JP3468308B2 - Method for producing phenolic resin and method for producing epoxy resin - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a phenol resin having a good hue derived from an unsaturated cyclic hydrocarbon compound such as dicyclopentadiene and a phenol compound, and a method for producing an epoxy resin using the phenol resin as a raw material. Regarding More specifically, in addition to being excellent in mechanical properties, electrical properties, moisture resistance, thermal shock resistance, crack resistance, etc.,
Further, the present invention relates to a method for producing a phenol resin and an epoxy resin, which are useful as a resin for a semiconductor encapsulating material or a resin for a laminated plate because of their excellent hue.

[0002]

2. Description of the Related Art Up to now, a dicyclopentadiene type phenolic resin and the phenolic resin have been epoxidized from the viewpoint of excellent heat resistance and moisture resistance as a resin used for electrical and electronic insulating materials such as electric laminates. Dicyclopentadiene type epoxy resins are known. These resins are usually prepared by reacting dicyclopentadiene and phenol with a catalyst in an autoclave at a temperature of 200 ° C. or higher, or both of them, a boron trifluoride complex, aluminum trichloride, sulfuric acid, a heteropoly acid. When a phenol resin of interest is obtained by a method of reacting in the presence of a catalyst such as a dicyclopentadiene type phenol resin, and further epoxidized, the phenol resin is produced by a method of reacting with epichlorohydrin. .

[0003]

However, when the dicyclopentadiene type phenolic resin and the dicyclopentadiene type epoxy resin are produced by the above-mentioned conventional method, the phenolic resin produced in the step of producing the dicyclopentadiene type phenolic resin. However, there is a problem in that it is intensely colored and exhibits a blackish brown color and its use is limited.

The dicyclopentadiene type epoxy resin made from this phenol resin is also severely colored and has a problem in hue in electric laminates, insulating powder coatings and coating applications. .

The problem to be solved by the present invention is to produce a dicyclopentadiene type phenolic resin and a dicyclopentadiene type epoxy resin in order to obtain a resin excellent in appearance, particularly hue. To provide.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have made the polyaddition reaction of dicyclopentadiene and phenol react under an acidic catalyst,
By stirring and mixing the obtained reaction product and an inorganic porous material in an aromatic organic solvent, the reaction product is decolorized, and a dicyclopentadiene type phenol resin having an excellent hue is obtained. The inventors have found that an epoxy resin obtained by reacting a compound with epihalohydrin also has an excellent hue, and completed the present invention.

That is, according to the present invention, an unsaturated cyclic hydrocarbon compound and a hydroxyl group-containing aromatic compound are reacted under an acidic catalyst, and after the reaction is completed, the acidic catalyst is removed from the reaction solution,
Then, the obtained reaction product is activated clay in an organic solvent ,
Acid clay, silica magnesia type decolorizing deoxidizing synthetic gel and
Selected from the group consisting of silica-alumina-based decolorizing and deoxidizing synthetic gels
And a method for producing an epoxy resin characterized in that the phenol resin obtained by this production method is further reacted with epihalohydrin.

The present invention will be described in more detail. The unsaturated cyclic hydrocarbon compound used as a raw material component in the production method of the present invention is not particularly limited, but includes dicyclopentadiene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4, 7, Examples thereof include 7a-tetrahydroindene, α-pinene, β-pinene, limonene, and the like, and dicyclopentadiene is preferable from the viewpoint that the resulting resin is excellent in heat resistance, moisture resistance, and mechanical properties.

The aromatic hydroxyl group-containing compound is not particularly limited, and examples thereof include phenols such as monohydric or dihydric phenols, bisphenols, and naphthols. Specifically, phenol, o- Cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, pn-propylphenol, p-sec
-Butylphenol, p-tert-butylphenol, p-cyclohexylphenol, octylphenol, nonylphenol, dodecylphenol, p-chlorophenol, o-bromophenol, p-bromophenol, resorcin, catechol, hydroquinone,
2,2-bis (4-hydroxyphenyl) propane,
4,4'-thiodiphenol, dihydroxydiphenylmethane, α-naphthol, β-naphthol and the like can be mentioned.

The reaction ratio of the unsaturated cyclic hydrocarbon compound and the aromatic hydroxyl group-containing compound is particularly limited because the molecular weight and the melt viscosity can be adjusted to appropriate ranges by changing the molar ratio of the both. However, the range of unsaturated cyclic hydrocarbon compound / aromatic hydroxyl group-containing compound = 1/1 to 1/15 is usually mentioned. Among them, when the molar ratio of unsaturated cyclic hydrocarbon compound is made small, the molecular weight becomes small and the melt viscosity becomes low, and it is possible to highly fill the filler in applications such as semiconductor encapsulation materials and reduce the linear expansion coefficient. In addition, water resistance is improved, and specifically, unsaturated cyclic hydrocarbon compound / aromatic hydroxyl group-containing compound = 1/1.
The range of up to 1/15 is preferable.

Examples of the acidic catalyst used in the method for producing a phenol resin of the present invention include ion exchange resins, boron trifluoride, boron trifluoride ethers, boron trifluoride complexes such as phenol, water, amine or alcohol complexes, Aluminum compounds such as aluminum trichloride and diethylaluminum monochloride, iron chloride, titanium tetrachloride, sulfuric acid, hydrogen fluoride, trifluoromethanesulfonic acid, p-
Toluenesulfonic acid, a zeolite catalyst, or a mixture thereof can be preferably used. Among these, an ion exchange resin is preferable because the reaction product is less likely to be colored.

The reaction between the unsaturated cyclic hydrocarbon compound and the aromatic hydroxyl group-containing compound can be carried out without using a solvent, but of course, it may be used, and in that case, as a usable solvent, Is not particularly limited as long as it does not hinder the reaction, and preferable examples thereof include aromatic hydrocarbon compounds such as benzene, toluene and xylene. 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 acidic catalyst used, but are preferably 10 to 100 ° C. and 2 hours to 60 hours.

After completion of the reaction, the acidic catalyst is removed from the reaction solution, the reaction solution is filtered and then concentrated to obtain a desired reaction product. It is when the filtration can be improved or adding a solvent, the workability by processing for raising the temperature of the filtrate.

Then, the obtained reaction product is mixed with the inorganic porous material in an organic solvent with stirring to obtain a phenol resin having an excellent hue. The inorganic porous material used here is not particularly limited, but normally, an apparent specific gravity of 0.25 to 0.85 is used, but the adsorption of impurities in the reaction product is easy. The particle size is preferably smaller from the viewpoint that it is carried out, and the contact area with the reaction liquid during stirring and mixing is large and the decolorizing effect is good, and specifically, the one having a fineness of 200 mesh of 75% or more. Is preferred.

Specific examples of such an inorganic porous material include activated clay, acid clay, silica magnesia type decolorizing deoxidizing synthetic gel and silica alumina type decolorizing deoxidizing synthetic gel .
It is selected from the group consisting of the following . Among them, activated clay is preferable because it has a good decolorizing effect. The activated clay preferably used in the present invention has a component of silicon dioxide 75 to 8
5% and aluminum oxide 9 to 13% are preferable because the effect of the present invention becomes more remarkable.

The organic solvent used here is not particularly limited, but aromatic organic solvents are preferable, and specific examples thereof include benzene, toluene, xylene and the like.

The method of stirring and mixing the reaction product, the inorganic porous material, and the organic solvent is not particularly limited, but a mixture of the reaction product and the organic solvent may be used as the inorganic porous material. Substances may be added and mixed by stirring,
Further, the reaction product may be added to the mixed liquid of the organic solvent and the inorganic porous substance and mixed by stirring, but the former is preferable because it is excellent in the decolorizing effect. Although the amount of the organic solvent used is not particularly limited, the content of the nonvolatile component is usually 2 with respect to the reaction product.
The content of the inorganic porous material is preferably 5 to 60% by weight, and the inorganic porous material may be used in an amount of 5% by weight or more based on the reaction product, but is preferably 10 to 40% by weight. preferable.

The conditions of mixing and stirring are not particularly limited, but usually, it can be carried out in a tank-type stirrer at 60 ° C. to 120 ° C. for 10 minutes to 120 minutes, and among them, 60 to 120 from the viewpoint of excellent decolorizing effect. It is preferably minutes. Further, in the present invention, the properties of the produced phenol resin are not changed by the mixing and stirring.

The phenol resin thus obtained is
Although the use thereof is not particularly limited, it is useful as a curing agent of an epoxy resin for a semiconductor encapsulating material or a laminated board or a raw material of an epoxy resin.

Next, the method of further reacting the thus obtained phenol resin with epihalohydrin can be carried out by a conventional method for producing an epoxy resin. 0.5 to 15 equivalents of epichlorohydrin are added and dissolved, and then an aqueous solution of NaOH is added at a temperature of 50 to 80 ° C. for 3 times.
Take ~ 5 hours and add dropwise. 0.5 to 2 at that temperature after dropping
Continue stirring for about an hour and allow it to stand, then discard the lower layer saline.
Then, excess epichlorohydrin is recovered by distillation to obtain a crude resin. To this, add an organic solvent such as toluene or MIBK,
The desired dicyclopentadiene type epoxy resin is obtained through the steps of washing with water, dehydration, filtration and solvent removal.

Examples of epihalohydrin include epichlorohydrin, epibromhydrin and the like.

The dicyclopentadiene type epoxy resin thus obtained is not particularly limited in its epoxy equivalent, but it is usually from 200 to 300, preferably from 230 to 280.

Further, the dicyclopentadiene type epoxy resin obtained by the present invention has excellent hue, mechanical properties, electrical properties, moisture resistance, thermal shock resistance, crack resistance, etc. It is useful as an epoxy resin for laminated boards.

[0024]

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.

Example 1 500 equipped with reflux condenser and Liebig condenser
A ml reactor was charged with 320 g of phenol and 32 g of toluene, heated to 160 ° C., and azeotropically distilled with toluene to dehydrate the water content in the system to 60 ppm and distill off the toluene. Next, after adding 2.7 g of boron trifluoride / phenol complex at 50 ° C. to make it uniform,
At a reaction temperature of 60 ° C., 45 g of dicyclopentadiene having a water content of 20 ppm was gradually added dropwise over 2 hours under a nitrogen atmosphere, the temperature was raised to 80 ° C. after completion of the addition, and the mixture was further heated and stirred for 20 hours. After completion of the reaction, 100 g of toluene and 9 g of calcium hydroxide were added, the mixture was stirred for 30 minutes to deactivate the acidic catalyst, and then the reaction solution was filtered. The obtained clear filtrate was distilled under reduced pressure to obtain 103 g of dark red phenol resin (1). The obtained phenol resin was dissolved in toluene (N.
V. (40%) 10.3 g of activated clay was added and mixed by heating with stirring at 100 ° C. for 1 hour, and the reaction solution was filtered. The resulting clear filtrate was distilled off under reduced pressure to obtain 105 g of a yellow phenol resin.
Got

The softening point of the obtained phenol resin (1) was 93 ° C. The equivalent of phenolic hydroxyl group determined by reverse titration after acetylation with acetic anhydride was 168 g / equivalent. Further, the Gardner color of the phenolic resin (1) was measured using a "Hedgeridge Comparator" manufactured by Herridge Co. as a colorimeter and a "Hedgeridge Color Disk" manufactured by Herridge Co. as a standard color plate.
It was -8. Further, the number average molecular weight of this resin was determined by gel permeation chromatography (hereinafter referred to as GPC) analysis to be 395.

Example 2 100 g of the obtained phenol resin (1) was dissolved in 235 g of epichlorohydrin, and 20% NaO was added at 70 ° C.
127 g of H were added over 3 hours. Then at the same temperature
The mixture was stirred for 1 hour, allowed to stand still for liquid separation, and the saline layer was discarded. Then, excess epichlorohydrin was recovered by distillation, and
After dissolving in 150 g of BK, followed by washing with water, dehydration and filtration, 130 g of a pale yellow epoxy resin (1) was obtained.

The softening point of the obtained epoxy resin (1) is 5
It was 9 ° C. The epoxy equivalent determined by perchloric acid titration was 268 g / eq. Further, when the Gardner color of the resin was measured in the same manner as in Example 1, 4-
It was 5. Further, the number average molecular weight of this resin was determined by GPC analysis to be 604.

Example 3 Instead of boron trifluoride / phenol complex as an acidic catalyst, an ion exchange resin ("K2411" manufactured by Bayer Co., Ltd.)
The reaction and stirring and mixing were carried out in the same manner as in Example 1 except that was used to obtain 104 g of a pale yellow phenol resin.

The softening point of the obtained phenol (2) resin was 83 ° C. The equivalent of phenolic hydroxyl group determined by inverse titration after acetylation with acetic anhydride was 164 g / equivalent. Further, the Gardner color of the resin was measured in the same manner as in Example 1 and found to be 5-6. Furthermore, the number average molecular weight of this resin was determined by gel permeation chromatography analysis to be 360.

Example 4 101 g of the obtained phenol resin (2) was used in Example 2
Epoxidation was carried out by the same method as above to obtain 133 g of a pale yellow epoxy resin.

The softening point of the obtained epoxy resin (2) is 5
It was 4 ° C. The epoxy equivalent determined by perchloric acid titration was 252 g / eq. Further, when the Gardner color of the resin was measured in the same manner as in Example 1, 2-
It was 3. Further, the number average molecular weight of this resin was found to be 483 by GPC analysis.

Example 5 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 100 ° C., and then stirring and mixing were carried out in the same manner as in Example 1 except that xylene was used as a solvent. Resin (3) 106g was obtained.

The softening point of the obtained phenol (3) is 95.
It was ℃. The equivalent of phenolic hydroxyl group determined by reverse titration after acetylation with acetic anhydride was 169 g / equivalent. The Gardner color of the resin was measured in the same manner as in Example 1 and found to be 12-13. Furthermore, the number average molecular weight of this resin was 400 by gel permeation chromatography analysis and found to be 400.

Example 6 100 g of the obtained phenol resin was epoxidized in the same manner as in Example 2 to give a yellow epoxy resin (3).
133 g were obtained.

The softening point of the obtained epoxy resin (3) is 6
It was 0 ° C. The epoxy equivalent determined by perchloric acid titration was 268 g / eq. Further, when the Gardner color of the resin was measured in the same manner as in Example 1, it was 9-
It was 10. Further, the number average molecular weight of this resin was determined by GPC analysis to be 620.

Example 7 The reaction and stirring and mixing were carried out in the same manner as in Example 1 except that the acid clay was used instead of the activated clay to obtain 103 g of a brownish brown phenol resin (4).

The softening point of the obtained phenol (4) is 94.
It was ℃. The equivalent of phenolic hydroxyl group determined by reverse titration after acetylation with acetic anhydride was 168 g / equivalent. The Gardner color of the resin was measured in the same manner as in Example 1 and found to be 11-12. Further, the number average molecular weight of this resin was determined by gel permeation chromatography analysis to be 390.

Example 8 101 g of the obtained phenol resin (4) was used in Example 2
Epoxidation was carried out by the same method as above to obtain 130 g of yellow epoxy resin (4).

The softening point of the obtained epoxy resin (4) is 6
It was 1 ° C. The epoxy equivalent determined by perchloric acid titration was 267 g / eq. Moreover, when the Gardner color of the resin was measured in the same manner as in Example 1, it was 8−
It was 9. Furthermore, the number average molecular weight of this resin was found to be 610 by GPC analysis.

Example 9 Reaction and stirring mixing were carried out in the same manner as in Example 1 except that Nikka Gel M-30 (eg, Nihon Activated Shirato Co., Ltd., silica magnesia type decolorizing deoxidizing synthetic gel) was used in place of the activated clay. This was carried out to obtain 102 g of a dark brown phenol resin (5).

The softening point of the obtained phenol (5) is 93.
It was ℃. The equivalent of phenolic hydroxyl group determined by reverse titration after acetylation with acetic anhydride was 168 g / equivalent. The Gardner color of the resin was measured in the same manner as in Example 1 and found to be 11-12. Further, the number average molecular weight of this resin was determined by gel permeation chromatography analysis and found to be 413.

Example 10 101 g of the resulting phenol resin (5) was used in Example 2
Epoxidation was carried out by the same method as above to obtain 133 g of a yellow epoxy resin (5).

The softening point of the obtained epoxy resin (5) is 6
It was 1 ° C. The epoxy equivalent determined by perchloric acid titration was 268 g / eq. Moreover, when the Gardner color of the resin was measured in the same manner as in Example 1, it was 8−
It was 9. Further, the number average molecular weight of this resin was determined by GPC analysis to be 605.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the decolorizing treatment step with activated clay was not carried out to obtain 105 g of a blackish brown phenol resin (6).

The softening point of the obtained phenol (6) is 94.
It was ℃. The equivalent of phenolic hydroxyl group determined by reverse titration after acetylation with acetic anhydride was 168 g / equivalent. Further, the Gardner color of the resin was measured in the same manner as in Example 1 and found to be 17-18. Further, the number average molecular weight of this resin was determined by gel permeation chromatography analysis to be 405.

Comparative Example 2 101 g of the resulting phenol resin (6) was used in Example 2
Epoxidation was carried out by the same method as above to obtain 131 g of a brown epoxy resin (6).

The softening point of the obtained epoxy resin (6) is 5
It was 9 ° C. The epoxy equivalent determined by perchloric acid titration was 268 g / eq. Further, the Gardner color of the resin was measured in the same manner as in Example 1 to find 15
It was -16. Further, the number average molecular weight of this resin was determined by GPC analysis to be 615.

The results of Examples 1 to 10 and Comparative Examples 1 and 2 are summarized in Table 1.

[0050]

[Table 1]

[0051]

According to the present invention, it is possible to provide a dicyclopentadiene type phenolic resin and a dicyclopentadiene type epoxy resin having an excellent hue as never before.

Further, the phenol resin and epoxy resin obtained by the present invention have an excellent appearance when processed in various applications such as electric laminates, insulating powder coatings and coatings, and also have excellent high heat resistance and low heat resistance. It has both water absorbency.

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Claims (6)

(57) [Claims] 1. An unsaturated cyclic hydrocarbon compound and a hydroxyl group-containing aromatic compound are reacted under an acidic catalyst to give a reaction.
After the completion of the reaction, the acidic catalyst was removed from the reaction solution, and then the obtained reaction product was treated with activated clay, acid clay and silica in an organic solvent.
Camagnesia-based decolorizing deoxidizing synthetic gel and silica-alumina
A method for producing a pale phenolic resin, which comprises stirring and mixing with an inorganic porous substance selected from the group consisting of a system decolorizing deoxidizing synthetic gel . 2. The production method according to claim 1, wherein the reaction product and the inorganic porous material are stirred and mixed in an organic solvent solution at 60 to 120 ° C. 3. The reaction product was dissolved in an organic solvent, prior to
The method according to claim 1 or 2, wherein the inorganic porous material is added and mixed by stirring. 4. The method according to claim 1, 2 or 3 , wherein the organic solvent is toluene or xylene. 5. The unsaturated cyclic hydrocarbon compound is dicyclopentadiene, A process according to hydroxyl group-containing aromatic compound is any one of claims 1-4 phenols. 6. A method for producing an epoxy resin, which comprises reacting the phenol resin obtained by the method according to any one of claims 1 to 5 with epihalohydrin.