Production of novolak resin having decreased inpurity metal content

[Detailed Description of the Invention]

(Field of the Invention) The present invention relates to the manufacturing process of the novolac resin in which the impure metallic component was reduced, and relates to the manufacturing process of the novolac resin in which the impure metallic component for using it for photoresist solution or a flat-ized agent in more detail was reduced. (PRIOR ART) In a semiconductor manufacturing process, if the impure metallic component containing mobile ion, such as sodium, potassium, steel, and iron, is contained, the problem of degrading a semiconductor will be produced. In recent years, in the detailed circuit, the thickness of the insulating film instead of foolish Si with a narrow interval of the four directions of an element itself is also thin by high integration. Therefore, it is desired for the concentration of the impure metallic component of the photoresist solution for forming a pattern to be low. photoresist solution mainly consists of novolac resin and a sensitization agent -- Yo Si refining is comparatively easy for Si and a sensitization agent by the re-crystallizing method. On the other hand, reduction of the impure metallic component of novolac resin is difficult. - As for abbreviation 100~s o o ppb, sodium and iron are contained in novolac resin by a target practice manufacturing process. Photoresist solution using such resin. Sodium and iron are contained abbreviation 100~300 ppb. Concentration of the impure metallic component of Ah Si and the novolac resin contained in photoresist solution for that purpose must be carried out below 100 ppb below by impure metallic component concentration Fis o pIb of the photoresist solution desired. the manufacturing process of high purity novolac resin is shown in 1% Opening No. 34009 [ 61 to ] gazette, or % Opening No. 212409 [ 62 to ] gazette -- although Si and its method are the methods of washing the resin compounded nine times by 120~200 degreeC just before the end of a synthetic reaction By this method, there is also a problem which 1 synthetic process complicates and from which foolish not but an impure metallic component is not fully removed. 4! Opening No. 6026 [ 63 to ] gazette is made to dissolve novolac resin in a certain solvent, and the method of the product made from e carrying out is shown to it by by performing liquid extraction using acid water. An impure metallic component can be reduced in this method. Since moisture in novolac resin increases, moisture in the photoresist u solution which used this novolac resin increases, and it is not desirable on the characteristic. (Object of the Invention) The present invention provides the manufacturing process of the novolac resin in which the impure metallic component was reduced, and the novolac resin in which the impure metallic component for using it for photoresist solution or a flat-ized agent in more detail was reduced. (Means for solving problem) These artificers found out the manufacturing process of the novolac resin in which it inquired wholeheartedly and an impure metallic component, especially sodium were reduced as for the following result, in order to achieve the above-mentioned object. The synthetic iron pot which reduces an impure metallic component by distillation or refining which used ion-exchange resin and by which an impure metallic component is not eluted at the time of the following composition materials and composition is used for the present invention, And it is related with the manufacturing process of the novolac resin in which the impure metallic component which blows inactive gas as a part for 0 and 5~1.5 liter (25"C, latm)/, and compounds it was reduced. In the present invention, novolac resin is Yo Si profitable To be resin polymerizing phenol and aldehyde under acid conditions. It is here and phenol is phenol, cresol, and Xylenol. That of an owner Sour book corresponds phenolic hydroxyl, such as resorcinol, and what has aldehyde groups, such as formaldehyde, benzaldehyde, and rose formaldehyde ", with aldehyde corresponds. Again. As a catalyst made into acid conditions, novolac-ized reaction catalysts, such as chloride, oxalic acid, and sulfuric acid, correspond. the synthetic materials in the present invention are needed to refining which used Yo Si or ion-exchange resin for distillation for such synthetic materials of novolac resin in which phenol and aldehyde are shown -- an impure metallic component is reduced. Thus, synthetic materials in which the obtained impure metallic component was reduced. The iron pot made from quartz, l!I! It puts into the synthetic iron pot by which impure metallic components, such as a washed glass iron pot, are not eluted. inactive gas, such as nitrogen and argon, -- 0, 5~1, and 5 liters (it comes out to obtain 25"C and the novolac resin in which it blew in as a part for latml/, compounded, and the impure metallic component was reduced -- 1 -- To.) The flow of inactive gas is 0.5 liter (since there are few amounts of inactive gas inside a reaction vessel when it is 25'C and less than [ jatm > 7 minute ], an external impure metallic component trespasses upon the inside of a reaction vessel, and easy Si and impure metallic component concentration become high.). When the flow of inactive gas exceeds a part for 1.5 liter (25degreeC, latm)/, it becomes impossible on the contrary, for Without to control dialdehyde concentration with easy aldehyde from the inside of a reaction vessel. (EXAMPLE) An example explains the 1 present invention below. Example 1 They are meta-cresol (the 1st class of the Wako Ginseng reagent), and the Parakou resol (the 1st class of the Wako Ginseng reagent) respectively 20mmHg and 10 (distillation under reduced pressure is carried out by 1~130 degreeC, and it is a sense.) About 37 Tipol marine solution (the 1st class of the Wako Ginseng reagent), it is Amberlyst 15 (highly acidic positive ion exchange MR type.). 300g of ORGANO CORP. make is used for 37 Tipol marine solution 20 to 9, Yo Seed on exchange refining is carried out at a column method, and he is a friend. These refine and Result is shown in Table 1. Na concentration and Fe concentration conducted atomic absorption analysis using the atomic spectrum photometer (made in a high dregs factory, AA-670G). It was shown in Table 1 and 715 Meta- cresol 585 Tobarra cresol refined nine times and 673 g of 3 Fuchihoru marine solution were supplied to the 2-liter iron pot made from quartz by which it is not eluted in an impure metallic component. Occasion. Oxalic acid 5g was thrown in as an acid catalyst. It agitated by the shuttlecock made from Teflon, and blew nitrogen gas by a part for 0.851J Tuttle (25degreeC, latm) /into 9 reaction vessels. It was made to react at flowing-back temperature for 4 hours, and water was removed from the inside of the system of reaction to the 1st order. After making it dry, raise the temperature in an iron pot to 180degreeC, and it is made to react for further 2 hours, and it is mourning. Then, nitrogen gas blowing in is stopped and it is under decompression (30~40Torr). It applied for 30 minutes by 180 degreeC, and removed freak resol. 60 ppb and Fe concentration of Na concentration of the cresol resin obtained in this way were 60 ppb. 1 weight section of cresol resin is dissolved in 3 weight sections of acetic acid-2-ethoxyethyl for electronic industry, an atomic spectrum photometer (high dregs factory AA-670G) is used about the varnish, and it is I gone about atomic absorption analysis. Na of varnish and Fe concentration are made into 4 times, and it is Na of cresol resin. It was considered as Fe concentration. In the following examples and a comparative example, it carried out similarly. Example 2 it is shown in Table 1 and synthetic materials refined nine times are shown in Example 1 -- light -- carrying out acid cleaning by combination preparation [ like ] -- 9 -- it supplied to the 2-liter glass iron pots which carried out acid cleaning. The acid cleaning of glass iron pots was based on the following cleaning methods. Dilute nitric acid 18009 of 3 weight - was put into 2-liter glass iron pots, and it stirred by the shuttlecock made from Teflon for 10 hours. Then, dilute nitric acid was discarded, and ion-exchange-water 1800 s was put in, and it stirred by the shuttlecock made from Teflon for 10 hours, and, subsequently discarded the ion exchange water in an iron pot. Cresol resin was compounded on the same conditions as Example 1 after throwing in synthetic materials. 70 ppb and Fe concentration of Na concentration of the cresol resin obtained in this way were 60 ppb. Comparative example 1 It was shown in Table 1 and the following-refined synthetic materials were fed into the 2-liter glass iron pots which have not carried out acid cleaning by the combination preparation which was shown as for example IK. Cresol resin was compounded on the same conditions as Example 1 after throwing in synthetic materials. Nm concentration of the cresol resin obtained in this way is 300 ppl. Fe concentration is 200 ppb and is Buddy 9. It adheres to elution or the glass iron pots of the impure metallic component from glass iron pots, and it is thought that ] and cresol resin were polluted by elution of the mourning impure metallic component. Comparative example 2 Synthetic materials refined table IK example 9 were fed into the iron pot made from quartz by which it is shown in Example 1 and an impure metallic component is not eluted by hole combination ° preparation. Others compounded cresol resin for blowing in of inactive gas on the same conditions as Example 1 to To do after the injection. 150 ppb and Fe1[of Na concentration of the cresol resin obtained in this way were 60 ppb. Since inactive gas was not blown, it is thought that an impure metallic component, especially Na invaded in the reaction vessel, and polluted cresol resin. (EFFECT OF THE INVENTION) Yo Si and the novolac resin in which the impure metallic component was reduced can be manufactured to the present invention. This resin has useful existence of an impure metallic component in especially the semiconductor manufacture field that is not preferred.