JP3110488B2 - Novel phenylphenol resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phenylphenol resin and a method for producing the same. This phenyl phenol resin can be used as a usual phenol resin to provide a thermosetting resin with hexamine or the like, and can also be used as an epoxy resin raw material or a curing agent for an epoxy resin, and further as an additive to various resins. . In particular, it is useful as a raw material for a resin for semiconductor encapsulation.

[0002]

2. Description of the Related Art Conventionally, phenol novolak resins, which are the most typical phenol resins, have drawbacks of structural factors such as poor oxidation resistance and mechanical factors such as hard and brittle when used as a cured composition. For the purpose of improving such factors, a phenol resin having a dicyclopentane bond using dicyclopentadiene instead of a formalin bond of the phenol resin has been developed (US Pat.
No. 536,734, JP-A-54-99160, JP-A-Sho-6
2-104830).

[0003] However, in recent years, the performance required for matrix resins for composite materials is required to be higher in heat resistance, mechanical strength, oxidation resistance and water resistance. It is hard to say that a phenolic resin using an alkyl-substituted phenol as a raw material can satisfy the required performance, and a significant improvement in water resistance is particularly desired. As a method for improving the water resistance, it is conceivable to use a phenol compound having a large molecular weight as a raw material. This is the idea of increasing the hydrophobicity by reducing the hydroxyl group density per unit molecule.While introducing a long-chain alkyl group into a phenol compound in this way improves the water resistance, on the other hand, the heat resistance is improved. The disadvantage is that it is significantly reduced.

[0004] In recent years, semiconductor encapsulants have been required to have a material that is excellent not only in mechanical strength and adhesiveness but also in both water resistance and heat resistance in accordance with high density and high integration. However, in general, the water resistance and heat resistance are reduced as described above, if the water resistance is improved, and the heat resistance is improved by introducing a heat-resistant functional group or increasing the functional group density. Therefore, the water resistance is reduced, and in each situation, there is a need to make a selection with any sacrifice.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a phenolic resin used in a matrix resin for a composite material or a resin for encapsulating a semiconductor, in such a use, to provide an excellent balance between heat resistance and water resistance. And to provide a resin having a novel structure.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object. As a result, the present invention has been completed. That is, the present invention relates to a compound represented by the general formula (I):

[0007]

Embedded image Wherein n represents an integer of 0 to 100, wherein phenylphenol resin and phenylphenols are reacted with dicyclopentadiene in the presence of an acid catalyst. The present invention relates to a method for producing a phenylphenol resin.

In the phenylphenol resin of the present invention, the number of repeating units n in the general formula (I) is from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20, and the softening point of the resin (JIS) -K-2548) is 70-1.
It is characterized by a temperature range of 80 ° C., and has a smaller hydroxyl group density per unit weight than conventionally known novolak resins and phenol / dicyclopentadiene resins, but has a rigid dicyclopentane bond. Since it has a biphenyl skeleton, when a cured composition with an epoxy resin or the like is obtained, heat resistance and mechanical properties are comparable, but water resistance is excellent. Therefore, the use of the phenolic resin capable of providing such performance satisfies the problem demanded as an advanced composite material.

Hereinafter, the method for obtaining the phenylphenol resin of the present invention will be specifically described. The phenylphenol used in the present invention is o-phenylphenol, m
-Phenylphenol or p-phenylphenol. The molar ratio of the charged phenylphenols and dicyclopentadiene in this reaction is from 1 to 15 mol, preferably from 1.1 to 10 mol per mol of dicyclopentadiene.
Is a mole. As the catalyst used in the present invention, a Friedel-Crafts type catalyst, organic and inorganic sulfonic acids, super strong acids,
Heteropoly acids, solid acids and the like can be used. Acid-type ion-exchange resins, 12-tungstophosphoric acid, silica-alumina-based zeolite catalysts and the like are included. These catalysts can be used alone or in combination. The amount of the catalyst used is about 0.0001 to 10% by weight, preferably about 0.001 to 3% by weight, based on the total weight of phenylphenol and dicyclopentadiene. Reaction temperature is 2
The temperature is 0 to 180 ° C, preferably 40 to 150 ° C. The reaction temperature may be constant, or may be changed during the reaction as needed. The reaction time varies depending on the conditions, but is about 1 to 20 hours. After completion of the reaction, by removing unreacted phenylphenol by any means such as vacuum distillation,
The desired phenylphenol resin can be obtained.

[0010]

Next, the present invention will be described in more detail by way of examples. Example 1 A reactor equipped with a stirrer and a thermometer was charged with 255 g (1.5 mol) of o-phenylphenol and 0.64 g of trifluoromethanesulfonic acid as a catalyst, and the internal temperature was kept at 50 ° C. Next, 66.1 g (0.5 mol) of dicyclopentadiene was added dropwise with stirring over 4 hours.
After completion of the dropping, the mixture was aged at the same temperature for 3 hours.
The temperature was raised to 0 ° C. and aging was performed for 5 hours, and the temperature was further raised to 150 ° C. and aging was performed for 3 hours to complete the reaction. After completion of the reaction, unreacted o-phenylphenol was removed by vacuum distillation, and the residual reddish-brown resin was discharged while hot. Yield 2
The softening point (JIS-K-2548) was 109 ° C. with 03 g. The hydroxyl equivalent (g / eq) of this resin was 273. FIG. 1 shows the infrared absorption spectrum of this resin. Resin composition by high performance liquid chromatography (A
(rea%) is such that n = 0 in the general formula (I) is 53.4.
%, N = 1 was 26.9%, and n ≧ 2 was 19.7%.

Example 2 In Example 1, p-phenylphenol was used instead of p-phenylphenol.
The reaction was carried out in the same manner as in Example 1 except that 170 g (1 mol) of -phenylphenol was used to obtain 162 g of p-phenylphenol resin. The softening point of this resin is 1
The temperature was 32 ° C., and the hydroxyl equivalent (g / eq) was 322. Resin composition by high performance liquid chromatography (A
(rea%), n = 0 in the general formula (I) is 26.1.
%, N = 1 is 19.8%, n = 2 is 13.5%, n = 3
Was 11.2% and n ≧ 4 was 29.5%.

Use Example 1 As a curing agent for orthocresol novolak type epoxy resin (manufactured by Nippon Kayaku; EOCN102S), the resin obtained in Example 1 was blended under the conditions shown in Table 1 and a mixture thereof. Of the cured product obtained by casting was measured for its water absorption and thermal properties. The results are shown in Table 1. Comparative Example 1 The curing agent in Use Example 1 was replaced with a phenol novolak resin (manufactured by Showa Kobunshi; BRG # 558) and compounded as shown in Table 1, and the mixture was cast to obtain a cured product. The water absorption and thermal properties were measured in the same manner as in Use Example 1, and the results are shown in Table 1.

[0013]

[Table 1]

[0014]

As described above, the novel phenylphenol resin provided by the present invention is excellent in both heat resistance and water resistance, which have been strongly demanded in its use. Therefore, this resin is suitable for use as an advanced composite material, and its utility value is great.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a resin obtained in Example 1 by a KBr tablet method.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 61/00-61/12 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the general formula (I): (Wherein, n represents an integer of 0 to 100) represented by softening
Phenylphenol resin at a point of 70-180 ° C. 2. The method for producing a phenylphenol resin according to claim 1, wherein the phenylphenol is reacted with dicyclopentadiene in the presence of an acid catalyst.