TWI437019B - Method for manufacturing dicyclopentadienes-denaturalized phenol - Google Patents

Description

Method for producing dicyclopentadiene-modified phenol resin

The present invention relates to a method for producing a phenol resin by reacting a phenol with a dicyclopentadiene.

A phenol resin obtained by reacting a phenol with a dicyclopentadiene (hereinafter also referred to as a dicyclopentadiene-modified phenol resin or a modified phenol resin) can be usefully used as fluidity and moisture absorption. An epoxy resin which is excellent in the properties of the epoxy resin which is obtained by epoxidizing the phenol resin can be used as a material for a semiconductor encapsulant or a laminate for a printed wiring board.

The dicyclopentadiene-based modified phenol resin is produced by heating a phenol and a dicyclopentadiene (hereinafter also referred to as DCPD) together with an acid catalyst. Acid catalysts such as: boron trifluoride, boron trifluoride. Phenol complex, boron trifluoride. Ether complexes and the like. The acid catalyst is deactivated by neutralization using an alkaline catalyst neutralizer after the reaction is completed. In order to prevent the acid catalyst from remaining after the completion of the reaction, the reaction may be excessively carried out in the subsequent step of subjecting the unreacted phenol to distillation.

The reaction product liquid after the neutralization of the acid catalyst can be classified into a solid portion composed of a neutralizing agent and an acid catalyst residue, and a filtrate containing an unreacted phenol and a dicyclopentadiene-modified phenol resin. The filtrate was subjected to vacuum distillation, and the unreacted phenols were distilled off, and the dicyclopentadiene-modified phenol resin was recovered.

When a dicyclopentadiene-based modified phenol resin is used as a material for a semiconductor encapsulant or a laminate, since there is a possibility that electrical insulation or the like is lowered, it is necessary to carry out the reaction when the modified phenol resin is produced. The phenols and impurities in the formation liquid are sufficiently removed. In particular, it is necessary to remove the boron compound derived from the acid catalyst and the fluorine compound, preferably to 25 ppm or less, particularly preferably 22 ppm or less. However, since a part of the boron compound and the fluorine compound are dissolved in the phenol, even if filtration is performed, there is a problem that remains in the reaction product liquid.

Conventionally, in the production of the above modified phenol resin, the catalyst neutralizing agent uses calcium carbonate or sodium hydroxide. Such a catalyst neutralizing agent cannot adsorb a boron compound and a fluorine compound, and a boron compound and a fluorine compound are likely to remain in the reaction product liquid. On the other hand, it is proposed in Japanese Patent No. 3028385 to use hydrotalcites in a catalyst neutralizer. The hydrotalcite type has an effect of neutralizing an acid catalyst, and adsorbs a boron compound and a fluorine compound, thereby reducing impurities in the reaction product liquid. However, in the use of a laminate for a semiconductor encapsulant or a printed wiring board, further reduction of impurities is required, and when the hydrotalcite is used for neutralization of an acid catalyst, there is a problem that the reduction of impurities is insufficient.

In the Japanese Patent Publication No. Hei 11-199659, it is proposed to add a powder containing adsorbed water to the obtained reaction product solution by neutralizing and deactivating the acid catalyst with an inorganic base such as calcium hydroxide. (for example, activated clay, acid clay, activated carbon, etc.), and a method of hydrolyzing the complex formed by neutralization to obtain a modified phenol resin having a small content of a boron compound and a fluorine compound. However, this method has a problem that the adsorbed water in the powder is dissolved in the unreacted phenol. Therefore, after the completion of the reaction, the excess phenol distilled from the modified phenol resin contains moisture. As a result, when the next modified phenol resin is produced by using the recovered phenol, part of the acid catalyst is deactivated by moisture, resulting in a problem that the reaction efficiency is lowered and the characteristics of the modified phenol resin are lowered.

An object of the present invention is to provide a method for producing a dicyclopentadiene-based modified phenol resin which can reduce the amount of impurities to a level which can be used as a semiconductor sealant or a raw material for a laminate for a printed wiring board.

The present invention relates to a method for producing a dicyclopentadiene-based modified phenol resin, which comprises: using a phenol and a dicyclopentadiene as a reaction raw material and reacting in the presence of an acid catalyst to produce a dicyclopentane a reaction step (I) of a diene-modified phenol resin; and an acid catalyst for deactivating the acid catalyst by adding a basic compound and a zeolite to the reaction product obtained in the reaction step (I) Activation step (II).

The method for producing a dicyclopentadiene-based modified phenol resin of the present invention preferably comprises: the above-mentioned zeolite, acid catalyst and not from the reaction product obtained by the above-mentioned acid catalyst deactivation step (II) The reaction raw material is removed to obtain a resin recovery step (III) of the dicyclopentadiene-based modified phenol resin.

The embodiments of the present invention are described in detail below, but these are merely examples of the embodiments of the present invention, and the present invention is of course not limited to the contents.

The phenol used in the present invention is not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol or a mixture thereof. Among them, phenol is preferred from the viewpoint of properties and economy of the resin.

The DCPD used in the present invention is also not particularly limited, and is preferably dicyclopentadiene (hereinafter also referred to as DCPD) or dicyclopentadiene substituted with at least one alkyl group or vinyl group or a mixture thereof. The alkyl group is a methyl group, an ethyl group or the like. Among them, dicyclopentadiene is preferably used from the viewpoint of the properties of the resin and the ease of availability.

When the phenols are reacted with the DCPD type, the softening point of the obtained modified phenol resin can be adjusted by adjusting the feed molar ratio (phenol/DCPD type). That is, when the feed molar ratio of the phenol is increased, the softening point of the modified phenol resin is lowered, whereas if the feed molar ratio of the phenol is decreased, the softening point of the modified phenol resin is increased. In order to obtain a modified phenolic resin having an industrially meaningful softening point (70 to 150 ° C, preferably 80 to 140 ° C), the feed molar ratio is preferably set to 1/1 to 15/1, especially 2/1~10/1 is better.

The acid catalyst to be used for the reaction between the phenols and the DCPDs may, for example, be boron trifluoride, boron trifluoride ‧ phenol complex, boron trifluoride ‧ ether complex or the like. Among them, a boron trifluoride ‧ phenol complex which is easy to handle and has a large yield of a modified phenol resin per unit amount of the catalyst is preferable. The amount of the acid catalyst used is, in the case of a boron trifluoride ‧ phenol complex, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass per 100 parts by mass of the DCPD.

The reaction temperature of the phenols and the DCPDs varies depending on the type of the acid catalyst, and in the case of the boron trifluoride ‧ phenol complex, it is set to 20 to 170 ° C, preferably 50 to 150 ° C.

The reaction is preferably carried out in a state where the amount of water is as small as possible, and is preferably 100 ppm by mass or less.

When the viscosity rise of the reaction product is stagnant, the heating is stopped, and the acid catalyst in the reaction product is deactivated. The deactivation of the acid catalyst adds a basic compound and zeolite to the reaction product, and is carried out at 10 to 150 ° C (preferably 30 to 90 ° C) for 10 minutes to 10 hours (preferably 20 minutes to 5 hours). Heating and stirring. The addition of the basic compound and the zeolite can be carried out simultaneously or in individual steps. The end of the activation of the acid catalyst is confirmed by, for example, dissolving in methyl isobutyl ketone, adding water to the solution, stirring, and measuring the pH of the aqueous layer.

The main component of the zeolite used in the acid catalyst deactivation step is an alkali metal or alkaline earth metal aluminosilicate having M ₂ /nO‧Al ₂ O ₃ /xSiO ₂ /yH ₂ O (wherein M represents a metal ion, n represents the valence of the atom, and x, y represents an integer), such as Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]‧27H ₂ O (type 4A) or Na ₈₆ [(AlO ₂ An adsorbent having a composition of ₈₆ (SiO ₂ ) ₁₀₆ ]‧276H ₂ O (type 13X).

The zeolite system sufficiently adsorbs impurities such as an acid catalyst residue, a boron compound, a fluorine compound, and an alkali (earth) metal which are formed during the neutralization of the acid catalyst, thereby increasing the purity of the reaction product. The reason why zeolite can sufficiently adsorb these impurities is that the zeolite has numerous pores, and impurities that intrude into the pores are adsorbed by the inner wall of the pores.

The average pore diameter of the zeolite used in the acid catalyst deactivation step is not particularly limited, and is preferably set to 1 to 20 (0.1~2nm), especially 5~15 (0.5 to 1.5 nm) is preferred, and the adsorption ability of the boron compound and the fluorine compound can be excellent. The specific surface area of the zeolite is not particularly limited, and is preferably 500 to 1,500 m ² /g, particularly preferably 700 to 1300 m ² /g.

The particle size and shape of the zeolite are also not particularly limited. In the case of a powder, the average particle diameter is 1 to 150 μm, preferably 5 to 100 μm, and in the case of granular, the average particle diameter is preferably 0.5 to 0.5. 4mm. When the particle diameter exceeds the upper limit, the adsorptivity of the boron compound or the fluorine compound may be lowered. When the particle diameter is smaller than the lower limit value, the filtration rate may be lowered, and thus it is preferable to avoid it.

From the viewpoint of efficiently adsorbing the boron compound and the fluorine compound, and from the viewpoint of both the filterability, the powdery zeolite having an average particle diameter of 1 to 100 μm (preferably 10 to 50 μm is preferable) is preferable. When the average particle diameter exceeds the above upper limit, the adsorptivity of the boron compound or the fluorine compound may be lowered. When the average particle diameter is less than the above lower limit value, the filtration rate may be lowered, and thus it is preferable to avoid it.

An adsorbent having pores inside the zeolite system, for example, a pore size of the type 4A is about 0.35 nm, and can pass a molecule having an effective diameter of 0.4 nm.

The amount of the zeolite used is 10 to 1000 parts by mass, preferably 50 to 500 parts by mass per 100 parts by mass of the basic compound.

The method for producing the zeolite is not particularly limited, and examples thereof include a method of producing from a reagent, a method of producing from a natural mineral, and the like. As a method of producing from a reagent, a method using sodium citrate or sodium aluminate as a starting material can be used. A method of producing from natural minerals is a method of producing from acid white clay, kaolin, nacre, feldspar, or the like. For example, calcination of kaolin minerals to form metakaolin, addition of sodium hydroxide by increasing reactivity, or grinding of kaolin and volcanic glass, addition of sodium hydroxide after destruction of crystal structure, etc. .

The basic compound used in the acid catalyst deactivation step is not particularly limited, and is preferably, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonia, or the like. Especially calcium hydroxide is preferred. The amount of the basic compound to be added is not particularly limited, and is 1 to 10 times by mass, preferably 2 to 5 times by mass, based on 1 part by mass of the acid catalyst. When the amount of the basic compound added exceeds the upper limit amount, the filtration time becomes too long, and the productivity of the modified phenol resin is lowered. On the other hand, if the amount of the basic compound added is less than the lower limit amount, there is a problem that the deactivation of the acid catalyst is insufficient.

The reaction product to be activated by the acid catalyst is classified into a liquid and a solid by means of solid-liquid separation means such as distillation or filtration, and it is preferable to carry out filtration because it is relatively simple. The method and conditions for the filtration are not particularly limited, and the filtration is preferably vacuum filtration or pressure filtration. The filtration temperature is from room temperature to 150 ° C, preferably from 70 to 130 ° C.

The residue is a modified phenol resin which is recovered and used as a raw material for various purposes. The recovered modified phenol resin has a softening point of 70 to 150 ° C, preferably 80 to 140 ° C, a pH of 5.0 to 9.0, preferably 6.0 to 8.0, and a boron compound and a fluorine compound content of 25 ppm by mass or less, respectively. It is preferably 22 mass ppm or less, and a material such as a semiconductor sealant or a laminate for a printed wiring board can be suitably used without performing special treatment or purification.

The filtrate is distilled and unreacted phenol is recovered. This distillation can be carried out under reduced pressure or under normal pressure under reduced pressure, but it is preferably distilled under reduced pressure. The distillation temperature is 100 to 300 ° C, preferably 150 to 270 ° C, preferably 170 to 250 ° C.

Further, the purity of the recovered phenol is 90% by mass or more, and can be reused for the production of the next modified phenol resin.

Hereinafter, the present invention will be described in more detail by way of examples.

Further, the pH of the reaction product was about 0.5 g of the formation liquid dissolved in 20 cm ³ of methyl isobutyl ketone, and 20 cm ³ of water was added thereto, followed by thorough stirring. After stirring, it was allowed to stand for 30 minutes, and the pH of the aqueous layer was measured by a pH meter.

The softening point of the dicyclopentadiene-based modified phenol resin was measured using a ring and ball softening point measuring apparatus (manufactured by MEITECH Co., Ltd., model 25D5-ASP-MG) at a temperature elevation rate of 5 ° C /min.

The content of the boron compound and the fluorine compound in the dicyclopentadiene-based modified phenol resin was measured by an atomic absorption method using an atomic absorption device [manufactured by Shimadzu Corporation, model AA-6200].

(Example 1)

In a reaction vessel (separable flask: 1 L) equipped with a stirring device, a thermometer, a reflux device, an inert gas introduction tube, and an oil bath, 278 g (=2.9 mol) of a commercially available phenol was charged and heated to 80 °C. After completion of the heating, 2.5 g of boron trifluoride ‧ phenol complex was added, and the temperature was further raised to 140 ° C, and 100 g of DCPD (=0.76 mol) was slowly added for 2 hours to carry out a reaction. After the addition is completed, 7.5 g of calcium hydroxide and zeolite (manufactured by Wako Pure Chemical Industries, Ltd.), synthetic zeolite F9, powder, pore size 9 are added. (9 nm), an average particle diameter of 7 μm (200 mesh passage), a specific surface area of 1,100 m ^{2 /} g, and ^2.5 g, stirred for 30 minutes, neutralized by acid catalyst and deactivated. After the completion of the stirring, the reaction product liquid was filtered. The filtrate was heated to 220 ° C, and distillation under reduced pressure was carried out, and 183 g of unreacted phenol was distilled off.

The distillation residue (=phenol resin A) yield was 195 g. The softening point, pH, boron content, and fluorine content of the phenol resin were measured, and the results are shown in Table 1.

(Example 2)

The procedure of Example 1 was repeated except that in Example 1, the substitution of phenol instead of o-cresol was used. The softening point, pH, boron content, and fluorine content of the obtained resin were measured, and the results are shown in Table 1.

(Example 3)

The procedure of Example 1 was repeated except that in Example 1, the substitution of phenol was followed by the use of 2,6-xylenol. The softening point, pH, boron content, and fluorine content of the obtained resin were measured, and the results are shown in Table 1.

(Example 4)

In addition to the zeolite 1, [Compound Pure Chemicals (stock), synthetic zeolite F9, powder, pore size 9 (9 nm), an average particle diameter of 7 μm (200 mesh passage), a specific surface area of 1100 m ² /g], and the use of zeolite [Wako Pure Chemicals Co., Ltd., synthesis of zeolite A3, powder, pore size 3 The procedure of Example 1 was repeated except that (3 nm), an average particle diameter of 7 μm (200 mesh passage), and a specific surface area of 1000 m ^{2 /} g] of 2.5 g. The softening point, pH, boron content, and fluorine content of the modified phenol resin were measured, and the results are shown in Table 1.

(Example 5)

The procedure of Example 1 was repeated except that in Example 1, the substitution of 7.5 g of calcium hydroxide and 7.5 g of sodium hydroxide was used. The softening point, pH, boron content, and fluorine content of the modified phenol resin were measured, and the results are shown in Table 1.

(Comparative Example 1)

The procedure of Example 1 was repeated except that in Example 1, 7.5 g of calcium hydroxide was replaced with 2.5 g of zeolite and 10 g of calcium hydroxide was used instead. The softening point, pH, boron content, and fluorine content of the modified phenol resin were measured, and the results are shown in Table 1.

(Comparative Example 2)

The procedure of Example 1 was repeated except that in Example 1, 7.5 g of calcium hydroxide was replaced with 2.5 g of zeolite and 10 g of hydrotalcite was used instead. The softening point, pH, boron content, and fluorine content of the modified phenol resin were measured, and the results are shown in Table 1.

(Comparative Example 3)

Except that in Example 1, instead of 2.5 g of zeolite, the activated clay (manufactured by Tosho Kasei Co., Ltd., activated clay E, specific surface area of about 200 m ² /g, water content of 5% by mass) of 2.5 g was used instead. The procedure of Example 1 was repeated. The softening point, pH, boron content, and fluorine content of the modified phenol resin were measured, and the results are shown in Table 1.

(industrial availability)

According to the production method of the present invention, a dicyclopentadiene-modified phenol resin having a softening point and an impurity content of a raw material such as a semiconductor encapsulant or a laminate for a printed wiring board can be obtained. In other words, the compound obtained by epoxidizing the modified phenol resin obtained by the method of the present invention is excellent in electrical properties, and can be effectively used as a raw material for a semiconductor sealant or a laminate for a printed wiring board.

Claims (2)

A method for producing a dicyclopentadiene-based modified phenol resin, which comprises reacting a phenol and a dicyclopentadiene as a reaction raw material in the presence of an acid catalyst to produce a dicyclopentane a reaction step (I) of the olefin-modified phenol resin; and a basic compound and an average pore diameter of 1 to 20 Å of zeolite are added to the reaction product obtained in the reaction step (I), and the acid catalyst is removed. The activated acid catalyst deactivates step (II). The method for producing a cyclopentadiene-based modified phenol resin according to the first aspect of the patent application is characterized in that the zeolite or acid is obtained from the reaction product obtained by the above-mentioned acid catalyst deactivation step (II). The catalyst and the unreacted raw material are removed to obtain a resin recovery step (III) of the dicyclopentadiene-based modified phenol resin.