general formula (II).
It is a compound of 00-2000.

[0011]

[Chemical 4]

The allylnaphthol cocondensate of the present invention has an allyl group and a methyl group-substituted phenol introduced into the condensate of naphthols and aldehydes, and therefore has extremely low melt viscosity and excellent workability. . That is, the introduction of an allyl group causes a steric hindrance effect on the molecule to reduce the viscosity, and the combination with a methyl group-substituted phenol suppresses the production of a high molecular weight substance, thereby preventing an increase in the viscosity. Due to both of these effects, a cocondensate having a remarkably low viscosity can be obtained.

When the cocondensate of the present invention is used as a curing agent for an epoxy resin, the resulting cured epoxy resin exhibits a high glass transition temperature and is excellent in heat resistance, moisture resistance, adhesion and flexibility.

The allylnaphthol cocondensate of the present invention has a weight average molecular weight of 30 obtained by cocondensing allylnaphthols, methyl group-substituted phenols and aldehydes.
It is a compound of 0-2000.

In addition, the methyl group-substituted phenols 8
Co-condensates obtained by substituting 0% or less, preferably 70% or less with at least one of α-naphthol and β-naphthol are also useful because of their low viscosity.

The aldehydes are preferably aliphatic aldehydes selected from formaldehyde and paraformaldehyde, or aromatic aldehydes selected from benzaldehyde, hydroxybenzaldehyde, salicylaldehyde and terephthalaldehyde.

The allyl group of allylnaphthols is present in the naphthalene nucleus in an amount of 1 to 2, but preferably 1 in order to accelerate the condensation reaction.

The weight average molecular weight of the allylnaphthol cocondensate of the present invention is 300 to 2,000. If it is less than 300, the number of OH groups in the molecule is too small, and the curing with epoxy becomes insufficient, and if it exceeds 2000, the melting point and viscosity of the resin become high and the workability becomes poor.

The epoxy resin composition of the present invention comprises the above allylnaphthol cocondensate and an epoxy resin.

The epoxy resin composition of the present invention containing the above allylnaphthol cocondensate as a curing agent preferably contains a curing accelerator, and in that case, it is particularly effective as a semiconductor encapsulating composition.

In the present specification, "epoxy resin"
Unless otherwise specified, the term means not only a resinous epoxy compound but also a low molecular weight epoxy compound.

The allylnaphthol cocondensate of the present invention may be any compound having a molecular structure in which allylnaphthols, methyl group-substituted phenols and aldehydes are cocondensed, and can be produced, for example, by the following two methods. it can.

(Method A) Allyl naphthols are previously allylated to synthesize allyl naphthols, methyl group-substituted phenols and aldehydes are added thereto, and if necessary, acids and bases are added to dehydrate in the same manner as in the usual synthesis of novolaks. How to react.

(Method B) After preparing a condensate from naphthols, methyl group-substituted phenols and aldehydes in advance, allyl halide is reacted with a base and optionally water or an organic solvent to react the condensate with an allyl group. How to introduce.

In the case of Method A, the naphthols to be allylated can be those having one or more allyl groups introduced into the molecule and one or more positions to which aldehydes can be added, such as α-naphthol and Examples thereof include dihydroxynaphthalene and α-naphthol and dihydroxynaphthalene partially substituted with an alkyl group, and α-naphthol is particularly preferable.

To allylate naphthols, (1)
A method in which naphthols and a base are added to water to form a phenolate, and then an allyl halide is added to react with it, impurities are washed with water, and then Claisen rearrangement is carried out by heating, (2) In the method of (1) above, halogenation is performed. A method of adding allyl dropwise over a long period of time, (3) a method of adding naphthols and allyl halide and, if necessary, an organic solvent and adding an aqueous base solution to the reaction to wash the impurities, and then performing Claisen rearrangement. Any method may be used.

Even if some unreacted naphthols remain, there is no problem because they are taken into the molecule of the condensate in the next cocondensation reaction.

The methyl group-substituted phenols may be phenols in which the hydrogen atom of the benzene ring is substituted with a methyl group, and for example, o-cresol, m-cresol, p-cresol, xylenol and the like are preferable.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde,
Aliphatic aldehydes such as propylaldehyde, butyraldehyde and glyoxal, aromatic aldehydes such as benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde and terephthalaldehyde can be used,
Of these, paraformaldehyde, aromatic benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde, and terephthalaldehyde are preferable. One of these aldehydes may be used for the reaction, or two or more of them may be used in combination for the reaction. The amount of the aldehyde used is 0.30 to 1 mol of the total amount of the raw material allylnaphthols, the methyl group-substituted phenols, and α-naphthol and β-naphthol optionally added.
It is preferably 0.85 mol. If the amount of the aldehyde used is less than 0.30 mol, the average molecular weight of the cocondensate becomes small, and the heat resistance of the cured product of the epoxy resin composition decreases. On the other hand, if it exceeds 0.85 mol, a high molecular weight product is formed to have a high melt viscosity, resulting in poor workability and a problem in moldability. In particular, 0.50 to 0.75
Molar is preferred.

The molar ratio of allylnaphthols and methyl group-substituted phenols (including α-naphthol and β-naphthol added as necessary) in the condensation reaction is 1
The range of 0:90 to 50:50 is preferable. If the used molar ratio of allylnaphthols is less than this, the effect derived from the allyl group, low viscosity, flexibility, lipophilicity, adhesion, etc. are small, and if the used molar ratio of allylnaphthols exceeds this range. , The co-condensation reaction does not proceed smoothly.

The cocondensation reaction for obtaining the allylnaphthol cocondensation product of the present invention is carried out only by heating to a high temperature in order to facilitate the control of the number of naphthalene nuclei.
In this case, the reaction temperature is preferably 60 to 180 ° C, and particularly preferably 80 to 160 ° C. Reaction is usually 1-1
It will be finished in about 0 hours. If necessary, a catalyst such as acid or base may be used.

Although the reaction can be carried out without a solvent, it is preferable to use a solvent having a boiling point of 80 ° C. or higher and a low solubility in water, such as toluene, xylene or methyl isobutyl ketone.

After completion of the reaction, impurities may be removed by washing with water or the solvent and unreacted materials may be removed under reduced pressure, if necessary.

In the case of Method B, naphthols and methyl group-substituted phenols (α-naphthol and β as necessary) are used.
-Naphthol) and the above-mentioned aldehydes are used to synthesize a condensate in advance by the above-mentioned condensation method or the like, and then allylation is performed by the above-mentioned allylation method (1), (2), (3), The cocondensate of the present invention having the desired molecular structure is obtained.

When the allylnaphthol cocondensate of the present invention is used as a curing agent for an epoxy resin, it may be used alone, but it may be a compound having two or more, preferably three or more phenolic hydroxyl groups in the molecule. It can also be used in combination with another curing agent. As other curing agents, for example, phenol or a substituted phenol (o-cresol, p-cresol, t-butylphenol, cumylphenol, phenylphenol, etc.) and an aldehyde compound are reacted in the presence of an acid catalyst or a basic catalyst. Examples thereof include a usual phenol resin made to react; a reaction product of resorcin and an aldehyde compound; polyvinylphenol and the like. The proportion of other curing agents is 70% by weight or less, preferably 50% by weight, based on the total curing agents.
It is the following.

The type of epoxy resin is not particularly limited, and conventionally known ones can be used. Examples thereof include bisphenol type, phenol novolac type, and cresol novolac type epoxy resins. Among these resins, those having a melting point exceeding room temperature and exhibiting a solid state or a highly viscous solution state at room temperature bring about good results.

The bisphenol type epoxy resin usually has an epoxy equivalent of 160 to 200 and a melting point of 50 to 1.
The one having an epoxy equivalent of 180 to 300 and the melting point of 50 to 130 ° C. is used as the phenol novolac type epoxy resin, and the epoxy equivalent of the cresol novolac type epoxy resin is 180 to 21.
Those having a melting point of 0 and a melting point of 60 to 110 ° C. are generally used.

The ratio of the epoxy resin to the curing agent is such that the equivalent ratio of the phenolic hydroxyl group of the curing agent to the epoxy group of the epoxy resin (epoxy group / phenolic hydroxyl group) is usually 1 / 0.8 to 1.2, preferably The range of 1 / 0.9 to 1.1 is preferable. When the epoxy resin and the curing agent are used in such a ratio, a cured product having excellent heat resistance and moisture resistance can be obtained.

As the curing accelerator, a usual curing catalyst can be used, and the type thereof is not particularly limited. Specific examples of the curing accelerator include, for example, triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p.
-Phosphorus compounds such as tolylphosphine and triphenyl phosphite; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole; 2 -Tertiary amines such as dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzylmethylamine; 1,5-diazabicyclo [4.3.0] -5-nonene, 1,4-diazabicyclo [2.2. 2] Octane, organic bases of 1,8-diazabicyclo [5.4.0] -7-undecene, and the like.

The addition amount of the curing accelerator is preferably 0.1 to 3.0% by weight in the epoxy resin composition from the viewpoint of heat resistance and moisture resistance.

The epoxy resin composition of the present invention may contain additives as required. Examples of the additive include a filler, a surface treatment agent for treating the surface of the filler, a flame retardant, a release agent, a colorant, and a flexibility-imparting agent.

The kind of the filler is not particularly limited, and examples thereof include crystalline silica powder, fusible silica powder, quartz glass powder,
Talc, calcium silicate powder, zirconium silicate powder,
Examples thereof include alumina powder and calcium carbonate powder. Among these fillers, silica-based fillers are preferable. The proportion of filler is 60 to 90% by weight of the total composition, preferably 7%.
It is 0 to 85% by weight. If the compounding amount of the filler exceeds 90% by weight, the fluidity of the composition is lowered and molding becomes difficult, and if it is less than 60% by weight, thermal expansion tends to increase.

Examples of the surface treatment agent include known silane coupling agents, and examples of the flame retardant include antimony trioxide, antimony pentoxide, phosphate and bromide. Examples of the release agent include various waxes,
Carbon black etc. are mentioned as a coloring agent.
The flexibility-imparting agent includes, for example, silicone resin and butadiene-acrylonitrile rubber.

The method for preparing the epoxy resin composition of the present invention is not particularly limited and can be carried out according to a conventional method. In addition, conditions for encapsulating a semiconductor using the resin composition of the present invention can be appropriately selected and are not particularly limited. Explaining specifically an example of the sealing condition, for example, 175
Molding for 3 minutes at 100 ℃ / molding pressure 100kg / cm ² and
For example, after-curing at 80 ° C. for 5 hours. Usually, it is formed by transfer molding.

[0045]

EXAMPLES The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The analysis and identification of the compound were carried out by gel permeation chromatography (GPC method) and nuclear magnetic resonance spectrum (NMR). Below G
The measurement conditions of PC and NMR are shown.

(GPC analysis) Solvent: Tetrahydrofuran Flow rate: 0.8 ml / min Column: G4000H, G3000 manufactured by Tosoh Corporation
H and G2000H (series) with exclusion limit molecular weights of 400,000, 60,000 and 10,000, respectively.
Is. Carrier: Styrene / divinylbenzene copolymer (NMR) The NMR spectrum of the synthesized product was confirmed as being assigned to the following.

[Chemical 5]

Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, 144 g (1 mol) of α-naphthol, 440 g of a 10% aqueous sodium hydroxide solution and 144 g of methyl isobutyl ketone were charged. Then, the mixture was heated to 80 ° C. with stirring to homogenize it to form a phenolate. To this reaction solution, 84.2 g (1.1 mol) of allyl chloride was added dropwise using a dropping funnel over 3 hours, and after completion of the addition, the mixture was stirred for 1 hour to react. After the reaction was completed, the reaction mixture was separated and washed with water, and the solvent was completely distilled off under reduced pressure. Next, the obtained reaction product was transferred to a reaction vessel, heated to 140 ° C. and stirred for 2 hours to cause a reaction to obtain allylnaphthol (OH group equivalent 184).

61 g of the above allylnaphthol was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet.
(0.33 mol), o-cresol 72 g (0.66 mol) and paraformaldehyde 19.5 g (0.65 mol).
Mol and formaldehyde conversion (allylnaphthol and o
-Total cresol: paraformaldehyde = 1: 0.
65 (molar ratio)) was charged, and the mixture was heated to 140 ° C. and stirred under a nitrogen stream for 3 hours to cause a reaction. Next, the mixture was heated to 200 ° C. and the unreacted material and water were removed under reduced pressure to obtain an allylnaphthol cocondensate represented by the following formula. This compound has a melting point of 51 ° C. and a melt viscosity at 150 ° C. of 0.3 poise (hereinafter P
It was low and it was excellent in work performance. (In the following Examples and Comparative Examples, viscosity measurements were all made at 150 ° C.) Weight average molecular weight (GPC
Method, the same applies hereinafter) is 440 and the OH group equivalent is 145
Met.

[0050]

[Chemical 6]

Example 2 The same arylnaphthol 6 synthesized in the previous stage of Example 1.
1 g (0.33 mol), o-cresol 72 g (0.6
6 mol), 71 g of benzaldehyde (total of allylnaphthol and o-cresol: benzaldehyde = 1: 0.
66 (molar ratio)) and 0.2 g of hydrochloric acid are charged.
A cocondensate was produced in the same manner as in Example 1. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 61 ° C. and a low viscosity of 1.4 P, and was excellent in workability. The weight average molecular weight was 560 and the OH group equivalent was 184.

[0052]

[Chemical 7]

Example 3 The same arylnaphthol 6 as synthesized in the previous stage of Example 1.
1 g (0.33 mol), o-cresol 72 g (0.6
6 mol), p-hydroxybenzaldehyde 81.3 g
(Total of allylnaphthol and o-cresol: p-hydroxybenzaldehyde = 1: 0.66 (molar ratio)),
A cocondensate was produced in the same manner as in Example 1 except that 0.3 g of toluenesulfonic acid and 80 g of xylene were charged. Xylene was removed under heating and reduced pressure after the reaction. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 78 ° C. and a viscosity as low as 0.8 p and was excellent in workability. Weight average molecular weight is 650, OH group equivalent is 13
It was 2.

[0054]

[Chemical 8]

Example 4 73.2 g (0.4 mol) of the same allylnaphthol and 64.8 of o-cresol that were synthesized in the previous stage of Example 1 were used.
A cocondensate was produced in the same manner as in Example 3 except that 34 g of terephthalaldehyde was used instead of p-hydroxybenzaldehyde by using g (0.6 mol). The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 82 ° C. and a viscosity as low as 0.8 P and was excellent in workability. Weight average molecular weight is 700, OH group equivalent is 177
Met.

[0056]

[Chemical 9]

Example 5 A cocondensate was produced in the same manner as in Example 1 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 52 ° C. and a low viscosity of 0.2 P, and was excellent in workability. Weight average molecular weight is 450, OH group equivalent is 144
Met.

[0058]

[Chemical 10]

Example 6 A cocondensate was produced in the same manner as in Example 2 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 58 ° C. and a low viscosity of 0.8 P, and was excellent in workability. Weight average molecular weight is 550, OH group equivalent is 182
Met.

[0060]

[Chemical 11]

Example 7 A cocondensate was produced in the same manner as in Example 3 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 82 ° C. and a viscosity as low as 0.6 P, and was excellent in work performance. Weight average molecular weight is 640, OH group equivalent is 130
Met.

[0062]

[Chemical 12]

Example 8 A cocondensate was produced in the same manner as in Example 4 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 81 ° C. and a viscosity as low as 0.6 P and was excellent in workability. Weight average molecular weight is 710, OH group equivalent is 172
Met.

[0064]

[Chemical 13]

Example 9 A cocondensate was produced in the same manner as in Example 1 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 48 ° C. and a low viscosity of 0.2 P, and was excellent in workability. Weight average molecular weight is 440, OH group equivalent is 142
Met.

[0066]

[Chemical 14]

Example 10 A cocondensate was produced in the same manner as in Example 2 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 55 ° C. and a viscosity as low as 0.6 P, and was excellent in workability. Weight average molecular weight is 530, OH group equivalent is 180
Met.

[0068]

[Chemical 15]

Example 11 A cocondensate was produced in the same manner as in Example 3 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 76 ° C. and a low viscosity of 0.5 P, and was excellent in workability. The weight average molecular weight is 630 and the OH group equivalent is 128.
Met.

[0070]

[Chemical 16]

Example 12 A cocondensate was produced in the same manner as in Example 4 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 80 ° C. and a low viscosity of 0.5 P, and was excellent in workability. Weight average molecular weight is 700, OH group equivalent is 170
Met.

[0072]

[Chemical 17]

[0073] Example 13 3,5-xylenol 81. instead of o-cresol 81.
A cocondensate was produced in the same manner as in Example 1 except that 3 g was used. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 42 ° C. and a low viscosity of 0.1 P,
It had excellent workability. Weight average molecular weight is 470, O
The H group equivalent was 154.

[0074]

[Chemical 18]

Example 14 Instead of o-cresol, 3,5-xylenol 81.
A cocondensate was produced in the same manner as in Example 2 except that 3 g was used. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 48 ° C. and a low viscosity of 0.3 P,
It had excellent workability. Weight average molecular weight is 590, O
The H group equivalent was 194.

[0076]

[Chemical 19]

Example 15 3,5-xylenol 81.
A cocondensate was produced in the same manner as in Example 3 except that 3 g was used. The obtained allylnaphthol cocondensate (shown by the following formula) has a low melting point of 68 ° C. and a viscosity of 0.5 P,
It had excellent workability. Weight average molecular weight is 670, O
The H group equivalent was 141.

[0078]

[Chemical 20]

Example 16 61 g of 3,5-xylenol instead of o-cresol
A cocondensate was produced in the same manner as in Example 4 except that The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 71 ° C. and a viscosity of 0.6 P and was excellent in workability. The weight average molecular weight was 720 and the OH group equivalent was 185.

[0080]

[Chemical 21]

Comparative Example 1 144 g of α-naphthol and paraformaldehyde 2 were used without using the allylnaphthol synthesized in the previous stage of Example 1.
A condensate was produced in the same manner as in Example 1 except that 2 g was used. The obtained condensate has a melting point of 86 ° C and a viscosity of 1
High as 8.3P, poor fluidity, and poor workability.
The weight average molecular weight was 1280 and the OH group equivalent was 165.

Comparative Example 2 Instead of paraformaldehyde, formalin water (37
%) And 0.5 g of paratoluene sulfonic acid were used to produce a condensate in the same manner as in Comparative Example 1. The obtained condensate has a high melting point of 131 ° C. and a viscosity of 76P.
Poor fluidity and poor workability. The weight average molecular weight was 1320 and the OH group equivalent was 178.

Comparative Example 3 An allylnaphthol cocondensate was prepared in the same manner as in Example 1 except that 122.6 g (0.66 mol) of allylnaphthol and 35.6 g (0.33 mol) of o-cresol were charged. Obtained. The resulting product contained 30.6 g of unreacted allylnaphthol and had an OH group equivalent of 170.

Examples 17 to 32 and Comparative Examples 4 to 5 The following epoxy resins, curing agents, curing accelerators, fillers, antimony trioxide, silane coupling agents, waxes and carbon blacks are shown in Tables 1 to 4. Was mixed in a proportion (parts by weight) shown in (1), kneaded with a two-roll mill at a temperature of 70 to 110 ° C., then cooled and pulverized to prepare an epoxy resin composition for semiconductor encapsulation.

Epoxy resin: o-cresol novolac type epoxy resin (epoxy equivalent 195, melting point 85 ° C.) brominated phenol novolac type epoxy resin (epoxy equivalent 280, melting point 83 ° C.) Curing agent: Examples 1 to 16 and Comparative Examples Co-condensation product obtained in No. 3 Phenol novolac resin (hydroxyl group equivalent 106, melting point 8
0 ° C.) Curing accelerator: Triphenylphosphine filler: Spherical silica (BF1 of Mitsubishi Metals Co., Ltd.)
00)

The composition obtained was treated at 175 ° C. and 100 kg.
/ Cm ² , molded under curing conditions of 3 minutes, then 180
A post-cure was performed under the conditions of ° C and 6 hours to prepare a molded test piece. This test piece is an 80-pin four-way flat package (80-pin QFP, size 20 x 14 x 2 mm)
And the die pad size is 8 × 8 mm.

The semiconductor device thus obtained was subjected to a TCT test of −50 ° C./5 minutes to 150 ° C./5 minutes to check the number of cracks. In addition, the test piece,
A crack resistance test was performed by allowing the sample to stand in a constant temperature bath having a relative humidity of 85 ° C./85% RH to absorb moisture, and then immersing it in a solder melt at 260 ° C. for 10 seconds. The results are shown in Tables 5 to 8.

The bending strength (high temperature strength) at 200 ° C. of the obtained test piece, the glass transition temperature, the coefficient of thermal expansion,
The water absorption was examined after a humidification test at 85 ° C./85% RH for 500 hours. The results are shown in Tables 9-12.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Table 5]

[0094]

[Table 6]

[0095]

[Table 7]

[0096]

[Table 8]

[0097]

[Table 9]

[0098]

[Table 10]

[0099]

[Table 11]

[0100]

[Table 12]

[0101]

The allylnaphthol cocondensate of the present invention is
Has a low melting point and melt viscosity, and has excellent workability. When it is used as a curing agent for epoxy resin, the obtained epoxy resin cured product has a high glass transition temperature, heat resistance and moisture resistance, and cracks are less likely to occur in the package even during soldering.

A cured product of the epoxy resin composition of the present invention containing this allylnaphthol cocondensation product as a curing agent has a high glass transition temperature and excellent heat resistance, a large mechanical strength, a small water absorption rate and a moisture resistance. Excellent in occurrence of cracks even during soldering. Therefore, the epoxy resin composition of the present invention is useful as a semiconductor encapsulating composition.

Claims (4)

[Claims] 1. An allylnaphthol cocondensate represented by the following general formula (I) and having a weight average molecular weight of 300 to 2,000. [Chemical 1] 2. An allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000 represented by the following general formula (II). [Chemical 2] 3. An allylnaphthol cocondensation product having a weight average molecular weight of 300 to 2000, obtained by cocondensing allylnaphthols, methyl group-substituted phenols and aldehydes, wherein allyl is calculated by excluding aldehydes. An allylnaphthol cocondensate in which the proportion of naphthols is 10 to 50 mol%. 4. An epoxy resin composition comprising the allylnaphthol cocondensate according to any one of claims 1 to 3 and an epoxy resin.