JP4914146B2 - Papermaking process water sterilization method - Google Patents
Papermaking process water sterilization method Download PDFInfo
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- JP4914146B2 JP4914146B2 JP2006219070A JP2006219070A JP4914146B2 JP 4914146 B2 JP4914146 B2 JP 4914146B2 JP 2006219070 A JP2006219070 A JP 2006219070A JP 2006219070 A JP2006219070 A JP 2006219070A JP 4914146 B2 JP4914146 B2 JP 4914146B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 43
- 230000001954 sterilising effect Effects 0.000 title claims description 11
- 238000004659 sterilization and disinfection Methods 0.000 title claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 26
- 239000000460 chlorine Substances 0.000 claims description 26
- 229910052801 chlorine Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- 239000012895 dilution Substances 0.000 claims description 17
- 238000010790 dilution Methods 0.000 claims description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 18
- 239000000975 dye Substances 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UUIVKBHZENILKB-UHFFFAOYSA-N 2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N UUIVKBHZENILKB-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Paper (AREA)
Description
この発明は、製紙工程水の殺菌方法に関する。さらに詳しくは、この発明は、抄紙工程水などの製紙工程水を殺菌するために次亜塩素酸ナトリウムを使用する場合に、紙製品の白色度を向上させる目的で添加されている染料に影響することなく、製紙工程水を殺菌することのできる方法に関する。 The present invention relates to a method for sterilizing papermaking process water. More particularly, this invention affects dyes added for the purpose of improving the whiteness of paper products when using sodium hypochlorite to sterilize papermaking process water such as papermaking process water. The present invention relates to a method capable of sterilizing water without making paper.
紙パルプ製造工程では、原料となる木材に由来するセルロース、リグニン、ヘミセルロース、糖類などを栄養源として多くの微生物が製紙工程水中に繁殖する。これらの微生物が製紙工程中のパイプラインやピットなどの壁面に付着してスライムを形成し、スライムが原因となって紙切れによる生産効率の低下が生じたり、あるいは、紙製品の品質低下がもたらされることは、従来からよく知られている。これらの障害を防ぐために、種々の有機系殺菌剤が使用されているが、経済性や環境影響性の点からその使用量が制限される。そこで、酸化剤を用いた工業用水系の微生物制御方法が種々提案されている。 In the pulp and paper manufacturing process, many microorganisms are propagated in the papermaking process water by using cellulose, lignin, hemicellulose, saccharides and the like derived from wood as a raw material as nutrient sources. These microorganisms adhere to the walls of pipelines and pits during the paper making process to form slime, resulting in a decrease in production efficiency due to running out of paper due to slime, or a decrease in paper product quality. This is well known from the past. In order to prevent these obstacles, various organic fungicides are used, but the amount of use is limited from the viewpoint of economic efficiency and environmental impact. Thus, various industrial water-based microorganism control methods using an oxidizing agent have been proposed.
特開平５−１４６７８６号公報（特許文献１）には、高い塩素要求水における微生物を殺害し、そして生物汚染を制御するための方法であって、酸化体およびアンモニウム塩を混合し、そしてその混合物をすぐに、処理されるべき水性システムに添加することを含んで成る水の消毒のための方法およびその組成物が提案されている。さらに、酸化体として次亜塩素酸ナトリウム、アンモニウム塩として臭化アンモニウムからなる組成物による、ペーパーミル、スターチサイジングにおける生物汚染の制御を確認した試験例１４では、上記組成物はサイジング混合物に添加されるブルー染料と適合でき、次亜塩素酸ナトリウム単独の場合とは異なって、ブルースターチを漂白しなかったことが記載されている。しかしながら、製紙工程水における染料への影響性については触れられていない。 JP-A-5-146786 (Patent Document 1) discloses a method for killing microorganisms in high chlorine demand water and controlling biological contamination, comprising mixing an oxidant and an ammonium salt, and a mixture thereof. A method and composition for water disinfection has been proposed comprising immediately adding to the aqueous system to be treated. Furthermore, in Test Example 14 in which control of biological contamination in paper mill and starch sizing was confirmed with a composition comprising sodium hypochlorite as the oxidant and ammonium bromide as the ammonium salt, the composition was added to the sizing mixture. In contrast to the case of sodium hypochlorite alone, it is described that the blue starch was not bleached. However, there is no mention of the influence on the dye in papermaking process water.
また、特許第３４９７１７１号公報（特許文献２）には、酸化剤とアミン源を混合することによって製造した殺生物有効成分を液体に添加することによって、液体中の生物の増殖を阻害する液体処理方法であって、特定濃度に希釈した酸化剤およびアミン源を連続的に混合して殺生物有効成分を管路内で製造しながら、被処理液体中へ連続的に注入する方法およびそのための装置が提案されている。しかしながら、殺生物有効成分の染料への影響性に関する記載はない。 Japanese Patent No. 3497171 (Patent Document 2) discloses a liquid treatment that inhibits the growth of organisms in a liquid by adding a biocidal active ingredient produced by mixing an oxidizing agent and an amine source to the liquid. A method for continuously injecting a biocidal active ingredient in a pipeline by continuously mixing an oxidizing agent and an amine source diluted to a specific concentration into a liquid to be treated and an apparatus therefor Has been proposed. However, there is no description regarding the effect of biocidal active ingredients on dyes.
一方、塩素とアンモニアから発生させた結合塩素による殺菌効果は、特開昭６４−４３３９２号公報（特許文献３）に記載されているように古くから公知であり、製紙工程水のような塩素要求量の高い水系においても優れた殺菌効果が得られ、かつ、経済的でもあることから汎用されている。製紙工程水の殺菌を行なう場合は、塩素要求量として消費される次亜塩素酸ナトリウムのような酸化剤の添加量に、殺菌効果を得るのに必要な酸化剤をさらに上乗せして添加するのが一般的である。また、塩素要求量は工場や装置ごとに異なることから、しばしば過剰な添加量の酸化剤が製紙工程水に供給されてしまい、このことが、紙製品の白色度を向上させる目的で添加されている染料を漂白してしまうという悪影響を引き起こしていた。ここで塩素要求量とは、ＪＩＳ Ｋ ０１０１「工業用水試験方法」に規定されている通り、試料に塩素を加え、一定時間反応させた後の残留塩素が所定の濃度になるために必要な塩素の添加量のことである。 On the other hand, the bactericidal effect of combined chlorine generated from chlorine and ammonia has been known for a long time as described in Japanese Patent Application Laid-Open No. 64-43392 (Patent Document 3). It is widely used because an excellent sterilizing effect can be obtained even in a high-volume aqueous system and it is economical. When sterilizing papermaking process water, add an oxidizing agent necessary to obtain a sterilizing effect to the added amount of oxidizing agent such as sodium hypochlorite consumed as chlorine demand. Is common. In addition, since the chlorine requirement varies from factory to factory and equipment, an excessive amount of oxidizing agent is often supplied to the papermaking process water, which is added to improve the whiteness of paper products. It had the adverse effect of bleaching the dyes that were present. Here, the chlorine demand is the chlorine necessary for the residual chlorine to have a predetermined concentration after adding chlorine to the sample and reacting for a certain period of time, as defined in JIS K 0101 “Industrial water test method”. It is the amount of addition.
この発明は、製紙工程水を殺菌するために次亜塩素酸ナトリウムを使用する場合に、紙製品の白色度を向上させる目的で添加されている染料に影響することなく、確実に製紙工程水を殺菌することのできる方法を提供することを課題とする。 When using sodium hypochlorite to sterilize papermaking process water, this invention ensures that papermaking process water is used without affecting the dye added for the purpose of improving the whiteness of the paper product. It is an object to provide a method that can be sterilized.
この発明の発明者らは、上記課題を解決するために検討した結果、（ａ）次亜塩素酸ナトリウム水溶液と、（ｂ）硫酸アンモニウム水溶液および塩化アンモニウム水溶液から選ばれた少なくとも１種とを添加することによって、塩素要求量に影響されることなく確実に殺菌効果が得られ、かつ、染料への影響性が非常に小さいことを見出した。特に染料への影響性は、従来技術において染料への影響性が小さいことが知られている次亜塩素酸ナトリウムと臭化アンモニウムとを組合せる場合よりもはるかに小さいものであり、意外な事実であった。 As a result of investigations to solve the above-mentioned problems, the inventors of the present invention add (a) an aqueous sodium hypochlorite solution and (b) at least one selected from an aqueous ammonium sulfate solution and an aqueous ammonium chloride solution. Thus, the present inventors have found that a bactericidal effect can be reliably obtained without being influenced by the chlorine demand, and that the influence on the dye is very small. In particular, the effect on the dye is much smaller than the combination of sodium hypochlorite and ammonium bromide, which is known to have a small effect on the dye in the prior art, and it is a surprising fact. Met.
かくして、この発明によれば、製紙工程の白水ラインに流入するように設けられかつ上流側から（ａ）次亜塩素酸ナトリウム水溶液の添加ポイントおよび（ｂ）硫酸アンモニウム水溶液の添加ポイントの順に有効成分の添加ポイントが設けられた希釈水ラインの希釈水に、（ａ）成分と（ｂ）成分とを添加して、前記希釈水ライン中で（ａ）成分と（ｂ）成分との混合水溶液を調製し、前記混合水溶液を製紙工程の白水に添加することからなり、前記製紙工程の白水に対して前記（ａ）成分の濃度が有効塩素濃度として３０００〜９０００ｍｇ／Ｌ、前記（ｂ）成分の濃度が４０００〜１００００ｍｇ／Ｌであって、かつ前記（ａ）成分中の塩素と前記（ｂ）成分中の窒素とのモル比が１：１〜１：２であることを特徴とする製紙工程水の殺菌方法が提供される。 Thus, according to the present invention, the active ingredients are provided in the order of (a) the addition point of the aqueous sodium hypochlorite solution and (b) the addition point of the aqueous ammonium sulfate solution from the upstream side. (A) component and (b) component are added to the dilution water of the dilution water line provided with the addition point, and a mixed aqueous solution of (a) component and (b) component is prepared in the dilution water line And the mixed aqueous solution is added to white water in the papermaking process, and the concentration of the component (a) is 3000 to 9000 mg / L as an effective chlorine concentration with respect to the whitewater in the papermaking process, and the concentration of the component (b) Is made from 4000 to 10000 mg / L, and the molar ratio of chlorine in the component (a) and nitrogen in the component (b) is 1: 1 to 1: 2. Killing A method is provided.
この発明の製紙工程水の殺菌方法は、塩素要求量に影響されることなく確実に殺菌効果が得られ、かつ、紙製品の白色度を向上させる目的で添加されている染料への影響性が小さいことから、産業上極めて有用である。 The sterilization method of papermaking process water of the present invention has a sterilization effect reliably without being affected by chlorine demand, and has an influence on dyes added for the purpose of improving the whiteness of paper products. Since it is small, it is extremely useful in industry.
この発明の方法で使用する（ａ）次亜塩素酸ナトリウム水溶液としては、市販されている９〜１４％水溶液を好適に用いることができる。また、（ｂ）硫酸アンモニウム水溶液および／または塩化アンモニウム水溶液としては、市販されている硫酸アンモニウムおよび／または塩化アンモニウムを適宜水で希釈して、所望の濃度になるように調製すればよい。 As the (a) sodium hypochlorite aqueous solution used in the method of the present invention, a commercially available 9 to 14% aqueous solution can be suitably used. Further, (b) an aqueous ammonium sulfate solution and / or an aqueous ammonium chloride solution may be prepared so that a commercially available ammonium sulfate and / or ammonium chloride is appropriately diluted with water to obtain a desired concentration.
この発明の方法では、殺菌効果および染料影響性の点から、製紙工程水に添加する（ａ）次亜塩素酸ナトリウム水溶液の濃度は有効塩素濃度として３０００〜９０００ｍｇ／Ｌ、好ましくは６０００〜９０００ｍｇ／Ｌ、（ｂ）硫酸アンモニウム水溶液および／または塩化アンモニウム水溶液の濃度は、４０００〜１００００ｍｇ／Ｌ、好ましくは７０００〜１００００ｍｇ／Ｌであって、かつ、（ａ）成分中の塩素と（ｂ）成分中の窒素のモル比を１：１〜１：２とするのがよい。 In the method of the present invention, from the viewpoint of bactericidal effect and dye influence, the concentration of the aqueous sodium hypochlorite solution (a) added to the papermaking process water is 3000 to 9000 mg / L, preferably 6000 to 9000 mg / L as the effective chlorine concentration. The concentration of L, (b) ammonium sulfate aqueous solution and / or ammonium chloride aqueous solution is 4000-10000 mg / L, preferably 7000-10000 mg / L, and chlorine in component (a) and component (b) The molar ratio of nitrogen is preferably 1: 1 to 1: 2.
また、この発明の方法では、（ａ）次亜塩素酸ナトリウム水溶液と、（ｂ）硫酸アンモニウム水溶液および塩化アンモニウム水溶液から選ばれた少なくとも１種とを、同時にまたは別々に製紙工程水に添加する。このとき、予め希釈水に（ａ）成分と（ｂ）成分とを混合して混合溶液を調製し、当該混合溶液を製紙工程水に添加するのが好ましい実施態様である。上記実施態様を連続的に行なう例として、製紙工程水ラインに流入する希釈水ラインを設け、当該希釈水ライン中の希釈水に、この発明の方法の有効成分である（ａ）成分、（ｂ）成分が添加されるように、（ａ）成分添加ポイント、（ｂ）成分添加ポイントを設ける実施態様が挙げられる。このとき、希釈水に対しては、（ａ）成分を添加した後に（ｂ）成分を添加するのが染料影響性の点から好ましいので、当該希釈水ラインには、希釈水上流側から（ａ）成分添加ポイント、（ｂ）成分添加ポイントの順に有効成分添加ポイントを設けるとよい。こうすることで、希釈水ライン中において、最終的に（ａ）成分と（ｂ）成分との混合溶液が調製でき、当該混合溶液を製紙工程水ラインに流入させることができる。また、上記実施態様において、より効率よく確実な殺菌処理を行なうためには、希釈水中の塩素濃度を測定するための塩素計や、（ａ）成分と（ｂ）成分との混合溶液のｐＨを測定するためのｐＨ計を希釈水ラインに適宜設置するとよい。 In the method of the present invention, (a) an aqueous sodium hypochlorite solution and (b) at least one selected from an aqueous ammonium sulfate solution and an aqueous ammonium chloride solution are added simultaneously or separately to the papermaking process water. At this time, it is a preferred embodiment to prepare a mixed solution by previously mixing the components (a) and (b) with dilution water and add the mixed solution to papermaking process water. As an example of continuously carrying out the above embodiment, a dilution water line that flows into the papermaking process water line is provided, and the dilution water in the dilution water line is provided with the (a) component, (b) The embodiment which provides (a) component addition point and (b) component addition point so that a) component may be added is mentioned. At this time, since it is preferable to add the component (b) after the component (a) is added to the dilution water from the viewpoint of dye influence, the dilution water line is connected to the dilution water from the upstream side (a The active ingredient addition point may be provided in the order of () component addition point and (b) component addition point. By doing so, a mixed solution of the component (a) and the component (b) can be finally prepared in the dilution water line, and the mixed solution can be flowed into the papermaking process water line. Moreover, in the said embodiment, in order to perform a more efficient and reliable sterilization process, the chlorine meter for measuring the chlorine concentration in dilution water, pH of the mixed solution of (a) component and (b) component is set. A pH meter for measurement may be appropriately installed in the dilution water line.
この発明の方法において、予め希釈水に（ａ）成分と（ｂ）成分とを混合して混合溶液を調製する場合には、当該混合溶液のｐＨを８以上とするのが、殺菌効果および染料影響性の点から好ましい。当該混合溶液のｐＨが８未満の場合には、水酸化ナトリウム、水酸化カリウムなどのアルカリ剤を添加し、当該混合溶液のｐＨを８以上に調整した後、製紙工程水に添加するとよい。 In the method of the present invention, when a mixed solution is prepared by previously mixing the components (a) and (b) with dilution water, the pH of the mixed solution is adjusted to 8 or more. It is preferable from the point of influence. When the pH of the mixed solution is less than 8, an alkaline agent such as sodium hydroxide or potassium hydroxide is added to adjust the pH of the mixed solution to 8 or more, and then added to the papermaking process water.
また、この発明の方法は、この発明の効果を阻害しない限りにおいて、公知の殺菌剤を併用添加することもできる。 Moreover, the method of this invention can also add a well-known disinfectant together, unless the effect of this invention is inhibited.
この発明を以下の試験例により説明するが、この発明が、これらの試験例により限定されるものではない。 The present invention will be described with reference to the following test examples, but the present invention is not limited to these test examples.
（試験例１）白水における殺菌効果確認試験
某製紙工場のＰＤＦ白水（ｐＨ＝７．９１、ＯＲＰ＝４３８ｍＶ、菌数＝１×１０７ｃｆｕ／ｍＬ、アンモニア性窒素、硝酸性窒素および亜硝酸性窒素は不検出）を供試白水とし、表１に示す各供試薬剤をそれぞれの濃度で添加、１５分間接触させた後、白水中の菌数を測定した。その結果を表１に示す。表中の菌数はＬｏｇ値である。
なお、次亜塩素酸ナトリウム（ＮａＯＣｌ）溶液と硫酸アンモニウム（(ＮＨ４)２ＳＯ４）溶液あるいは次亜塩素酸ナトリウム（ＮａＯＣｌ）溶液と臭化アンモニウム（ＮＨ４Ｂｒ）溶液とを混合した供試薬剤は、それぞれの成分中の塩素および窒素のモル比が、塩素：窒素＝１：１となるように調製した。以下の試験例においても同様とする。
(Test Example 1) Bactericidal effect confirmation test in white water PDF white water of a paper mill (pH = 7.91, ORP = 438 mV, number of bacteria = 1 × 10 7 cfu / mL, ammoniacal nitrogen, nitrate nitrogen and nitrite) Nitrogen was not detected) was used as test white water, and each reagent agent shown in Table 1 was added at each concentration and allowed to contact for 15 minutes, and then the number of bacteria in the white water was measured. The results are shown in Table 1. The number of bacteria in the table is the Log value.
In addition, the reagent agent which mixed sodium hypochlorite (NaOCl) solution and ammonium sulfate ((NH 4 ) 2 SO 4 ) solution or sodium hypochlorite (NaOCl) solution and ammonium bromide (NH 4 Br) solution Was prepared such that the molar ratio of chlorine and nitrogen in each component was chlorine: nitrogen = 1: 1. The same applies to the following test examples.
（試験例２）白水中の染料への影響性確認試験
試験例１で用いた白水に、製紙用青色染料または製紙用赤色染料を添加したものを供試白水とし、表２に示す各供試薬剤をそれぞれの濃度で添加、９０分間接触させた後、それぞれの吸光度を測定して、ブランクの吸光度（＝０．５）に対する染料退色率を算出した。その結果を表２（青色染料）および表３（赤色染料）に示す。
(Test Example 2) Confirmation of influence on dye in white water Test white water obtained by adding blue dye for papermaking or red dye for papermaking to white water used in Test Example 1 is shown in Table 2. After adding a chemical | medical agent at each density | concentration and making it contact for 90 minutes, each light absorbency was measured and the dye fading rate with respect to the light absorbency (= 0.5) of a blank was computed. The results are shown in Table 2 (blue dye) and Table 3 (red dye).
試験例１および試験例２の結果より、殺菌効果は実施例と比較例との間にほとんど差はないが、染料影響性は実施例と比較例との間に顕著な差があることがわかる。 From the results of Test Example 1 and Test Example 2, it can be seen that the bactericidal effect has little difference between the Example and the Comparative Example, but the dye influence has a significant difference between the Example and the Comparative Example. .
（試験例３）塩素要求量の異なる白水における殺菌効果確認試験
国内の５製紙工場から採取した製紙工程白水をろ過したもの、および供試菌（菌種：Ｐｓｅｕｄｏｍｏｎａｓ．ｓｐ）を添加した液体培地溶液を試料とし、それぞれの塩素要求量をＪＩＳ Ｋ ０１０１−１９９８「工業用水試験方法」に準拠して測定した。その結果を図１に示す。
一方、各供試白水および培地溶液に、表４に示す供試薬剤をそれぞれの濃度で添加して、３０℃で６０分間接触させた後、菌数を測定した。その結果を表４に示す。表中の菌数はＬｏｇ値である。
(Test Example 3) Bactericidal Effect Confirmation Test in White Water with Different Chlorine Requirements A liquid medium solution to which white paper collected from 5 paper mills in Japan was filtered and to which a test bacterium (bacterial species: Pseudomonas.sp) was added Was used as a sample, and each chlorine requirement was measured according to JIS K 0101-1998 “Industrial Water Test Method”. The result is shown in FIG.
On the other hand, the reagent agents shown in Table 4 were added to each test white water and medium solution at respective concentrations, and contacted at 30 ° C. for 60 minutes, and then the number of bacteria was measured. The results are shown in Table 4. The number of bacteria in the table is the Log value.
図１および表４の結果より、比較例では、塩素要求量の変動により殺菌効果が変化するが、実施例では、塩素要求量の変動に影響されることなく一定の殺菌効果が得られていることがわかる。 From the results of FIG. 1 and Table 4, in the comparative example, the bactericidal effect changes due to fluctuations in the chlorine demand, but in the examples, a certain bactericidal effect is obtained without being affected by fluctuations in the chlorine demand. I understand that.
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