201033255 六、發明說明： 【發明所屬之技術領域】 本發明係關於可高產率地得到低熔融黏度、低分子量 的酚醛清漆樹脂之製造方法。 【先前技術】 酚樹脂具有耐熱性且被使用於各種領域。 例如：作爲環氧樹脂之硬化劑用時，耐熱性、密著性 及電氣絕緣性等優異，可被用於印刷基板用樹脂組成物、 使用於印刷基板及附有樹脂的銅箔之層間絕緣材料用樹脂 組成物、電子零件之封裝材料用樹脂組成物、光阻印墨、 導電糊、塗料、接著劑、複合材料等。 隨著近年來的技術革新，有提升環氧樹脂組成物之額 外的耐濕性、耐熱性及難燃性等之需求。 有增加塡充劑之使用量作爲其解決手段之一。 藉由增加塡充劑量可使成形品的線膨脹係數降低、吸 濕率降低、難燃性提升，但另一方面由於塡充量變多摻合 物的流動性降低，而有所謂成形性變差的問題產生，故有 樹脂成分之低熔融黏度化的需要產生。 酚醛清漆樹脂係在酸性觸媒的存在下加成縮合酚類及 醛類來製造。 通常，相對於酚類而言，醛類係在莫耳比爲〇.3〜〇.9 莫耳的範圍下使用，藉由調整莫耳比來控制所得到之樹脂 的分子量。 要降低樹脂的熔融黏度需要盡量減少高分子量成分， 201033255 但爲了得到分子量低的酚醛清漆樹脂，必須使莫耳比變 小’此種情形下會導致未反應的酚單體殘存變多。 雖然樹脂中之未反應的酚類單體可藉由在減壓下蒸餾 來降低’但由於需要藉由蒸餾來除去莫耳比低的樹脂中之 大量的酚類單體，故無法避免產率的降低。 一方面，酚類單體殘存於樹脂中時，因爲成型物的尺 寸安定性低下、容易引起孔隙之產生等，故樹脂中的酚類 單體最好是盡可能的降低。 〇 因爲在這樣的背景下，於是開始硏討酚醛清漆樹脂的 高產率化（參照專利文獻1及2)。 在專利文獻1中揭示在磷酸觸媒的存在下使酚類與三 聚甲醛進行非均質反應的方法。 雖然透過此方法時可提升酚類的反應率，但由於限定 觸媒爲磷酸，故與反應性比三聚甲醛低的醛類，例如：乙 醛或丁醛等的脂肪族醛、苯甲醛或柳醛等的芳香族醛反應 時，無法得到充分的反應性。 G 在專利文獻2中揭示在有機膦酸觸媒及水溶性中性鹽 的存在下，使酚類與醛類反應的方法，藉由形成存在觸媒 的水相與容易溶解樹脂的有機相來提升單體反應率。 然而，因爲此方法限定在觸媒爲有機膦酸，故與反應 性比前述甲醛低的醛類時，無法得到充分的反應性。 此外，提升觸媒效率因爲需要110 °C以上的溫度，而無 法避免高分子量體的生成，對於得到低分子量的酚醛清漆 樹脂而言是不適合的。 -4 - 201033255 再者，專利文獻2之中，爲了使有機相與水相能更明 確地分離之目的，而使用中性鹽增加水相的離子濃度° 因此，對中性鹽來說重要的是對水的溶解性要高’其 構成元素則並非特別重要。 使乙醛或丁醛等的脂肪族醛、苯甲醛或柳醛等的芳香 族醛與酚類反應時，需要大量地使用鹵化氫或磺酸系化合 物等比磷酸或有機膦酸更強的酸，且較高的反應溫度。 在這樣的條件下，由於變得容易生成高分子量成分， 〇 而難以得到低分子量的酚醛清漆樹脂。 因此，使用比甲醛或三聚甲醛反應性低的醛類’而想 要得到高產率的低分子量之酚醛清漆樹脂時’迄今並沒有 有效的製造手段。 [專利文獻] [專利文獻1]特開20〇4-3 3 925 7號公報 [專利文獻2]特開2002- 1 28 849號公報 【發明内容】 © <發明所欲解決之課題> 本發明係基於上述之情事而完成者，本發明之目的係提 供一種有效率地製造低熔融黏度、低分子量的酚醛清漆樹 脂之方法，其係在溫和的條件下使酚類與醛類（特別是碳原 子數爲2以上的脂肪族醛及芳香族醛）反應。 <解決課題的手段> 本案發明者發現藉由使用含有一般所使用的酸與氯化 鈣的觸媒可解決上述課題，進而完成本發明。 201033255 即，本發明要旨如下。 1· 一種酚醛清漆樹脂的製造方法，其特徵在於含氯化鈣及酸 的觸媒存在下，使酚類與醛類反應。 2. 如上述1之酚醛清漆樹脂的製造方法，其中酸爲草酸或磷 酸。 3. 如上述1或2之酚醛清漆樹脂的製造方法，其可獲得分散 度（重量平均分子量/數量平均分子量）爲i.3以下、且在 150°C之熔融黏度爲300mPa.s以下之酚醛清漆樹脂。 φ 根據本發明可藉由在含氯化鈣及酸的觸媒存在下，使酚 類與醛類反應’而能有效率地得到低分子量且低熔融黏度的 酚醛清漆樹脂。 【實施方式】 以下詳細地說明本發明。 本發明之酚醛清漆樹脂的製造方法係在含氯化鈣及酸 的觸媒存在下，使酚類與醛類反應。 就使用於本發明的酚類而言，只要是可被使用於一般的 φ 酚樹脂之製造即可，例如：苯酚、各種甲酚、各種乙苯酚、 各種二甲苯酚、各種乙苯酚、各種丁苯酚、各種辛苯酚、各 種壬苯酚、各種苯基苯酚、各種環己苯酚、各種三甲苯酚、 雙酚A、鄰苯二酚、間苯二酚、氫醌、各種萘酚、焦五倍子 酚等，可單獨或混合兩種以上使用。 此等當中，實用上較佳爲苯酚或各種甲酚。 一方面，作爲與酚類反應的醛類，只要是可被使用於酚 樹脂的製造的醛類即可以使用。 201033255 例如：甲醛、乙醛、三聚甲醛、各種丙醛、各種丁醛、 各種戊醛、各種己醛、乙二醛、巴豆醛、戊二醛、苯甲醛、 各種羥基本甲醒、各種二羥苯甲酸、各種涇基甲苯甲醒等， 可單獨或混合兩種以上使用。 相對於1莫耳酚類的合計量來說，最好是上述醛類的使 用量係以使用0.3〜1.0莫耳爲佳、更佳爲〇4~〇9莫耳的比 率。 酸類的使用量小於0.3莫耳時，由於殘存的酚類單體變 〇 多，而沒效率。 另一方面，醛類的使用量超過1.〇莫耳時，由於得到的 樹脂的分子量變高，而不佳。 就使用於本發明方法的酸而言，只要是可被使用於一般 的酚醛清漆樹脂之製造即可，可列舉例如：草酸、磷酸、對 甲苯磺酸及鹽酸等，可單獨或混合兩種以上使用。 考慮到對於反應設備的腐蝕等時，較佳爲草酸或磷酸。 相對於100質量份酚類而言，最好是酸的使用量以使用 〇 0.1~20質量份爲佳、較佳爲0.1〜10重量份、更佳爲0.2〜5 重量份的比率。 在本發明之中係進一步使用氯化鈣作爲觸媒成分。 氯化鈣可爲具有結晶水者與無水物，較佳爲無水物。 相對於100質量份酚類而言，最好是氯化鈣的使用量係 以使用1~20質量份，較佳爲2〜10質量份的比率》 氯化鈣的使用量小於1質量份時’由於酚類與醛類的反 應率下降而不佳；超過20質量份時’由於幾乎沒有提升反 201033255 應率的效果，故不實用。 以本發明之製造方法所得到的酚醛清漆樹脂之數量平 均分子量爲200~500、較佳爲250~400、更佳爲250~3 50。 數量平均分子量於上述範圍内時，可降低酚醛清漆樹脂 的熔融黏度，作爲環氧樹脂的硬化劑可發揮充分的效果。 此外，分散度（重量平均分子量/數量平均分子量）爲1·3 以下、更佳爲1.2以下。 分散度爲1.3以下者，意味著酚醛清漆樹脂中的多核體 0 較少。爲了降低酚醛清漆樹脂的熔融黏度，需要盡可能的減 少多核體的含有量。 再者，150°C下熔融黏度爲3 00mPa*s、較佳爲250mPa· s以下。 熔融黏度爲300mPa· s以下時，作爲環氧樹脂的硬化劑 使用時，由於提升摻合物的流動性，故可得到成形性優異的 摻合物。 使酚類與醛類反應的方法並沒有特別限制，可列舉例 φ 如：使酚類、醛類、氯化鈣及酸一起進料反應之方法、或進 料酚類、氯化鈣及酸後，在指定的反應溫度下添加醛類。 此時，在反應溫度爲3 0~ 120 °C之範圍者進行者爲佳。 小於30°C時反應的進行變慢，且由於殘存未反應的酚 類，而不佳；又，就超過120 °C的溫度而言，由於加快高分 子量成分的生成，而不佳。 反應時間並沒有特別的限制，若根據醛類、氯化鈣及酸 的量、反應溫度來調整爲佳。 201033255 反應時，當然也可使用有機溶劑。 作爲有機溶劑可單獨使用丙醇、丁醇等的醇類、乙二 醇、丙二醇等的二醇類、乙二醇單甲醚、乙二醇單乙醚、丙 二醇單甲醚、丙二醇單乙醚、丁二醇單甲醚、丁二醇單乙醚、 丁二醇單丙醚等的二醇醚類、甲基乙基酮、甲基異丁基酮等 的酮類、乙酸丙酯、乙酸丁酯、乳酸乙酯、乙二醇單甲醚乙 酸酯、丙二醇單甲醚乙酸酯等的酯類、1，4-二噚烷等的醚 類等，或二種以上合倂使用。 〇 相對於1〇〇質量份酚類而言，前述有機溶劑係可使用 0-1 000質量份、更佳爲10〜100質量份左右。 然而，以不使用水作爲溶劑爲佳。 由於氯化鈣水溶性高，水存在系統内時會立即溶解，當 變成氯化鈣水溶液時由於會使反應效率降低’故不佳。 此外，由於因酚類與醛類的反應而生成縮合水，伴隨著 反應的進行氯化鈣緩緩的吸收水，而變成溶化狀態，但只要 不完全地變成透明的狀態就沒有問題。 © 但是，爲了防止氯化鈣對水分的吸收之目的可使用硫酸 鈣、矽膠、分子篩等的乾燥劑。 相對於100質量份酚類化合物而言，前述乾燥劑係可使 用0〜20質量份、更佳爲〇〜10質量份左右。 反應終了後，藉由蒸餾去除縮合水。此外’亦可依需求 水洗來除去氯化鈣及酸。 再者，亦可進行減壓蒸餾或水蒸氣蒸餾，以除去未反應 之酚類或未反應之醛類。 201033255 <實施例> 以下顯示根據本發明之製造方法的酚醛清漆樹脂之實 施例及比較例，進一步地具體說明本發明，但本發明並不受 限於以下實施例。 實施例1 將苯酚l〇〇g、苯甲醛56g、氯化鈣5g及草酸lg進料至 備有冷卻管、攪拌機的燒瓶中，在50°C反應3小時。 接著，以純水100g進行3次洗淨，除去氯化鈣及草酸。 〇 其次’在180°C、50mmHg的減壓下，除去蒸餾出的部 分，得到酚醛清漆樹脂A 98g。 圖1中顯示樹脂A的凝膠滲透層析（GPC)圖。此外，橫 軸係表示溶出時間（分）。由圖1可知樹脂A爲低分子量的2 核體之主要生成物。 實施例2 除了使用磷酸lg代替草酸以外，與實施例1同樣地進 行，得到酚醛清漆樹脂B 98g。 ® 實施例3 除了使用異丁醛38g當作醛類以外，與實施例1同樣地 進行，得到酚醛清漆樹脂C 90g » 實施例4 除了使用鄰位甲酚l〇〇g當作酚類、異丁醛33g當作醛 類以外，與實施例1同樣地進行，得到酚醛清漆樹脂D 89g。 比較例1 將鄰位甲酚l〇〇g、苯甲醛49g及草酸lg進料至備有冷 -10- .201033255 卻管、攪拌機的燒瓶中，在100°C反應8小時，反應無法進 行而無法得到樹脂。 比較例2 將鄰位甲酚l〇〇g、苯甲醛49g、氯化鈉5g及草酸lg進 料至備有冷卻管、攪拌機的燒瓶中，在100°C反應8小時， 反應無法進行而無法得到樹脂。 比較例3 將苯酚100g、苯甲醛56g及對甲苯磺酸l〇g進料至備有 ❹ 冷卻管、攪拌機的燒瓶中，在l〇〇°C反應8小時。 接著，以氫氧化鈉水溶液中和後，以純水1 〇〇g進行5 次洗淨，除去生成的鹽。 其次，在180°c、5.0mmHg的減壓下，除去蒸餾出的部 分，得到酚醛清漆樹脂E 83g。 圖2中顯示樹脂E的凝膠滲透層析（GPC)圖。此外，橫 軸係表示溶出時間（分）。 由圖2可知樹脂E係爲2核體以外之大量的多核體生成 ® 者。 比較例4 除了使用鄰位甲酚當作酚類以外’與比較例3同樣地進 行反應，得到酚醛清漆樹脂F 77g。 關於在實施例1 ~3所得到之酚醛清漆樹脂、在比較例 3〜4所得之酚醛清漆樹脂，以下述分析方法所測定之値顯示 於表1。 樹脂之分析方法係如下所示 201033255 (1) 數量平均分子量、重量平均分子量、分散度 藉由凝膠滲透層析（GPC)來測定。 管柱構成係使用2支昭和電工（股）製造之KF-8 04’使用 四氫呋喃作爲溶劑，以流量lml/分鐘來測定。 分子量係以聚苯乙烯換算來算出，而含有率係以全波峰 面積中的百分率來算出。 分散度係以重量平均分子量/數量平均分子量來算出。 (2) 軟化點（t：) 〇 使用ELEX科學製氣相軟化點測定裝置EX-719PD，以 升溫速度2.5 °C /分鐘來測定。 (3)熔融黏度（mPa’s) 使用Research Equipment公司製造之ICI黏度計，在 150°C測定。 表1 樹脂A 樹脂B 樹脂C 樹脂D 樹脂E 樹脂F 數量平均分子量 310 300 290 290 670 610 重量平均分子量 370 360 340 320 1700 1300 分散度 1.2 1.2 1.2 1.1 2.5 2.1 產量(g) 98 98 90 89 83 77 熔融黏度(mPa.s) 225 210 31 34 2000 1000 軟化Ιέ(。。） 96 94 68 71 119 117 [産業利用性] 本發明之酚醛清漆樹脂由於熔融黏度低，故流動性 高’使用其作爲環氧樹脂之硬化劑的熱硬化性樹脂組成 -12- 201033255 物，其成形時之流動性顯著地提升。 使用本發明之酚醛清漆樹脂作爲半導體封裝材使用 時，藉由增加塡充劑量可使成形品的線膨脹係數降低、吸 濕率降低、難燃性提升。 此外’其硬化物具有良好的耐熱性、耐濕性、機械的 特性、電氣絕緣性、對金屬的接著性等，因此，在需要高 可靠性的電子材料用途方面係非常有用地。 具體而言，可被利用於電子零件之封裝材料用樹脂組 Ο 成物、印刷基板用樹脂組成物、使用於印刷基板及附有樹 脂的銅箔之層間絕緣材料用樹脂組成物、光阻印墨、導電 糊（含有導電性塡充劑）、塗料、接著劑、複合材料等。 【圖式簡單說明】 圖1爲實施例1中的酚醛清漆樹脂之GPC圖。 圖2爲比較例3中的酚醛清漆樹脂之GPC圖。 【主要元件符號說明】201033255 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a low-melting viscosity, low molecular weight novolak resin which can be obtained in high yield. [Prior Art] Phenolic resins are heat resistant and are used in various fields. For example, when used as a curing agent for an epoxy resin, it is excellent in heat resistance, adhesion, electrical insulation, and the like, and can be used for a resin composition for a printed circuit board, and for interlayer insulation of a printed circuit board and a resin-attached copper foil. Resin composition for materials, resin composition for encapsulating materials for electronic parts, photoresist ink, conductive paste, paint, adhesive, composite material, and the like. With the recent technological innovations, there is a need to increase the moisture resistance, heat resistance, and flame retardancy of the epoxy resin composition. There is an increase in the use of sputum as one of its solutions. By increasing the charge amount, the linear expansion coefficient of the molded article can be lowered, the moisture absorption rate can be lowered, and the flame retardancy can be improved. On the other hand, the fluidity of the blend is decreased due to the decrease in the amount of the charge, and the so-called formability is deteriorated. The problem arises, so there is a need for a low melt viscosity of the resin component. The novolac resin is produced by adding a condensed phenol and an aldehyde in the presence of an acidic catalyst. Generally, the aldehyde is used in the range of 莫.3 to 〇.9 摩尔 with respect to the phenol, and the molecular weight of the obtained resin is controlled by adjusting the molar ratio. To reduce the melt viscosity of the resin, it is necessary to minimize the high molecular weight component, 201033255. However, in order to obtain a novolak resin having a low molecular weight, the molar ratio must be made small. In this case, the residual amount of unreacted phenol monomer is increased. Although the unreacted phenolic monomer in the resin can be lowered by distillation under reduced pressure, the yield cannot be avoided because a large amount of phenolic monomer in the resin having a low molar ratio is required to be removed by distillation. The reduction. On the other hand, when the phenolic monomer remains in the resin, the phenolic monomer in the resin is preferably reduced as much as possible because the dimensional stability of the molded article is low and the occurrence of voids is likely to occur.在 In the background, the high yield of the novolak resin is started (see Patent Documents 1 and 2). Patent Document 1 discloses a method of heterogeneously reacting phenols with paraformaldehyde in the presence of a phosphoric acid catalyst. Although the reaction rate of phenols can be increased by this method, since the limiting catalyst is phosphoric acid, it is an aldehyde which is lower in reactivity than trioxane, for example, an aliphatic aldehyde such as acetaldehyde or butyraldehyde, benzaldehyde or When an aromatic aldehyde such as salicylaldehyde is reacted, sufficient reactivity cannot be obtained. G Patent Document 2 discloses a method of reacting a phenol with an aldehyde in the presence of an organic phosphonic acid catalyst and a water-soluble neutral salt, by forming an aqueous phase in which a catalyst is present and an organic phase in which a resin is easily dissolved. Increase the monomer reaction rate. However, since this method is limited to the organic phosphonic acid in the catalyst, sufficient reactivity cannot be obtained when it is an aldehyde having a lower reactivity than the above-mentioned formaldehyde. Further, the improvement of the catalyst efficiency is not suitable for obtaining a low molecular weight novolak resin because a temperature of 110 ° C or higher is required, and the formation of a high molecular weight body cannot be avoided. -4 - 201033255 Further, in Patent Document 2, in order to separate the organic phase and the aqueous phase more clearly, the neutral salt is used to increase the ion concentration of the aqueous phase. Therefore, it is important for the neutral salt. It is highly soluble in water. The constituent elements are not particularly important. When an aromatic aldehyde such as acetaldehyde or butyraldehyde or an aromatic aldehyde such as benzaldehyde or salicyl is reacted with a phenol, it is necessary to use a large amount of an acid such as a hydrogen halide or a sulfonic acid compound which is stronger than phosphoric acid or an organic phosphonic acid. And a higher reaction temperature. Under such conditions, it is difficult to obtain a low molecular weight novolak resin because it is easy to produce a high molecular weight component. Therefore, when an aldehyde having a lower reactivity than formaldehyde or trioxane is used, and a low-molecular-weight novolak resin having a high yield is desired, there has been no effective production means. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. The present invention has been completed based on the above circumstances, and an object of the present invention is to provide a method for efficiently producing a low melt viscosity, low molecular weight novolak resin which is capable of imparting phenols and aldehydes under mild conditions (especially It is a reaction of an aliphatic aldehyde having a carbon number of 2 or more and an aromatic aldehyde. <Means for Solving the Problem> The inventors of the present invention have found that the above problems can be solved by using a catalyst containing a generally used acid and calcium chloride, and the present invention has been completed. 201033255 That is, the gist of the present invention is as follows. A method for producing a novolak resin, which comprises reacting a phenol with an aldehyde in the presence of a catalyst containing calcium chloride and an acid. 2. The method for producing a novolac resin according to the above 1, wherein the acid is oxalic acid or phosphoric acid. 3. The method for producing a novolak resin according to the above 1 or 2, wherein a phenolic having a degree of dispersion (weight average molecular weight/number average molecular weight) of i.3 or less and a melt viscosity of 150 mPa.s or less at 150 ° C is obtained. Varnish resin. According to the present invention, a novolak resin having a low molecular weight and a low melt viscosity can be efficiently obtained by reacting a phenol with an aldehyde in the presence of a catalyst containing calcium chloride and an acid. [Embodiment] Hereinafter, the present invention will be described in detail. The method for producing a novolak resin of the present invention is to react a phenol with an aldehyde in the presence of a catalyst containing calcium chloride and an acid. The phenol used in the present invention may be used in the production of a general φ phenol resin, for example, phenol, various cresols, various phenols, various xylenols, various phenols, various butyl groups. Phenol, various octylphenols, various phenols, various phenylphenols, various cyclohexyl phenols, various tricresols, bisphenol A, catechol, resorcinol, hydroquinone, various naphthols, pyrogallol, etc. They may be used alone or in combination of two or more. Among these, phenol or various cresols are preferably used practically. On the other hand, the aldehyde which reacts with the phenol can be used as long as it is an aldehyde which can be used for the production of a phenol resin. 201033255 For example: formaldehyde, acetaldehyde, trioxane, various propionaldehydes, various butyraldehydes, various valeraldehydes, various hexanal, glyoxal, crotonaldehyde, glutaraldehyde, benzaldehyde, various hydroxyl groups, all kinds of two Hydroxybenzoic acid, various mercaptotoluene, etc., may be used singly or in combination of two or more. The amount of the above aldehyde is preferably from 0.3 to 1.0 mol, more preferably from 4 to 〇9 mol, based on the total amount of the 1 molar solvent. When the amount of the acid used is less than 0.3 mol, the residual phenolic monomer is too much, and it is inefficient. On the other hand, when the amount of the aldehyde used exceeds 1. mole, the molecular weight of the obtained resin becomes high, which is not preferable. The acid to be used in the method of the present invention may be used in the production of a general novolak resin, and examples thereof include oxalic acid, phosphoric acid, p-toluenesulfonic acid, and hydrochloric acid, and may be used alone or in combination of two or more. use. In view of corrosion or the like to the reaction equipment, oxalic acid or phosphoric acid is preferred. The amount of the acid to be used is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by weight, still more preferably from 0.2 to 5 parts by weight, per 100 parts by mass of the phenol. In the present invention, calcium chloride is further used as a catalyst component. The calcium chloride may be a person having crystal water and an anhydride, preferably an anhydride. The amount of calcium chloride used is preferably from 1 to 20 parts by mass, preferably from 2 to 10 parts by mass, per 100 parts by mass of the phenol. When the amount of calcium chloride used is less than 1 part by mass 'The reaction rate of phenols and aldehydes is not good. When it exceeds 20 mass parts, it is not practical because it has almost no effect of increasing the rate of anti-201033255. The novolak resin obtained by the production method of the present invention has an average molecular weight of 200 to 500, preferably 250 to 400, more preferably 250 to 3 50. When the number average molecular weight is within the above range, the melt viscosity of the novolak resin can be lowered, and a sufficient effect can be exhibited as a curing agent for the epoxy resin. Further, the degree of dispersion (weight average molecular weight / number average molecular weight) is preferably 1.3 or less, more preferably 1.2 or less. A dispersion of 1.3 or less means that the polynuclear body 0 in the novolac resin is small. In order to reduce the melt viscosity of the novolak resin, it is necessary to reduce the content of the polynuclear body as much as possible. Further, the melt viscosity at 150 ° C is 300 mPa*s, preferably 250 mPa·s or less. When the melt viscosity is 300 mPa·s or less, when used as a curing agent for an epoxy resin, since the fluidity of the blend is improved, a blend having excellent moldability can be obtained. The method for reacting the phenol with the aldehyde is not particularly limited, and examples thereof include a method of feeding a phenol, an aldehyde, a calcium chloride, and an acid together, or feeding a phenol, a calcium chloride, and an acid. Thereafter, the aldehyde is added at the specified reaction temperature. In this case, it is preferred that the reaction temperature is in the range of from 30 to 120 °C. When the temperature is less than 30 °C, the progress of the reaction becomes slow, and it is not preferable because residual unreacted phenol remains. Further, in the case of a temperature exceeding 120 °C, it is not preferable because the formation of a high molecular weight component is accelerated. The reaction time is not particularly limited, and it is preferably adjusted depending on the amount of the aldehyde, calcium chloride, and acid, and the reaction temperature. 201033255 Of course, organic solvents can also be used in the reaction. As the organic solvent, an alcohol such as propanol or butanol, a glycol such as ethylene glycol or propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or butyl can be used alone. a glycol ether such as diol monomethyl ether, butanediol monoethyl ether or butanediol monopropyl ether; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; propyl acetate; butyl acetate; Ethyl lactate, ethylene glycol monomethyl ether acetate, esters such as propylene glycol monomethyl ether acetate, ethers such as 1,4-dioxane, or the like, or two or more kinds thereof.前述 The organic solvent may be used in an amount of from 0 to 1000 parts by mass, more preferably from 10 to 100 parts by mass, per part by mass of the phenol. However, it is preferred to use no water as a solvent. Since calcium chloride has high water solubility, water dissolves immediately when it is present in the system, and when it becomes an aqueous solution of calcium chloride, the reaction efficiency is lowered, which is not preferable. In addition, the condensed water is formed by the reaction of the phenols and the aldehydes, and the calcium chloride gradually absorbs water in accordance with the reaction, and becomes molten. However, there is no problem as long as it is not completely transparent. © However, in order to prevent the absorption of moisture by calcium chloride, a desiccant such as calcium sulfate, tannin or molecular sieve can be used. The desiccant may be used in an amount of from 0 to 20 parts by mass, more preferably from about 10 parts by mass to 100 parts by mass per 100 parts by mass of the phenolic compound. After the end of the reaction, the condensed water was removed by distillation. In addition, it can also be washed with water to remove calcium chloride and acid. Further, vacuum distillation or steam distillation may be carried out to remove unreacted phenols or unreacted aldehydes. 201033255 <Examples> The present invention will be further specifically described below with reference to examples and comparative examples of the novolac resin of the production method of the present invention, but the present invention is not limited to the following examples. Example 1 100 g of phenol, 56 g of benzaldehyde, 5 g of calcium chloride and lg of oxalic acid were fed to a flask equipped with a cooling tube and a stirrer, and reacted at 50 ° C for 3 hours. Then, it was washed three times with 100 g of pure water to remove calcium chloride and oxalic acid. 〇 Next, the distilled portion was removed under reduced pressure of 180 ° C and 50 mmHg to obtain 98 g of novolak resin A. A gel permeation chromatography (GPC) chart of Resin A is shown in FIG. Further, the horizontal axis indicates the elution time (minutes). It is understood from Fig. 1 that the resin A is a main product of a low molecular weight 2-nuclear body. Example 2 In the same manner as in Example 1, except that lg of phosphoric acid was used instead of oxalic acid, 98 g of novolak resin B was obtained. ® Example 3 A novolak resin C 90 g was obtained in the same manner as in Example 1 except that 38 g of isobutyraldehyde was used as the aldehyde. Example 4 In addition to the use of o-cresol 〇〇g as a phenol, In the same manner as in Example 1, except that 33 g of butyraldehyde was used as the aldehyde, 89 g of a novolak resin D was obtained. Comparative Example 1 An ortho-cresol l〇〇g, a benzaldehyde 49 g, and an oxalic acid lg were fed to a flask equipped with a cold -10.201033255 tube and a stirrer, and reacted at 100 ° C for 8 hours, and the reaction could not proceed. Unable to get the resin. Comparative Example 2 An ortho-cresol l〇〇g, benzaldehyde 49 g, sodium chloride 5 g, and oxalic acid lg were fed to a flask equipped with a cooling tube and a stirrer, and reacted at 100 ° C for 8 hours, and the reaction could not proceed. The resin was obtained. Comparative Example 3 100 g of phenol, 56 g of benzaldehyde, and 10 g of p-toluenesulfonic acid were fed to a flask equipped with a crucible cooling tube and a stirrer, and reacted at 10 ° C for 8 hours. Subsequently, after neutralizing with an aqueous sodium hydroxide solution, it was washed five times with 1 g of pure water to remove the salt formed. Next, the distilled portion was removed under reduced pressure of 180 ° C and 5.0 mmHg to obtain 83 g of a novolak resin E. A gel permeation chromatography (GPC) chart of Resin E is shown in FIG. Further, the horizontal axis indicates the elution time (minutes). It can be seen from Fig. 2 that the resin E is a large number of multinuclear products other than the two cores. Comparative Example 4 The reaction was carried out in the same manner as in Comparative Example 3 except that ortho-cresol was used as the phenol, and 77 g of the novolak resin F was obtained. The novolak resins obtained in Examples 1 to 3 and the novolak resins obtained in Comparative Examples 3 to 4 were measured by the following analytical methods and shown in Table 1. The analysis method of the resin is as follows: 201033255 (1) The number average molecular weight, the weight average molecular weight, and the degree of dispersion are determined by gel permeation chromatography (GPC). The column structure was measured using KF-8 04' manufactured by Showa Denko Electric Co., Ltd. using tetrahydrofuran as a solvent at a flow rate of 1 ml/min. The molecular weight was calculated in terms of polystyrene, and the content ratio was calculated as a percentage of the total peak area. The degree of dispersion is calculated by weight average molecular weight / number average molecular weight. (2) Softening point (t:) 〇 The ELEX Scientific Vapor Softening Point Measuring Device EX-719PD was used and measured at a heating rate of 2.5 °C / min. (3) Melt viscosity (mPa's) Measured at 150 ° C using an ICI viscometer manufactured by Research Equipment. Table 1 Resin A resin B resin C resin D resin E resin F number average molecular weight 310 300 290 290 Melt viscosity (mPa.s) 225 210 31 34 2000 1000 Softening Ιέ (..) 96 94 68 71 119 117 [Industrial Applicability] The novolak resin of the present invention has high fluidity due to its low melt viscosity, and is used as a ring. The thermosetting resin composition of the hardener of the oxygen resin is -12-201033255, and the fluidity at the time of molding is remarkably improved. When the novolak resin of the present invention is used as a semiconductor package, the linear expansion coefficient of the molded article can be lowered, the moisture absorption rate can be lowered, and the flame retardancy can be improved by increasing the amount of the charge. Further, the cured product has excellent heat resistance, moisture resistance, mechanical properties, electrical insulating properties, adhesion to metals, and the like, and is therefore very useful in applications requiring high reliability of electronic materials. Specifically, it can be used for a resin composition for a packaging material for an electronic component, a resin composition for a printed substrate, a resin composition for an interlayer insulating material used for a printed substrate and a copper foil with a resin, and a photoresist Ink, conductive paste (containing conductive chelating agent), paint, adhesive, composite material, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a GPC chart of a novolak resin in Example 1. 2 is a GPC chart of a novolak resin in Comparative Example 3. [Main component symbol description]
Srrr 撕。 ❹ -13-Srrr tears. ❹ -13-