JPH02300160A - Preparation of o-naphthoquinonediazide sulfonic acid ester - Google Patents
Preparation of o-naphthoquinonediazide sulfonic acid esterInfo
- Publication number
- JPH02300160A JPH02300160A JP11816489A JP11816489A JPH02300160A JP H02300160 A JPH02300160 A JP H02300160A JP 11816489 A JP11816489 A JP 11816489A JP 11816489 A JP11816489 A JP 11816489A JP H02300160 A JPH02300160 A JP H02300160A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- sulfonic acid
- naphthoquinonediazide sulfonic
- solution
- buffer solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003459 sulfonic acid esters Chemical class 0.000 title claims abstract description 7
- -1 phenol compound Chemical class 0.000 claims abstract description 19
- 239000007853 buffer solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 239000000872 buffer Substances 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 229910000402 monopotassium phosphate Inorganic materials 0.000 abstract description 12
- 235000019796 monopotassium phosphate Nutrition 0.000 abstract description 12
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 abstract description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 8
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 150000005691 triesters Chemical class 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229940079877 pyrogallol Drugs 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940032007 methylethyl ketone Drugs 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はフォトレジスト用感光剤の製造法に関し、さら
に詳しくは、副反応の少ないＯ−ナフトキノンジアジド
スルホン酸エステルの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a photosensitizer for photoresists, and more particularly, to a method for producing an O-naphthoquinone diazide sulfonic acid ester that causes fewer side reactions.
（従来の技術）
従来、Ｏ−ナフトキノンジアジドスルホン酸エステルの
製造法としては、一般に極性有機溶剤、たとえばジオキ
サン、アセトン、メチルエチルケトンまたはこれらの混
合溶剤中で、無機塩基、たとえばアルカリ金属炭酸塩、
アルカリ金属重炭酸塩、アルカリ土類金属炭酸塩を添加
するか、三級アミン、たとえばトリエチルアミン、ピリ
ジン、ルチジン等を添加する方法が用いられる。(Prior Art) Conventionally, the method for producing O-naphthoquinonediazide sulfonic acid ester generally involves adding an inorganic base, such as an alkali metal carbonate, in a polar organic solvent such as dioxane, acetone, methyl ethyl ketone, or a mixed solvent thereof
A method of adding an alkali metal bicarbonate, an alkaline earth metal carbonate, or a tertiary amine such as triethylamine, pyridine, lutidine, etc. is used.
しかしこの方法では、用いる塩基に対して不安定なフェ
ノール類とＯ−ナフトキノンジアジドスルホン酸クロリ
ドを原料として用いる場合、副反応が生じるという欠点
があった。However, this method has the disadvantage that side reactions occur when phenols and O-naphthoquinonediazide sulfonic acid chloride, which are unstable to the base used, are used as raw materials.
特に、塩基性条件下で酸素と反応しやすい化合物を原料
に用いる場合は、反応中常時空気との遮断に留意する必
要がある。しかし微量の酸素の混入は通常避けられず、
具体的にはピロガロールとナフトキノンジアジド−４−
スルホン酸クロリドとをジオキサン中でトリエチルアミ
ンで縮合する場合、反応系が黒色化し単離したエステル
化物の純度が大幅に低下した。In particular, when a compound that easily reacts with oxygen under basic conditions is used as a raw material, care must be taken to keep it out from air at all times during the reaction. However, the contamination of trace amounts of oxygen is usually unavoidable;
Specifically, pyrogallol and naphthoquinone diazide-4-
When sulfonic acid chloride was condensed with triethylamine in dioxane, the reaction system turned black and the purity of the isolated ester product decreased significantly.
（発明が解決しようとする課題）
本発明者らは前記欠点を解決すべく鋭意研究の結果、０
−ナフトキノンジアジドスルホン酸ハロゲン化物と一価
または多価のフェノール化合物とを縮合するに際し、塩
基性成分を含むｐＨが７以下となるような緩衝液を用い
れば、０−ナフトキノンジアジドスルホン酸エステルを
副反応少なく製造できることを見出し、この知見に基づ
いて本発明を完成するに到った。(Problems to be Solved by the Invention) As a result of intensive research to solve the above-mentioned drawbacks, the present inventors have found that
- When condensing a naphthoquinonediazide sulfonic acid halide with a monovalent or polyvalent phenol compound, if a buffer solution containing a basic component with a pH of 7 or less is used, 0-naphthoquinonediazide sulfonic acid ester can be used as a sub-agent. It was discovered that it can be produced with less reaction, and based on this knowledge, the present invention was completed.
（課題点を解決するための手段）
か（して本発明によれば、Ｏ−ナフトキノンジアジドス
ルホン酸ハロゲン化物と一価または多価のフェノール化
合物とを縮合するに際し、塩基性成分を含むｐＨが７以
下となるような緩衝液を用いるＯ−ナフトキノンジアジ
ドスルホン酸エステルの製造法が提供される。(Means for Solving the Problems) According to the present invention, when condensing an O-naphthoquinonediazide sulfonic acid halide and a monovalent or polyvalent phenol compound, the pH containing the basic component is Provided is a method for producing an O-naphthoquinonediazide sulfonic acid ester using a buffer solution having a concentration of 7 or less.
本発明に用いられる塩基性成分を含む緩衝液は、ｐＨが
７以下の物であれば何れでも良く、特にｐＨが５〜７の
範囲が好ましい。ｐＨが７をこえると塩基に不安定なフ
ェノール類と０−ナフトキノンジアジドスルホン酸クロ
リドとの組み合わせの場合、急激に着色が進み、得られ
るエステルの純度が低下する。The buffer solution containing a basic component used in the present invention may be any buffer solution having a pH of 7 or less, and a pH range of 5 to 7 is particularly preferred. When the pH exceeds 7, in the case of a combination of base-labile phenols and 0-naphthoquinonediazide sulfonic acid chloride, coloring rapidly progresses and the purity of the resulting ester decreases.
具体的な緩衝液の例としては重炭酸ソーダを含むりん酸
二水素カリウムのｐＨ＝６の水溶液、水酸化ナトリウム
を含むりん酸二水素カリウムのｐＨ＝６．６の水溶液な
どが挙げられる。Specific examples of buffer solutions include an aqueous solution of potassium dihydrogen phosphate (pH=6) containing sodium bicarbonate, and an aqueous solution of potassium dihydrogen phosphate (pH=6.6) containing sodium hydroxide.
反応に用いる溶媒としては緩衝液が溶解する物ならば何
れでも良く、特にジオキサン、アセトン、メチル−エチ
ルケトン等が好ましい。The solvent used in the reaction may be any solvent as long as it dissolves the buffer solution, with dioxane, acetone, methyl-ethyl ketone and the like being particularly preferred.
反応温度は特に制限はないが、通常１０°Ｃ〜４０°Ｃ
が有利である。There is no particular restriction on the reaction temperature, but it is usually 10°C to 40°C.
is advantageous.
０−ナフトキノンジアジドスルホン酸ハロゲン化物とし
ては、塩化物が容易に入手できるが、臭化物を用いるこ
とも可能である。ハロゲン化スルホニル基の位置は対応
するナフタレン核の３−１４−１５−１６−１７−また
は８位に存在しうるが、通常は４−スルホン酸または５
−スルホン酸が用いられる。As the 0-naphthoquinonediazide sulfonic acid halide, chloride is easily available, but bromide can also be used. The position of the halogenated sulfonyl group can be at the 3-14-15-16-17- or 8-position of the corresponding naphthalene nucleus, but is usually 4-sulfonic acid or 5-position.
- Sulfonic acids are used.
一価または多価のフェノール化合物は本発明の性格上回
れでも良いが、フェノール性ヒドロキシル基を有する低
分子化合物、フェノール性ヒドロキシル基を有する重合
体化合物またはそれらの混合物を使用することができる
。Any monovalent or polyvalent phenol compound may be used, but a low molecular weight compound having a phenolic hydroxyl group, a polymer compound having a phenolic hydroxyl group, or a mixture thereof can be used.
反応の方法は一般に、０−ナフトキノンジアジドスルホ
ン酸ハロゲン化物及びフェノール化合物を、室温で適当
な溶剤に溶解し、次いで縮合反応に必要な塩基性成分を
含む緩衝液（ｐＨが７以下）を反応混合物の温度を１０
’Ｃ〜４０°Ｃに保ちなが添加する。緩衝液の添加が完
了したら更に攪拌を続け、０−ナフトキノンジアジドス
ルホン酸ハロゲン化物が消失するまで反応を続ける。The reaction method is generally to dissolve the 0-naphthoquinonediazide sulfonic acid halide and the phenol compound in a suitable solvent at room temperature, and then add a buffer solution (pH 7 or less) containing the basic components necessary for the condensation reaction to the reaction mixture. temperature of 10
Add while keeping the temperature between 40°C and 40°C. After the addition of the buffer solution is completed, stirring is continued and the reaction is continued until the 0-naphthoquinonediazide sulfonic acid halide disappears.
ハロゲン化物の消失はＧＰＣ（ゲル・パーミェーション
・クロマトグラフィー）により確認できる。Disappearance of halides can be confirmed by GPC (gel permeation chromatography).
次いで該反応混合物を水中へ添加し、沈澱物を分離し、
繰り返し水で洗浄した後乾燥することによりエステルを
単離できるが、エステルの回収方法はこれに限定される
ものではない。The reaction mixture is then added to water, the precipitate is separated,
Although the ester can be isolated by repeatedly washing with water and drying, the method for recovering the ester is not limited thereto.
（発明の効果）
か（して本発明によれば、従来技術に比較して副反応の
少ないＯ−ナフトキノンジアジドスルホン酸エステルを
得ることができる。(Effects of the Invention) According to the present invention, an O-naphthoquinonediazide sulfonic acid ester having fewer side reactions compared to the prior art can be obtained.
（実施例）
以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例及び比較例中の部及び％は特に断りのな
いかぎり重量基準である。(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.
実施例−１
ナフトキノン−（１，２）−ジアジド−（２）−４−ス
ルホニルクロリド２９．５部およびピロガロール５．８
部を、ジオキサン４５９部に溶解し、これに重炭酸ソー
ダ１３．８部とりん酸二水素カリウム３３．６部を含む
水溶液３９３部（ｐＨ＝ ６ ）を添加した。Example-1 29.5 parts of naphthoquinone-(1,2)-diazide-(2)-4-sulfonyl chloride and 5.8 parts of pyrogallol
1 part was dissolved in 459 parts of dioxane, and 393 parts of an aqueous solution (pH=6) containing 13.8 parts of sodium bicarbonate and 33.6 parts of potassium dihydrogen phosphate were added thereto.
添加が完了した後に、更に攪拌を１０時間続けた。反応
ｔ＆ ヲゲル・パーミェーション・クロマトグラフィー
で分析した結果、ナフトキノン−（１，２）−ジアジド
−（２）−４−スルホニルクロリドは検出されなかった
。After the addition was complete, stirring was continued for an additional 10 hours. As a result of reaction analysis by gel permeation chromatography, naphthoquinone-(1,2)-diazide-(2)-4-sulfonyl chloride was not detected.
次いで、この反応液をシュウ酸１２．５部と脱イオン水
６０５０部の溶液中へ投入し、生じた沈澱物を公知の方
法で吸引濾過した。脱イオン水約３０００部を用い該沈
澱物を洗浄し、水に易溶の重炭酸ソーダ、塩化ナトリウ
ム、りん酸二水素カリウム等の無機化合物を除去した。Next, this reaction solution was poured into a solution of 12.5 parts of oxalic acid and 6,050 parts of deionized water, and the resulting precipitate was suction-filtered by a known method. The precipitate was washed with about 3000 parts of deionized water to remove inorganic compounds such as sodium bicarbonate, sodium chloride, and potassium dihydrogen phosphate that are easily soluble in water.
次いで沈澱物を乾燥することによりピロガロールのモノ
、ビス、トリエステルの混合物２７、Ｏ部を得た。この
混合物をゲル・パーミェーション・クロマトグラフィー
で分析した結果、モノ、ビス、トリエステルの合計は全
体の９８面積％であった。Next, the precipitate was dried to obtain O part 27 of a mixture of mono-, bis-, and triester of pyrogallol. Analysis of this mixture by gel permeation chromatography revealed that the total amount of mono-, bis-, and triester was 98% by area.
得られた混合物はポジ型フォトレジスト用の感光剤とし
て用いられる。The resulting mixture is used as a photosensitizer for positive photoresists.
実施例−２
ナフトキノン−（１，２）−ジアジド−（２）−５−ス
ルホニルクロリド２９．５部およびピロガロール５．８
部を、ジオキサン４５９部に溶解し、これに重炭酸ソー
ダ１３．８部とりん酸二水素カリウム３３．６部を含む
水溶液３９３部（ｐＨ＝ ６ ）を添加した。Example-2 29.5 parts of naphthoquinone-(1,2)-diazide-(2)-5-sulfonyl chloride and 5.8 parts of pyrogallol
1 part was dissolved in 459 parts of dioxane, and 393 parts of an aqueous solution (pH=6) containing 13.8 parts of sodium bicarbonate and 33.6 parts of potassium dihydrogen phosphate were added thereto.
添加が完了した後に、更に攪拌を３時間続けた。After the addition was complete, stirring was continued for an additional 3 hours.
反応液をゲル・パーミェーション・クロマトクラフィー
で分析した結果、ナフトキノン−（１，２）−ジアジド
ー（２）−５−スルホニルクロリドは検出されなかった
。As a result of analyzing the reaction solution by gel permeation chromatography, naphthoquinone-(1,2)-diazido(2)-5-sulfonyl chloride was not detected.
次いで、この反応液をシュウ酸１２．５部と脱イオン水
６０５０部の溶液中へ投入し、生じた沈澱物を公知の方
法で吸引が過した。脱イオン水約３０００部を用い該沈
澱物を洗浄し、水に易溶の重炭酸ソーダ、塩化ナトリウ
ム、りん酸二水素カリウム等の無機化合物を除去した。This reaction solution was then poured into a solution of 12.5 parts of oxalic acid and 6050 parts of deionized water, and the resulting precipitate was filtered off by suction using a known method. The precipitate was washed with about 3000 parts of deionized water to remove inorganic compounds such as sodium bicarbonate, sodium chloride, and potassium dihydrogen phosphate that are easily soluble in water.
次いで沈澱物を乾燥することによりピロガロールのモノ
、ビス、トリエステルの混合物２７．５部を得た。この
混合物をゲル・パーミェーション・クロマトグラフィー
で分析した結果、モノ、ビス、トリエステルの合計は全
体の９９面積％であった。Then, the precipitate was dried to obtain 27.5 parts of a mixture of mono-, bis-, and triester of pyrogallol. Analysis of this mixture by gel permeation chromatography revealed that the total amount of mono-, bis-, and triester was 99% by area.
得られた混合物はポジ型フォトレジスト用の感光剤とし
て用いられる。The resulting mixture is used as a photosensitizer for positive photoresists.
実施例−３
ナフトキノン−（１，２）−ジアジド−（２）−４−ス
ルホニルクロリド２９．５部および２．３．４−トリヒ
ドロキシベンゾフェノン１０．６部を、ジオキサン１０
４０部に溶解し、これに水酸化ナトリウム６．６部とり
ん酸二水素カリウム６３、Ｏ部を含む水溶液７８６部（
ｐＨ＝ ６．６ ）を添加した。Example-3 29.5 parts of naphthoquinone-(1,2)-diazide-(2)-4-sulfonyl chloride and 10.6 parts of 2.3.4-trihydroxybenzophenone were mixed with 10 parts of dioxane.
786 parts of an aqueous solution containing 6.6 parts of sodium hydroxide and 63 parts of potassium dihydrogen phosphate and 0 parts (
pH=6.6) was added.
添加が完了した後に、更に撹拌を３時間続けた。After the addition was complete, stirring was continued for an additional 3 hours.
反応液をゲル・パーミェーション・クロマトグラフィー
で分析した結果、ナフトキノン−（１，２）−ジアジド
＝（２）−４−スルホニルクロリドは検出されなかった
。As a result of analyzing the reaction solution by gel permeation chromatography, naphthoquinone-(1,2)-diazide=(2)-4-sulfonyl chloride was not detected.
次いで、この反応液をシュウ酸１２．５部と脱イオン水
１２６００部の溶液中へ投入し、生じた沈澱物を公知の
方法で吸引が過した。脱イオン水約３０００部を用い該
沈澱物を洗浄し、水に易溶の水酸化ナトリウム、塩化ナ
トリウム、りん酸二水素カリウム等の無機化合物を除去
した。This reaction solution was then poured into a solution of 12.5 parts of oxalic acid and 12,600 parts of deionized water, and the resulting precipitate was filtered off with suction using a known method. The precipitate was washed with about 3000 parts of deionized water to remove inorganic compounds such as sodium hydroxide, sodium chloride, and potassium dihydrogen phosphate that are easily soluble in water.
次いで沈澱物を乾燥することにより２，３．４−トリＨ
のモノ、ビス、トリエステルの混合物３１．２部を得た
。この混合物をゲル・パーミェーション・クロマトグラ
フィーで分析した結果、モノ、ビス、トリエステルの合
計は全体の９７面積％であった。Then, by drying the precipitate, 2,3,4-triH
31.2 parts of a mixture of mono-, bis-, and triester were obtained. Analysis of this mixture by gel permeation chromatography revealed that the total amount of mono-, bis-, and triester was 97% by area.
得られた混合物はポジ型フォトレジスト用の感光剤とし
て用いられる。The resulting mixture is used as a photosensitizer for positive photoresists.
比較例−１
ナフトキノン−（１，２）−ジアジド−（２）−４−ス
ルホニルクロリド２９．５部およびピロガロール５．８
部を、ジオキサン４５９部に溶解し、これにトリエチル
アミン１３．３部を含むジオキサン溶液６６．５部を添
加した。Comparative Example-1 29.5 parts of naphthoquinone-(1,2)-diazide-(2)-4-sulfonyl chloride and 5.8 parts of pyrogallol
1 part was dissolved in 459 parts of dioxane, and 66.5 parts of a dioxane solution containing 13.3 parts of triethylamine was added thereto.
添加が完了した後に、更に撹拌を５分間続けた。Stirring was continued for an additional 5 minutes after the addition was complete.
反応液をゲル・パーミェーション・クロマトクラフィー
で分析した結果、ナフトキノン−（１，２）−ジアジド
−（２）−４−スルホニルクロリドは検出されなかった
。反応液は黒色化した。As a result of analyzing the reaction solution by gel permeation chromatography, naphthoquinone-(1,2)-diazide-(2)-4-sulfonyl chloride was not detected. The reaction solution turned black.
次いで、この反応液をシュウ酸１２．５部と脱イオン水
６０５０部の溶液中へ投入し、生じた沈澱物を公知の方
法で吸引濾過した。脱イオン水約３０００部を用い該沈
澱物を洗浄した。Next, this reaction solution was poured into a solution of 12.5 parts of oxalic acid and 6,050 parts of deionized water, and the resulting precipitate was suction-filtered by a known method. The precipitate was washed with about 3000 parts of deionized water.
次いで沈澱物を乾燥することによりピロガロールのモノ
、ビス、トリエステルの混合物２７．５部を得た。この
混合物をゲル・パーミェーション・クロマトグラフィー
で分析した結果、モノ、ビス、トリエステルの合計は全
体の６５面積％であった。Then, the precipitate was dried to obtain 27.5 parts of a mixture of mono-, bis-, and triester of pyrogallol. Analysis of this mixture by gel permeation chromatography revealed that the total amount of mono-, bis-, and triester was 65% by area of the total.
得られた混合物は黒色ないしは暗緑色をしていた。The resulting mixture was black to dark green in color.
比較例−２
ナフトキノン−（１，２）−ジアジド−（２）−４−ス
ルホニルクロリド２９．５部およびピロガロール５．８
部を、ジオキサン４５９部に溶解し、これに重炭酸ソー
ダ１３．８部とりん酸二水素カリウム５．６部を含む水
溶液３４５部（ｐＨ＝７．６）を添加した。Comparative Example-2 29.5 parts of naphthoquinone-(1,2)-diazide-(2)-4-sulfonyl chloride and 5.8 parts of pyrogallol
1 part was dissolved in 459 parts of dioxane, and 345 parts of an aqueous solution (pH=7.6) containing 13.8 parts of sodium bicarbonate and 5.6 parts of potassium dihydrogen phosphate were added thereto.
添加が完了した後に、更に攪拌を１０時間続けた。反応
液をゲル・パーミェーション・クロマトグラフィーで分
析した結果、ナフトキノン−（１，２）−ジアジド−（
２）−４−スルホニルクロリドは検出されなかった。After the addition was complete, stirring was continued for an additional 10 hours. Analysis of the reaction solution by gel permeation chromatography revealed that naphthoquinone-(1,2)-diazide-(
2) -4-sulfonyl chloride was not detected.
次いで、この反応液をシュウ酸１２．５部と脱イオン水
６０５０部の溶液中へ投入し、生じた沈澱物を公知の方
法で吸引濾過した。脱イオン水約３０００部を用い該沈
澱物を洗浄し、水に易溶の重炭酸ソーダ、塩化ナトリウ
ム、りん酸二水素カリウム等の無機化合物を除去した。Next, this reaction solution was poured into a solution of 12.5 parts of oxalic acid and 6,050 parts of deionized water, and the resulting precipitate was suction-filtered by a known method. The precipitate was washed with about 3000 parts of deionized water to remove inorganic compounds such as sodium bicarbonate, sodium chloride, and potassium dihydrogen phosphate that are easily soluble in water.
次いで沈澱物を乾燥することによりピロガロールのモノ
、ビス、トリエステルの混合物２７、Ｏ部を得た。この
混合物をゲル・パーミェーション・クロマトグラフィー
で分析した結果、モノ、ビス、トリエステルの合計は全
体の９０面積％であった。Next, the precipitate was dried to obtain O part 27 of a mixture of mono-, bis-, and triester of pyrogallol. Analysis of this mixture by gel permeation chromatography revealed that the total amount of mono-, bis-, and triester was 90% by area of the total.
得られた混合物は暗緑色をしていた。The resulting mixture had a dark green color.
Claims (1)
と一価または多価のフェノール化合物を用い溶剤中でエ
ステル化反応を行い、次いでエステルを沈澱させ、かつ
乾燥することによりＯ−ナフトキノンジアジドスルホン
酸エステルを製造する方法において、 エステル化反応を、塩基性成分を含むｐＨが７以下とな
るような緩衝液を用いて行うことを特徴とするＯ−ナフ
トキノンジアジドスルホン酸エステルの製造法。 ２、緩衝液が、重炭酸のアルカリ金属塩及び、またはア
ルカリ金属水酸化物とりん酸系化合物とを含む水溶液で
ある特許請求の範囲第１項記載の製造法。[Claims] 1. O-naphtho- A method for producing O-naphthoquinonediazide sulfonic acid ester, characterized in that the esterification reaction is carried out using a buffer containing a basic component and having a pH of 7 or less. 2. The manufacturing method according to claim 1, wherein the buffer solution is an aqueous solution containing an alkali metal salt of bicarbonate and/or an alkali metal hydroxide and a phosphoric acid compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11816489A JPH02300160A (en) | 1989-05-11 | 1989-05-11 | Preparation of o-naphthoquinonediazide sulfonic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11816489A JPH02300160A (en) | 1989-05-11 | 1989-05-11 | Preparation of o-naphthoquinonediazide sulfonic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02300160A true JPH02300160A (en) | 1990-12-12 |
Family
ID=14729694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11816489A Pending JPH02300160A (en) | 1989-05-11 | 1989-05-11 | Preparation of o-naphthoquinonediazide sulfonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02300160A (en) |
-
1989
- 1989-05-11 JP JP11816489A patent/JPH02300160A/en active Pending
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