JP3689937B2 - Method for producing naphthoquinone diazide photosensitizer - Google Patents

Description

【００１０】
式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は互いに独立に、水素、水酸基、炭素数６以下のアルキル、炭素数６以下のシクロアルキル又は炭素数６以下のアルコキシを表し、Ｒ¹⁹及びＲ²⁰は互いに独立に、水素、炭素数６以下のアルキル、炭素数６以下のシクロアルキル、又は、水酸基、炭素数６以下のアルキル、炭素数６以下のシクロアルキル及び炭素数６以下のアルコキシからなる群より選ばれる置換基で置換されていてもよいフェニルを表す；
【００１１】

【００１２】
式中、Ｒ²¹及びＲ²²は互いに独立に、水素、水酸基又は炭素数６以下のアルキルを表し、Ｒ²³、Ｒ²⁴、Ｒ²⁵及びＲ²⁶は互いに独立に、水素若しくは炭素数６以下のアルキルを表すか、又はＲ²³とＲ²⁴が一緒になり、そしてＲ²⁵とＲ²⁶が一緒になって、それぞれが結合する炭素原子とともに炭素数６以下のシクロアルカン環を形成する；
【００１３】

【００１４】
式中、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴は互いに独立に、水素又は炭素数６以下のアルキルを表し、 ｍ及びｎは互いに独立に０〜３の整数を表すが、ｍ＋ｎ≧２であり、Ｙは−Ｃ(Ｒ³⁵)(Ｒ³⁶)−又は−Ｃ(Ｒ³⁷)(Ｒ³⁸)−Ar−Ｃ(Ｒ³⁹)(Ｒ⁴⁰)−を表し、ここにＲ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸、Ｒ³⁹及びＲ⁴⁰は互いに独立に、水素、炭素数６以下のアルキル、炭素数６以下のシクロアルキル、又は、水酸基、炭素数６以下のアルキル、炭素数６以下のシクロアルキル及び炭素数６以下のアルコキシからなる群より選ばれる置換基で置換されていてもよいフェニルを表し、Arは炭素数６以下のアルキル及び水酸基からなる群より選ばれる置換基で置換されていてもよいフェニレンを表す；
【００１５】

【００１６】
式中、Ｒ⁴¹及びＲ⁴²は互いに独立に、水素、炭素数６以下のアルキル又は炭素数１０以下のアリールを表し、 ｑ及びｒは互いに独立に０〜３の整数を表すが、ｑ＋ｒ≧２である。
【００１７】
フェノール性水酸基を有する化合物、例えば上記一般式（Ｉ）〜（IV）で示される化合物の、１，２−ナフトキノンジアジド−４−又は−５−スルホン酸エステルは、かかるフェノール性水酸基を有する化合物を、１，２−ナフトキノンジアジド−４−又は−５−スルホニルハライドと縮合させることにより得られる。ここで、スルホニルハライドとしては、特にスルホニルクロライドが好ましく用いられる。
【００１８】
この反応は通常、塩基の存在下で行われる。ここで用いる塩基としては、トリメチルアミン、トリエチルアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ピリジンのようなアミン類、炭酸ナトリウム、炭酸水素ナトリウムのような無機塩基などが挙げられる。塩基は、１，２−ナフトキノンジアジド−４−又は−５−スルホニルハライドに対して、通常１〜１.5のモル比、好ましくは１.0５〜１.3のモル比で用いられる。
【００１９】
本発明では、このエステル化反応の反応溶媒として、１，３−ジオキソランを用いる。反応溶媒は、フェノール性水酸基を有する化合物と１，２−ナフトキノンジアジド−４−又は−５−スルホニルハライドの合計量を基準に、通常は２〜１０重量倍の範囲で、好ましくは３〜６重量倍の範囲で使用される。１，３−ジオキソランを溶媒として用いることにより、１，４−ジオキサンを用いた場合に比べ、反応速度が速くなり、しかも、反応後の晶析で粒径の大きい結晶が得られるため、濾過時間が短縮されるという効果を奏する。
【００２０】
したがって本発明においては、通常は１，３−ジオキソラン単独の溶媒を用いるのが好ましいが、本発明の目的を阻害しない範囲で、他の溶媒、例えば、テトラヒドロフランのようなエーテル類、酢酸アミル、γ−ブチロラクトンのようなエステル類、アセトン、２−ヘプタノンのような脂肪族ケトン類などを併用することもできる。他の溶媒を併用する場合でも、全溶媒量を基準に、１，３−ジオキソランが５０重量％以上、さらには７０重量％以上、あるいは８０重量％以上となるようにするのが好ましい。
【００２１】
この反応は、常圧下、常温付近で進行し、一般的には１０〜４０℃程度の範囲の温度が採用される。反応時間は、フェノール性水酸基を有する化合物及びナフトキノンジアジドスルホニルハライドの種類によっても異なるが、通常は０.5〜６時間程度反応が行われる。
【００２２】
反応終了後は、必要により酢酸のような酸で中和し、固形物を濾過したあと、濾液を薄い酸水溶液、例えば０.1〜２重量％程度の濃度の酢酸水溶液と混合すれば、目的物であるエステルの結晶が沈澱してくる。これを濾過、水洗及び乾燥して、感光剤を固体として取り出すことができる。
【００２３】
【実施例】
次に実施例を挙げて、本発明をさらに具体的に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。例中、部及び％は、特にことわらないかぎり重量基準である。
【００２４】
実施例１
１リットルの四つ口フラスコに、２，３，４，４′−テトラヒドロキシベンゾフェノンを２５.6７ｇ、１，２−ナフトキノンジアジド−５−スルホニルクロライドを７０.0３ｇ及び１，３−ジオキソランを５７４ｇ仕込んで完溶させた。そこへ、２０〜３０℃でトリエチルアミン２７.6９ｇを１時間かけて滴下した。滴下終了後、３０℃で１時間攪拌した。次に反応混合物を濾過し、得られた濾過残を１，３−ジオキソラン１４０ｇで洗浄した。濾液及び洗液を酢酸１０.7１ｇ及びイオン交換水２１４３ｇの混合液中に注入し、１時間攪拌した。析出した結晶を濾過し、得られたケーキをイオン交換水３９４ｇで攪拌洗浄し、さらに濾過及びイオン交換水３９４ｇでの攪拌洗浄を３回繰り返した。その後濾過し、得られたウェットケーキ１３３.3ｇを４０℃で乾燥して、８１.2ｇの感光剤Ａを得た。
【００２５】
比較例１
１，３−ジオキソランに代えて１，４−ジオキサンを同量使用する以外は、実施例１と同様の操作を行って、感光剤Ｂを合成した。ウェットケーキは２２８.4ｇ、乾燥ケーキは８０.4ｇであった。
【００２６】
実施例２
１リットルの四つ口フラスコに、 ２，４，４−トリメチル−２′，３′，４′，７，８−ペンタヒドロキシフラバン（次式の構造を有する）
【００２７】

【００２８】
を１６.6２ｇ、 １，２−ナフトキノンジアジド−５−スルホニルクロライドを６３.1４ｇ及び１，３−ジオキソランを３９８.8ｇ仕込んで完溶させた。そこへ２０〜３０℃でトリエチルアミン２８.5４ｇを１時間かけて滴下した。滴下終了後、３０℃で１時間攪拌した。次に反応混合物を濾過し、得られた濾過残を１，３−ジオキソラン６３.1ｇで洗浄した。濾液及び洗液を、酢酸１３.8６ｇ及びイオン交換水１３８６ｇの混合液中に注入し、１時間攪拌した。析出した結晶を濾過し、得られたケーキをイオン交換水２８０ｇで攪拌洗浄し、さらに濾過及びイオン交換水２８０ｇでの攪拌洗浄を３回繰り返した。その後濾過し、得られたウェットケーキ１２７.7ｇを４０℃で乾燥して、６８.2ｇの感光剤Ｃを得た。
【００２９】
比較例２
１，３−ジオキソランに代えて１，４−ジオキサンを同量使用する以外は、実施例２と同様の操作を行って、感光剤Ｄを合成した。ウェットケーキは２０２.4ｇ、乾燥ケーキは６７.0ｇであった。
【００３０】
以上の実施例１及び２並びに比較例１及び２の結果を表１に示す。
【００３１】
【表１】

^*1 ＤＰ₅₀は、レーザー回折式粒度分布測定法による５０容量％値を表す。
^*2 晶析マスの沈降距離は、晶析マスを１リットルのメスシリンダーに入れて攪拌し、静置後６秒経過したときに結晶が沈降した距離（上澄み透明液の高さ）を表す。
【００３２】
表１からわかるように、１，３−ジオキソランを用いて合成した感光剤Ａ及びＣは、１，４−ジオキサンを用いて合成した感光剤Ｂ及びＤに比べて、ウェットケーキ中の固形分が多いことから、乾燥速度が速くなり、また粒径が大きいこと及び沈降距離が大きいことから、濾過速度も速くなる。
【００３３】
実施例３
５００mlの四つ口フラスコに、４，４′−メチレンビス〔２−（２−ヒドロキシ−５−メチルベンジル）−３，６−ジメチルフェノール〕（次式の構造を有する）
【００３４】

【００３５】
を２５.0０ｇ、 １，２−ナフトキノンジアジド−５−スルホニルクロライドを２７.0５ｇ及び１，３−ジオキソランを２６０.2ｇ仕込んで完溶させた。そこへ２０〜３０℃でトリエチルアミン１２.2２ｇを１時間かけて滴下した。滴下終了後１時間以内で１，２−ナフトキノンジアジド−５−スルホニルクロライドの消失が確認され、反応が終了した。
【００３６】
なお、４,４′−メチレンビス〔２−(２−ヒドロキシ−５−メチルベンジル）−３，６−ジメチルフェノールは、以下のようにして合成した。三つ口フラスコにパラクレゾール１４４.1６部、トルエン８１.5７部および３６％塩酸０.4３部を仕込み、５０℃に保ちながら４，４′−メチレンビス（２−ヒドロキシメチル−３，６−ジメチルフェノール）１８.9８部を１時間で分割投入し、その後さらに同温度で３時間攪拌した。冷却後濾過し、得られた濾過物を酢酸エチル２６９部に溶解し、蒸留水４７部を加えて水洗し、この水洗操作をさらに４回繰り返した。次に酢酸エチル層を濃縮し、トルエン１０７.5部を仕込んで、析出した結晶を濾過し、さらにこの結晶をトルエン４４.5４部で洗浄し、このトルエン洗浄をもう１度繰り返した。こうして得られたウェットケーキを６０℃にて一昼夜減圧乾燥して、４，４′−メチレンビス〔２−（２−ヒドロキシ−５−メチルベンジル）−３，６−ジメチルフェノール〕を得た。
【００３７】
比較例３
１，３−ジオキソランに代えて１，４−ジオキサンを同量使用する以外は、実施例３と同様の操作を行ったところ、トリエチルアミンの滴下終了後３.5時間で反応が終了した。
【００３８】
実施例４
１，２−ナフトキノンジアジド−５−スルホニルクロライドに代えて１，２−ナフトキノンジアジド−４−スルホニルクロライドを同量用いる以外は、実施例３と同様の操作を行ったところ、トリエチルアミンの滴下終了後２時間で反応が終了した。
【００３９】
比較例４
１，３−ジオキソランに代えて１，４−ジオキサンを同量使用する以外は、実施例４と同様の操作を行ったところ、トリエチルアミンの滴下終了時から反応終了までに２０時間を要した。
【００４０】
以上の実施例３及び４並びに比較例３及び４における反応終了までの時間を、表２にまとめた。
【００４１】
【表２】

【００４２】
表２からわかるように、１，３−ジオキソランを使用することにより、１，４−ジオキサンを用いた場合に比べて反応加速効果が認められ、特に１，２−ナフトキノンジアジド−４−スルホニルハライドを縮合させる場合に、その効果が大きい。
【００４３】
【発明の効果】
本発明は、フェノール性水酸基を有する化合物を１，２−ナフトキノンジアジド−４−又は−５−スルホン酸エステル化するにあたり、 安全性に問題のない１，３−ジオキソランを溶媒に用いるものである。しかもそれによって、反応速度が速くなり、また反応後の晶析で粒径の大きい結晶が得られるため、濾過時間が短縮されるという効果を奏する。したがって本発明の方法は、ナフトキノンジアジド系感光剤の製造に極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a naphthoquinone diazide photosensitizer used for, for example, a positive resist composition.
[0002]
[Prior art]
It is known to convert a compound having a phenolic hydroxyl group into a quinonediazide sulfonic acid ester and use it as a photosensitive agent in a positive resist composition for semiconductor microfabrication. In quinonediazide sulfonate esterification, 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide is usually used, and a photosensitizer is produced by condensing it with a compound having a phenolic hydroxyl group. . This reaction is generally carried out in a solvent. As the reaction solvent, 1,4-dioxane, acetone, γ-butyrolactone, or a mixture of two or more thereof is known, and in particular, 1,4-dioxane is used. Many are used.
[0003]
However, 1,4-dioxane must be handled with care because of safety issues, and when this is used, depending on the type of the photosensitizer, the particle size of the photosensitizer after crystallization becomes small, so the filtration time is reduced. There was a problem such as becoming longer.
[0004]
[Problems to be solved by the invention]
One of the objects of the present invention is to produce a naphthoquinonediazide-based photosensitizer using a reaction solvent that does not cause safety problems.
[0005]
Another object of the present invention is to use a specific reaction solvent in the condensation reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonyl halide to facilitate the reaction and facilitate subsequent processing. It is in.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve this object, the present inventors have found that 1,3-dioxolane has no safety problem, and this is condensed with a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonyl halide. It has been found that excellent results can be obtained by using it as a reaction solvent in the reaction, and the present invention has been completed.
[0007]
That is, the present invention relates to a naphthoquinone diazide photosensitizer by condensing a compound having a phenolic hydroxyl group and 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide in a solvent containing 1,3-dioxolane. The method of manufacturing is provided.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the compound having a phenolic hydroxyl group which is a target of quinonediazide sulfonic acid esterification can be various compounds used for making a photosensitizer in the resist field. That is, it is a phenolic compound having at least 1, preferably 2 or more, and more preferably 3-6 phenolic hydroxyl groups in the molecule. Preferable phenolic compounds for quinonediazide sulfonic acid esterification according to the present invention include, for example, compounds represented by the following general formulas (I) to (IV).
[0009]

[0010]
In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently of each other hydrogen, hydroxyl group, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms or Represents an alkoxy having 6 or less carbon atoms, and R ¹⁹ and R ²⁰ are independently of each other hydrogen, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms, hydroxyl group, alkyl having 6 or less carbon atoms, carbon number 6 Represents phenyl which may be substituted with a substituent selected from the group consisting of the following cycloalkyl and alkoxy having 6 or less carbon atoms;
[0011]

[0012]
In the formula, R ²¹ and R ²² each independently represent hydrogen, hydroxyl group or alkyl having 6 or less carbon atoms, and R ²³ , R ²⁴ , R ²⁵ and R ²⁶ independently represent hydrogen or alkyl having 6 or less carbon atoms. Or R ²³ and R ²⁴ together, and R ²⁵ and R ²⁶ together form a cycloalkane ring having 6 or less carbon atoms together with the carbon atom to which each is bonded;
[0013]

[0014]
In the formula, R ³¹ , R ³² , R ³³ and R ³⁴ independently represent hydrogen or alkyl having 6 or less carbon atoms, and m and n each independently represent an integer of 0 to 3, but m + n ≧ 2 Y represents —C (R ³⁵ ) (R ³⁶ ) — or —C (R ³⁷ ) (R ³⁸ ) —Ar—C (R ³⁹ ) (R ⁴⁰ ) —, wherein R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are independently of each other hydrogen, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms, hydroxyl group, alkyl having 6 or less carbon atoms, cyclohexane having 6 or less carbon atoms. Represents phenyl optionally substituted with a substituent selected from the group consisting of alkyl and alkoxy having 6 or less carbon atoms, Ar is substituted with a substituent selected from the group consisting of alkyl having 6 or less carbon atoms and hydroxyl group; Represents good phenylene;
[0015]

[0016]
In the formula, R ⁴¹ and R ⁴² each independently represent hydrogen, alkyl having 6 or less carbon atoms or aryl having 10 or less carbon atoms, and q and r each independently represent an integer of 0 to 3, but q + r ≧ 2 It is.
[0017]
1,2-naphthoquinone diazide-4- or -5-sulfonic acid ester of a compound having a phenolic hydroxyl group, for example, a compound represented by the above general formulas (I) to (IV) is a compound having such a phenolic hydroxyl group. , 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide. Here, as the sulfonyl halide, sulfonyl chloride is particularly preferably used.
[0018]
This reaction is usually performed in the presence of a base. Examples of the base used here include trimethylamine, triethylamine, triethanolamine, N, N-dimethylaniline, N, N-diethylaniline, amines such as pyridine, and inorganic bases such as sodium carbonate and sodium bicarbonate. It is done. The base is usually used in a molar ratio of 1 to 1.5, preferably 1.05 to 1.3, relative to 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide.
[0019]
In the present invention, 1,3-dioxolane is used as a reaction solvent for this esterification reaction. The reaction solvent is usually in the range of 2 to 10 times by weight, preferably 3 to 6 weights based on the total amount of the compound having a phenolic hydroxyl group and 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide. Used in double range. By using 1,3-dioxolane as a solvent, the reaction rate is faster than when 1,4-dioxane is used, and a crystal having a large particle size is obtained by crystallization after the reaction. Has the effect of shortening.
[0020]
Therefore, in the present invention, it is usually preferable to use a solvent of 1,3-dioxolane alone, but other solvents such as ethers such as tetrahydrofuran, amyl acetate, γ -Esters such as butyrolactone, aliphatic ketones such as acetone and 2-heptanone, and the like can also be used in combination. Even when another solvent is used in combination, it is preferable that 1,3-dioxolane is 50% by weight or more, further 70% by weight or more, or 80% by weight or more based on the total amount of the solvent.
[0021]
This reaction proceeds near normal temperature under normal pressure, and generally a temperature in the range of about 10 to 40 ° C is employed. Although the reaction time varies depending on the type of the compound having a phenolic hydroxyl group and the naphthoquinonediazide sulfonyl halide, the reaction is usually carried out for about 0.5 to 6 hours.
[0022]
After completion of the reaction, neutralize with an acid such as acetic acid if necessary, filter the solid, and mix the filtrate with a thin acid aqueous solution, for example, an acetic acid aqueous solution having a concentration of about 0.1 to 2% by weight. Crystals of the ester are precipitated. This can be filtered, washed with water and dried to remove the photosensitizer as a solid.
[0023]
【Example】
EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. In the examples, parts and% are based on weight unless otherwise specified.
[0024]
Example 1
A 1 liter four-necked flask is charged with 25.67 g of 2,3,4,4'-tetrahydroxybenzophenone, 70.03 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 574 g of 1,3-dioxolane. And completely dissolved. Thereto, 27.69 g of triethylamine was added dropwise at 20 to 30 ° C. over 1 hour. After completion of dropping, the mixture was stirred at 30 ° C. for 1 hour. The reaction mixture was then filtered and the resulting filter residue was washed with 140 g of 1,3-dioxolane. The filtrate and washings were poured into a mixed solution of 10.71 g of acetic acid and 2143 g of ion-exchanged water, and stirred for 1 hour. The precipitated crystals were filtered, and the resulting cake was stirred and washed with 394 g of ion-exchanged water. Further, filtration and stirring and washing with 394 g of ion-exchanged water were repeated three times. Thereafter, filtration was performed, and 133.3 g of the obtained wet cake was dried at 40 ° C. to obtain 81.2 g of photosensitive agent A.
[0025]
Comparative Example 1
Photosensitive agent B was synthesized in the same manner as in Example 1 except that the same amount of 1,4-dioxane was used instead of 1,3-dioxolane. The wet cake was 228.4 g and the dry cake was 80.4 g.
[0026]
Example 2
In a 1 liter four-necked flask, 2,4,4-trimethyl-2 ', 3', 4 ', 7,8-pentahydroxyflavan (having the structure of the following formula)
[0027]

[0028]
16.62 g, 63.14 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 398.8 g of 1,3-dioxolane were charged and completely dissolved. Thereto, 28.54 g of triethylamine was added dropwise at 20 to 30 ° C. over 1 hour. After completion of dropping, the mixture was stirred at 30 ° C. for 1 hour. The reaction mixture was then filtered and the resulting filter residue was washed with 63.1 g of 1,3-dioxolane. The filtrate and washings were poured into a mixed solution of 13.86 g of acetic acid and 1386 g of ion-exchanged water and stirred for 1 hour. The precipitated crystals were filtered, and the resulting cake was stirred and washed with 280 g of ion-exchanged water. Further, filtration and stirring and washing with 280 g of ion-exchanged water were repeated three times. Thereafter, filtration was carried out, and 127.7 g of the obtained wet cake was dried at 40 ° C. to obtain 68.2 g of photosensitive agent C.
[0029]
Comparative Example 2
Photosensitive agent D was synthesized in the same manner as in Example 2, except that the same amount of 1,4-dioxane was used instead of 1,3-dioxolane. The wet cake was 202.4 g and the dry cake was 67.0 g.
[0030]
The results of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 1.
[0031]
[Table 1]

^{* 1} DP ₅₀ represents a 50% by volume value measured by a laser diffraction particle size distribution measurement method.
^{* 2} The sedimentation distance of the crystallization mass indicates the distance (the height of the supernatant transparent liquid) when the crystallization mass settled in a 1 liter measuring cylinder and stirred for 6 seconds after standing.
[0032]
As can be seen from Table 1, the photosensitizers A and C synthesized using 1,3-dioxolane are more solid than the photosensitizers B and D synthesized using 1,4-dioxane. Since the amount is large, the drying rate is high, and because the particle size is large and the settling distance is large, the filtration rate is also high.
[0033]
Example 3
In a 500 ml four-necked flask, 4,4'-methylenebis [2- (2-hydroxy-5-methylbenzyl) -3,6-dimethylphenol] (having the structure of the following formula)
[0034]

[0035]
25.00 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 27.05 g and 1,3-dioxolane, 260.2 g, were completely dissolved. Thereto, 12.22 g of triethylamine was added dropwise at 20 to 30 ° C. over 1 hour. The disappearance of 1,2-naphthoquinonediazide-5-sulfonyl chloride was confirmed within 1 hour after the completion of dropping, and the reaction was completed.
[0036]
In addition, 4,4'-methylenebis [2- (2-hydroxy-5-methylbenzyl) -3,6-dimethylphenol was synthesized as follows. A three-necked flask was charged with 144.16 parts of paracresol, 81.57 parts of toluene and 0.43 parts of 36% hydrochloric acid, and maintained at 50 ° C., while maintaining 4,4′-methylenebis (2-hydroxymethyl-3,6-dimethyl). Phenol) 18.98 parts was added portionwise in 1 hour, and then further stirred at the same temperature for 3 hours. After cooling, the mixture was filtered, and the obtained filtrate was dissolved in 269 parts of ethyl acetate, and 47 parts of distilled water was added and washed with water. Next, the ethyl acetate layer was concentrated, 107.5 parts of toluene was added, the precipitated crystals were filtered, the crystals were further washed with 44.54 parts of toluene, and this toluene washing was repeated once more. The wet cake thus obtained was dried under reduced pressure at 60 ° C. overnight to obtain 4,4′-methylenebis [2- (2-hydroxy-5-methylbenzyl) -3,6-dimethylphenol].
[0037]
Comparative Example 3
The same operation as in Example 3 was performed except that the same amount of 1,4-dioxane was used instead of 1,3-dioxolane, and the reaction was completed in 3.5 hours after completion of the dropwise addition of triethylamine.
[0038]
Example 4
The same operation as in Example 3 was performed except that the same amount of 1,2-naphthoquinonediazide-4-sulfonyl chloride was used instead of 1,2-naphthoquinonediazide-5-sulfonyl chloride. After completion of the dropwise addition of triethylamine, 2 The reaction was complete in time.
[0039]
Comparative Example 4
Except that the same amount of 1,4-dioxane was used instead of 1,3-dioxolane, the same operation as in Example 4 was carried out, and it took 20 hours from the end of the dropwise addition of triethylamine to the end of the reaction.
[0040]
Table 2 summarizes the time until the end of the reaction in Examples 3 and 4 and Comparative Examples 3 and 4 described above.
[0041]
[Table 2]

[0042]
As can be seen from Table 2, by using 1,3-dioxolane, a reaction accelerating effect is recognized as compared with the case of using 1,4-dioxane, and in particular, 1,2-naphthoquinonediazide-4-sulfonyl halide is used. In the case of condensation, the effect is great.
[0043]
【The invention's effect】
The present invention uses 1,3-dioxolane as a solvent, which is safe in terms of converting a compound having a phenolic hydroxyl group into 1,2-naphthoquinonediazide-4- or -5-sulfonic acid ester. In addition, the reaction rate is increased, and a crystal having a large particle diameter is obtained by crystallization after the reaction, so that the filtration time is shortened. Therefore, the method of the present invention is extremely useful for the production of naphthoquinone diazide photosensitizers.

Claims (3)

A method for producing a naphthoquinone diazide photosensitizer, comprising condensing a compound having a phenolic hydroxyl group and 1,2-naphthoquinone diazide-4- or -5-sulfonyl halide in a solvent containing 1,3-dioxolane. . The method according to claim 1, wherein the 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide is 1,2-naphthoquinonediazide-4- or -5-sulfonyl chloride. A process according to claim 1 or 2, wherein the solvent consists essentially of 1,3-dioxolane.