JPH0649181A - Production of phenol resin, and epoxy resin composition and semiconductor-sealing epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a phenol resin useful as a curative of an epoxy resin for a sealing material, a laminated board, etc. CONSTITUTION:A phenol resin is obtd. by reacting at least one unsatd. cyclic hydrocarbon selected from the group consisting of 4-vinylcyclohexene, 5- vinylnorborn-2-ene, 3a,4,7,7a-tetrahydroindene, dicyclopentadiene, alpha-pinene, beta- pinene, and limonene with at least one hydroxylated condensed polycyclic arom. compd. in the presence of an acid catalyst. The phenol resin is compounded as a curing agent with a curable epoxy resin to give an epoxy resin compsn. for semiconductor sealing, which has high reactivity, curing rate, moisture resistance, and Tg, and is free from interfacial degradation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a phenol resin useful as a curing agent for epoxy resins for encapsulating materials and laminates, and mechanical properties, electrical properties, moisture resistance, and heat resistance containing phenol resin as an essential component. The present invention relates to an epoxy resin composition excellent in impact resistance and the like, and an epoxy resin composition for semiconductor encapsulation.

[0002]

2. Description of the Related Art Recently, science and technology have been rapidly advancing mainly in the electronics industry, and in particular, semiconductor-related technology has been remarkably advancing. In semiconductors, wiring is becoming finer and chips are becoming thinner with the increase in the degree of integration of memory. With the improvement in the degree of integration, the mounting method is also shifting from through-hole mounting to surface mounting.

In the automated surface mounting line, the semiconductor package undergoes a rapid temperature change during soldering of the lead wires, which causes cracks in the resin molding portion and deterioration of the interface between the lead wire resins. As a result, there is a problem that the moisture resistance is lowered.

In order to solve the above-mentioned problems, methods such as addition of silicone compounds, addition of thermoplastic oligomers or silicone modification have been proposed for the purpose of mitigating thermal shock when the semiconductor package is immersed in a solder bath. However, in any of the methods, a crack is generated in the molded product after dipping the solder, and a reliable resin composition for semiconductor encapsulation cannot be obtained.

In the semiconductor resin composition, a phenol resin is mainly used as a curing agent for the epoxy resin, and as the phenol resin, a novolac phenol resin or a novolac cresol resin is generally used. However, when the novolac phenol resin is used, the semiconductor package has a strong hygroscopic property, and as a result, there is a problem that cracks cannot be avoided when the solder bath is immersed. Therefore, recently, in order to improve the heat resistance of the resin for semiconductor encapsulation, some attempts have been proposed to improve the phenol resin which is a curing agent for the epoxy resin composition.

For example, a dicyclopentadiene-modified phenol resin has been proposed as a heat-resistant phenol resin having excellent moisture resistance (Japanese Patent Laid-Open No. 62-201922). However, the above-mentioned dicyclopentadiene modified product has a problem that the reactivity is low and the moldability is poor, and there is a problem that heat resistance and moisture resistance, particularly heat resistance are not sufficient.

[0007]

The object of the present invention is to use an epoxy resin having a high reactivity, a high curing rate, a high glass transition point and an excellent moisture resistance by using a specific phenol resin as a curing agent. It is to provide a resin composition.

Another object of the present invention is to provide an epoxy resin composition for semiconductor encapsulation which is excellent in mechanical properties, electrical properties, moisture resistance, heat resistance and the like, and which does not cause cracks and interface deterioration due to rapid temperature changes. To provide.

[0009]

According to the present invention, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4,7,7a-tetrahydroindene, dicyclopentadiene, α-in the presence of an acid catalyst. An unsaturated cyclic hydrocarbon compound selected from the group consisting of pinene, β-pinene and limonene, or a mixture of two or more kinds of the unsaturated cyclic hydrocarbon compounds, and a hydroxyl group-containing condensed polycyclic aromatic compound or its 2 A method for producing a phenolic resin is provided, which comprises reacting with a mixture of one or more species.

According to the present invention, there is also provided an epoxy resin composition containing (a) a curable epoxy resin, (b) a phenol resin obtained by the above-mentioned production method, and (c) a curing accelerator as essential components.

Further, according to the present invention, a semiconductor encapsulation containing (a) a curable epoxy resin, (b) a phenol resin obtained by the above-mentioned production method, (c) a curing accelerator and (d) an inorganic filler as essential components. A stopping epoxy resin composition is provided.

The present invention will be described in more detail below.

The method for producing a phenolic resin of the present invention is characterized in that a specific unsaturated cyclic hydrocarbon compound is reacted with a hydroxyl group-containing condensed polycyclic aromatic compound in the presence of an acid catalyst.

The unsaturated cyclic hydrocarbon compound used as a raw material component in the production method of the present invention is 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a,
Examples include 4,7,7a-tetrahydroindene, dicyclopentadiene, α-pinene, β-pinene, and limonene, and these may be used as a mixture of two or more kinds. In the other raw material component, a hydroxyl group-containing condensed polycyclic aromatic compound or a mixture of two or more thereof,
The hydroxyl group-containing condensed polycyclic aromatic compound is a compound having a hydroxyl group in the molecular skeleton and having a plurality of benzene rings sharing a π electron cloud, and is not particularly limited, and examples thereof include α-naphthol. , Β-naphthol,
1,1-bis (hydroxynaphthyl) methane, dihydroxynaphthalene and the like can be mentioned. At this time, dihydroxynaphthalene is 1,6-, 1,5-, 2,6-, 2,7
Any isomer of − and 2,3-can be used.

The unsaturated cyclic hydrocarbon compound or 2
Charge for reacting a mixture of two or more species (hereinafter referred to as "(A) component") with a hydroxyl group-containing condensed polycyclic aromatic compound or a mixture of two or more species thereof (hereinafter referred to as "(B) component") The ratio is preferably such that the charged amount of the component (B) is 0.8 to 12 times the molar equivalent of the charged amount of the component (A), and more preferably 1 to 5 times the molar equivalent.
Charge ratio of the component (B) to the component (A) is 0.8 to 1.
When the amount is 2 times the molar equivalent, the molecular weight can be adjusted within an appropriate range, the melt viscosity can be reduced, and the heat resistance and the humidity resistance can be improved.

Further, in the present invention, phenol, cresol or the like may be used in combination with these raw material components.

The molecular structure and the molecular weight of the phenolic resin obtained by the production method of the present invention are not particularly limited, but the molecular weight is preferably 268 to 6000, particularly preferably 268 to 2,000. Preferable examples thereof include a phenol resin represented by the following general formula 1.

[0018]

[Chemical 1]

More specifically, phenolic resins represented by the following structural formulas 2 to 9 can be preferably mentioned.

[0020]

[Chemical 2]

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

Examples of the acid catalyst used in the method for producing a phenol resin of the present invention include boron trifluoride, boron trifluoride ether, boron trifluoride complex such as phenol, water, amine or alcohol complex, aluminum trichloride,
Aluminum compounds such as diethyl aluminum monochloride, iron chloride, titanium tetrachloride, sulfuric acid, hydrogen fluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid,
Zeolite catalysts, various metals such as magnesium, calcium, strontium, barium, boron, aluminum, gallium, selenium, platinum, rhenium, nickel,
Cobalt, iron, copper, germanium, rhodium, osmium, iridium, molybdenum, tungsten, silver or a mixture thereof and a solid acid composed of zeolite or a mixture thereof can be preferably used. In particular, from the viewpoint of activity and easy removal of catalyst, boron trifluoride, boron trifluoride / ether complex, boron trifluoride / phenol complex, boron trifluoride / water complex, boron trifluoride / alcohol complex, Boron fluoride / amine complex is preferable, and boron trifluoride and boron trifluoride / phenol complex are most preferable.

In the production method of the present invention, although the amount of the acid catalyst used varies depending on the catalyst used, the component (A) component 1
0.01 to 50 parts by weight is preferable with respect to 00 parts by weight,
Specifically, for example, in the case of a boron trifluoride / phenol complex, 0.1 to 20 parts by weight is preferable, and particularly preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the unsaturated cyclic hydrocarbon compound.
It is 5 to 10 parts by weight.

The production method of the present invention can be carried out with or without a solvent. When no solvent is used, the charged amount of the component (B) is the charged amount of the component (A). On the other hand, it is preferable to use 1-fold molar equivalent or more, and particularly 3 to 8-fold molar equivalent. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit the reaction, and specific examples thereof include benzene, toluene, and aromatic hydrocarbon compounds such as xylene. be able to. At this time, the amount of the solvent used is preferably 20 to 300 parts by weight with respect to 100 parts by weight of the unsaturated cyclic hydrocarbon compound. The reaction conditions vary depending on the type of catalyst used, but are preferably 10 to 200 ° C.
30 minutes to 7 hours, specifically 20 to 160 ° C., preferably 5 for boron trifluoride / phenol complex.
It is in the range of 0 to 150 ° C. The reaction temperature is 10 to 20
When the temperature is in the range of 0 ° C, the catalyst does not decompose, side reactions can be prevented, and the reaction time can be shortened.

In order to make the reaction proceed smoothly in the production method of the present invention, it is preferable to reduce the water content in the system as much as possible, and it is particularly preferable to keep the water content at 100 ppm by weight or less. Further, since this reaction is accompanied by remarkable heat generation, it is preferable to carry out by a method of sequentially adding the unsaturated cyclic hydrocarbon compound from the viewpoint of safety.

After completion of the reaction, the desired phenol resin can be obtained by removing the catalyst from the reaction solution and then concentrating the reaction solution. The method for removing the catalyst varies depending on the type of the catalyst used. For example, in the case of boron trifluoride / phenol complex, potassium hydroxide, magnesium hydroxide, hydrotalcites, etc. are added in a molar amount 1 to 10 times that of the catalyst. After deactivating the catalyst, the catalyst can be filtered, deactivated with an aqueous alkali solution such as caustic soda water, or washed. In the filtration, the workability can be improved by adding a solvent or by increasing the temperature of the filtrate.

The epoxy resin composition of the present invention comprises (a) a curable epoxy resin (hereinafter referred to as "component (a)"), (b) a phenol resin obtained by the above production method (hereinafter referred to as "component (b)"), (C) A curing accelerator (hereinafter referred to as "component (c)") is contained as an essential component.

The curable epoxy resin used as the component (a) in the epoxy resin composition of the present invention is a resin having at least one, preferably two or more epoxy groups in the molecule, such as epichlorohydrin and bisphenol A. Epoxy resin synthesized from novolac resin, alicyclic epoxy resin such as dicyclopentadiene, monocyclodiene compound such as vinylcyclohexene, tetramethylbisphenol diglycidyl ether, triglycidyl isocyanurate, special epoxy resin such as tetraglycidyl diaminodiphenylmethane and Epoxy resins in which halogen atoms such as chlorine atom or bromine atom are introduced into these epoxy resins can be mentioned. When used, they can be used alone or as a mixture of two or more of these epoxy resins. It can be. Moreover, a commercial item can also be used as said (a) component, for example, as a novolac epoxy resin, it is a brand name "Epiclon N-66.
0 "(manufactured by Dainippon Ink and Chemicals, Inc.)," Sumiepoxy ESCN-195X "(manufactured by Sumitomo Chemical Co., Ltd.),
"QUATREX 2410" (Dow Chemical Co., Ltd.)
Manufactured), "EOCN-100" (manufactured by Nippon Kayaku Co., Ltd.),
"YDCN-702P" (manufactured by Tohto Kasei Co., Ltd.), special epoxy resins include "YX-4000" (manufactured by Yuka Shell Epoxy Co., Ltd.), "EPICLON EXA-15".
14 "," EPICLON HP-4032 "," EPI
CLON EXA-1857 "(manufactured by Dainippon Ink and Chemicals, Inc.)," Epicoat 157S65 "," Epicoat YL933 "(manufactured by Yuka Shell Epoxy Co., Ltd.)," V "
G-3101 "(manufactured by Mitsui Petrochemical Co., Ltd.) and the like.

The phenolic resin used as the component (b) in the epoxy resin composition of the present invention is not particularly limited as long as it is a phenolic resin obtained by the above-mentioned production method of the present invention, but preferably the above general formula 1
And a phenolic resin having a molecular weight of 268 to 2000. Further, as the above-mentioned phenol resin, it is also possible to use the one in which the phenol resin is not isolated and which contains an unreacted material or a reaction material other than the phenol resin as it is.

The curing accelerator of the component (c) used in the epoxy resin composition of the present invention may be any one that accelerates the reaction between the epoxy group and the phenolic hydroxyl group, and is generally used for semiconductor encapsulation. For example, tertiary phosphines, imidazoles, tertiary amines and the like can be used. Specifically, examples of the tertiary phosphines preferably include triethylphosphine, tributylphosphine, triphenylphosphine, and the like. Examples of the tertiary amine include dimethylethanolamine, dimethylbenzylamine, 2,
4,6-Tris (dimethylamino) phenol, 1,8
-Diazabicyclo [5.4.0] undecene and the like can be preferably mentioned. As the imidazoles,
For example, 2-ethyl-4-methylimidazole, 2,4-
Dimethyl imidazole, 2-methyl imidazole, 2-
Undecyl imidazole, 2-heptadecyl imidazole, 1-vinyl-2-methyl imidazole, 1-propyl-2-methyl imidazole, 2-isopropyl imidazole, 1-cyanoethyl-2-ethyl imidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole,
1-Cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-
Phenyl-4,5-dihydroxymethylimidazole,
2-Phenyl-4-methyl-5-hydroxymethylimidazole and the like can be mentioned. Particularly preferable examples of the component (c) include 2-methylimidazole, diazabicycloundecene (DBU), triphenylphosphine, dimethylbenzylamine, and mixtures thereof.

The mixing ratio of each of the components (a) to (c) used in the epoxy resin composition of the present invention is 100 parts of the component (a).
The component (b) is preferably 20 to 180 parts by weight, more preferably 30 to 120 parts by weight, and the component (c) is preferably 0.01 to 7.0 parts by weight, more preferably 0.5 to 100 parts by weight. ~ 5.0 parts by weight.

The epoxy resin composition for semiconductor encapsulation of the present invention further contains (d) an inorganic filler (hereinafter referred to as "component (d)") as an essential component in addition to the components (a) to (c). It is characterized by doing.

In the epoxy resin composition for semiconductor encapsulation of the present invention, as the components (a), (b) and (c) used as essential components, any of the resins and compounds listed in the above epoxy resin composition is used. It can be preferably used. As the inorganic filler used as the component (d), silica powder filler or the like can be generally preferably used. The silica powder filler may be melted before use.

The compounding ratio of each of the components (a) to (d) used in the epoxy resin composition for semiconductor encapsulation of the present invention is (a).
The component (b) is preferably 20 per 100 parts by weight of the component.
To 180 parts by weight, more preferably 30 to 120 parts by weight, component (c) is preferably 0.01 to 7.0 parts by weight,
It is more preferably 0.5 to 5.0 parts by weight, and the blending ratio of the component (d) is preferably 50 to 90% by weight, more preferably 65% by weight, based on the entire epoxy resin composition for semiconductor encapsulation. To 85% by weight.

The epoxy resin composition for semiconductor encapsulation of the present invention contains the components (a) to (d) as essential components, but may contain a phenol resin other than the component (b) if necessary. It can also be included. Examples of the phenol resin other than the component (b) include trade names "Tamanol-758", "Tamanol-759" (manufactured by Arakawa Chemical Industry Co., Ltd.), "ECN-1280" (manufactured by Ciba Geigy Co., Ltd.) and the like. Novolak type phenol resin, brominated novolak type phenol resin, polyvinylphenol,
Examples thereof include polyhydric phenol compounds such as brominated polyvinylphenol and tetrabromobisphenol A. The amount of the phenol resin other than the component (b) used is
100 parts by weight or less based on 100 parts by weight of the component (b),
In particular, it is preferably 50 parts by weight or less. If the amount used exceeds 100 parts by weight, the moisture resistance deteriorates, which is not preferable.

The epoxy resin composition for semiconductor encapsulation of the present invention includes a silane coupling agent, a brominated epoxy resin,
Flame retardants such as antimony trioxide and hexabromobenzene,
Various additives such as colorants such as carbon black and red iron oxide, releasing agents such as natural wax and synthetic wax, low stress additives such as silicone oil and rubber, and the like can be appropriately added.

In order to prepare a molding material using the epoxy resin composition for semiconductor encapsulation of the present invention, after the essential components and, if necessary, other additives are sufficiently mixed with a mixer or the like. Alternatively, it can be obtained by melt-kneading with a hot roll or a kneader, and pulverizing after injection or cooling.

[0044]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these.

[0045]

Example 1 In a 5 liter reactor equipped with a reflux condenser and a Liebig condenser, 1442 g of α-naphthol was added.
And 700g of toluene were charged and heated to 160 ° C,
By azeotropic distillation with toluene, water in the system was dehydrated to 60 ppm and 250 g of toluene was distilled off.
Then, the system is cooled to 100 ° C. and boron trifluoride.
After 20 g of the phenol complex was added and homogenized, 330 g of dicyclopentadiene having a water content of 20 ppm was gradually added dropwise over 1.5 hours at a reaction temperature of 100 ° C., and the mixture was heated and stirred for another 2.5 hours after completion of the addition. . After completion of the reaction, 600 g of toluene, magnesium compound "KW-1000"
(Product name: Kyowa Chemical Industry Co., Ltd.) 80 g was added,
After stirring for 30 minutes to deactivate the catalyst, the reaction solution was filtered. The obtained transparent filtrate was distilled under reduced pressure at 240 ° C. using a thin film distillation apparatus to obtain 910 g of phenol resin (1).

The softening point of the obtained phenol resin (1) was 110 ° C. The equivalent of phenolic hydroxyl group determined by inverse titration after acetylation with acetic anhydride was 225 g / equivalent. Further, ¹ H-NMR analysis revealed δ 6.5.
Protons attached to the aromatic ring at ~ 8 ppm also have δ0.
Protons of the naphthene ring were observed at 8-2.5 ppm,
No absorption of protons bound to the double bond was observed. When the phenolic hydroxyl group equivalent was determined from the peak area ratio of δ 6.5 to 8 ppm and δ 0.8 to 2.5 ppm, it was 225 g / equivalent as above. Furthermore, gel permeation chromatography (hereinafter referred to as GPC)
The number average molecular weight of this resin was found by analysis to be 58
It was 0.

[0047]

Example 2 Reaction was carried out in the same manner as in Example 1 except that 1442 g of β-naphthol was used instead of α-naphthol and 270 g of 4-vinylcyclohexene was used instead of dicyclopentadiene, and the phenol resin (2) was used. 59
0 g was obtained.

The obtained phenol resin (2) had a softening point of 108 ° C. and a phenolic hydroxyl group equivalent of 211 g / equivalent. The number average molecular weight of this resin determined by GPC analysis was 550.

[0049]

Example 3 1,1-bis (hydroxynaphthyl) methane (1800 g) instead of α-naphthol, 3a, 4,7,7a-tetrahydroindene 120 g and 5-vinylnorborna-2 instead of dicyclopentadiene.
-The reaction was performed in the same manner as in Example 1 except that 120 g of ene was used. After the reaction was completed, 1000 g of toluene and 60 g of slaked lime were added to the reaction solution, the catalyst was deactivated by stirring, and the reaction solution was filtered and concentrated by vacuum distillation at 240 ° C. to obtain a hydroxyl group equivalent of 175 g / equivalent. (3) 2002g was obtained.

When the concentrate (3) was analyzed by GPC, 42% by weight of unreacted 1,1-bis (hydroxynaphthyl) methane in the concentrate (3) was 3a, 4,7,7a.
An adduct of one molecule of tetrahydroindene with one molecule of 1,1-bis (hydroxynaphthyl) methane and an adduct of one molecule of 5-vinylnorborna-2-ene with one molecule of 1,1-bis (hydroxynaphthyl) methane 7 % By weight, and 51% by weight of a polymer (phenol resin) of 3a, 4,7,7a-tetrahydroindene, 5-vinylnorborna-2-ene and 1,1-bis (hydroxynaphthyl) methane.

From the concentrate (3), unreacted 1,1-bis (hydroxynaphthyl) was detected by column chromatogram.
After removing the methane and the adduct, the phenolic hydroxyl group equivalent of the obtained polymer was analyzed by the same method as in Example 1 and found to be 187 g / equivalent. The number average molecular weight of the polymer was analyzed by using a mass spectrometer.
It was 72.

[0052]

Example 4 1600 g of 1,6-dihydroxynaphthalene was used instead of α-naphthol, and an unsaturated hydrocarbon solution consisting of 90 g of α-pinene, 80 g of β-pinene and 90 g of limonene was used instead of dicyclopentadiene. The reaction was carried out in the same manner as in Example 1. After the reaction was completed, 1000 g of toluene was added, and the reaction solution was deactivated with 1000 g of a 2 wt% potassium hydroxide aqueous solution. After washing with water, the reaction solution was concentrated by distillation under reduced pressure at 240 ° C. to obtain 965 g of a phenol resin (4) which was an adduct with α-pinene, β-pinene and limonene. The hydroxyl group equivalent of this phenol resin (4) was 125 g / equivalent. The number average molecular weight of this resin measured by a mass spectrometer was 521.

[0053]

Example 5 Phenolic resin (1) produced in Example 1
51 g, novolac epoxy resin (trade name "Epiclon N-660", manufactured by Dainippon Ink and Chemicals, Inc.) 49
g, 0.2 g of triphenylphosphine, 353 g of fused silica powder (trade name "FUUSELEX RD-8", manufactured by Tatsumori Co., Ltd.), and the additive shown in Table 1 were prepared, and the composition The product was melt-kneaded at 85 ° C. for 10 minutes using a kneader, cooled and pulverized to obtain an epoxy resin molding material.

The obtained molding material was tabletted, and the tabletted molding material was sealed with a low-pressure transfer molding machine under the conditions of 175 ° C., 70 kg / cm ² , 120 seconds, and then 180 ° C. for 5 hours. Post-cured. still,
The mold releasability during transfer molding was good. 6 x 6 for solder crack test using the obtained cured product
mm chip is sealed in a 52p package, and for solder moisture resistance test, a 6x6mm chip is 16pSOP
A test element was manufactured by sealing in a package. The following solder crack test and solder moisture resistance test were performed on the sealed test element. The results are shown in Table 1.

Solder crack test: The sealed test element was treated in an environment of 85 ° C. and 85% RH for 48 hours and 72 hours, then immersed in a solder bath at 280 ° C. for 10 seconds, and external cracks were observed with a microscope. .

Solder moisture resistance average life (hours); the sealed test element was treated for 48 hours and 72 hours in an environment of 85 ° C. and 85% RH, and then immersed in a solder bath of 280 ° C. for 10 seconds and then pressure cooker. Test (125 ℃, 100
% RH) and the time until 50% of the circuit oven defects occurred was measured.

[0057]

Examples 6 to 8 The same procedure as in Example 5 was repeated except that the phenol resins (2), (4) and the concentrate (3) produced in Examples 2 to 4 were used in place of the phenol resin (1). A molding material was obtained and each test was conducted. The results are shown in Table 1.

[0058]

[Comparative Example 1] The same procedure as in Example 5 was repeated except that the phenol resin (1) was replaced only with the phenol novolac resin (trade name "Tamanol 758" manufactured by Arakawa Chemical Industry Co., Ltd.) and the compounding ratios shown in Table 1 were used. Then, a molding material was obtained and a test was conducted.
The results are shown in Table 1.

[0059]

Comparative Example 2 Phenol 12 instead of α-naphthol
The reaction was carried out in the same manner as in Example 1 using 00 g. After completion of the reaction, 1000 g of toluene was added, and the reaction solution was deactivated with 500 g of a 2% aqueous potassium hydroxide solution. After washing with water, the reaction solution was concentrated by vacuum distillation at 240 ° C. to obtain a phenol resin (5) which is an adduct of dicyclopentadiene and phenol.
Was obtained. The hydroxyl equivalent of this phenol resin (5) was 170 g / equivalent.

A molding material was obtained and tested in the same manner as in Example 5 except that the above-synthesized phenol resin (5) was used in place of the phenol resin (1) and the compounding ratios shown in Table 1 were used. The results are shown in Table 1.

170 ° C., 70 kg / cm ² , 120
The sealed product obtained by transfer molding at ℃ was inferior in releasability.

[0062]

[Table 1]

[0063]

Example 9 Phenolic resin (1) obtained in Example 1
And the commercially available epoxy resin shown in Table 2 is mixed with the curing accelerator shown in Table 2 to obtain an epoxy resin composition, and then the solvent shown in Table 2 is mixed to obtain an epoxy resin varnish (resin component is 60% by weight). ), An E glass cloth was dipped in the epoxy resin varnish. 160 pieces of this varnish impregnated cloth
It was dried in a drying chamber at 0 ° C. for 4 minutes to obtain a B-stage prepreg.

The obtained prepreg was cut into 8 prepregs, 8 prepregs were further laminated, and two 35 μm-thick electrolytic copper foils were laminated on both sides to obtain 40 kg /
While pressurizing at cm ² , the laminate was heated at 175 ° C. for 120 minutes under pressure. Table 2 shows the physical properties of the obtained cured laminate.

[0065]

Examples 10 to 12 Instead of the phenol resin (1), the phenol resin (2) produced in Examples 2 to 4,
A laminate was prepared in the same manner as in Example 9 except that (4) and the concentrate (3) were used. The test results are shown in Table 2.

[0066]

Comparative Example 3 The same as Example 9 except that the phenol resin (1) was replaced only with the phenol novolac resin (trade name “Tamanol 758” manufactured by Arakawa Chemical Industry Co., Ltd.) and the compounding ratios shown in Table 2 were used. To produce a laminate. The test results are shown in Table 2.

[0067]

Comparative Example 4 A laminated board was prepared in the same manner as in Example 9 except that the phenol resin (5) synthesized in Comparative Example 2 was used in place of the phenol resin (1) and the compounding ratios shown in Table 2 were used. , A test was conducted. The results are shown in Table 2.

[0068]

[Table 2]

[0069]

INDUSTRIAL APPLICABILITY In the method for producing a phenol resin of the present invention,
Since an unsaturated cyclic hydrocarbon compound and a hydroxyl group-containing condensed polycyclic aromatic compound, both of which are industrially easily available, are used as raw material components and are reacted in the presence of an acid catalyst, a phenol resin is produced in good yield. The phenol resin thus obtained is useful for applications such as laminated boards for printed wiring boards, powder coating materials, phenol resin molding materials, and brake shoes.

Since the epoxy resin composition of the present invention contains the phenol resin obtained by the above-mentioned specific production method having excellent reactivity as a curing agent, the curing rate is high and the glass transition point Tg of the obtained cured product is high. The moisture resistance can be improved as well.

Since the epoxy resin composition for semiconductor encapsulation of the present invention contains the phenol resin obtained by the above-mentioned specific manufacturing method, the obtained molding material has excellent mechanical properties, electrical properties, heat resistance and moisture resistance. Therefore, it can be applied to the sealing of electronic parts such as transistors, diodes, LSIs and LEDs, or the covering and insulation of electric parts such as coils of transformers. Furthermore, the semiconductor package cured by using the epoxy resin composition for semiconductor encapsulation has excellent heat resistance, and even in the case of a rapid temperature change during soldering of lead wires, the occurrence of cracks in the resin molding portion, It is possible to prevent deterioration of the interface between the lead wire resins.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location H01L 23/29 23/31 (72) Inventor Yu Otsuki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Japan Petroleum Co., Ltd. Central Research Laboratory (72) Inventor Ichiro Ogura, No. 12, Yawata Kaigan Dori, Ichihara City, Chiba Dai Nippon Inki Chemical Industry Co., Ltd.

Claims (4)

[Claims] 1. 4-Vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4, 7, in the presence of an acid catalyst.
7a-tetrahydroindene, dicyclopentadiene,
An unsaturated cyclic hydrocarbon compound selected from the group consisting of α-pinene, β-pinene and limonene, or a mixture of two or more of the unsaturated cyclic hydrocarbon compounds, and a hydroxyl group-containing condensed polycyclic aromatic compound or A method for producing a phenol resin, which comprises reacting a mixture of two or more thereof. 2. The condensed polycyclic aromatic compound having a hydroxyl group is α-naphthol, β-naphthol, 1,1.
The method for producing a phenolic resin according to claim 1, wherein the phenolic resin is an aromatic hydroxyl group-containing compound selected from the group consisting of bis (hydroxynaphthyl) methane and dihydroxynaphthalene. 3. An epoxy resin composition comprising (a) a curable epoxy resin, (b) a phenol resin obtained by the production method according to claim 1, and (c) a curing accelerator as essential components. 4. A semiconductor-encapsulating epoxy containing (a) a curable epoxy resin, (b) a phenol resin obtained by the method according to claim 1, (c) a curing accelerator and (d) an inorganic filler as essential components. Resin composition.