JP3075496B2 - Polyphenol resin, polyphenol epoxy resin and production method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenol resin and a polyphenol epoxy resin useful as a highly reliable semiconductor encapsulating resin, and a method for producing the same.

[0002]

2. Description of the Related Art Compounds of phenols and naphthols are used in various fields as resin raw materials. In recent years, a large number of resins containing naphthols as main raw materials have been developed, and their cured products are highly evaluated for their physical properties such as heat resistance and moisture resistance.

In recent years, however, with the development of the electric and electronic fields in particular, further improvements in various properties such as heat resistance and moisture resistance have been demanded. Although many proposals have been made for agents and the like, resins that sufficiently satisfy these properties such as heat resistance and moisture resistance have not yet been developed.

[0004]

SUMMARY OF THE INVENTION The present invention provides a resin which can be used as a highly reliable resin for encapsulating a semiconductor which gives excellent heat resistance and moisture resistance in a cured product thereof, and a method for producing these resins. It is.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for imparting and improving the above-mentioned properties, and have found a novel resin containing naphthols and phenols and have completed the present invention. It is. That is, the present invention provides:

[0006]

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(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0 to 30). (2) Equation (2)

[0008]

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(In the formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 0 to 30 and G represents a glycidyl group. ), A polyphenol epoxy resin represented by the formula (3):
Equation (3)

[0010]

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(In the formula (3), R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A naphthol represented by the formula (4):

[0012]

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(In the formula (4), R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.) 2. The reaction of the formula (1) according to claim 1, wherein the halogen-containing phenol represented by the formula (1) is reacted with an alkali metal hydroxide, and if necessary, the reaction is carried out with epihalohydrin in the presence of an alkali metal hydroxide. And a method for producing a polyphenol epoxy resin represented by the formula (2).

In R ₁ and R ₂ of the formulas (1) to (4),
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a t-butyl group. X in the formula (4) includes a chlorine atom, a bromine atom and the like. Further, in the formulas (1) and (2), a preferable value of n is 0 to 5. In the formula (2), G represents a glycidyl group, that is, the formula (G).

[0015]

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In the present invention, the polyphenol resin represented by the above formula (1) comprises a naphthol represented by the above formula (3), a halogen-containing phenol represented by the formula (4), and an alkali metal hydroxide. Can be obtained by reacting Here, examples of the naphthols include 1-naphthol, 2-methyl-1-naphthol, 4-methyl-1-naphthol, 2-naphthol, and the like, and 1-naphthol is preferred in view of its reactivity.

As the halogen-containing phenols, 2,4-
Dibromophenol, 2,6-dibromophenol,
2,4-dibromo 6-methylphenol, 2,6-dibromo-4-methylphenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 2,4-dichloro6-
Methylphenol, 2,6-dichloro-4-methylphenol, 3,5-dichlorophenol and the like are used,
It is not limited to these, and it is particularly preferable to use a brominated product due to its reactivity.

As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide or the like is used as a solid or as an aqueous solution. These alkali metal hydroxides can be mixed in advance with a mixture of naphthols and halogen-containing phenols and reacted.However, it is necessary to react while adding to a mixture of molten naphthols and halogen-containing phenols. Can also. This reaction is usually performed at a temperature of 80 to 220 ° C. for 0.5 to 10 hours.

For example, a naphthol represented by the formula (3) and a halogen-containing phenol represented by the formula (4) are mixed and melted by heating, and then an alkali metal hydroxide such as sodium hydroxide is added. Then, a temperature of 80 to 220 ° C. is reacted. In this case, the naphthol is used in an amount of usually 2 to 10 mol, preferably 2.5 to 6 mol, per 1 mol of the halogen-containing phenol. The amount of the alkali metal hydroxide used is 1.5 to 1 mol of the halogen-containing phenol.
10 to 10 mol, preferably 1.9 to 2.2 mol.
This reaction is not only oxidized and colored in the presence of air (oxygen), but also easily produces ether. Therefore, it is preferable to perform the reaction in an atmosphere such as nitrogen.

Usually, these reactants are cooled in a temperature range that does not solidify, and after adding and dissolving a solvent such as toluene and methyl isobutyl ketone in an amount sufficient to dissolve the reaction products and unreacted materials, water is added. If necessary, neutralize the system so that the system becomes neutral, and further repeat washing with water, and then use a rotary evaporator or the like from the oil layer under reduced pressure to 150-
By distilling off the solvent and unreacted substances at 250 ° C., the polyphenol resin represented by the formula (1) can be obtained.

Reacting the polyphenol epoxy resin represented by the formula (2) and the polyphenol resin represented by the formula (1) with epihalohydrin in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Can be obtained. Epichlorohydrin, epipromhydrin, etc. are used as epihalohydrin,
Epichlorohydrin, which is easily available industrially and is inexpensive, is preferred. This reaction can be carried out according to a conventionally known method for obtaining a polyglycidyl ether from a novolak-type phenol resin and epihalohydrin.

That is, a solid of an alkali metal hydroxide is added to a mixture of a polyphenol resin and an excess of epihalohydrin, or the mixture is reacted at a temperature of 20 to 120 ° C. while adding the solid. In addition, an aqueous solution of the alkali metal hydroxide may be used. In such a case, the aqueous solution of the alkali metal hydroxide is continuously added, and water and epichloroform are continuously added under reduced pressure or normal pressure from the reaction system. A method may be employed in which rohydrin is distilled off, the liquid is separated, water is removed, and epihalohydrin is returned into the reaction system. The amount of epihalohydrin used is usually 1 to 20 with respect to 1 equivalent of phenolic hydroxyl group of polyphenol resin.
Mol, and the amount of the alkali metal hydroxide used is usually 0.1 to 1 equivalent of the phenolic hydroxyl group of the polyphenol resin.
8 to 1.5 mol.

The reaction is carried out with alcohols such as methanol and ethanol, ketones such as acetone and methyl isobutyl ketone, and dimethyl sulfoxide (hereinafter referred to as DMS).
The reaction can be carried out in the presence of an aprotic local solvent such as O), and the use of DMSO is particularly preferable from the viewpoint of increasing the reaction rate and reducing hydrolyzable chlorine in the product. Also, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride can be used as the halohydrination catalyst.
These reactions are usually carried out for 1 to 20 hours.

The polyphenol resin of the present invention can be used as a curing agent for the polyphenol epoxy resin of the present invention.
It can also be used as a curing agent for other known epoxy resins such as gresol novolak type epoxy resin, biphenol type epoxy resin and bisphenol type epoxy resin.

The polyphenol epoxy resin of the present invention comprises
Alone or in combination with other epoxy resins, similar to ordinary epoxy resins, polyamine curing agents such as aliphatic polyamines, aromatic polyamines, polyamide polyamines, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. Curing with an acid anhydride-based curing agent, a phenol-based curing agent such as phenol novolak and cresol novolak, a Lewis acid or a salt thereof such as boron trifluoride, and a curing agent such as dicyandiamide.

If necessary, various additives such as a curing accelerator and an inorganic or organic filler can be added. The polyphenol resin and the polyphenol epoxy resin of the present invention provide a cured product having excellent heat resistance and moisture resistance.
It can be used in a wide range of fields such as sealing materials and laminates.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. The softening point in the examples is a value according to JIS K2425 (ring and ball method), and the amount of hydrolyzable chlorine is 1N-KOH in dioxane.
-The amount of chlorine, the hydroxyl equivalent, and the epoxy equivalent which are titrated when decomposed under reflux for 30 minutes with ethanol are g / g
eq. Further, the present invention is not limited to these examples.

Example 1 288 parts by weight of 1-naphthol (2 mol), 2,4-, were added to a flask equipped with a thermometer, a cooling pipe, a liquid separator, and a stirrer.
126 parts by weight (0.5 mol) of dibromophenol were charged and dissolved at 150 ° C. Next, 41 parts by weight (1.0 mol) of flaky sodium hydroxide (99% by weight of pure content)
Was added all at once and reacted at 170 ° C. for 2 hours. The reaction temperature rose temporarily to 210 ° C. During the reaction, generated water and phenol were distilled out, but after cooling,
The water was removed and the oil was returned to the reaction system. After the reaction is over, 1
Cool to 20 ° C and stir with methyl isobutyl ketone 400
After adding 300 parts by weight of water and 300 parts by weight of water, the mixture was allowed to stand, and the aqueous phase was removed. After neutralization with a 20% aqueous solution of sodium dihydrogen phosphate, washing with water was repeated. Thereafter, methyl isobutyl ketone, unreacted 1-naphthol, and the like are removed from the oil layer using a rotary evaporator under heating and reduced pressure, and a pale yellow, transparent, solid polyphenol resin (A) of the present invention at room temperature
179 parts by weight were obtained.

The obtained resin (A) has a softening point of 121 ° C.
The ICI viscosity at 150 ° C. was 15 poise, and the hydroxyl equivalent was 143. When this resin (A) was analyzed by the following GPC analyzer using tetrahydrofuran (THF) as a solvent, the molecular weight distribution curve shown in FIG. 1 was obtained.

GPC apparatus: L-6000 (manufactured by Hitachi, Ltd.) Column: GPC KF-803 (one) + GPC KF-802.5 (two) + GPC KF-802 (one) (Showa Denko) Solvent: tetrahydrofuran 1 ml / min Detector: RI SE-61 (Showa Denko)

The resin (A) was analyzed by the following direct mass analyzer to find that M ⁺ 378, M ⁺ 470, M ⁺ 378
⁺ 612, was obtained, with further inner R ₁ = H resin This resin is represented by the formula (1) since the hydroxyl equivalent as described above were obtained, R ₂ = H following formula (5) It was confirmed that the polyphenol resin was represented by the formula (n = 0.8).

Direct mass analyzer Ion source temperature: 190 ° C. Ionization voltage: 70 eV DI heater: 8-10

[0033]

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Example 2 A reaction was conducted in the same manner as in Example 1 except that 144 parts by weight (1 mol) of 1-naphthol was used, and 182 parts by weight of a pale yellow, transparent, solid polyphenol resin (B) of the present invention at room temperature was used. I got

The obtained resin (B) has a softening point of 155 ° C.
The ICI viscosity at 200 ° C. was 33 poise, and the hydroxyl equivalent was 136. The resin (B) was analyzed using the same GPC analyzer as in Example 1 using tetrahydrofuran (THF) as the solvent, and the molecular weight distribution curve shown in FIG. 2 was obtained.

When this resin (B) was analyzed by a direct mass analyzer in the same manner as in Example 1, it was found that M ⁺ 378, M
⁺ 470, M ⁺ 612, is obtained, further an inner R ₁ = H resin This resin is represented by the formula (1) since the hydroxyl equivalent as described above were obtained, R ₂ = H in the formula It was confirmed that it was a polyphenol resin (n = 1.9) represented by (5).

Example 3 172 parts by weight (1.2 hydroxyl equivalents) of the polyphenol resin (A) obtained in Example 1 and 666 parts by weight (6 mol) of epichlorohydrin in a flask equipped with a thermometer, a condenser and a stirrer. And 167 parts by weight of DMSO were charged, and after the resin content was dissolved, the temperature was raised to 40 ° C. Next, 51 parts by weight of flaky sodium hydroxide (99% pure content) was added to the system under stirring over 100 minutes. After completion of the addition, the reaction was further performed at 40 ° C. for 1 hour, 50 ° C. for 1 hour, and 70 ° C. for 1 hour. After completion of the reaction, washing with water was repeated, the aqueous layer was separated and removed, and the oil layer was heated to reduce excess epichlorohydrin under reduced pressure, and 500 parts by weight of methyl isobutyl ketone was added to the residue to dissolve the residue.

Further, the solution of methyl isobutyl ketone was heated to 70 ° C., 16 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 225 parts by weight of a light yellow, transparent, solid polyphenol epoxy resin (C) of the present invention at room temperature.

The obtained epoxy resin (C) has a softening point of 8
The ICI viscosity at 6 ° C. and 150 ° C. is 3.5 ps, the epoxy equivalent is 216, and the amount of hydrolyzable chlorine is 310.
ppm. The epoxy resin (C) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and a molecular weight distribution curve shown in FIG. 3 was obtained.

When this epoxy resin (C) was analyzed using a direct mass analyzer (analysis conditions were the same as in Example 1), M ⁺ 546, M ⁺ 694, and M ⁺ 892 were obtained. In the resin represented by (2), R
It was confirmed that this was a polyphenol epoxy resin (n = 1.1) represented by the following formula (6) where ₁ = H and R ₂ = H.

[0041]

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Example 4 An epoxidation reaction was carried out in the same manner as in Example 3 except that 164 parts by weight of the polyphenol resin (B) obtained in Example 2 was used. 213 parts by weight of a polyphenol epoxy resin (D) were obtained. The softening point of the obtained polyphenol epoxy resin (D) is 138.
° C, the ICI viscosity at 200 ° C is 14 poise,
Epoxy equivalent is 212, hydrolyzable chlorine is 350 ppm
Met. When this resin (D) was analyzed using the same GPC analyzer as in Example 1 using tetrahydrofuran (THF) as a solvent, a molecular weight distribution curve shown in FIG. 4 was obtained.

The polyphenol epoxy resin (D) was analyzed by a direct mass spectrometer in the same manner as in Example 1. As a result, M ⁺ 546, M ⁺ 694, and M ⁺ 892 were obtained. Among the resins represented by (2), R ₁ = H and R ₂ = H in the above formula (6)
Polyphenol epoxy resin represented by the formula (n = 2.4)
Was confirmed.

Test Examples 1 and 2 and Comparative Example 1 The polyphenol resins (A) and (B) obtained in Examples 1 and 2 were used, and phenol novolak type resin (E) (Nippon Kagaku) was used as Comparative Example 1. Product name PN-, manufactured by Yakuhin Co., Ltd.
80, hydroxyl equivalent 106 g / eq, I at 150 ° C.
CI viscosity of 1.5 ps) was used as a curing agent, and 100 parts by weight of these curing agents were compared to an o-crosol novolak type epoxy resin (F) (trade name: EOCN-1020, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight). (ICI viscosity at 200, 150 ° C., 3.2 ps) and a curing accelerator (triphenylphosphine) were blended in the amounts shown in Table 1, and a resin molded body was prepared by transfer molding and cured under the curing conditions shown in Table 1. Was. Table 1 shows the results of measuring the heat distortion temperature and the water absorption of the cured product thus obtained.

Table 1 Test Example 1 Test Example 2 Comparative Example 1 Curing agent ABE Epoxy resin (F) wt part 140 147 189 Curing accelerator wt part 1.4 1.5 1.9 Curing conditions 160 ° C. × 2 hours + 180 ° C × 8 hours Heat deformation temperature * 1 ° C 175 185 167 Water absorption * 2 wt part 1.0 1.0 1.3

* 1 According to JIS K7207 * 2 Specimen diameter × thickness 50 mm × 3 mm disk Water absorption based on weight increase after 24 hours in boiling water

Test Examples 3 and 4 and Comparative Example 2 The polyphenol epoxy resins (C) and (D) obtained in Examples 3 and 4 were used as Comparative Example 2 to obtain an o-cresol novolac epoxy resin (F) ( Nippon Kayaku Co., Ltd., trade name EOCN-1020, epoxy equivalent 200, 150
CIC viscosity at 3.2 ° C.)
To 150 parts by weight of these epoxy resins, a phenol novolak resin (F) (Nippon Kayaku Co., Ltd.) was used as a curing agent.
PN-80, hydroxyl equivalent 106 g / eq, 1
An ICI viscosity at 50 ° C. of 1.5 ps) and a curing accelerator (triphenylfin) were blended in the amounts shown in Table 2, and a resin molded product was prepared by transfer molding.
The curing was carried out under the curing conditions shown in Table 2 shows the results of measuring the heat distortion temperature and the water absorption of the thus obtained cured product.

Table 2 Test Example 3 Test Example 4 Comparative Example 2 Epoxy resin C DF Curing agent (E) wt part 74 75 80 Curing accelerator wt part 1.5 1.5 1.5 Curing conditions 160 ° C. × 2 hours + 180 ° C. × 8 hours Heat deformation temperature * 1 ° C. 176 183 167 Water absorption * 2 wt part 1.1 1.0 1.3 * 1 According to JIS K7207 * 2 Test piece Diameter × thickness 50 mm × 3 mm disk Boiling water 24 Water absorption by weight increase after time

[0049]

The resin of the present invention can provide excellent heat resistance and moisture resistance in a cured product thereof, and can be provided as a highly reliable semiconductor sealing resin. or,
According to the production method of the present invention, these resins can be easily obtained in high yield.

[Brief description of the drawings]

FIG. 1 is a molecular weight distribution curve of a product (A) obtained in Example 1.

FIG. 2 is a molecular weight distribution curve of a product (B) obtained in Example 2.

FIG. 3 is a molecular weight distribution curve of a product (C) obtained in Example 3.

FIG. 4 is a molecular weight distribution curve of a product (D) obtained in Example 4.

Continuation of the front page (56) References JP-A-3-90075 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/00-61/02 CA (STN) REGISTRY ( STN)

Claims (3)

(57) [Claims] (1) Formula (1) (In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0
~ 30. Polyphenol resin represented by). (2) Formula (2) (In the formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0
~ 30. G represents a glycidyl group. Polyphenol epoxy resin represented by). (3) Formula (3) (In the formula (3), R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms.
4 represents an alkyl group. And a naphthol represented by the formula (4): (In the formula (4), R ₂ is a hydrogen atom or a group having 1 to 1 carbon atoms.
4 represents an alkyl group. X represents a halogen atom. 2. The method according to claim 1, wherein the halogen-containing phenol represented by the formula (1) is reacted with an alkali metal hydroxide, and further reacted with epihalohydrin in the presence of an alkali metal hydroxide if necessary. The method for producing a polyphenol resin represented by the formula (2) or the polyphenol epoxy resin represented by the formula (2) according to claim 2.