JPS6363643A - Stable quaternary alkylhydroxyalkylammonium hydroxide aqueous solution - Google Patents
Stable quaternary alkylhydroxyalkylammonium hydroxide aqueous solutionInfo
- Publication number
- JPS6363643A JPS6363643A JP20672886A JP20672886A JPS6363643A JP S6363643 A JPS6363643 A JP S6363643A JP 20672886 A JP20672886 A JP 20672886A JP 20672886 A JP20672886 A JP 20672886A JP S6363643 A JPS6363643 A JP S6363643A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- hydroxide
- alkylhydroxyalkylammonium
- quaternary
- hydrazine
- 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.)
- Granted
Links
- 239000007864 aqueous solution Substances 0.000 title claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 26
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000004040 coloring Methods 0.000 description 8
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 7
- 229960001231 choline Drugs 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- -1 ammonium sulfite Chemical compound 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical group [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 229920001744 Polyaldehyde Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HJSFCSCCEIXTCZ-UHFFFAOYSA-N 2,2-dihydroxyethyl(diethyl)azanium;hydroxide Chemical group [OH-].CC[NH+](CC)CC(O)O HJSFCSCCEIXTCZ-UHFFFAOYSA-N 0.000 description 1
- FSJQUYQAQKLXGK-UHFFFAOYSA-N 2,2-dihydroxyethyl(dimethyl)azanium;hydroxide Chemical group [OH-].C[NH+](C)CC(O)O FSJQUYQAQKLXGK-UHFFFAOYSA-N 0.000 description 1
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 description 1
- AJEUSSNTTSVFIZ-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;hydroxide Chemical group [OH-].C[N+](C)(C)CCCO AJEUSSNTTSVFIZ-UHFFFAOYSA-M 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は、安定な第四級アルキルヒドロキシアルキル
アンモニウムハイドロキサイド水溶液に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to a stable aqueous quaternary alkylhydroxyalkylammonium hydroxide solution.
［従来の技術］
第四級アルキルヒドロキシアルキルアンモニウムハイド
ロオキサイド水溶液、例えばコリン水溶液は、医薬品、
コバルトヤフエロシアン化物の比色定量試薬あるいはカ
リウムの定量試薬、ざらには合成中間体等として有用で
あるだけでなく、半導体の製造工程におけるシリコンウ
ェハの洗浄、像露光したレジスト、例えば感光性キノン
ジアジド組成物層の現像、リンス及びレジスト剥離等の
薬品として大量に使用されている。[Prior Art] A quaternary alkylhydroxyalkylammonium hydroxide aqueous solution, such as a choline aqueous solution, is used for pharmaceuticals,
It is useful not only as a colorimetric reagent for cobalt ferrocyanide or as a quantitative reagent for potassium, but also as a synthetic intermediate, etc., as well as for cleaning silicon wafers in the semiconductor manufacturing process, image-exposed resists, e.g. photosensitive quinone diazide. It is used in large quantities as a chemical for developing, rinsing, and removing resists for composition layers.
特に、最近の半導体工業における微細加工技術の進歩は
めざましく、集積回路、特に超ＬＳＩの１チップ当りの
素子数は飛躍的に増加しており、かかる微細な加工技術
が要求される超ＬＳＩ製造プロセスにおいて使用される
第四級アルキルヒドロキシアルキルアンモニウムハイド
ロオキサイド水溶液については、たとえ僅かな不純物で
あってもそれが洗浄工程、現像工程あるいは剥離工程で
悪影響を及し、デバイスの劣化や不良化につながる場合
が多いので、かかる不純物を可及的完全に除去した超高
純度のものが要求されている。In particular, recent advances in microfabrication technology in the semiconductor industry have been remarkable, with the number of elements per integrated circuit, especially VLSI chip, increasing dramatically, and VLSI manufacturing processes that require such microfabrication technology. Regarding the quaternary alkylhydroxyalkylammonium hydroxide aqueous solution used in Therefore, there is a demand for ultra-high purity products in which such impurities are removed as completely as possible.
ところで、このような第四級アルキルヒドロキシアルキ
ルアンモニウムハイドロオキサイド水溶液は、高純度の
アルキレンオキサイド及びトリアルキルアミン並びに超
純水を原料にして、厳密な工程管理の下に製造されてお
り、その製造直後には高純度のものとして得ることがで
きる。By the way, such an aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide is manufactured under strict process control using high-purity alkylene oxide, trialkylamine, and ultrapure water as raw materials. can be obtained in high purity.
しかしながら、この第四級アルキルヒドロキシアルキル
アンモニウムハイドロオキサイド水溶液にはその濃度や
温度が高くなるにつれて貯蔵中や輸送中経時的に着色す
るという傾向があり、着色すると単にその商品価値が低
下するだけでなく、＠色の原因物質が不純物として取込
まれ、これを半導体の製造工程で使用した場合に洗浄剤
、現像剤あるいは剥離剤としての挙動に変化をきたし、
製造される半導体に重大な悪影響を及す。そして、この
第四級アルキルヒドロキシアルキルアンモニウムハイド
ロオキナイド水溶液の着色原因については、そのヒドロ
キシアルキル基が酸１ヒされ分解されてアルデヒドが生
成し、このアルデヒドが重合してポリアルデヒドとなり
、このポリアルデヒドが原因物質となって徐々に着色し
黒化するものと考えられている。However, this aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide has a tendency to become colored over time during storage and transportation as its concentration and temperature increase, and coloring not only reduces its commercial value but also ,@ Color-causing substances are taken in as impurities, and when used in the semiconductor manufacturing process, the behavior as a cleaning agent, developer, or stripping agent changes,
This will have a serious negative impact on the semiconductors being manufactured. The reason for the coloring of this aqueous solution of quaternary alkylhydroxyalkylammonium hydroquinide is that the hydroxyalkyl group is decomposed by acid and aldehyde is produced, and this aldehyde is polymerized to form polyaldehyde. It is thought that this is the causative agent that causes the color to gradually turn black.
そこで、従来においてはこのような問題を解決するため
、第四級アルキルヒドロキシアルキルアンモニウムハイ
ドロオキサイド水溶液中に安定化濃度の亜硫酸塩、例え
ば亜硫酸アンモニウムを添加し、第四級アルキルヒドロ
キシアルキルアンモニウムハイドロオキサイド水溶液中
に生成したアルデヒドと付加物を形成させ、これによっ
て着色原因物質であるボリアルチルヒトの生成を防止す
るようにしたもの（米国特許第４，２９４，９１１号朋
細書）や、第四級アルキルヒドロキシアルキルアンモニ
ウムハイドロオキサイド水溶液中に安定化濃度のセミカ
ルバジドを添加し、第四級アルキルヒドロキシアルキル
アンモニウムハイドロオキサイド水溶液中に生成したア
ルデヒドと縮合反応させてセミカルバゾンを形成させ、
これによって着色原因物質であるボリアルチルヒトの生
成を防止するようにしたちのく特開昭６０−４２．７５
４号公報）や、第四級アルキルヒドロキシアルキルアン
モニウムハイドロオキサイド水溶液の原料系及び反応系
からアルデヒドが生成する原因となる酸素をほぼ完全に
カットし、アルデヒドの生成を防止する方法（特開昭６
０−１０４，０４７号公報）等が提案されている。Conventionally, in order to solve this problem, a stabilizing concentration of sulfite, such as ammonium sulfite, is added to an aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide, and the aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide is (U.S. Pat. No. 4,294,911) and quaternary alkylhydroxyalkyl, which forms an adduct with the aldehyde generated in Adding a stabilizing concentration of semicarbazide to an aqueous ammonium hydroxide solution and causing a condensation reaction with the aldehyde generated in an aqueous quaternary alkylhydroxyalkylammonium hydroxide solution to form semicarbazone;
This prevents the formation of boreal chloride, which is a substance that causes coloration.
4), and a method for preventing the formation of aldehydes by almost completely cutting out oxygen, which causes the formation of aldehydes, from the raw material system and reaction system of an aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide (Japanese Unexamined Patent Publication No. 6)
0-104,047) etc. have been proposed.
［発明が解決しようとする問題点］
しかしながら、安定剤として安定化濃度の亜硫酸塩、例
えば亜硫酸アンモニウムを使用する方法においては、特
開昭６０−４２，７５４号公報にも記載されているよう
に、第四級アルキルヒドロキシアルキルアンモニウムハ
イドロオキサイド水溶液を高濃度の濃縮液の形に調製し
、搬送しまた貯蔵して使用時に最適なｐＨ及び濃度に希
釈する際に、このｐＨ及び濃度を正確に決定することが
できないという問題があり、また、安定剤として安定化
濃度のセミカルバジドを使用する方法においては、亜硫
酸塩を使用する時のような問題はないが、セミカルバジ
ドそのものが水溶性に乏しいために実際には塩酸塩、硫
酸塩、燐酸塩等の塩の形で使用され、このため第四級ア
ルキルヒドロキシアルキルアンモニウムハイドロオキサ
イド水溶液中にこれらの酸イオンが存在し、超ＬＳＩの
製造の際にこの酸イオンが悪影響を及すという別の問題
が生じ、さらに、原料系及び反応系からアルデヒドが生
成する原因となる酸素をほぼ完全にカットする方法にお
いては、製造工程に厳密な管理が要求されてその製造コ
ストが極めて高くなるという問題があった。[Problems to be Solved by the Invention] However, in the method of using a stabilizing concentration of sulfite, such as ammonium sulfite, as a stabilizer, as described in JP-A-60-42,754, Accurately determine the pH and concentration of an aqueous quaternary alkylhydroxyalkyl ammonium hydroxide solution when preparing it in the form of a highly concentrated concentrate, transporting and storing it, and diluting it to the optimum pH and concentration before use. In addition, the method of using semicarbazide at a stabilizing concentration as a stabilizer does not have the same problems as using sulfites, but semicarbazide itself has poor water solubility, so in practice are used in the form of salts such as hydrochloride, sulfate, and phosphate. Therefore, these acid ions are present in the aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide, and these acids are used in the production of VLSIs. Another problem arises in that ions have an adverse effect.Furthermore, the method of almost completely cutting out oxygen, which causes aldehyde formation from the raw material system and reaction system, requires strict control of the manufacturing process. There was a problem in that the manufacturing cost was extremely high.
従って、本発明の目的は、簡便な方法で確実に着色を防
止することができ、しかも、使用時に容易かつ正確にｐ
Ｈ及びａ度の調整とその確定をすることができる安定な
第四級アルキルヒドロキシアルキルアンモニウムハイド
ロオキサイド水溶液を提供することにおる。Therefore, an object of the present invention is to be able to reliably prevent coloring using a simple method, and to easily and accurately prevent coloring during use.
The object of the present invention is to provide a stable aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide, which allows adjustment and determination of H and a degrees.
［問題点を解決するための手段］
すなわち、本発明は、安定剤として有効濃度のヒドラジ
ンを含有する安定な第四級アルキルヒドロキシアルキル
アンモニウムハイドロキサイド水溶液である。[Means for Solving the Problems] That is, the present invention is a stable aqueous quaternary alkylhydroxyalkylammonium hydroxide solution containing an effective concentration of hydrazine as a stabilizer.
本発明において対象となる第四級アルキルヒドロキシア
ルキルアンモニウムハイドロキサイド水溶液としては、
例えば、下記一般式（Ｉ）及び（ＩＩ＞
（但し、式中Ｒ１、Ｒ２及びＲ３は低級アルキル基を示
し、ｎは１〜６の整数である。〕で表される化合物の水
溶液を挙げることができ、好ましくはアルキル基Ｒ１、
Ｒ２及びＲ３が炭素数１〜４のアルキル基であって、ｎ
が２〜４の整数である化合物の水溶液である。このよう
な第四級アルキルヒドロキシアルキルアンモニウムハイ
ドロキサイド水溶液の具体例としては、例えば、第四級
トリメチルヒドロキシエチルアンモニウムハイドロキサ
イド（コリン）、第四級ジメチルジヒドロキシエチルア
ンモニウムハイドキサイド、第四級トリメチルヒドロキ
シエチルアンモニウムハイドロキサイド、第四級ジエチ
ルジヒドロキシエチルアンモニウムハイドロキサイド、
第四級トリプロピルヒドロキシエチルアンモニウムハイ
ドロキサイド、第四級トリメチルヒドロキシプロピルア
ンモニウムハイドロキサイド等の水溶液を挙げることが
できる。The quaternary alkylhydroxyalkylammonium hydroxide aqueous solution targeted in the present invention includes:
For example, an aqueous solution of a compound represented by the following general formulas (I) and (II> (wherein R1, R2, and R3 represent a lower alkyl group, and n is an integer from 1 to 6) is mentioned. , preferably an alkyl group R1,
R2 and R3 are alkyl groups having 1 to 4 carbon atoms, and n
is an aqueous solution of a compound in which is an integer of 2 to 4. Specific examples of such quaternary alkylhydroxyalkylammonium hydroxide aqueous solutions include quaternary trimethylhydroxyethylammonium hydroxide (choline), quaternary dimethyldihydroxyethylammonium hydroxide, quaternary trimethylhydroxyethylammonium hydroxide, quaternary diethyldihydroxyethylammonium hydroxide,
Examples include aqueous solutions of quaternary tripropylhydroxyethylammonium hydroxide, quaternary trimethylhydroxypropylammonium hydroxide, and the like.
そして、この第四級アルキルヒドロキシアルキルアンモ
ニウムハイドロキサイド水溶液の濃度にいては、特に制
限があるものではなく、どのような濃度の水溶液につい
ても適用できるものであるが、本発明の効果が顕著に発
揮されるのは、通常５重量％以上、好ましくは７重量％
以上の水溶液であり、５重量％より低いとその水溶液自
体の着色の問題が少なくなる。There is no particular restriction on the concentration of this quaternary alkylhydroxyalkylammonium hydroxide aqueous solution, and the present invention can be applied to an aqueous solution of any concentration. Usually 5% by weight or more, preferably 7% by weight
If the content of the aqueous solution is less than 5% by weight, the problem of coloring of the aqueous solution itself will be reduced.
また、上記第四級アルキルヒドロキシアルキルアンモニ
ウムハイドロキサイド水溶液中にその安定剤として添加
されるヒドラジンとしては、無水ヒドラジンであっても
よいが、取扱上の観点から好ましくは１水和物である水
加ヒドラジンおるいはその水溶液である。The hydrazine added as a stabilizer to the aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide may be anhydrous hydrazine, but from the viewpoint of handling, it is preferable to use hydrazine, which is a monohydrate. hydrazine or its aqueous solution.
そして、このヒドラジンの添加量については、第四級ア
ルキルヒドロキシアルキルアンモニウムハイドロキサイ
ド水溶液中に無水ヒドラジンに換算して通常０．００５
〜２．０重量％、好ましくは０．０５〜１．０重但％の
範囲内で添加する。The amount of hydrazine added is usually 0.005 in terms of anhydrous hydrazine in the quaternary alkylhydroxyalkylammonium hydroxide aqueous solution.
It is added in an amount of 2.0% by weight, preferably 0.05% to 1.0% by weight.
この添加口が０．００５重量％より少ないと長期間に亘
って着色を防止するのが難しくなり、また、２．０重量
％より多くしても着色防止の効果にあまり変化がない。If the addition amount is less than 0.005% by weight, it will be difficult to prevent coloring over a long period of time, and if it is more than 2.0% by weight, the effect of preventing coloration will not change much.
なお、本発明において、第四級アルキルヒドロキシアル
キルアンモニウムハイドロキサイド水溶液中の酸素を可
及的に減少せしめることにより、安定剤としてのヒドラ
ジンの添加量を減少させることができるので、特開昭６
（）−１０４，０４７号公報に記載されているように、
原料系及び反応系からアルデヒドが生成する原因となる
酸素を可能な範囲でカットし、アルデヒドの生成をでき
るだけ防止して第四級アルキルヒドロキシアルキルアン
モニウムハイドロキサイド水溶液を製造し、これに少量
のヒドラジンを添加するようにするのがよい。In addition, in the present invention, the amount of hydrazine added as a stabilizer can be reduced by reducing the oxygen in the quaternary alkylhydroxyalkylammonium hydroxide aqueous solution as much as possible.
As stated in Publication No. ()-104,047,
A quaternary alkylhydroxyalkylammonium hydroxide aqueous solution is produced by cutting oxygen, which causes aldehyde production, from the raw material system and reaction system to the extent possible and preventing the production of aldehydes as much as possible, and then adding a small amount of hydrazine to this aqueous solution. It is best to add .
［作用］
本発明で安定剤として使用されるヒドラジンは、第四級
アルキルヒドロキシアルキルアンモニウムハイドロキサ
イド水溶液中に溶存する酸素と反応して水と窒素ガスと
に分解するので、アルデヒドの生成を抑制することがで
き、また、生成したアルデヒドと反応してヒドラゾンに
なることにより着色の原因となるポリアルデヒドの生成
を防止することができるものと考えられる。[Function] Hydrazine used as a stabilizer in the present invention reacts with oxygen dissolved in the quaternary alkylhydroxyalkylammonium hydroxide aqueous solution and decomposes into water and nitrogen gas, so it suppresses the production of aldehydes. It is also considered possible to prevent the formation of polyaldehyde, which causes coloration by reacting with the generated aldehyde to form hydrazone.
［実施例］
以下、実施例、比較例及び試験例に基いて、本発明を具
体的に説明する。[Examples] The present invention will be specifically described below based on Examples, Comparative Examples, and Test Examples.
実施例１〜６及び比較例１〜２
第１表に示す濃度のコリン水溶液を調製し、これに安定
剤として水加ヒドラジン（純度６４重量％）を添加し、
第１表に示すヒドラジン濃度（無水ヒドラジンとして）
のコリン水溶液をＥＩ’Ｊした。Examples 1 to 6 and Comparative Examples 1 to 2 A choline aqueous solution having the concentration shown in Table 1 was prepared, and hydrazine hydrate (purity 64% by weight) was added thereto as a stabilizer.
Hydrazine concentration shown in Table 1 (as anhydrous hydrazine)
An aqueous solution of choline was subjected to EI'J.
これら各実施例及び比較例のコリン水溶液を通常のポリ
エチレン容器に入れて密封し、第１表に示す温度条件で
保存し、分光光度計の４４Ｏｎｌｌｌラインを使用して
吸光度を測定することによりその着色の程度を経時的に
調べた。結果を第１図に示す。The choline aqueous solutions of these Examples and Comparative Examples were placed in a regular polyethylene container and sealed, stored under the temperature conditions shown in Table 1, and colored by measuring the absorbance using the 44Onllll line of a spectrophotometer. The degree of this was investigated over time. The results are shown in Figure 1.
試験例
５重量％コリン水溶液に水加ヒドラジンを添加し、ヒド
ラジン濃度がＯ重量％、０．００６４重量％、０．０３
２重量％、０．０６ｄ重量％及び０．１９２重母％のサ
ンプル現像液を調製し、各サンプル現像液について以下
の方法によりその現像性能を調べた。Test Example: Hydrazine hydrate was added to a 5% by weight choline aqueous solution, and the hydrazine concentration was 0% by weight, 0.0064% by weight, and 0.03% by weight.
Sample developers of 2% by weight, 0.06d% by weight, and 0.192% by weight were prepared, and the developing performance of each sample developer was examined by the following method.
すなわち、シリコンウェハをヘキサメチレンジシラザン
の雰囲気中に５分間晒した後、このシリコンウェハの上
にフェノールノボラック型の樹脂成分とナフトキノンジ
アジド系の感光成分との混合物を基材とするポジ型フｔ
トレジストを用いてスピンコードし、ホットプレート上
に９５℃で４分間おいてベーキングすることにより残存
する溶剤を除去し、厚さ１．５μｍのレジストフィルム
を調製した。このようにして得られたレジストフィルム
を縮小投影型露光装置にセットして露光を行い、３０℃
の上記サンプル現像液で３０秒間スプレー現像した後、
これを超純水ですすぎ乾燥した。各サンプル現像液に関
して常法により、残膜率、最少露光量、コントラストの
指標として用いられるγ値並びに３０秒、６０秒及び９
０秒における未露光部膜減り量を現像性能の判定のため
に測定した。結果を第２表に示す。That is, after exposing a silicon wafer to an atmosphere of hexamethylene disilazane for 5 minutes, a positive film containing a mixture of a phenol novolac type resin component and a naphthoquinone diazide type photosensitive component was placed on the silicon wafer.
A resist film was spin-coded using a resist, and the remaining solvent was removed by baking on a hot plate at 95° C. for 4 minutes to prepare a resist film with a thickness of 1.5 μm. The resist film thus obtained was set in a reduction projection type exposure device and exposed at 30°C.
After spray developing for 30 seconds with the above sample developer,
This was rinsed with ultrapure water and dried. For each sample developer, the residual film rate, minimum exposure amount, γ value used as an index of contrast, and 30 seconds, 60 seconds, and 9
The amount of film loss in the unexposed area at 0 seconds was measured to determine development performance. The results are shown in Table 2.
第２表の結果から明らかなように、ヒドラジン無添加の
サンプル現像液とヒドラジンを各濃度で添加して調製し
たサンプル現像液との間に各現像性能の上で格別な相違
は認められず、ヒドラジン添加による現像性能への悪影
響はほとんど認められなかった。As is clear from the results in Table 2, no particular difference in developing performance was observed between the sample developer without the addition of hydrazine and the sample developer prepared by adding hydrazine at various concentrations. Almost no adverse effect on development performance was observed due to the addition of hydrazine.
第２表
［発明の効果］
本発明の第四級アルキルヒドロキシアルキルアンモニウ
ムハイドロキサイド水溶液には、その安定剤として有効
濃度のヒドラジンが添加されているので、長期間に亘っ
てその着色が防止され、また、使用時に容易かつ正確に
ｐＨ及び濃度の調整とその確定をすることができる。Table 2 [Effects of the Invention] Since an effective concentration of hydrazine is added as a stabilizer to the quaternary alkylhydroxyalkylammonium hydroxide aqueous solution of the present invention, its coloring is prevented for a long period of time. Furthermore, the pH and concentration can be easily and accurately adjusted and determined during use.
第１図は本発明の各実施例及び比較例に係るコリン水溶
液の着色試験の結果を示すグラフ図である。
特許出願人 多摩化学工業株式会社
同 上 モーゼス レイク インダストリーズ
インコーホレイテッドFIG. 1 is a graph showing the results of a coloring test of aqueous choline solutions according to each example and comparative example of the present invention. Patent applicant Tama Chemical Industry Co., Ltd. Moses Lake Industries
Incoholated
Claims (3)
とを特徴とする安定な第四級アルキルヒドロキシアルキ
ルアンモニウムハイドロキサイド水溶液。(1) A stable aqueous quaternary alkylhydroxyalkylammonium hydroxide solution containing an effective concentration of hydrazine as a stabilizer.
００５〜２．０重量％である特許請求の範囲第１項記載
の安定な第四級アルキルヒドロキシアルキルアンモニウ
ムハイドロキサイド水溶液。(2) The content of hydrazine is 0.0 as anhydrous hydrazine.
The stable aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide according to claim 1, wherein the aqueous solution is from 0.005 to 2.0% by weight.
ハイドロキサイド水溶液の濃度が５重量％以上である特
許請求の範囲第１項又は第２項記載の安定な第四級アル
キルヒドロキシアルキルアンモニウムハイドロキサイド
水溶液。(3) The stable aqueous quaternary alkylhydroxyalkylammonium hydroxide solution according to claim 1 or 2, wherein the concentration of the aqueous quaternary alkylhydroxyalkylammonium hydroxide solution is 5% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61206728A JPH0745443B2 (en) | 1986-09-04 | 1986-09-04 | Stable quaternary alkyl hydroxyalkyl ammonium hydroxide aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61206728A JPH0745443B2 (en) | 1986-09-04 | 1986-09-04 | Stable quaternary alkyl hydroxyalkyl ammonium hydroxide aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6363643A true JPS6363643A (en) | 1988-03-22 |
| JPH0745443B2 JPH0745443B2 (en) | 1995-05-17 |
Family
ID=16528121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61206728A Expired - Lifetime JPH0745443B2 (en) | 1986-09-04 | 1986-09-04 | Stable quaternary alkyl hydroxyalkyl ammonium hydroxide aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745443B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58104205A (en) * | 1981-12-11 | 1983-06-21 | 日本メクトロン株式会社 | Marking of male mold for fabricating wig |
| EP0346048A2 (en) * | 1988-06-09 | 1989-12-13 | Nikken Chemical Laboratory Co, Ltd. | Silver master plate recovery solution |
| US5175078A (en) * | 1988-10-20 | 1992-12-29 | Mitsubishi Gas Chemical Company, Inc. | Positive type photoresist developer |
| JPH06163495A (en) * | 1992-11-20 | 1994-06-10 | Toshiba Corp | Semiconductor wafer treatment liquid |
| CN103874679A (en) * | 2012-04-13 | 2014-06-18 | 亨斯迈石油化学有限责任公司 | Using novel amines to stabilize quaternary trialkylalkanolamines |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294911A (en) * | 1979-06-18 | 1981-10-13 | Eastman Kodak Company | Development of light-sensitive quinone diazide compositions using sulfite stabilizer |
| JPS6042754A (en) * | 1983-07-22 | 1985-03-07 | イ−ストマン コダツク カンパニ− | Developing composition |
| JPS60104047A (en) * | 1983-11-10 | 1985-06-08 | Tama Kagaku Kogyo Kk | Production of aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide |
| JPS60254043A (en) * | 1984-05-30 | 1985-12-14 | Yotsukaichi Gosei Kk | Developing agent for positive type photosensitive material |
| JPS6198527U (en) * | 1984-12-02 | 1986-06-24 |
-
1986
- 1986-09-04 JP JP61206728A patent/JPH0745443B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294911A (en) * | 1979-06-18 | 1981-10-13 | Eastman Kodak Company | Development of light-sensitive quinone diazide compositions using sulfite stabilizer |
| JPS6042754A (en) * | 1983-07-22 | 1985-03-07 | イ−ストマン コダツク カンパニ− | Developing composition |
| JPS60104047A (en) * | 1983-11-10 | 1985-06-08 | Tama Kagaku Kogyo Kk | Production of aqueous solution of quaternary alkylhydroxyalkylammonium hydroxide |
| JPS60254043A (en) * | 1984-05-30 | 1985-12-14 | Yotsukaichi Gosei Kk | Developing agent for positive type photosensitive material |
| JPS6198527U (en) * | 1984-12-02 | 1986-06-24 |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58104205A (en) * | 1981-12-11 | 1983-06-21 | 日本メクトロン株式会社 | Marking of male mold for fabricating wig |
| JPS6363643B2 (en) * | 1981-12-11 | 1988-12-08 | ||
| EP0346048A2 (en) * | 1988-06-09 | 1989-12-13 | Nikken Chemical Laboratory Co, Ltd. | Silver master plate recovery solution |
| US5175078A (en) * | 1988-10-20 | 1992-12-29 | Mitsubishi Gas Chemical Company, Inc. | Positive type photoresist developer |
| JPH06163495A (en) * | 1992-11-20 | 1994-06-10 | Toshiba Corp | Semiconductor wafer treatment liquid |
| CN103874679A (en) * | 2012-04-13 | 2014-06-18 | 亨斯迈石油化学有限责任公司 | Using novel amines to stabilize quaternary trialkylalkanolamines |
| JP2015516390A (en) * | 2012-04-13 | 2015-06-11 | ハンツマン ペトロケミカル エルエルシーＨｕｎｔｓｍａｎ Ｐｅｔｒｏｃｈｅｍｉｃａｌ ＬＬＣ | Use of new amines to stabilize quaternary trialkylalkanolamines. |
| EP2836479A4 (en) * | 2012-04-13 | 2015-10-28 | Huntsman Petrochemical Llc | Using novel amines to stabilize quaternary trialkylalkanolamines |
| AU2013246183B2 (en) * | 2012-04-13 | 2017-03-16 | Huntsman Petrochemical Llc | Using novel amines to stabilize quaternary trialkylalkanolamines |
| US9670137B2 (en) | 2012-04-13 | 2017-06-06 | Huntsman Petrochemical Llc | Using novel amines to stabilize quaternary trialkylalkanolamines |
| CN107325009A (en) * | 2012-04-13 | 2017-11-07 | 亨斯迈石油化学有限责任公司 | Season trialkyl alkanolamine is stabilized using novel amine |
| JP2019055971A (en) * | 2012-04-13 | 2019-04-11 | ハンツマン ペトロケミカル エルエルシーＨｕｎｔｓｍａｎ Ｐｅｔｒｏｃｈｅｍｉｃａｌ ＬＬＣ | Using novel amines to stabilize quaternary trialkylalkanolamines |
| US10264785B2 (en) | 2012-04-13 | 2019-04-23 | Huntsman Petrochemical Llc | Using novel amines to stabilize quaternary trialkylalkanolamines |
| CN107325009B (en) * | 2012-04-13 | 2022-03-18 | 亨斯迈石油化学有限责任公司 | Stabilization of quaternary trialkylalkanolamines using novel amines |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745443B2 (en) | 1995-05-17 |
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