200925174 六、發明說明： 【發明所屬之技術領域] 本發明係關於使紛类員與二環戊二稀類進行反應而製造紛 樹脂的方法。 【先前技術】 由酚類與二環戊二烯類進行反應而獲得的酚樹脂（以下亦 稱為二環戊二烯類改質酚樹脂或改質酚樹脂），係可有用地 〇 使用作為流動性與吸濕性優異的環氧樹脂原料，將該酴樹月曰 施行環氧化而得的環氧樹脂係可使用作為半導體密封劑或 印刷佈線基板用積層板的材料。 二環戊二烯類改質酚樹脂係將酚類與二環戊二烯類（以下 亦稱DCPD類）與酸觸媒一起施行加熱而進行製造。酸觸媒係 有如：三氟化硼、三氟化硼•酚錯合物、三氟化棚·鍵錯合 物等。酸觸媒係待反應結束後，使用鹼性的觸媒中和劑進打 ❿中和而去活化。此係為了防止若反應結束後仍有酸觸媒殘 留’在後續之將未反應酚施行蒸餾除去的步驟中會使反應過 度進行。 將酸觸媒中和後的反應生成液係可分類為：由中和劑與酸 觸媒殘渣構成的固形份、以及含有未反應紛類與二環戊二烯 類改質酚樹脂的濾液。將濾液施行減壓蒸餾，將未反應酚類 蒸餾除去，再將二環戊二烯類改質酚樹脂回收。 當將二環戊二烯類改質酚樹脂使用作為半導體密封劑或 97138836 3 200925174 積^板的材料時’因為有造成電絕緣性等降低的可能性，因 而當進行改質紛樹脂製造之際，必需將反應生成液中的紛 類、雜質充分地去除。特別係必需將源自_媒的魏合物 與氟化°物’最好去除至25ppm以下，尤以22ppra以下為佳。 然而’因為佩合物與氟化合物的—部分會溶解於紛類中， 即使施行過濾，仍有殘留於反應生成液中的問題發生。 $知，在上述改質酚樹脂之製造時，觸媒中和劑係使用碳 ❺酸約或氫氧化納。此種觸媒中和劑無法將蝴化合物與氟化合 物吸附，導致在反應生成液中容易殘留硼化合物與氟化合 物。相對於此，在日本專利第3028385號中提案將水滑石類 使用於觸媒中和劑中。水滑石類係具有將酸觸媒中和的效 果，且會吸附硼化合物與氟化合物，因而可減少反應生成液 中的雜質。然而，在半導體密封劑、印刷佈線基板用積層板 用途中，係要求更進一步的雜質削減，利用水滑石類施行酸 ❹觸媒的中和時，會發生雜質之削減仍嫌不足的問題。 再者，在日本專利特開平11-199659號公報中提案：將酸 觸媒利用氫氧化鈣等無機鹼施行中和而去活化後，於所獲得 之反應生成液中添加含有吸附水的粉體（例如活性白土、& 性白土、活性碳等），再將經中和所生成的錯合物施行水解， 而獲得硼化合物與氟化合物之含有量少之改質酚樹脂的# 法。但是，該方法係有粉體中的吸附水溶解於未反應酚中的 問題。因而，待反應結束後，於從改質酚樹脂所蒸餾回收的 97138836 4 200925174 過剩盼中’係成為含有水分。其結果，當使用該回收酚進行 下一次的改質酚樹脂製造時，部分的酸觸媒因水分而去活 化’導致反應效率降低、改質酚樹脂特性降低的問題發生。 本發明之目的在於提供將雜質含有量減少至能使用作為 半導體密封劑、印刷佈線基板用積層板之原始材料（raw material)程度的二環戊二烯類改質酚樹脂之製造方法。 【發明内容】 〇 本發明係關於二環戊二烯類改質酚樹脂之製造方法，其包 括有：將盼類及二環戊二烯類作為反應原料並在酸觸媒存在 下進行反應，而製造二環戊二烯類改質酚樹脂的反應步驟 (I) ;以及在依該反應步驟（I)所獲得之反應生成液中添加鹼 性化合物及沸石，而將該酸觸媒去活化的酸觸媒去活化步驟 (II) 。 本發明的二環戊二烯類改質酚樹脂之製造方法，最好包括 ❹有：從依上述賴媒去活化步驟⑴）所獲得之反應生成液中 將上述沸石、酸觸媒及未反應原料除去，而獲得U二稀 類改質盼樹脂的樹脂回收步驟（111)。 【實施方式】 以下針對本發明之實郷態進行詳纟H㈣等僅為本 發明實施形態之-例，本發明當然不偈限於該等内容。 本發明所使用的酚類並無特別的服 J丨艮制，最佳可舉出例如： 酚、鄰曱酚、間甲酚、對曱酚、2, 6、_ m 〜曱笨酚或該等的混合 97138836 5 200925174 物。其中’從樹脂的特性與經濟 本發明所使用的_類亦無特:= 二烯（以下亦稱DCPD)或由至幻 』取好為一故戍 .環紅烯或料㈣合物。妓係取tr :樹脂的特性與取得容易度的觀點而言，最好使用二環戍二200925174 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a method for producing a resin by reacting a genus with a dicyclopentadiene. [Prior Art] 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 An epoxy resin material which is excellent in fluidity and hygroscopicity, and an epoxy resin obtained by epoxidizing the eucalyptus eucalyptus 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. The acid catalyst system is, for example, boron trifluoride, boron trifluoride phenol complex, trifluorochemical shed, and key mismatch. The acid catalyst is deactivated by the neutralization of the oxime with an alkaline catalyst neutralizer after the reaction is completed. This is to prevent the acid catalyst from remaining if the reaction is completed. The reaction is excessively carried out in the subsequent step of subjecting the unreacted phenol to distillation. The reaction product liquid after neutralization by the acid catalyst can be classified into a solid portion composed of a neutralizing agent and an acid catalyst residue, and a filtrate containing unreacted condensed and 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 semiconductor encapsulant or a material of a 97138836 3 200925174 laminate, 'because there is a possibility of causing a decrease in electrical insulation or the like, when the modified resin is produced, It is necessary to sufficiently remove the impurities and impurities in the reaction product liquid. In particular, it is necessary to remove the derivative and the fluorinated material from the medium to 25 ppm or less, particularly preferably 22 ppra or less. However, since the part of the composition and the fluorine compound is dissolved in the genus, even if filtration is performed, the problem remaining in the reaction product liquid occurs. It is understood that in the manufacture of the above modified phenol resin, the catalyst neutralizing agent uses carbonic acid or sodium hydroxide. Such a catalyst neutralizing agent cannot adsorb the butterfly compound and the fluorinated compound, and the boron compound and the fluorinated compound are likely to remain in the reaction product. On the other hand, it is proposed in Japanese Patent No. 3028385 to use hydrotalcites in a catalyst neutralizing agent. 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 the neutralization of the acid catalyst, the reduction of impurities is still 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, & white clay, activated carbon, etc.), the complex formed by neutralization is hydrolyzed 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, 97138836 4 200925174 which is distilled from the modified phenol resin is excessively desired to be contained. As a result, when the recycled phenol resin is used for the production of the next modified phenol resin, some of the acid catalyst is deactivated by moisture, which causes a problem that the reaction efficiency is lowered and the properties of the modified phenol resin are lowered. It is an object of the present invention 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. SUMMARY OF THE INVENTION The present invention relates to a method for producing a dicyclopentadiene-based modified phenol resin, which comprises reacting a diphenylpentadiene as a reaction raw material and reacting in the presence of an acid catalyst. And a reaction step (I) for producing a dicyclopentadiene-modified phenol resin; and adding a basic compound and a zeolite to the reaction product obtained in the reaction step (I) to deactivate the acid catalyst The acid catalyst is deactivated in step (II). The method for producing a dicyclopentadiene-based modified phenol resin of the present invention preferably comprises: reacting the zeolite, the acid catalyst, and the unreacted reaction from the reaction product obtained by the above-mentioned solvent deactivation step (1)) The raw material is removed to obtain a resin recovery step (111) of the U diuretic modified resin. [Embodiment] The following is a detailed description of the actual state of the present invention. H (4) and the like are merely examples of the embodiments of the present invention, and the present invention is of course not limited to the contents. The phenols used in the present invention are not particularly preferred, and are preferably, for example, phenol, o-nonylphenol, m-cresol, p-nonylphenol, 2,6, _m-nonylphenol or Etc. Mix 97138836 5 200925174. Among them, the characteristics and economy of the resin are also unspecified in the invention: = diene (hereinafter also referred to as DCPD) or from illusion is taken as a ring. Red cycloolefin or material (tetra) compound.妓 is taken from tr: the characteristics of the resin and the ease of availability, it is best to use two-ring bismuth
〇 备使朌類與請類進行反應時，藉由調整其進料莫耳比 _/_貞），便可調節所獲得之_ _旨__。 即，若增力增類的進料莫耳比，則改質盼樹脂的軟化點便降 低，反之，若減少_的進料莫耳比，則改質_脂的軟化 點便上升。為能製得具有工業上有意義的軟化點(?〇〜15〇 C，最好為8〇〜14〇。〇的改質盼樹脂，進料莫耳比最好設為 1/1〜15/1，尤以2/M0/1為佳。 在使酚類與DCPD類進行反應之際所使用的酸觸媒，係可 舉例如：三氟化硼、三氟化硼•酚錯合物、三氟化硼•醚錯 合物等。其中，最好為處置容易且每單位觸媒量的改質酚樹 月曰之產率大之三氟化硼•驗錯合物。酸觸媒的使用量係當二 氟化蝴•紛錯合物的情況，為DCPD類每1〇〇質量份使用 〇. 1〜20質量份，最好為〇 5〜1〇質量份。 酚類與DCPD類的反應溫度係依照酸觸媒的種類而異，當 二氟化侧•酚錯合物的情況，係設為20〜17〇乞，最好為 50〜150°C。 97138836 6 200925174 該反應最好在水分儘可能少的狀態下實施，最好在100 質量ppm以下。 當反應生成物的黏度上升停滯’則中止加熱，施行反應生 成物中的酸觸媒之去活化。該酸觸媒的去活化係在反應生成 物中添加鹼性化合物及沸石，在10〜15(rc(最好為3〇〜9(rc) 下施行10分〜10小時（最好為2〇分〜5小時）的加熱攪拌。鹼 性化合物及沸石的添加係可同時實施，亦可依個別步驟實 ©施。酸觸媒去活化的結束係利用例如溶解於甲基異丁酮中， 並在該溶液中添加水且施行攪拌，再測定水層的pH便可進 行確認。 在酸觸媒去活化步驟中所使用的沸石係主成分為驗金屬 或鹼土族金屬的鋁矽酸鹽，具有依M2/n〇 · Al2〇3/xSi〇2/yH2〇(式中，μ表示金屬離子，n表示原子價，X、 y表示整數）所示組成，例如Nai2[(Al〇2)12(si〇2)12] · Ο W 27H2〇⑽型）或 Na86[(Al〇2)86(Si〇2)丨〇6] · 276Μ)(1Π 型）等組 成的吸附劑。 沸石係將在酸觸媒中和時所生成的酸觸媒殘渣、硼化合 物、氟化合物、驗（土族）金屬等雜質充分地予以吸附，提升 反應生成液的純度。沸石之所以可充分吸附該等雜質的理 由’係因沸石中具有無數細孔，侵入該細孔内部的雜質會被 細孔内部的内壁所吸附。 在酸觸媒去活化步驟中所使用之沸石的平均細孔徑並無 97138836 7 200925174 特別的限制，最好設定為1〜20Α(0· ，尤以 5〜15Α(0· 5〜1· 5nm)為佳’硼化合物與氟化合物的吸附能力可 較優異。該沸石的比表面積並無特別的限制，係設定為 50(M500m2/g，尤以 7〇〇~1300m2/g 為佳。When the cockroach is reacted with the class, the _____ can be adjusted by adjusting the feed molar ratio _/_贞. That is, if the molar ratio of the feed is increased, the softening point of the resin is lowered, and if the feed molar ratio of _ is decreased, the softening point of the modified fat rises. In order to obtain an industrially meaningful softening point (?〇~15〇C, preferably 8〇~14〇. 改 改 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼In particular, it is preferable that 2/M0/1 is used. The acid catalyst used for the reaction between the phenol and the DCPD may, for example, be boron trifluoride or boron trifluoride or a phenol complex. A boron trifluoride ether complex, etc. Among them, a boron trifluoride complex which is easy to handle and has a large yield per unit amount of the catalyst, and a large amount of boron trifluoride complex. The amount used is in the case of a difluorinated compound, and is used for each part of the DCPD type. 1 to 20 parts by mass, preferably 〇5 to 1 part by mass. Phenol and DCPD The reaction temperature varies depending on the type of the acid catalyst, and in the case of the difluorinated side phenol complex, it is set to 20 to 17 Torr, preferably 50 to 150 ° C. 97138836 6 200925174 In the state where the water content is as small as possible, it is preferably 100 mass ppm or less. When the viscosity of the reaction product rises and stagnates, the heating is stopped, and the acid catalyst in the reaction product is deactivated. The deactivation system of the acid catalyst adds a basic compound and zeolite to the reaction product, and performs 10 minutes to 10 hours (preferably 2 minutes) at 10 to 15 (rc (preferably 3 to 9 (rc)). Heating and stirring for ~5 hours). The addition of the basic compound and the zeolite can be carried out at the same time, or can be carried out according to individual steps. The end of the acid catalyst deactivation is utilized, for example, in the dissolution of methyl isobutyl ketone, and Water is added to the solution and stirred, and the pH of the aqueous layer can be determined. The main component of the zeolite used in the acid catalyst deactivation step is an aluminum citrate of a metal or alkaline earth metal. M2/n〇· Al2〇3/xSi〇2/yH2〇 (wherein, μ represents a metal ion, n represents an atomic valence, and X and y represent an integer), for example, Nai2[(Al〇2)12(si 〇2)12] · Ο W 27H2〇(10) type) or Na86[(Al〇2)86(Si〇2)丨〇6] · 276Μ) (1Π type) and other adsorbents. The zeolite system will be in acid touch The acid catalyst residue, boron compound, fluorine compound, and (earth metal) metal generated during the neutralization of the medium are sufficiently adsorbed to enhance the purity of the reaction liquid. The reason why zeolite can sufficiently adsorb these impurities is because the zeolite has numerous pores, and impurities that intrude into the pores are adsorbed by the inner wall of the pores. The zeolite used in the acid catalyst deactivation step The average pore diameter is not particularly limited by 97138836 7 200925174. It is preferably set to 1~20Α(0·, especially 5~15Α(0·5~1·5nm) is preferred. The adsorption capacity of boron compound and fluorine compound can be The specific surface area of the zeolite is not particularly limited, and is set to 50 (M500 m 2 /g, particularly preferably 7 〇〇 to 1300 m 2 /g).
該沸石的粒徑、形狀亦均無特別的限制，當粉末狀的情 況，平均粒徑為尤以5~1〇〇#m為佳，當粒狀的 情況，平均粒徑最好為0.5〜4mm。若粒徑超越上限值，會有 硼化合物、氟化合物的吸附性降低之情況，若粒徑較小於下 限值，則有過濾速度降低的情況’因而最好避免。 從可有效率地將魏合物與氟化合物吸附之觀點以及兼 顧過濾性的觀點而言，最好平均粒徑為丨〜丨⑽#^(尤以 1〇〜50_為佳）的粉末㈣石。料均粒徑超過上述上限 值’會有合物、氟化合物的吸附性降低之情況，若平均 粒徑小於上述下限值，則有職速度降低的情況，因而最好 避免。 彿石係内部具有細孔的吸附劑，例如从型的細孔徑係約 0. 35ηιη，可通過有效直徑達〇 4ηπι的分子。 該沸石的使用量係驗性化合物每刚質量份使用叫綱 質量份，最好為50〜500質量份。 沸石之製造方法並無特別的限制，可舉__ 的方法、從夭然礦物進行製造的方法等。作為從試製= 造的方法’#可為以料制、崎納作為起始原料丁表 97138836 8 200925174 =天然礦物進仃製造的方法，係可舉出從酸性白土、高嶺 真珠石、長石等進行製造的方法。例如將高嶺土礦物施 行锻境而形成雜高嶺土（metakac)lin)，經提高反應性之後再 .添加氫氧化_方法，或者將高嶺土、火山玻璃施行磨碎， 故破壞結晶結構之後再添加氫氧化納的方法等。 在酸觸媒去活化步針所使㈣驗性化合物並無特別的 希】最好為如.氫氧化鈉、氫氧化鉀、氫氧化弼、碳酸舞、 ❹碳酸氫納、碳酸細、氨等，尤錢氧化_佳。臉性化合 物的添加量並無特別的限制，相對於酸觸媒^質量份係添加 卜10質量倍’最好為2〜5質量倍。若驗性化合物的添加量 超過該上限量’騎濾時間變得過久，改質_脂的生產性 降低。反之，右驗性化合物的添加量少於該下限量，則有酸 觸媒的去活化不足之問題發生。 將酸觸媒去活化的反應生成物，係利用蒸餾、過濾等固液 〇分離手段，分類為液體與固形份，最好採行過濾，因為較為 簡便。該過濾的方法、條件並無特別的限制，過濾最好係為 減壓過濾或加壓過濾。過濾溫度係室溫〜15(rc，最好為 70〜130〇C。 過;慮殘渣係改質紛樹脂，經回收並使用作為各種用途的原 始材料。經回收的改質酚樹脂係軟化點7〇〜15〇<t，最好為 80〜14(TC，PH為5. 0〜9. 0，最好為6. 〇〜8· 〇，硼化合物與氟 化合物含有量分別在25質量ppm以下，最好為22質量ppm 97138836 9 200925174 以下’可絲施行特別處理、 為半導體密封劑、 濾液係經蒸餾， 持別處理、精製的情況下，適當地使用作 印刷佈線基板用積層板等的材料。The particle size and shape of the zeolite are also not particularly limited. In the case of a powder, the average particle diameter is preferably 5 to 1 〇〇 #m, and in the case of granules, the average particle diameter is preferably 0.5 〜. 4mm. When the particle diameter exceeds the upper limit, the adsorptivity of the boron compound or the fluorine compound may be lowered. If the particle diameter is smaller than the lower limit value, the filtration rate may be lowered. From the viewpoint of efficiently adsorbing the Wei compound and the fluorine compound, and from the viewpoint of both the filterability, it is preferable that the average particle diameter is 丨~丨(10)#^ (especially 1〇~50_ is preferable) powder (4) stone. When the average particle diameter exceeds the above upper limit value, the adsorptivity of the compound or the fluorine compound may be lowered. When the average particle diameter is less than the above lower limit value, the occupational speed may be lowered, and thus it is preferable to avoid it. The sorbent having pores inside the buddha system, for example, a type of pore diameter of about 0.35 ηηη, can pass through a molecule having an effective diameter of 〇 4 η πι. The amount of the zeolite to be used is usually from 50 to 500 parts by mass per part by mass of the test compound. The method for producing the zeolite is not particularly limited, and examples thereof include a method of producing a zeolite, a method of producing from a cumin mineral, and the like. As a method of trial production = production, it can be used as a starting material for the production of raw materials, and it is a raw material. The method of producing natural minerals is as follows: acid white clay, kaolinite, feldspar, etc. The method of manufacture. For example, kaolin minerals are subjected to forging to form metakac lin), and after the reactivity is increased, the oxidization method is added, or kaolin and volcanic glass are ground, so that the crystal structure is destroyed and then sodium hydride is added. Method etc. In the acid catalyst to activate the stylus, (4) the test compound is not particularly singular, such as sodium hydroxide, potassium hydroxide, barium hydroxide, carbonated dance, sodium hydrogencarbonate, carbonic acid, ammonia, etc. , especially money oxidation _ good. The amount of the face compound to be added is not particularly limited, and is preferably 10 parts by mass or more preferably 2 to 5 times by mass based on the mass of the acid catalyst. If the amount of the test compound added exceeds the upper limit amount, the riding time becomes too long, and the productivity of the modified fat is lowered. On the other hand, if the amount of the right-handed 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 which is 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 preferred 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. Filtration temperature is room temperature ~ 15 (rc, preferably 70 ~ 130 〇 C. Over; consider the residue is modified resin, recovered and used as raw materials for various purposes. Recycled modified phenol resin softening point 7〇~15〇<t, preferably 80~14 (TC, PH is 5. 0~9. 0, preferably 6. 〇~8· 〇, boron compound and fluorine compound content are respectively 25 mass In the case of ppm or less, it is preferably 22 mass ppm. 97138836 9 200925174 The following is a special treatment for the wire, and the semiconductor sealing agent and the filtrate are subjected to distillation, and when they are subjected to separate treatment and purification, they are suitably used as a laminate for a printed wiring board. s material.
另外，該回收盼的純度為90 並回收未反應的盼。該蒸餘係可在加壓下 ，但最好為減壓蒸餾。蒸餾溫度係 150〜270°C，尤以170〜25(TC為佳。 90質量％以上’可再利用於下一 次的改質酚樹脂製造。 ©以下’湘實施例針對本發明進行更詳盡的說明。 另外’反應生成液的PH係將約0· 5g之生成液溶解於2〇cifl3 的甲基異丁酮中，添加20cm3之水並充分擾拌。經搜拌後， 靜置30分鐘，再利用PH儀測定水層的pH。 一裱戊二烯類改質酚樹脂的軟化點係使用環球式軟化點 測定裝置（MEITECH公司製，25D5_ASP_MG型），於甘油浴中， 依5 C/分的升溫速度進行測定。 二環戊二烯類改質酚樹脂的硼化合物及氟化合物之含有 量’係使用原子吸光裝置[島津製作所（股）製，型號 AA-6200]，利用原子吸光法進行測定。 (實施例1)In addition, the purity of the recovery is 90 and unreacted is recovered. The steaming system can be under pressure, but is preferably distilled under reduced pressure. The distillation temperature is 150 to 270 ° C, especially 170 to 25 (TC is preferred. 90% by mass or more 'can be reused for the next modified phenol resin production. © The following 'Xiang embodiment' for the present invention is more detailed In addition, the pH of the reaction product solution was dissolved in about 0.5 μg of methyl isobutyl ketone in 2 cifl3, and 20 cm 3 of water was added and fully scrambled. After mixing, it was allowed to stand for 30 minutes. The pH of the water layer was measured by a pH meter. The softening point of the pentadiene-based modified phenol resin was measured by a global softening point measuring device (manufactured by MEITECH, model 25D5_ASP_MG) in a glycerin bath at 5 C/min. The amount of the boron compound and the fluorine compound in the dicyclopentadiene-based modified phenol resin was measured by atomic absorption method using an atomic absorption device [manufactured by Shimadzu Corporation, model AA-6200]. Determination. (Example 1)
在具備有攪拌裝置、溫度計、回流裝置、非活性氣體導入 管及油浴的反應容器（可分離式燒瓶：1L)中，進料入市售酚 278g〇2. 9mol)，並加熱至80°c。待加熱結束後，添加三氟 化硼•酚錯合物2. 5g，進一步升溫至14(TC，將DcpD 97138836 10 200925174 100g(=0. 76mol)歷時2小時徐緩添加而進行反應。待添加結 束後，添加氫氧化鈣7. 5g與沸石[和光純藥（股）製，合成沸 石F9，粉末，細孔徑9A(9nm)，平均粒徑7#m(2〇〇篩目通 過物），比表面積n〇Om2/g]2. 5g，攪拌30分鐘，將酸觸媒 中和而去活化。待攪拌結束後，將反應生成液過濾。將濾液 升溫至220°C，施行減壓蒸顧，而將未反應的紛iggg蒸顧 除去。 ❹ 蒸餾殘渣（=酚樹脂A)產量係195g。測定酚樹脂的軟化 點、pH、硼含有量及氟含有量，結果如表1所示。 (實施例2) 除在實施例1中’取代紛而改為使用鄰曱盼之外，其餘均 重複實施例1的步驟。測定所獲得樹脂的軟化點、pH、爛含 有量及氟含有量，結果如表1所示。 (實施例3) ® 除在實施例1中，取代酚而改為使用2,6-二曱苯酚之外， 其餘均重複實施例1的步驟。測定所獲得樹脂的軟化點、 pH、溯含有量及氟含有量’結果如表1所示。 (實施例4) 除在實施例1中，取代沸石[和光純藥（股）製，合成沸石 F9，粉末，細孔徑9A(9nm) ’平均粒徑7//111(200篩目通過 物），比表面積n〇〇m2/g]，改為使用沸石[和光純藥（股）製， 合成沸石A3，粉末，細孔徑3A(3nm)，平均粒徑 97138836 11 200925174 篩目通過物），比表面積1000m2/g]2. 5g之外，其餘均重複 實施例1的步驟。測定改質酚樹脂的軟化點、pH、硼含有量 及氟含有量，結果如表1所示。 " (實施例5) 除在實施例1中，取代氳氧化鈣7. 5g而改為使用氫氧化 鈉7. 5g之外，其餘均重複實施例1的步驟。測定改質酚樹 脂的軟化點、pH、硼含有量及氟含有量，結果如表1所示。 ❹（比較例1) 除在實施例1中，取代氫氧化鈣7. 5g與沸石2. 5g而改為 使用氬氧化鈣10g之外，其餘均重複實施例1的步驟。測定 改質酚樹脂的軟化點、pH、硼含有量及氟含有量，結果如表 1所示。 (比較例2) 除在實施例1中，取代氫氧化#5 7. 5g與沸石2. 5g而改為 〇 使用水滑石10g之外，其餘均重複實施例1的步驟。測定改 質酚樹脂的軟化點、pH、硼含有量及氟含有量，結果如表1 所示。 (比較例3) . 除在實施例1中，取代沸石2. 5g而改為使用活性白土 [東 新化成（股）製，活性白土 E，比表面積約200m2/g，水分量5 質量％]2. 5g之外，其餘均重複實施例1的步驟。測定改質 酚樹脂的軟化點、pH、硼含有量及氟含有量，結果如表1 97138836 12 200925174 所示。 [表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, the commercially available phenol 278 g 〇 2. 9 mol) was heated and heated to 80 ° C. . After the completion of the heating, a boron trifluoride phenol complex was added in an amount of 2.5 g, and the temperature was further raised to 14 (TC, and DcpD 97138836 10 200925174 100 g (=0.76 mol) was slowly added for 2 hours to carry out the reaction. After adding calcium hydroxide 7. 5g and zeolite [Wako Pure Chemicals Co., Ltd., synthetic zeolite F9, powder, pore size 9A (9nm), average particle size 7#m (2〇〇 mesh passage), ratio The surface area is n〇Om2/g]2. 5g, stirred for 30 minutes, neutralized by acid catalyst and deactivated. After the stirring is completed, the reaction product liquid is filtered. The filtrate is heated to 220 ° C, and decompression is carried out. The unreacted iggg was removed by steaming. 产量 The distillation residue (= phenol resin A) 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 the substitution was repeated in Example 1, and the softening point, pH, rotten content, and fluorine content of the obtained resin were measured. As shown in Table 1. (Example 3) ® Except that in Example 1, instead of phenol, instead of using 2,6-diphenyl phenol The procedure of Example 1 was repeated, and the softening point, pH, traceability, and fluorine content of the obtained resin were measured as shown in Table 1. (Example 4) In addition to Example 1, the substituted zeolite [ Wako Pure Chemicals Co., Ltd., synthetic zeolite F9, powder, pore size 9A (9nm) 'average particle size 7//111 (200 mesh passage), specific surface area n〇〇m2/g], use zeolite instead [Wako Pure Chemicals Co., Ltd., synthetic zeolite A3, powder, pore size 3A (3nm), average particle size 97138836 11 200925174 mesh passage), specific surface area 1000m2 / g] 2. 5g, the rest are repeated The steps of Example 1. 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 calcium oxyhydroxide was replaced by 7. 5 g instead of sodium hydroxide of 7. 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. ❹ (Comparative Example 1) The procedure of Example 1 was repeated except that in Example 1, the calcium hydroxide was replaced by 7. 5 g and the zeolite 2. 5 g instead of using 10 g of calcium argon oxide. 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, except that the hydroxide #57.5 g was replaced with the zeolite 2. 5 g and the hydrotalcite was used in an amount of 10 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. (Comparative Example 3). In the first embodiment, instead of the zeolite 2. 5 g, the activated clay was used instead [manufactured by Tosho Kasei Co., Ltd., activated clay E, specific surface area of about 200 m 2 /g, moisture content of 5 mass %] The procedure of Example 1 was repeated except for the 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 97138836 12 200925174. [Table 1]
(產業上之可利用性） ❹ 根據本發明之製造方法，可獲 劑、印刷佈線基板用積層板等’、 ‘、、、體密封 二環戊二賴改質酚:之軟化點與雜質含有量的 改質盼樹脂施行環氧化伸、依照本發明方法所製得之 Ο 異，可有效使用為半導體密_化°物’係屬於電氣特性優 的原料。 在封劑、印刷佈線基板用積層板等 97138836 13(Industrial Applicability) ❹ According to the production method of the present invention, a replenisher, a laminated board for a printed wiring board, or the like, a ', ', and a body-sealed bicyclopentadiene-modified phenol: softening point and impurity content The amount of modification is expected to be carried out by the epoxidation and stretching of the resin, and the difference in the method of the present invention can be effectively used as a material having excellent electrical characteristics. Sealing agent, laminated board for printed wiring board, etc. 97138836 13