[0002] 異氰脲酸衍生物及其合成方法自過去以來即已知。例如非專利文獻1之第393頁至第396頁中，記載關於單烷基異氰脲酸酯之合成方法。進而非專利文獻4中，雖記載關於非專利文獻1之第394頁之詳細內容，但第3618頁之關於具有CH3
基及sec-C4
H9
基之單烷基異氰脲酸衍生物之合成之記載係在250℃之高溫條件下進行反應，除此以外，均限定於烷基者。且，非專利文獻2中，介紹2,4,6-三(苄氧基)-1,3,5-三嗪、4,6-雙(苄氧基)-1,3,5-三嗪-2,4(1H,3H)-二酮及6-(苄氧基)-1,3,5-三嗪-2,4(1H,3H)-二酮中之6-(苄氧基)-1,3,5-三嗪-2,4(1H,3H)-二酮作為苄基化試藥顯示出最出色反應性之研究結果。非專利文獻3中，記載使用四丁基銨異氰尿酸酯之N-甲基化，均生成單、二及三甲基異氰脲酸酯。亦即，藉由該非專利文獻3記載之方法，無法避免非選擇性地生成該等3種N-甲基化異氰脲酸酯之混合物。 [0003] 異氰脲酸衍生物可使用於各種用途。例如專利文獻1中記載含異氰脲酸衍生物之微影用抗反射膜形成組成物。專利文獻2中記載包含使異氰脲酸衍生物與其他單體聚合而得之聚合物的接著劑組成物。 ［先前技術文獻］ ［非專利文獻］ [0004] 非專利文獻1：Edwin M. Smolin; Lorence Rapoport. “Isocyanuric acid and derivatives”. The chemistry of heterocyclic compounds. s- Triazines and derivatives., INTERSCIENCE PUBLISHERS, INC., pp.389-422(1959) 非專利文獻2：Journal of Organic Chemistry, 80, pp. 11200-11205(2015) 非專利文獻3：Tetrahedron Letters, 44, pp4399-4402(2003) 非專利文獻4：Journal of American Chemical Society, 75, pp. 3617-3618(1953) ［專利文獻］ [0005] 專利文獻1：國際公開WO02/086624號 專利文獻2：國際公開WO2013/035787號[0002] Isocyanuric acid derivatives and methods of their synthesis have been known since the past. For example, pages 393 to 396 of Non-Patent Document 1 describe methods for synthesizing monoalkyl isocyanurates. Furthermore, in Non-Patent Document 4, although details on page 394 of Non-Patent Document 1 are described, on page 3618 is a monoalkyl isocyanuric acid derivative having a CH 3 group and a sec-C 4 H 9 group. The description of the synthesis is that the reaction is performed under a high temperature condition of 250 ° C, and all are limited to those having an alkyl group. In addition, Non-Patent Document 2 introduces 2,4,6-tri (benzyloxy) -1,3,5-triazine, 4,6-bis (benzyloxy) -1,3,5-triazine -2,4 (1H, 3H) -dione and 6- (benzyloxy) -1,3,5-triazine-2,4 (1H, 3H) -dione 6- (benzyloxy) -1,3,5-triazine-2,4 (1H, 3H) -dione as the benzylation reagent showed the best reactivity. Non-Patent Document 3 describes that N-methylation of tetrabutylammonium isocyanurate produces mono, di, and trimethyl isocyanurate. That is, by the method described in Non-Patent Document 3, it is impossible to avoid the non-selective formation of a mixture of the three N-methylated isocyanurates. [0003] Isocyanuric acid derivatives can be used in various applications. For example, Patent Document 1 describes an anti-reflection film-forming composition for lithography containing an isocyanuric acid derivative. Patent Document 2 describes an adhesive composition containing a polymer obtained by polymerizing an isocyanuric acid derivative and another monomer. [Prior Art Literature] [Non-Patent Literature] [0004] Non-Patent Literature 1: Edwin M. Smolin; Lorence Rapoport. "Isocyanuric acid and derivatives". The chemistry of heterocyclic compounds. S- Triazines and derivatives., INTERSCIENCE PUBLISHERS, INC ., pp.389-422 (1959) Non-Patent Document 2: Journal of Organic Chemistry, 80, pp. 11200-11205 (2015) Non-Patent Document 3: Tetrahedron Letters, 44, pp4399-4402 (2003) Non-Patent Document 4 : Journal of American Chemical Society, 75, pp. 3617-3618 (1953) [Patent Literature] [0005] Patent Literature 1: International Publication WO02 / 086624 Patent Literature 2: International Publication WO2013 / 035787
［發明欲解決之課題］ [0006] 本發明之目的在於提供可期待作為例如抗蝕劑下層膜形成組成物之原料的用途之新穎異氰脲酸酯衍生物及其新穎製造方法。 ［用以解決課題之手段］ [0007] 本發明之發明人為解決前述課題而重複積極研究之結果，確認可合成具有一個包含烷氧基之取代基作為與氮原子鍵結之取代基的異氰脲酸酯化合物，因而完成本發明。亦即，本發明係一種下述式(1)表示之具有一個包含烷氧基之取代基的異氰脲酸衍生物，(式中，R1
表示碳原子數1至10之烷基，R2
表示碳原子數1至5之伸烷基，n表示0至5之整數)。 [0008] 本發明亦係一種下述式(1’)表示之具有一個包含烷氧基之取代基的異氰脲酸衍生物，其係前述以式(1)表示之異氰脲酸衍生物之製造中間體，(式中，R1
、R2
及n分別與前述式(1)同義，Bn表示苯環之至少一個氫原子可經甲基取代之苄基)。 [0009] 前述式(1)及式(1’)中之R1
表示例如碳原子數1或2之烷基。 [0010] 前述式(1)及式(1’)中之R2
表示例如碳原子數1或2之伸烷基。 [0011] 本發明又係一種具有一個包含烷氧基之取代基的異氰脲酸衍生物之製造方法，其包含下述步驟： 於選自由芳香族烴類及醚類所成之群中之至少一種溶劑中使下述式(2)表示之化合物與鹼金屬碳酸鹽反應後，藉由與下述式(3)表示之化合物反應而獲得含有下述式(1’)表示之化合物(但式(3)及式(1’)中，n表示0)之溶液的第一步驟，及 於使前述含有式(1’)表示之化合物之溶液與醇化合物，在三氟甲烷磺酸或三氟甲烷磺酸三甲基矽烷酯之存在下反應而得之反應產物中，添加有機鹼並使該反應產物濃縮，隨後使用選自由酯類所成之群中之至少一種溶劑對其進行洗淨，而獲得下述式(1)表示之化合物(但式中，n表示0)之第二步驟， 且所有步驟係在不超過100℃之溫度進行。 且再者，本發明係一種具有一個包含烷氧基之取代基的異氰脲酸衍生物之製造方法，其包含下述步驟： 於選自由芳香族烴類及醚類所成之群中之至少一種溶劑中使下述式(2)表示之化合物與鹼金屬碳酸鹽反應後，藉由與下述式(3)表示之化合物反應而獲得含有下述式(1’)表示之化合物(但式(3)及式(1’)中，n表示1至5之整數)之溶液的第一步驟，及 於使前述含有式(1’)表示之化合物之溶液與醇化合物，在三氟甲烷磺酸或三氟甲烷磺酸三甲基矽烷酯之存在下反應而得之反應產物中，添加有機鹼並使該反應產物濃縮，接著溶解於非質子性極性溶劑中，隨後使用選自由酯類所成之群中之至少一種溶劑使其再結晶，而獲得下述式(1)表示之化合物(但式中n表示1至5之整數)之第二步驟， 且所有步驟係在不超過100℃之溫度進行，(式中，R1
表示碳原子數1至10之烷基，R2
表示碳原子數1至5之伸烷基，n表示0或1至5之整數，Bn表示苯環之至少一個氫原子可經甲基取代之苄基，X表示氯基、溴基或碘基)。 [0012] 作為前述以式(3)表示之化合物之例，n表示0時，為例如氯甲基甲基醚、溴甲基甲基醚或氯甲基乙基醚，且n表示1至5時，為例如2-甲氧基乙氧基甲基氯。 [0013] 前述第一步驟所用之鹼金屬碳酸鹽為例如碳酸鉀或碳酸銫。 [0014] 前述第一步驟所用之芳香族烴類及醚類分別為例如甲苯及環戊基甲基醚。 [0015] 前述第二步驟所用之至少一種溶劑為例如乙酸乙酯。 [0016] 前述不超過100℃之溫度係0℃至100℃，例如0℃至50℃。 ［發明效果］ [0017] 本發明之具有一個包含烷氧基之取代基的異氰脲酸衍生物可期待作為抗蝕劑下層膜形成組成物等之聚合物或寡聚物成分之原料之用途。且本發明之具有一個包含烷氧基之取代基的異氰脲酸衍生物藉由成為與多官能環氧化合物等之反應產物，估計可提高自含該反應產物之抗蝕劑下層膜形成組成物等形成之膜的蝕刻速率及提高溶解性。再者，本發明之具有一個包含烷氧基之取代基的異氰脲酸衍生物之製造方法，並無必要單離第一步驟所得之中間體，即可進行第二步驟中之反應，由於貫徹全製程不存在以超過100℃之溫度進行之步驟，故工業上有用。[Problems to be Solved by the Invention] [0006] An object of the present invention is to provide a novel isocyanurate derivative which can be expected to be used as a raw material for a resist underlayer film forming composition, and a novel production method thereof. [Means for Solving the Problem] [0007] As a result of repeated researches by the inventors of the present invention in order to solve the aforementioned problems, it was confirmed that an isocyanate having a substituent containing an alkoxy group as a substituent bonded to a nitrogen atom can be synthesized. Urate compounds, thus completing the present invention. That is, the present invention is an isocyanuric acid derivative represented by the following formula (1) having a substituent containing an alkoxy group, (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkylene group having 1 to 5 carbon atoms, and n represents an integer of 0 to 5). [0008] The present invention is also an isocyanuric acid derivative represented by the following formula (1 ') having a substituent containing an alkoxy group, which is the aforementioned isocyanuric acid derivative represented by the formula (1) Manufacturing intermediates, (In the formula, R 1 , R 2 and n are respectively synonymous with the aforementioned formula (1), and Bn represents a benzyl group in which at least one hydrogen atom of the benzene ring may be substituted with a methyl group). [0009] R 1 in the aforementioned formula (1) and formula (1 ′) represents, for example, an alkyl group having 1 or 2 carbon atoms. [0010] R 2 in the formula (1) and the formula (1 ′) represents, for example, an alkylene group having 1 or 2 carbon atoms. [0011] The present invention is also a method for producing an isocyanuric acid derivative having a substituent containing an alkoxy group, which comprises the following steps: selected from the group consisting of aromatic hydrocarbons and ethers After reacting a compound represented by the following formula (2) with an alkali metal carbonate in at least one solvent, the compound represented by the following formula (1 ') is obtained by reacting with a compound represented by the following formula (3) (but In formula (3) and formula (1 '), n is a first step of a solution, and the solution containing the compound represented by formula (1') and an alcohol compound are mixed with trifluoromethanesulfonic acid or trifluoromethanesulfonic acid. To the reaction product obtained by the reaction in the presence of trimethylsilyl fluoromethanesulfonate, an organic base is added and the reaction product is concentrated, and then it is washed with at least one solvent selected from the group consisting of esters. The second step is to obtain a compound represented by the following formula (1) (wherein n represents 0), and all steps are performed at a temperature not exceeding 100 ° C. Furthermore, the present invention is a method for producing an isocyanuric acid derivative having a substituent containing an alkoxy group, which comprises the following steps: In a group selected from the group consisting of aromatic hydrocarbons and ethers After reacting a compound represented by the following formula (2) with an alkali metal carbonate in at least one solvent, the compound represented by the following formula (1 ') is obtained by reacting with a compound represented by the following formula (3) (but In formula (3) and formula (1 '), n is a first step of a solution of n), and the solution and the alcohol compound containing the compound represented by formula (1') are mixed with trifluoromethane. To the reaction product obtained by the reaction in the presence of sulfonic acid or trimethylsilyl trifluoromethanesulfonate, an organic base is added and the reaction product is concentrated, and then dissolved in an aprotic polar solvent. At least one solvent in the formed group is recrystallized to obtain a second step of the compound represented by the following formula (1) (where n represents an integer of 1 to 5), and all steps are not more than 100 ℃ temperature, (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkylene group having 1 to 5 carbon atoms, n represents an integer of 0 or 1 to 5, and Bn represents at least one hydrogen atom of a benzene ring Benzyl which may be substituted by methyl, X represents chloro, bromo or iodo). [0012] As an example of the aforementioned compound represented by formula (3), when n represents 0, it is, for example, chloromethyl methyl ether, bromomethyl methyl ether, or chloromethyl ethyl ether, and n represents 1 to 5 In this case, it is, for example, 2-methoxyethoxymethyl chloride. [0013] The alkali metal carbonate used in the aforementioned first step is, for example, potassium carbonate or cesium carbonate. [0014] The aromatic hydrocarbons and ethers used in the first step are, for example, toluene and cyclopentyl methyl ether. [0015] At least one solvent used in the aforementioned second step is, for example, ethyl acetate. [0016] The aforementioned temperature not exceeding 100 ° C is 0 ° C to 100 ° C, such as 0 ° C to 50 ° C. [Effects of the Invention] [0017] The isocyanuric acid derivative of the present invention having a substituent containing an alkoxy group is expected to be used as a raw material for polymer or oligomer components such as a resist underlayer film-forming composition. . In addition, the isocyanuric acid derivative having a substituent containing an alkoxy group of the present invention is expected to improve the composition of the underlayer film formed from the resist containing the reaction product by becoming a reaction product with a polyfunctional epoxy compound or the like. Etching rate and solubility of the film formed by materials and the like. Furthermore, in the method for producing an isocyanuric acid derivative having a substituent containing an alkoxy group according to the present invention, it is not necessary to separate the intermediate obtained in the first step, and the reaction in the second step can be performed. There is no step for carrying out the whole process at a temperature exceeding 100 ° C, so it is industrially useful.
[0019] 本發明之具有一個包含烷氧基之取代基的異氰脲酸衍生物係前述式(1)表示。該式(1)中，R1
表示之碳原子數1至10之烷基可為直鏈狀、分支鏈狀、環狀任一者。作為該烷基舉例為例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、正戊基、正己基、正庚基、正辛基、正戊基、正壬基、正癸基、環己基甲基、及環戊基甲基。且該式(1)中，作為R2
表示之碳原子數1至5之伸烷基舉例為例如亞甲基、伸乙基、伸丙基、三亞甲基、伸丁基及伸戊基。 [0020] 作為本發明之具有一個包含烷氧基之取代基的異氰脲酸衍生物舉例為例如下述式(1-1)至式(1-20)表示之化合物。[0021] 於上述本發明之製造方法之任一者，均於第一步驟中，係使前述式(2)表示之化合物於溶劑中與鹼金屬碳酸鹽反應後，與前述式(3)表示之化合物反應。前述式(3)表示之化合物之使用量，相對於前述式(2)表示之化合物1莫耳當量，較好為1莫耳當量至1.5莫耳當量，更好1.25莫耳當量。鹼金屬碳酸鹽之使用量，相對於前述式(2)表示之化合物1莫耳當量，較好為1莫耳當量至1.5莫耳當量，更好1.25莫耳當量。作為前述溶劑較好為芳香族烴類或醚類。作為前述芳香族烴類，除前述甲苯以外，作為較佳例舉例為苯、二甲苯、均三甲苯、氯苯、二氯苯、硝基苯及四氫萘。選擇醚類作為前述溶劑時，除前述環戊基甲基醚以外，作為較佳之例舉例為二乙醚、二異丙醚、甲基第三丁基醚、四氫呋喃及二噁烷。為了藉由上述第一步驟，再現性良好地獲得前述式(1’)表示之化合物亦即中間體，事先使前述式(2)表示之化合物與鹼金屬碳酸鹽於溶劑中，於反應溫度為40℃至100℃，較好40℃至60℃，反應時間為30分鐘至2小時，較好30分鐘至1小時進行反應。認為藉由該反應，自前述式(2)表示之化合物之-NH-基拔除氫原子，形成陰離子。該陰離子與前述式(3)表示之化合物反應。前述式(2)表示之化合物與鹼金屬碳酸鹽於溶劑中，於反應溫度未達40℃且反應時間未達30分鐘反應時，前述式(2)表示之化合物與鹼金屬碳酸鹽未完全反應。因此，殘存未反應之前述式(3)表示之化合物，該式(3)表示之化合物藉由鹼金屬碳酸鹽優先分解，故前述式(1’)表示之化合物之收率降低。前述式(2)表示之化合物與鹼金屬碳酸鹽於溶劑中反應後，添加前述式(3)表示之化合物時之反應溫度並未特別限制，但通常為0℃至25℃，較好0℃至5℃。反應時間通常為30分鐘至2小時，較好為30分鐘至1小時。對於由上述反應所得之反應物進行分液操作，藉此可獲得含前述式(1’)表示之化合物之反應溶液。 [0022] 於上述本發明之製造方法之任一者，均於本發明之製造方法之第二步驟中，使前述含有式(1’)表示之化合物之反應溶液與醇化合物，在三氟甲烷磺酸或三氟甲烷磺酸三甲基矽烷酯之存在下反應。作為前述醇化合物，除甲醇以外，舉例為乙醇、異丙醇、正丙醇、第二丁醇、第三丁醇、正丁醇、環己醇及苯酚。前述醇化合物之使用量，相對於前述式(2)表示之化合物1莫耳當量，較好為2莫耳當量至3莫耳當量，更好2.4莫耳當量。前述三氟甲烷磺酸或三氟甲烷磺酸三甲基矽烷酯之使用量，相對於前述式(2)表示之化合物1莫耳當量，較好為0.1莫耳當量至0.5莫耳當量，更好0.2莫耳當量至0.3莫耳當量。前述三氟甲烷磺酸或三氟甲烷磺酸三甲基矽烷酯以0.6莫耳當量以上使用並反應時，會副生與成為目的之前述式(1)表示之化合物不同之雜質。因此，使前述式(1)表示之化合物的純度及收率降低。上述反應時之溫度並未特別限制，但通常為0℃至40℃，較好20℃至30℃。反應時間為1小時至5小時，較好為1小時至2小時。 [0023] 接著，於藉由於上述第二步驟之反應而得之反應產物中添加有機鹼並使該反應產物濃縮，隨後使用酯類作為溶劑對其進行洗淨，藉此獲得前述式(1)表示之化合物(但，式中n表示0)。作為前述有機鹼，作為較佳之例舉例為吡啶、4-二甲胺基吡啶、三乙胺、三丁胺、N,N-二甲基苯胺及1,8-二氮雜雙環[5.4.0]-7-十一碳烯。前述有機鹼之使用量，相對於前述式(2)表示之化合物1莫耳當量，較好為1.0莫耳當量至2.0莫耳當量，更佳為1.2莫耳當量。作為前述酯類，除前述乙酸乙酯以外，作為較佳之例舉例為乙酸甲酯、乙酸丁酯及丙酸甲酯。前述酯類之使用量，相對於前述式(2)表示之化合物，較好為2.0質量倍至5.0質量倍，更佳為3.0質量倍。前述洗淨時之溫度並未特別限定，但通常為0℃至40℃，較佳為20℃至30℃。洗淨時間通常為10分鐘至1小時，較佳為10分鐘至30分鐘。 [0024] 且，於藉由於上述第二步驟之反應而得之反應產物中添加有機鹼並使該反應產物濃縮，溶解於非質子性極性溶劑中，隨後使用酯類作為溶劑使其再結晶，藉此獲得前述式(1)表示之化合物(但，式中n表示1至5之整數)。作為前述有機鹼，作為較佳之例舉例為吡啶、4-二甲胺基吡啶、三乙胺、三丁胺、N,N-二甲基苯胺及1,8-二氮雜雙環[5.4.0]-7-十一碳烯。前述有機鹼之使用量，相對於前述式(2)表示之化合物1莫耳當量，較好為1.0莫耳當量至2.0莫耳當量，更佳為1.2莫耳當量。作為非質子性極性溶劑，舉例為二甲基亞碸、N-甲基吡咯啶酮、二甲基乙醯胺及二甲基甲醯胺。作為前述酯類，除前述乙酸乙酯以外，作為較佳之例舉例為乙酸甲酯、乙酸丁酯及丙酸甲酯。前述非質子性極性溶劑之使用量，相對於前述式(2)表示之化合物，較好為0.5質量倍至1.0質量倍，更佳為0.8質量倍。前述溶解時之溫度並未特別限定，但通常為90℃至120℃，較佳為100℃至110℃。溶解時間通常為10分鐘至1小時，較佳為10分鐘至30分鐘。前述酯類之使用量，相對於前述式(2)表示之化合物，較好為6.0質量倍至10.0質量倍，更佳為8.0質量倍。前述再結晶時之溫度並未特別限定，但通常為0℃至40℃，較佳為0℃至5℃。再結晶時間通常為30分鐘至2小時，較佳為1小時至2小時。 實施例 [0025] 以下列舉實施例說明本發明之具有一個包含烷氧基之取代基的異氰脲酸衍生物之製造方法。但，本發明不限定於以下舉例之具體例。 [0026] ［HPLC分析件］ 後述之例所示之選擇率係利用HPLC所致之測定結果，測定條件等如下。 裝置：島津製作所(股)製，LC-2010A 管柱：XBridge[註冊商標] BEH C18管柱，130Å，5μm，4.6mm×250mm(日本WATERS(股)) 溶離液：乙腈/0.2%乙酸銨水溶液=3/7(v/v)(0分鐘~5分鐘)、自3/7(v/v)至8/2(v/v)變更組成比(5分鐘~10分鐘)、8/2(v/v)(10分鐘~15分鐘) 流量：1.0mL/分鐘 檢測器：UV(210nm) 管柱溫度：40℃ 分析時間：25分鐘 注入量：1.0μL 稀釋溶劑：乙腈/水=1/1(w/w) [0027] ［選擇率算出方法］ 後述之實施例及比較例所示之選擇率係以百分率算出由HPLC分析條件所得之式(1’-1)或式(1’-2)表示之中間體之面積值、及圖1所示之滯留時間13.88分鐘或圖2所示之滯留時間13.82分鐘之副產物之比例者。 [0028] ［收率算出方法］ 後述之合成例及實施例所示之收率係使用所得化合物之質量與理論收量以百分率算出者。又，前述理論收量係藉由使合成使用之原料化合物之莫耳數與所得化合物之分子量相乘而算出者。 [0029] ［原料化合物之合成］ ＜合成例1＞氰脲醯氯(東京化成工業(股)製) 100.00g、苄基醇(關東化學(股)製) 234.56g及氯仿600.00g混合，邊攪拌邊冷卻至0℃。於其中，滴加使二異丙基乙基胺280.33g及氯仿300.00g混合所得之溶液。滴加結束後，升溫至25℃進行15小時攪拌，於反應溶液中添加飽和NH4
Cl水溶液200.00g，進行分液，取出有機層。接著，於該有機層中添加飽和食鹽水200.00g，該分液操作重複進行2次。所得有機層於減壓下餾除溶劑後，殘渣於40℃減壓乾燥。於其中添加乙醇200.00g並於0℃進行30分鐘攪拌。攪拌後過濾，過濾物以乙醇100.00g洗淨2次。所得結晶於40℃減壓乾燥，藉此作為淡黃色固體獲得127.24g之上述式(4)表示之三嗪化合物(收率71.2%)。 [0030]所得之上述式(4)表示之三嗪化合物127.24g、乙酸(關東化學(股)製)46.62g及甲醇636.20g混合，冷卻至5℃。於其中邊攪拌邊添加N-甲基嗎啉(東京化成工業(股)製)157.07g。接著，升溫至25℃進行30分鐘攪拌，於反應溶液中添加氯仿1272.40g、1M HCl 1272.40g進行分液。進而於有機層中添加飽和食鹽水1272.40g進行分液，取出有機層。該有機層於40℃減壓乾燥，添加甲苯254.48g並於25℃進行10分鐘攪拌。攪拌後過濾，過濾物以甲苯127.24g洗淨2次。所得結晶於40℃減壓乾燥，藉此作為白色固體獲得109.21g之上述式(2)表示之三嗪酮化合物(收率90.9%)。 [0031] ＜實施例1＞合成例1所得之前述式(2)表示之三嗪酮化合物100.00g、碳酸銫(東京化成工業(股)製)131.67g及甲苯1000.00g混合，於40℃攪拌30分鐘。攪拌後，冷卻至25℃，於其中滴加氯甲基甲基醚(東京化成工業(股)製)32.54g。滴加結束後，於0℃進行30分鐘攪拌，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-1)表示之中間體之選擇率為91.2%。該測定所得之圖譜示於圖1。 [0032] ＜實施例2＞ 除了使用合成例1所得之前述式(2)表示之三嗪酮化合物1.00g及作為溶劑使用環戊基甲基醚10.00g代替甲苯以外，與實施例1同樣進行，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-1)表示之中間體之選擇率為85.8%。 [0033] ＜比較例1＞ 除了使用合成例1所得之前述式(2)表示之三嗪酮化合物1.00g及作為溶劑使用二甲基亞碸10.00g代替甲苯以外，與實施例1同樣進行，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-1)表示之中間體之選擇率為32.0%。 [0034] ＜比較例2＞ 除了使用合成例1所得之前述式(2)表示之三嗪酮化合物1.00g及作為溶劑使用氯仿10.00g代替甲苯以外，與實施例1同樣進行，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-1)表示之中間體之選擇率為82.0%。 [0035] ＜比較例3＞ 除了使用合成例1所得之前述式(2)表示之三嗪酮化合物1.00g及作為溶劑使用乙酸乙酯10.00g代替甲苯以外，與實施例1同樣進行，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-1)表示之中間體之選擇率為83.1%。 [0036] ＜比較例4＞ 除了使用合成例1所得之前述式(2)表示之三嗪酮化合物1.00g及作為溶劑使用丙酮10.00g代替甲苯以外，與實施例1同樣進行，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-1)表示之中間體之選擇率為63.5%。 [0037] 上述實施例1及實施例2、以及比較例1至比較例4之結果彙總於下述表1。下述表1中，“Tol”為甲苯之簡稱，“CPME”為環戊基甲基醚之簡稱，“DMSO”為二甲基亞碸之簡稱，“EtOAc”為乙酸乙酯之簡稱。 [表1]
[0038] ＜實施例3＞將實施例1所得之含有上述式(1’-1)表示之中間體之反應溶液過濾，藉此去除碳酸銫殘渣，以甲苯100.00g進行2次洗淨。隨後，於濾液中添加水1000.00g，進行2次分液，取出有機層。不單離上述式(1’-1)表示之中間體而於所得之前述有機層中混合甲醇24.86g，邊攪拌邊於25℃滴加三氟甲烷磺酸(東京化成工業(股)製)14.56g。滴加結束後，於25℃進行2小時攪拌，於反應溶液中添加三乙胺39.26g。減壓下自反應溶液餾除溶劑後，殘渣於40℃減壓乾燥。接著，添加乙酸乙酯300.00g，於25℃進行10分鐘攪拌。攪拌後，過濾，進而過濾物以乙酸乙酯100.00g洗淨2次。所得結晶於40℃減壓乾燥，藉此作為白色固體獲得上述式(1-1)表示之單甲氧基甲基異氰脲酸26.33g(收率47.0%)。又，測定該化合物之1
HNMR(500MHz, DMSO-d6
)後為 δ 11.50(s, 2H), 5.00(s, 2H), 3.27(s, 3H)。 [0039] ＜實施例4＞將合成例1所得之前述式(2)表示之三嗪酮化合物100.00g、碳酸銫(東京化成工業(股)製)131.67g及甲苯1000.00g混合，於40℃攪拌30分鐘。攪拌後，冷卻至25℃，於其中滴加2-甲氧基乙氧基甲基氯(東京化成工業(股)製)50.34g。滴加結束後，於0℃進行30分鐘攪拌，獲得含化合物之反應溶液。所得化合物以HPLC進行分析後，上述式(1’-2)表示之中間體之選擇率為90.3%。該測定所得之圖譜示於圖2。 [0040] ＜實施例5＞將實施例4所得之含有上述式(1’-2)表示之中間體之反應溶液過濾，藉此去除碳酸銫殘渣，以甲苯100.00g進行2次洗淨。隨後，於濾液中添加水1000.00g，進行2次分液，取出有機層。不單離上述式(1’-2)表示之中間體而於所得之前述有機層中混合甲醇24.86g，邊攪拌邊於25℃滴加三氟甲烷磺酸(東京化成工業(股)製)9.70g。滴加結束後，於25℃進行2小時攪拌，於反應溶液中添加三乙胺39.26g。於減壓下自反應溶液餾除溶劑後，殘渣於40℃減壓乾燥。接著，添加二甲基亞碸80.00g，於100℃完全溶解後，冷卻至25℃，且添加乙酸乙酯800.00g，於0℃進行1小時攪拌。攪拌後，過濾，進而過濾物以乙酸乙酯100.00g洗淨2次。所得結晶於40℃減壓乾燥，藉此作為白色固體獲得上述式(1-13)表示之單甲氧基乙氧基甲基異氰脲酸26.44g(收率37.7%)。又，測定該化合物之1
HNMR(500MHz, DMSO-d6
)後為δ 11.51(s, 2H), 5.10(s, 2H), 3.63(t, 2H), 3.40(t, 2H), 3.22(s, 3H)。 ［產業上之可利用性］ [0041] 本發明之具有一個烷氧基之取代基的異氰脲酸衍生物可適用於例如微影用抗反射膜形成組成物、抗蝕劑下層膜形成組成物、抗蝕劑上層膜形成組成物、光硬化性樹脂組成物、熱硬化性樹脂組成物、平坦化膜形成組成物、接著劑組成物、其他組成物。[0019] The isocyanuric acid derivative having a substituent containing an alkoxy group of the present invention is represented by the aforementioned formula (1). In the formula (1), the alkyl group having 1 to 10 carbon atoms represented by R 1 may be any of linear, branched, and cyclic. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-pentyl, and n-nonyl Methyl, n-decyl, cyclohexylmethyl, and cyclopentylmethyl. In the formula (1), examples of the alkylene group having 1 to 5 carbon atoms represented by R 2 are, for example, methylene, ethylene, propyl, trimethylene, butylene, and butyl. [0020] Examples of the isocyanuric acid derivative having a substituent containing an alkoxy group according to the present invention include compounds represented by the following formulae (1-1) to (1-20). [0021] In any one of the production methods of the present invention described above, in the first step, after the compound represented by the formula (2) is reacted with an alkali metal carbonate in a solvent, it is represented by the formula (3). Of compounds. The used amount of the compound represented by the aforementioned formula (3) is preferably 1 mole equivalent to 1.5 mole equivalents, more preferably 1.25 mole equivalents, relative to the compound represented by the formula (2). The use amount of the alkali metal carbonate is preferably 1 mol equivalent to 1.5 mol equivalent, and more preferably 1.25 mol equivalent, relative to 1 mol equivalent of the compound represented by the aforementioned formula (2). The solvent is preferably an aromatic hydrocarbon or an ether. As the aromatic hydrocarbons, in addition to the toluene, preferred examples include benzene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetrahydronaphthalene. When ethers are selected as the solvent, in addition to the cyclopentyl methyl ether, preferred examples include diethyl ether, diisopropyl ether, methyl third butyl ether, tetrahydrofuran, and dioxane. In order to obtain the compound represented by the formula (1 ′), that is, an intermediate, with good reproducibility through the first step, the compound represented by the formula (2) and an alkali metal carbonate in a solvent are prepared in advance at a reaction temperature of The reaction is carried out at 40 ° C to 100 ° C, preferably 40 ° C to 60 ° C, and the reaction time is 30 minutes to 2 hours, preferably 30 minutes to 1 hour. It is considered that by this reaction, a hydrogen atom is removed from the -NH- group of the compound represented by the aforementioned formula (2) to form an anion. This anion is reacted with the compound represented by the aforementioned formula (3). When the compound represented by the above formula (2) reacts with an alkali metal carbonate in a solvent, and the reaction temperature does not reach 40 ° C and the reaction time does not reach 30 minutes, the compound represented by the above formula (2) does not completely react with the alkali metal carbonate. . Therefore, the unreacted compound represented by the aforementioned formula (3) remains, and the compound represented by the formula (3) is preferentially decomposed by the alkali metal carbonate, so the yield of the compound represented by the aforementioned formula (1 ') is reduced. After the compound represented by the formula (2) and the alkali metal carbonate are reacted in a solvent, the reaction temperature when the compound represented by the formula (3) is added is not particularly limited, but is usually 0 ° C to 25 ° C, preferably 0 ° C. To 5 ° C. The reaction time is usually 30 minutes to 2 hours, and preferably 30 minutes to 1 hour. A liquid separation operation is performed on the reactant obtained from the above reaction, thereby obtaining a reaction solution containing the compound represented by the aforementioned formula (1 ′). [0022] In any one of the above-mentioned production methods of the present invention, in the second step of the production method of the present invention, the aforementioned reaction solution containing the compound represented by the formula (1 ′) and an alcohol compound are mixed with trifluoromethane Reaction in the presence of sulfonic acid or trimethylsilyl trifluoromethanesulfonate. Examples of the alcohol compound include ethanol, isopropanol, n-propanol, second butanol, third butanol, n-butanol, cyclohexanol, and phenol in addition to methanol. The amount of the alcohol compound used is preferably 2 mol equivalent to 3 mol equivalent, more preferably 2.4 mol equivalent, relative to 1 mol equivalent of the compound represented by the aforementioned formula (2). The used amount of the aforementioned trifluoromethanesulfonic acid or trimethylsilyl trifluoromethanesulfonate is preferably 0.1 mol equivalent to 0.5 mol equivalent, relative to 1 mol equivalent of the compound represented by the aforementioned formula (2). Good 0.2 mol equivalent to 0.3 mol equivalent. When the aforementioned trifluoromethanesulfonic acid or trimethylsilyl trifluoromethanesulfonate is used and reacted at 0.6 mol equivalent or more, impurities different from those of the compound represented by the aforementioned formula (1) as an object are by-producted. Therefore, the purity and yield of the compound represented by the formula (1) are reduced. The temperature during the above reaction is not particularly limited, but is usually 0 ° C to 40 ° C, preferably 20 ° C to 30 ° C. The reaction time is 1 hour to 5 hours, preferably 1 hour to 2 hours. [0023] Next, an organic base is added to the reaction product obtained as a result of the reaction in the second step described above and the reaction product is concentrated, followed by washing with an ester as a solvent, thereby obtaining the aforementioned formula (1) (Wherein, n is 0). As the aforementioned organic base, as preferred examples, pyridine, 4-dimethylaminopyridine, triethylamine, tributylamine, N, N-dimethylaniline, and 1,8-diazabicyclo [5.4.0 ] -7-undecene. The use amount of the organic base is preferably 1.0 mol equivalent to 2.0 mol equivalent, more preferably 1.2 mol equivalent, relative to 1 mol equivalent of the compound represented by the formula (2). As the aforementioned esters, in addition to the aforementioned ethyl acetate, preferred examples include methyl acetate, butyl acetate, and methyl propionate. The usage-amount of the said ester is 2.0 mass times-5.0 mass times with respect to the compound represented by said Formula (2), More preferably, it is 3.0 mass times. The temperature during the aforementioned washing is not particularly limited, but is usually 0 ° C to 40 ° C, and preferably 20 ° C to 30 ° C. The washing time is usually 10 minutes to 1 hour, and preferably 10 minutes to 30 minutes. [0024] Moreover, an organic base is added to the reaction product obtained by the reaction in the second step described above and the reaction product is concentrated, dissolved in an aprotic polar solvent, and then recrystallized using an ester as a solvent, Thus, a compound represented by the aforementioned formula (1) is obtained (however, n in the formula represents an integer of 1 to 5). As the aforementioned organic base, as preferred examples, pyridine, 4-dimethylaminopyridine, triethylamine, tributylamine, N, N-dimethylaniline, and 1,8-diazabicyclo [5.4.0 ] -7-undecene. The use amount of the organic base is preferably 1.0 mol equivalent to 2.0 mol equivalent, more preferably 1.2 mol equivalent, relative to 1 mol equivalent of the compound represented by the formula (2). Examples of the aprotic polar solvent include dimethylsulfinium, N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. As the aforementioned esters, in addition to the aforementioned ethyl acetate, preferred examples include methyl acetate, butyl acetate, and methyl propionate. The use amount of the aprotic polar solvent is preferably 0.5 to 1.0 mass times, and more preferably 0.8 mass times relative to the compound represented by the formula (2). The temperature during the dissolution is not particularly limited, but is usually 90 ° C to 120 ° C, preferably 100 ° C to 110 ° C. The dissolution time is usually 10 minutes to 1 hour, preferably 10 minutes to 30 minutes. The usage-amount of the said ester is 6.0 mass times-10.0 mass times with respect to the compound represented by said Formula (2), More preferably, it is 8.0 mass times. The temperature during the aforementioned recrystallization is not particularly limited, but is usually 0 ° C to 40 ° C, preferably 0 ° C to 5 ° C. The recrystallization time is usually 30 minutes to 2 hours, and preferably 1 hour to 2 hours. EXAMPLES [0025] The following examples illustrate the method for producing an isocyanuric acid derivative having a substituent containing an alkoxy group according to the present invention. However, the present invention is not limited to the following specific examples. [HPLC analysis] The selectivity shown in the examples described below are the measurement results by HPLC, and the measurement conditions and the like are as follows. Device: Shimadzu Corporation, LC-2010A Column: XBridge [registered trademark] BEH C18 column, 130 Å, 5 μm, 4.6 mm × 250 mm (Japanese WATERS (stock)) Eluent: acetonitrile / 0.2% ammonium acetate aqueous solution = 3/7 (v / v) (0 minutes to 5 minutes), changing composition ratio (5 minutes to 10 minutes) from 3/7 (v / v) to 8/2 (v / v), 8/2 ( v / v) (10 minutes to 15 minutes) Flow rate: 1.0 mL / min Detector: UV (210 nm) Column temperature: 40 ° C Analysis time: 25 minutes Injection volume: 1.0 μL Dilution solvent: acetonitrile / water = 1/1 (w / w) [Calculation method of selectivity] The selectivity shown in the examples and comparative examples described later is a formula (1'-1) or a formula (1'-2) obtained by HPLC analysis conditions as a percentage. The ratio of the area value of the intermediate represented by) and the by-products with a retention time of 13.88 minutes shown in FIG. 1 or a retention time of 13.82 minutes shown in FIG. 2. [Method of Calculating Yield] The yields shown in the Synthesis Examples and Examples described later are calculated by using the mass and theoretical yield of the obtained compound as a percentage. The theoretical yield is calculated by multiplying the molar number of the raw material compound used in the synthesis with the molecular weight of the obtained compound. [Synthesis of Raw Material Compound] <Synthesis Example 1> 100.00 g of cyanuric chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 234.56 g of benzyl alcohol (manufactured by Kanto Chemical Co., Ltd.) and 600.00 g of chloroform were mixed, and cooled to 0 ° C. while stirring. A solution obtained by mixing 280.33 g of diisopropylethylamine and 300.00 g of chloroform was added dropwise thereto. After completion of the dropwise addition, the temperature was raised to 25 ° C., and the mixture was stirred for 15 hours. 200.00 g of a saturated NH 4 Cl aqueous solution was added to the reaction solution to separate the liquid, and the organic layer was taken out. Next, 200.00 g of saturated saline was added to the organic layer, and this liquid separation operation was repeated twice. The obtained organic layer was distilled off the solvent under reduced pressure, and the residue was dried under reduced pressure at 40 ° C. 200.00 g of ethanol was added thereto, and the mixture was stirred at 0 ° C for 30 minutes. After stirring, the mixture was filtered, and the filtrate was washed twice with 100.00 g of ethanol. The obtained crystal was dried under reduced pressure at 40 ° C, whereby 127.24 g of a triazine compound represented by the above formula (4) was obtained as a pale yellow solid (yield: 71.2%). [0030] 127.24 g of the obtained triazine compound represented by the above formula (4), 46.62 g of acetic acid (manufactured by Kanto Chemical Co., Ltd.), and 636.20 g of methanol were mixed and cooled to 5 ° C. To this was added 157.07 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) while stirring. Then, the temperature was raised to 25 ° C. and the mixture was stirred for 30 minutes. To the reaction solution, 1272.40 g of chloroform and 1272.40 g of 1M HCl were added to separate the liquid. Further, 1127.40 g of saturated saline was added to the organic layer to separate the liquid, and the organic layer was taken out. This organic layer was dried under reduced pressure at 40 ° C, and 254.48 g of toluene was added, followed by stirring at 25 ° C for 10 minutes. After stirring, the mixture was filtered, and the filtrate was washed twice with 127.24 g of toluene. The obtained crystal was dried under reduced pressure at 40 ° C., thereby obtaining 109.21 g of a triazinone compound represented by the above formula (2) as a white solid (yield 90.9%). [0031] <Example 1> 100.00 g of the triazinone compound represented by the aforementioned formula (2) obtained in Synthesis Example 1, 131.67 g of cesium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1000.00 g of toluene were mixed and stirred at 40 ° C. for 30 minutes. After stirring, it was cooled to 25 ° C, and 32.54 g of chloromethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto. After completion of the dropwise addition, stirring was performed at 0 ° C for 30 minutes to obtain a compound-containing reaction solution. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-1) was 91.2%. The graph obtained by this measurement is shown in FIG. 1. [Example 2] The same procedure as in Example 1 was performed except that 1.00 g of the triazinone compound represented by the aforementioned formula (2) obtained in Synthesis Example 1 was used, and 10.00 g of cyclopentyl methyl ether was used as a solvent instead of toluene. To obtain a reaction solution containing the compound. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-1) was 85.8%. [Comparative Example 1] The same procedure as in Example 1 was carried out, except that 1.00 g of the triazinone compound represented by the aforementioned formula (2) obtained in Synthesis Example 1 and 10.00 g of dimethylsulfinium were used as a solvent instead of toluene. A compound-containing reaction solution was obtained. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-1) was 32.0%. [Comparative Example 2] The same procedure as in Example 1 was performed except that 1.00 g of the triazinone compound represented by the aforementioned formula (2) obtained in Synthesis Example 1 and 10.00 g of chloroform as a solvent were used instead of toluene. Reaction solution. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-1) was 82.0%. [Comparative Example 3] The same procedure as in Example 1 was carried out except that 1.00 g of the triazinone compound represented by the aforementioned formula (2) obtained in Synthesis Example 1 and 10.00 g of ethyl acetate were used as a solvent instead of toluene. Compound reaction solution. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-1) was 83.1%. [Comparative Example 4] The same procedure as in Example 1 was performed except that 1.00 g of the triazinone compound represented by the aforementioned formula (2) obtained in Synthesis Example 1 and 10.00 g of acetone were used as a solvent instead of toluene. Reaction solution. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-1) was 63.5%. [0037] The results of the above-mentioned Examples 1 and 2 and Comparative Examples 1 to 4 are summarized in Table 1 below. In the following Table 1, "Tol" is an abbreviation of toluene, "CPME" is an abbreviation of cyclopentyl methyl ether, "DMSO" is an abbreviation of dimethyl sulfene, and "EtOAc" is an abbreviation of ethyl acetate. [Table 1] [Example 3] The reaction solution containing the intermediate represented by the formula (1'-1) obtained in Example 1 was filtered to remove the cesium carbonate residue, and washed twice with 100.00 g of toluene. Subsequently, 1000.00 g of water was added to the filtrate, and liquid separation was performed twice, and the organic layer was taken out. Without separating the intermediate represented by the above formula (1'-1), 24.86 g of methanol was mixed in the obtained organic layer, and trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 25 ° C while stirring. g. After completion of the dropwise addition, stirring was performed at 25 ° C for 2 hours, and 39.26 g of triethylamine was added to the reaction solution. After distilling off the solvent from the reaction solution under reduced pressure, the residue was dried under reduced pressure at 40 ° C. Next, 300.00 g of ethyl acetate was added, and it stirred at 25 degreeC for 10 minutes. After stirring, the mixture was filtered, and the filtrate was washed twice with 100.00 g of ethyl acetate. The obtained crystal was dried under reduced pressure at 40 ° C, whereby 26.33 g of monomethoxymethyl isocyanuric acid represented by the above formula (1-1) was obtained as a white solid (yield 47.0%). The 1 H NMR (500 MHz, DMSO-d 6 ) of the compound was measured to be δ 11.50 (s, 2H), 5.00 (s, 2H), 3.27 (s, 3H). [0039] <Example 4> 100.00 g of the triazinone compound represented by the above formula (2) obtained in Synthesis Example 1, 131.67 g of cesium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1000.00 g of toluene were mixed and stirred at 40 ° C. for 30 minutes. After stirring, it was cooled to 25 ° C, and 50.34 g of 2-methoxyethoxymethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto. After completion of the dropwise addition, stirring was performed at 0 ° C for 30 minutes to obtain a compound-containing reaction solution. After the obtained compound was analyzed by HPLC, the selectivity of the intermediate represented by the above formula (1'-2) was 90.3%. The measured spectrum is shown in FIG. 2. [Example 5] The reaction solution containing the intermediate represented by the above formula (1'-2) obtained in Example 4 was filtered to remove the cesium carbonate residue, and washed twice with 100.00 g of toluene. Subsequently, 1000.00 g of water was added to the filtrate, and liquid separation was performed twice, and the organic layer was taken out. Without separating the intermediate represented by the above formula (1'-2), 24.86 g of methanol was mixed in the obtained organic layer, and trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 25 ° C while stirring. g. After completion of the dropwise addition, stirring was performed at 25 ° C for 2 hours, and 39.26 g of triethylamine was added to the reaction solution. After distilling off the solvent from the reaction solution under reduced pressure, the residue was dried under reduced pressure at 40 ° C. Next, 80.00 g of dimethyl fluorene was added, and after completely dissolving at 100 ° C., it was cooled to 25 ° C. and 800.00 g of ethyl acetate was added, followed by stirring at 0 ° C. for 1 hour. After stirring, the mixture was filtered, and the filtrate was washed twice with 100.00 g of ethyl acetate. The obtained crystal was dried under reduced pressure at 40 ° C, whereby 26.44 g of monomethoxyethoxymethyl isocyanuric acid represented by the above formula (1-13) was obtained as a white solid (yield: 37.7%). The 1 H NMR (500 MHz, DMSO-d 6 ) of this compound was measured to be δ 11.51 (s, 2H), 5.10 (s, 2H), 3.63 (t, 2H), 3.40 (t, 2H), 3.22 (s , 3H). [Industrial Applicability] The isocyanuric acid derivative having one alkoxy group substituent according to the present invention can be suitably used in, for example, an anti-reflection film-forming composition for lithography and a resist underlayer film-forming composition. Material, resist upper film forming composition, photocurable resin composition, thermosetting resin composition, planarizing film forming composition, adhesive composition, and other compositions.