JPH0380837B2 - - Google Patents
Info
- Publication number
- JPH0380837B2 JPH0380837B2 JP61015537A JP1553786A JPH0380837B2 JP H0380837 B2 JPH0380837 B2 JP H0380837B2 JP 61015537 A JP61015537 A JP 61015537A JP 1553786 A JP1553786 A JP 1553786A JP H0380837 B2 JPH0380837 B2 JP H0380837B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- slime
- cleaning agent
- water
- copolymer
- 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.)
- Expired - Lifetime
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000012459 cleaning agent Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- DWHJJLTXBKSHJG-HWKANZROSA-N (e)-5-hydroxy-2-methylpent-2-enoic acid Chemical compound OC(=O)C(/C)=C/CCO DWHJJLTXBKSHJG-HWKANZROSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- NJMYQRVWBCSLEU-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanoic acid Chemical compound OCCC(=C)C(O)=O NJMYQRVWBCSLEU-UHFFFAOYSA-N 0.000 description 1
- DWHJJLTXBKSHJG-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid Chemical compound OC(=O)C(C)=CCCO DWHJJLTXBKSHJG-UHFFFAOYSA-N 0.000 description 1
- HKXJTVOFQVGDPK-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid prop-2-enoic acid Chemical compound OCCC=C(C(=O)O)C.C(C=C)(=O)O HKXJTVOFQVGDPK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 amine salts Chemical class 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
〔産業上の利用分野〕
本発明は工業用水、上水、地下水、海水等を使
用する空調設備や工場等における熱交換器、配管
などに発生したスライムを効率良く洗浄、除去す
ることができるスライムの洗浄剤に関するもので
ある。
〔従来の技術〕
工業用水、上水、地下水、海水等を使用する空
調設備や工場等における熱交換器、配管にはスラ
イムが発生し、放置すると熱交換器や配管の不
良、水量の低下など、機器および装置本来の機能
を阻害してしまう。
従来、これらの阻害を回避するため、ポリアク
リル酸ソーダと過酸化水素とを含む溶液で対象水
系を洗浄する方法が提案されている（特開昭51−
9030号公報）。
〔発明が解決しようとする問題点〕
この方法は洗浄効果自体は極めて良好であるも
のの、対象水系のカルシウム硬度が50mg／（炭
酸カルシウムとして、以下同じ）を超えると、ポ
リアクリル酸ソーダが水中のカルシウム硬度成分
と反応を起こしてゲル化してしまい、分散能を失
なつてしまうという問題点があつた（一般的に冷
却水系のカルシウム硬度は50〜300mg／程度で
ある）。
また、過酸化水素とポリアクリル酸ソーダとを
含む溶液においては、過酸化水素の安定性が長期
間保持されず、比較的短期間で過酸化水素が分解
してしまうという問題点もあつた。
〔問題点を解決するための手段〕
本発明者らは、これら従来技術の有する問題点
を解決するために鋭意研究を行なつた結果、本発
明を完成したものである。
本発明は過酸化水素と、マレイン酸系重合体ま
たはアクリル酸系共重合体とを含むことを特徴と
するスライムの洗浄剤である。
過酸化水素は市販の製品を使用することができ
る。洗浄剤中の含有濃度は通常0.1〜50W／Ｖ％
を目安とする。
本発明の洗浄剤の他方の必須成分であるマレイ
ン酸系重合体またはアクリル酸系共重合体（以
下、単にポリマーという場合がある）としては、
マレイン酸やその水溶性塩のホモ重合体、または
マレイン酸とイソブチレンやペンテンなどのアル
ケン、アクリル酸やメタクリル酸、フマル酸など
の不飽和カルボン酸またはその水溶性塩などとの
共重合体、アクリル酸、メタクリル酸またはこれ
らの水溶性塩とヒドロキシエチルメタクリル酸や
ヒドロキシエチルアクリル酸、アクリル酸メチル
などの不飽和カルボン酸エステル、マレイン酸、
無水マレイン酸、フマル酸などの不飽和カルボン
酸又はそれらの水溶性塩などが具体的に例示され
ている。なお、これらの共重合体においては、さ
らにノニオン系単量体が入つて三元共重合体とな
つていてもよい。これらのうち、とりわけアクリ
ル酸塩−２−ヒドロキシエチルメタクリル酸共重
合体は極めて良好な洗浄性能を発揮するので好ま
しい。
これら重合体または共重合体及びその水溶性塩
の分子量は特に制限されないが、通常500〜
200000程度とする。
共重合体においては、アクリル酸またはマレイ
ン酸と他の単量体とのモル比は99：１〜１：99と
する。
重合体、及び共重合体の水溶性塩は、ナトリウ
ム、カリウム、アンモニウムおよびアミンなどの
塩が例示される。
これらの重合体または共重合体の洗浄剤中の含
有濃度は通常0.001〜10W／Ｖ％程度とする。
本発明の洗浄剤は、対象水系のスライム量に応
じて異なつてくるが、一般的な添加量としては過
酸化水素が1000〜100000mg／、重合体または共
重合体が10〜1000mg／程度とする。
本発明のスライムの洗浄剤は、対象水系内に所
定量添加して、一過式または循環式でスライムと
洗浄剤を接触させて洗浄するように使用すること
ができる。また、洗浄剤溶液中に対象物を浸漬さ
せて洗浄することも可能である。
〔作用〕
過酸化水素がスライム中の粘質物を分解し、粘
着力を消失せしめるとともに、同時に発泡作用に
より、物理的にスライムを剥離、分散する。
一方、重合体または共重合体は、過酸化水素に
よつて剥離、分散されたスライムをさらに微細に
分散することにより、スライム粒子の凝集や再付
着を防止する。なお、スライムと同時にスケール
も共存する場合には、スケールも剥離、分散され
る。
次に本発明の実験例、実施例を示す。
〔発明の実施例〕
実験例
500mlのコニカルビーカーに蒸留水を500mlとホ
ウ酸ナトリウム緩衝液10mlとを加え、PHを8.4に
調整した後、カルシウム硬度が50、100、300、
500mg／となるように塩化カルシウムを添加し
た。次に、表−１に示すポリマーを所定量添加し
た後、容器を密閉し、50℃で１時間放置した。そ
の後、ゲル化の有無を肉眼観察により判定した。
結果を表−１に示す。
[Industrial Application Field] The present invention provides a slime that can efficiently clean and remove slime generated in heat exchangers, piping, etc. in air conditioning equipment, factories, etc. that use industrial water, tap water, groundwater, seawater, etc. The invention relates to a cleaning agent. [Conventional technology] Slime forms on heat exchangers and piping in air conditioning equipment, factories, etc. that use industrial water, tap water, groundwater, seawater, etc., and if left untreated, it can cause defects in heat exchangers and piping, decrease in water flow, etc. , which may impede the original functions of equipment and equipment. Conventionally, in order to avoid these inhibitions, a method has been proposed in which the target aqueous system is cleaned with a solution containing sodium polyacrylate and hydrogen peroxide (Japanese Patent Application Laid-Open No. 1989-1999).
Publication No. 9030). [Problems to be solved by the invention] Although this method has an extremely good cleaning effect, if the calcium hardness of the target water system exceeds 50 mg/(as calcium carbonate, the same shall apply hereinafter), the sodium polyacrylate in the water will degrade. There was a problem in that it reacted with the calcium hardness component and gelled, resulting in a loss of dispersibility (generally, the calcium hardness of a cooling water system is about 50 to 300 mg/approx.). Further, in a solution containing hydrogen peroxide and sodium polyacrylate, there was a problem in that the stability of hydrogen peroxide was not maintained for a long period of time, and the hydrogen peroxide decomposed in a relatively short period of time. [Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive research to solve the problems of the prior art. The present invention is a slime cleaning agent characterized by containing hydrogen peroxide and a maleic acid-based polymer or an acrylic acid-based copolymer. Commercially available hydrogen peroxide products can be used. Concentration in cleaning agent is usually 0.1~50W/V%
As a guideline. The maleic acid polymer or acrylic acid copolymer (hereinafter sometimes simply referred to as polymer), which is the other essential component of the cleaning agent of the present invention, includes:
Homopolymers of maleic acid and its water-soluble salts, copolymers of maleic acid with alkenes such as isobutylene and pentene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and fumaric acid, or their water-soluble salts, acrylic acids, methacrylic acid or their water-soluble salts and unsaturated carboxylic acid esters such as hydroxyethyl methacrylic acid, hydroxyethyl acrylic acid, methyl acrylate, maleic acid,
Specific examples include unsaturated carboxylic acids such as maleic anhydride and fumaric acid, and water-soluble salts thereof. Note that these copolymers may further contain a nonionic monomer to form a terpolymer. Among these, acrylate-2-hydroxyethyl methacrylic acid copolymer is particularly preferred because it exhibits extremely good cleaning performance. The molecular weight of these polymers or copolymers and their water-soluble salts is not particularly limited, but is usually 500-
Approximately 200,000. In the copolymer, the molar ratio of acrylic acid or maleic acid to other monomers is 99:1 to 1:99. Examples of water-soluble salts of polymers and copolymers include sodium, potassium, ammonium, and amine salts. The concentration of these polymers or copolymers in the cleaning agent is usually about 0.001 to 10 W/V%. The cleaning agent of the present invention differs depending on the amount of slime in the target aqueous system, but the general amount added is about 1000 to 100000 mg/of hydrogen peroxide and 10 to 1000 mg/of polymer or copolymer. . The slime cleaning agent of the present invention can be used by adding a predetermined amount into a target water system and cleaning the slime by bringing the cleaning agent into contact with the slime in a one-time or circulating system. It is also possible to wash the object by immersing it in a cleaning agent solution. [Function] Hydrogen peroxide decomposes the sticky substance in the slime and eliminates its adhesive force, and at the same time physically peels off and disperses the slime due to its foaming action. On the other hand, the polymer or copolymer further finely disperses the slime that has been exfoliated and dispersed with hydrogen peroxide, thereby preventing agglomeration and redeposition of slime particles. Note that if scale coexists with slime, the scale will also be peeled off and dispersed. Next, experimental examples and examples of the present invention will be shown. [Embodiments of the invention] Experimental example 500 ml of distilled water and 10 ml of sodium borate buffer were added to a 500 ml conical beaker, and after adjusting the pH to 8.4, the calcium hardness was 50, 100, 300,
Calcium chloride was added at a concentration of 500 mg/kg. Next, after adding a predetermined amount of the polymer shown in Table 1, the container was sealed and left at 50°C for 1 hour. Thereafter, the presence or absence of gelation was determined by visual observation. The results are shown in Table-1.
【表】【table】
【表】
○…ゲル化せず ×…ゲル化する
表−１から、従来のポリアクリル酸ソーダでは
カルシウム硬度が50mg／を超えるとゲル化を起
こすのに対し、本発明の場合には、100mg／で
もゲル化せず、２−ヒドロキシエチルメタクリル
酸・アクリル酸ソーダ共重合体にいたつては500
mg／においてもゲル化しないことがわかる。
実施例 １
ビーカーに蒸留水500mlをとり、この中に過酸
化水素が30％、表−２に示したポリマーが１％と
なるようにそれぞれ添加し、室温にて静置した。
１、10、100日後に液中の過酸化水素の残留濃度
を測定した。
結果を表−２に示す。[Table] ○...No gelling ×...gelling From Table 1, gelation occurs when the calcium hardness exceeds 50 mg/kg in the conventional sodium polyacrylate, whereas in the case of the present invention, gelation occurs when the calcium hardness exceeds 100 mg/kg. / But it did not gel, and when it came to 2-hydroxyethyl methacrylic acid/sodium acrylate copolymer, it was 500
It can be seen that gelation does not occur even at mg/. Example 1 500 ml of distilled water was placed in a beaker, and 30% hydrogen peroxide and 1% of the polymer shown in Table 2 were added thereto, and the mixture was allowed to stand at room temperature.
After 1, 10, and 100 days, the residual concentration of hydrogen peroxide in the solution was measured. The results are shown in Table-2.
本発明のスライムの洗浄剤においては、過酸化
水素と特定の重合体を配合するようにしたので、
予め一液化しても過酸化水素の分解がほぼ抑制さ
れる。また、対象水系のカルシウム硬度が高くな
つても、従来例のように簡単にゲル化することも
なく、実用上極めて有用な洗浄剤である。
In the slime cleaning agent of the present invention, since hydrogen peroxide and a specific polymer are blended,
Even if it is made into one liquid in advance, the decomposition of hydrogen peroxide is almost suppressed. In addition, even if the calcium hardness of the target water system increases, it does not easily gel like in conventional examples, making it an extremely useful cleaning agent in practice.
第１図は実施例２における結果を示すグラフで
ある。
FIG. 1 is a graph showing the results in Example 2.
Claims (1)
クリル酸系重合体とを含むことを特徴とするスラ
イムの洗浄剤。 ２ アクリル酸系共重合体がアクリル酸とヒドロ
キシエチルメタクリル酸との共重合体である特許
請求の範囲第１項記載の洗浄剤。 ３ 過酸化水素を0.1〜50W／Ｖ％、マレイン酸
系重合体またはアクリル酸系共重合体を0.001〜
10W／Ｖ％含有する特許請求の範囲第１項または
第２項に記載の洗浄剤。[Scope of Claims] 1. A slime cleaning agent characterized by containing hydrogen peroxide and a maleic acid polymer or an acrylic acid polymer. 2. The cleaning agent according to claim 1, wherein the acrylic acid copolymer is a copolymer of acrylic acid and hydroxyethyl methacrylic acid. 3 Hydrogen peroxide 0.1~50W/V%, maleic acid polymer or acrylic acid copolymer 0.001~
The cleaning agent according to claim 1 or 2, containing 10 W/V%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1553786A JPS62174300A (en) | 1986-01-27 | 1986-01-27 | Detergent for slime |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1553786A JPS62174300A (en) | 1986-01-27 | 1986-01-27 | Detergent for slime |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174300A JPS62174300A (en) | 1987-07-31 |
| JPH0380837B2 true JPH0380837B2 (en) | 1991-12-26 |
Family
ID=11891550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1553786A Granted JPS62174300A (en) | 1986-01-27 | 1986-01-27 | Detergent for slime |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62174300A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0643289B2 (en) * | 1987-11-11 | 1994-06-08 | 近畿パイプ技研株式会社 | Algae fungicide |
| JP6529238B2 (en) * | 2014-09-30 | 2019-06-12 | 株式会社竹中工務店 | Sand filter |
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| JPS55109498A (en) * | 1979-02-15 | 1980-08-22 | Ichiro Kudo | Silicic acid scale removing agent |
| JPS5825750A (en) * | 1981-08-07 | 1983-02-16 | Fujitsu Ltd | Test system for operation collation of dual time division channel |
| JPS59176312A (en) * | 1983-03-25 | 1984-10-05 | Kao Corp | Maleic acid copolymer, its production and scale inhibitor comprising same |
| JPS6024183A (en) * | 1983-04-22 | 1985-02-06 | ストル・リサ−チ・アンド・デベロプメント・コ−ポレ−シヨン | Cell culture method and apparatus |
| JPS61197697A (en) * | 1985-02-28 | 1986-09-01 | 花王株式会社 | Detergent composition for flash toilet bowl |
-
1986
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51111812A (en) * | 1975-03-06 | 1976-10-02 | Solvay | Liquid detergent composition |
| JPS55109498A (en) * | 1979-02-15 | 1980-08-22 | Ichiro Kudo | Silicic acid scale removing agent |
| JPS5825750A (en) * | 1981-08-07 | 1983-02-16 | Fujitsu Ltd | Test system for operation collation of dual time division channel |
| JPS59176312A (en) * | 1983-03-25 | 1984-10-05 | Kao Corp | Maleic acid copolymer, its production and scale inhibitor comprising same |
| JPS6024183A (en) * | 1983-04-22 | 1985-02-06 | ストル・リサ−チ・アンド・デベロプメント・コ−ポレ−シヨン | Cell culture method and apparatus |
| JPS61197697A (en) * | 1985-02-28 | 1986-09-01 | 花王株式会社 | Detergent composition for flash toilet bowl |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62174300A (en) | 1987-07-31 |
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