JP2002370906A - Industrial antimicrobial agent composition and antimicrobial method - Google Patents

Industrial antimicrobial agent composition and antimicrobial method

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Publication number
JP2002370906A
JP2002370906A JP2001175033A JP2001175033A JP2002370906A JP 2002370906 A JP2002370906 A JP 2002370906A JP 2001175033 A JP2001175033 A JP 2001175033A JP 2001175033 A JP2001175033 A JP 2001175033A JP 2002370906 A JP2002370906 A JP 2002370906A
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JP
Japan
Prior art keywords
industrial
antimicrobial
antibacterial
active ingredients
water
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
Application number
JP2001175033A
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Japanese (ja)
Other versions
JP4726333B2 (en
Inventor
Yoshiteru Kato
加藤  義晃
Hitoshi Egawa
均 江川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumika Enviro Science Co Ltd
Original Assignee
Shinto Fine Co Ltd
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Application filed by Shinto Fine Co Ltd filed Critical Shinto Fine Co Ltd
Priority to JP2001175033A priority Critical patent/JP4726333B2/en
Publication of JP2002370906A publication Critical patent/JP2002370906A/en
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Publication of JP4726333B2 publication Critical patent/JP4726333B2/en
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Abstract

PROBLEM TO BE SOLVED: To obtain an industrial antimicrobial composition having a strongly antimicrobial power which has been insufficient in a conventional combination so as to control microorganism and to provide an antimicrobial method. SOLUTION: This industrial antimicrobial composition is characterized by comprising glutaraldehyde, o-phthalaldehyde and 2-methyl-4-isothiazolin-3-one. This antimicrobial method comprises using these active ingredients.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明が属する技術分野】本発明は、工業用水系組成物
等の微生物汚染を制御する工業用抗菌組成物及び抗菌方
法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial antibacterial composition and an antibacterial method for controlling microbial contamination of industrial aqueous compositions and the like.

【0002】[0002]

【従来の技術】水性塗料、水性インキ、紙用塗工液、エ
マルジョン、ラテックス、デンプンスラリー、デンプン
糊液、無機スラリー等水をベースに作成されている工業
用の水系組成物は、細菌によって汚染されることにより
腐敗が生じ、臭気の発生や粘度低下、pH変動等の物性
劣化を引き起こしたり、真菌(糸状菌)が繁殖すること
によってストレーナーの目詰まり、着色等を引き起こ
す。また、紙パルプ工業分野における抄紙工程では、紙
を生産するために大量の水を使用しており、その水には
紙を生産するために必要な各種有機物が分散・溶解して
いるため、上記工業水系組成物同様、細菌、真菌による
汚染を受けやすい。これら細菌や真菌は、粘液状の代謝
産物を産出し、パルプ、填料など製紙工程中に分散して
いる製紙原料を取り込んで、水流の淀んだチェスト内の
壁面やフローボックス等にスライムを形成する。スライ
ムは徐々に増大しやがて離脱しパルプ等の製紙原料と共
に紙に抄き込まれ紙上の異物となってあらわれ品質低下
を引き起こしたり、その異物が原因で断紙となり、生産
性の低下を引き起こす。 工業用冷却水系においては、
水の循環使用により、やはり微生物が繁殖しスライムを
形成し、冷却水系を詰まらせたり、熱交換器や充てん物
の表面に付着して熱効率の低下を引き起こす。
2. Description of the Related Art Aqueous industrial compositions based on water, such as aqueous paints, aqueous inks, paper coating liquids, emulsions, latexes, starch slurries, starch paste liquids, inorganic slurries, etc., are contaminated by bacteria. As a result, rot occurs, causing deterioration of physical properties such as generation of odor, decrease in viscosity, and fluctuation in pH, and clogging and coloring of the strainer due to propagation of fungi (filamentous fungi). Also, in the papermaking process in the pulp and paper industry, a large amount of water is used to produce paper, and various organic substances necessary for producing paper are dispersed and dissolved in the water. Like industrial water-based compositions, they are susceptible to contamination by bacteria and fungi. These bacteria and fungi produce mucus metabolites, take in papermaking materials such as pulp and fillers that are dispersed during the papermaking process, and form slime on walls and flow boxes in chests where water flows. . The slime gradually increases and is gradually released, and is made into paper together with papermaking raw materials such as pulp, and appears as foreign matter on the paper. The foreign matter causes quality deterioration, and the foreign matter causes paper breakage, thereby reducing productivity. In industrial cooling water systems,
Recycling of water also causes microorganisms to propagate and form slime, clogging the cooling water system and adhering to the surfaces of heat exchangers and packing, causing a decrease in thermal efficiency.

【0003】工業用水系組成物、製紙工程水、工業用冷
却水の微生物汚染を防止するために抗菌剤として各種の
薬剤が使用されてきた。たとえば、5−クロロ−2−メ
チル−4−イソチアゾリン−3−オン、2−メチル−4
−イソチアゾリン−3−オン、1,2−ベンズイソチア
ゾリン−3−オン等のチアゾリン化合物や2−ブロモ−
2−ニトロプロパン−1,3−ジオール、2,2−ジブ
ロモ−2−ニトロエタノール、2,2−ジブロモ−3−
ニトリロプロピオンアミド等の臭素化合物、4,5−ジ
クロロ−1,2−ジチオール−3−オン、メチレンビス
チオシアネートなどの有機硫黄化合物、グルタルアルデ
ヒド、オルトフタルアルデヒド等のアルデヒド化合物な
どが使用されてきた。
[0003] Various chemicals have been used as antibacterial agents to prevent microbial contamination of industrial aqueous compositions, papermaking process waters, and industrial cooling water. For example, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4
Thiazoline compounds such as -isothiazolin-3-one, 1,2-benzisothiazolin-3-one and 2-bromo-
2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-
Bromine compounds such as nitrilopropionamide, organic sulfur compounds such as 4,5-dichloro-1,2-dithiol-3-one and methylenebisthiocyanate, and aldehyde compounds such as glutaraldehyde and orthophthalaldehyde have been used.

【0004】しかし単一薬剤の長期にわたる連続使用
は、耐性菌の出現を招きやすいため、過去に種々の2成
分又は3成分の組み合わせによる抗菌剤が使用されてき
た。たとえば、2成分の組み合わせには、特開昭61−
234860におけるグルタルアルデヒドと5−クロロ
−2−メチル−4−イソチアゾリン−3−オン他との組
み合わせ、特公平7−2605におけるグルタルアルデ
ヒドとメチレンビスチオシアネートとの組み合わせなど
多数開示されている。3成分の組み合わせには、特開平
7−187920における2,2−ジブロモ−3−ニト
リロプロピオンアミドと4,5−ジクロロ−1,2−ジ
チオール−3−オンと5−クロロ−2−メチル−4−イ
ソチアゾリン−3−オンの組み合わせ、特開平7−25
708における2,2−ジブロモ−3−ニトリロプロピ
オンアミドとメチレンビスチオシアネートと2,2−ジ
ブロモ−2−ニトロエタノールの組み合わせなどが開示
されている。これら組み合わせは、単一薬剤が長期にわ
たって使用されていた工業用水系組成物や製紙工程水や
工業用冷却水に対して良好な効力を持っているが、2成
分、3成分の組み合わせの薬剤が微生物を制御する手段
として一般的になり組み合わせ配合でも長期使用による
耐性菌が出現してきたため、更なる効果をもった低濃度
で有効な薬剤が望まれていた。
[0004] However, long-term continuous use of a single drug tends to cause emergence of resistant bacteria, and thus various antibacterial agents having a combination of two or three components have been used in the past. For example, a combination of two components is disclosed in
Numerous disclosures include a combination of glutaraldehyde with 5-chloro-2-methyl-4-isothiazolin-3-one and the like in 234860 and a combination of glutaraldehyde with methylenebisthiocyanate in JP-B-7-2605. The combination of the three components includes 2,2-dibromo-3-nitrilopropionamide, 4,5-dichloro-1,2-dithiol-3-one and 5-chloro-2-methyl-4 described in JP-A-7-187920. -Isothiazolin-3-one, JP-A-7-25
No. 708, a combination of 2,2-dibromo-3-nitrilopropionamide, methylenebisthiocyanate and 2,2-dibromo-2-nitroethanol. These combinations have a good effect on industrial water-based compositions, papermaking process water and industrial cooling water in which a single agent has been used for a long period of time. As a general means of controlling microorganisms, resistant bacteria have emerged after long-term use even in combination, and there has been a demand for a drug that is effective at a low concentration and has a further effect.

【0005】[0005]

【発明が解決しようとする課題】 本発明は、前記の
ような要望に応えるため、従来の組み合わせでは不充分
であった強力な抗菌力をもった、広範囲の微生物に有効
な薬剤を提供することにある。
DISCLOSURE OF THE INVENTION The present invention provides a drug effective against a wide range of microorganisms having a strong antibacterial activity, which was insufficient with conventional combinations, in order to meet the above demands. It is in.

【0006】[0006]

【課題を解決するための手段】本発明は、課題を解決す
るために各種成分の組み合わせにおける効果の確認を行
ない、鋭意研究を重ねた結果、グルタルアルデヒド及び
オルトフタルアルデヒド及び2−メチル−4−イソチア
ゾリン−3−オンの3種の有効成分を含有することを特
徴とする工業用抗菌組成物が、低濃度でも良好な殺菌
力、静菌力を併せ持つ非常に優れた抗菌組成物であるこ
とを見出した。すなわち本発明は、グルタルアルデヒド
及びオルトフタルアルデヒド及び2−メチル−4−イソ
チアゾリン−3−オンの3種の有効成分を含有すること
を特徴とする工業用抗菌組成物が、低濃度でも良好な抗
菌力をもつ非常に優れた抗菌組成物であること、またこ
れら3種の有効成分を工業用水系組成物又は製紙工程水
又は工業用冷却水に1〜20000ppm添加すること
が優れた抗菌方法であることを見出した。
According to the present invention, in order to solve the problems, effects of combinations of various components have been confirmed, and as a result of intensive studies, glutaraldehyde, orthophthalaldehyde and 2-methyl-4-methyl-4-aldehyde have been confirmed. An industrial antibacterial composition characterized by containing three kinds of active ingredients of isothiazolin-3-one is a very excellent antibacterial composition having good bactericidal and bacteriostatic properties even at a low concentration. I found it. That is, the present invention provides an industrial antibacterial composition characterized by containing three kinds of active ingredients of glutaraldehyde, orthophthalaldehyde and 2-methyl-4-isothiazolin-3-one. It is a very excellent antibacterial composition having power, and it is an excellent antibacterial method to add 1 to 20,000 ppm of these three active ingredients to an industrial water-based composition or papermaking process water or industrial cooling water. I found that.

【0007】本発明の抗菌方法としては、上記3種の有
効成分を含有した抗菌組成物を添加してもよいし、上記
3種の有効成分を別々に添加しても良い。
In the antibacterial method of the present invention, an antibacterial composition containing the above three kinds of active ingredients may be added, or the above three kinds of active ingredients may be added separately.

【0008】本発明の有効成分の工業用水系組成物、製
紙工程水、工業用冷却水への添加方法は、各々別々でも
製剤化した混合物でもよく、製剤化に際して用いられる
溶媒、界面活性剤などは特に限定されない。しかし、微
生物の増殖を引き起こす工業用水系組成物や製紙工程水
や工業用冷却水などは、水を主とした組成であるため、
溶媒は比較的親水性のものが望ましい。
The method of adding the active ingredient of the present invention to an industrial water-based composition, papermaking process water, or industrial cooling water may be a separate or formulated mixture, and a solvent, a surfactant, etc. used in the formulation. Is not particularly limited. However, since industrial water-based compositions, papermaking process water, and industrial cooling water that cause the growth of microorganisms are mainly water-based compositions,
The solvent is desirably relatively hydrophilic.

【0009】溶媒としては、エチレングリコール、プロ
ピレングリコール、ジエチレングリコール、トリエチレ
ングリコール、ジプロピレングリコール、へキシレング
リコール、ポリエチレングリコールなどのグリコール系
溶剤、ジエチレングリコールモノメチルエーテル、ジエ
チレングリコールモノエチルエーテル、ジエチレングリ
コールモノブチルエーテルなどのグリコールエーテル系
溶剤やプロピレンカーボネート、ジメチルアセトアミ
ド、ジメチルスルホキシド、水などが使用できる。これ
らは、単独で用いても良いし、2種以上を組み合わせて
も良く、有効成分の3種を溶解できる添加量があれば良
い。
Examples of the solvent include glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, and polyethylene glycol; and glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Ether solvents, propylene carbonate, dimethylacetamide, dimethylsulfoxide, water and the like can be used. These may be used alone or in combination of two or more types, as long as there is an added amount capable of dissolving three types of active ingredients.

【0010】界面活性剤は使用しても使用しなくてもよ
く、使用する場合は、非イオン界面活性剤、陰イオン界
面活性剤、陽イオン界面活性剤、両イオン界面活性剤の
いずれを用いてもかまわない。
The surfactant may or may not be used. When used, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant and a zwitterionic surfactant is used. It doesn't matter.

【0011】[0011]

【実施例】次に本発明の実施例および比較例をあげて説
明するが、本発明はこれらに限定されるものではない。
下表に示した配合比率はすべて重量%である。また、各
実施例の抗菌組成物は各実施例に示す各成分をそれぞれ
示す割合で常温において通常の攪拌によって調製した。
EXAMPLES Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
All the compounding ratios shown in the following table are% by weight. Further, the antimicrobial compositions of the respective examples were prepared by ordinary stirring at room temperature at the indicated ratios of the respective components shown in the respective examples.

【0012】実施例1〜3 表1に示す抗菌組成物を調製し、試験例1、試験例2に
よりその性能を調べた。なお表中の有効成分の表示は以
下の略語にて表す。
Examples 1 to 3 The antibacterial compositions shown in Table 1 were prepared, and their performance was examined by Test Examples 1 and 2. The indication of the active ingredients in the table is represented by the following abbreviations.

【0013】グルタルアルデヒド:GLA オルトフタルアルデヒド:OPA 2−メチル−4−イソチアゾリン−3−オン:MITGlutaraldehyde: GLA orthophthalaldehyde: OPA 2-methyl-4-isothiazolin-3-one: MIT

【0014】[0014]

【表1】表1実施例 [Table 1] Table 1 Example

【0015】比較例1〜6 表2に示す抗菌組成物を調製し、試験例1、試験例2、
によりその性能を調べた。
Comparative Examples 1 to 6 The antibacterial compositions shown in Table 2 were prepared and tested in Test Examples 1 and 2,
The performance was examined by

【0016】[0016]

【表2】表2比較例 [Table 2] Table 2 Comparative Example

【0017】試験例1デンプンスラリーの防腐試験 「試験方法」某社カチオン化タピオカデンプンの10%
スラリー(pH6.2)を調製し、滅菌ポリプロピレン
瓶に30gを分注し各薬剤を所定量添加した後、あらか
じめ腐敗させたデンプンスラリー(菌数:8.1×10
個/ml)を1%接種した。これを密封静置条件で3
0℃で培養し、TGC寒天平板混釈法によって経時的な
生菌数を測定し、抗菌効果を判定した。また、生菌数測
定後、腐敗させたデンプンスラリーを1週間毎に1%接
種した。 「試験結果」下記判定基準をもって判定し、試験結果を
表3に示した。 1ml中の菌数値(個) −:10個未満 +:10 以上104未満 ++:104以上106未満 +++:106以上10未満 ++++:107以上 「考察」表3に示したように比較例1〜3の1種の有効
成分配合の製剤品、及び比較例4〜6の2種の有効成分
の製剤品の28日目の評価結果は、++〜++++であ
るのに対して、実施例1〜3の3種の有効成分配合の製
剤品の評価結果は、−〜++で、有効成分各々単独また
は2種混合の製剤品に比べて、有効成分3種混合の製剤
品はデンプンスラリーに対して顕著な抗菌効果を示すこ
とが確認された。
Test Example 1 Preservative test of starch slurry "Test method" 10% of cationized tapioca starch by a certain company
A slurry (pH 6.2) was prepared, 30 g was dispensed into a sterilized polypropylene bottle, a predetermined amount of each drug was added, and then a starch slurry (previously spoiled) (number of bacteria: 8.1 × 10
7 / ml) was inoculated at 1%. This is sealed under static conditions.
The cells were cultured at 0 ° C., and the number of viable cells over time was measured by a TGC agar plate pour method to determine the antibacterial effect. After the viable cell count, 1% of the spoiled starch slurry was inoculated every week. "Test results" The test results were determined according to the following criteria, and the test results are shown in Table 3. Number of bacteria in 1 ml (number)-: less than 10 2 +: 10 2 or more and less than 10 4 ++: 10 4 or more and less than 10 6 ++++: 10 6 or more and less than 10 7 +++++: 10 7 or more As described above, the evaluation results on the 28th day of the preparations containing one active ingredient in Comparative Examples 1 to 3 and the preparations containing two active ingredients in Comparative Examples 4 to 6 were ++ to ++++. On the other hand, the evaluation results of the preparations containing the three kinds of active ingredients of Examples 1 to 3 are-to ++, and the preparations of the three kinds of the active ingredients are mixed as compared with the preparations of each of the active ingredients alone or two kinds of the mixture. It was confirmed that the product exhibited a remarkable antibacterial effect on starch slurry.

【0018】[0018]

【表3】表3デンプンスラリーに対する抗菌評価 Table 3 Antibacterial evaluation of starch slurry

【0019】試験例2 ラテックスの防腐試験 「試験方法」某社スチレンブタジエンラテックス(pH
6.8)を採取し、滅菌ポリプロピレン瓶に30g分注
し薬剤を所定量添加した後、あらかじめ腐敗させたラテ
ックス(菌数:7.2×107個/ml)を接種した。
これを密封静置条件で30で培養し、TGC寒天平板混
釈法によって経時的な生菌数を測定して抗菌効果を判定
した。また、生菌数測定後、腐敗させたラテックスを1
週間毎に1%接種した。「試験結果」試験例1の判定結
果に従って結果を表4に示した。「考察」表3に示した
ように比較例1〜3の1種の有効成分配合の製剤品、及
び比較例4〜6の2種の有効成分の製剤品の28日目の
評価結果は、+〜++++であるのに対して、実施例1
〜3の3種の有効成分配合の製剤品の評価結果は、−〜
++で、有効成分各々単独または2種混合の製剤品に比
べて、有効成分3種混合の製剤品はラテックスに対して
顕著な抗菌効果を示すことが確認された。
Test Example 2 Preservative test of latex "Test method" A certain company styrene butadiene latex (pH
6.8) was collected, 30 g was dispensed into a sterilized polypropylene bottle, and a predetermined amount of the drug was added thereto. Then, latex (bacterium count: 7.2 × 10 7 cells / ml) which had been putrefactive in advance was inoculated.
This was cultured at 30 in the sealed stationary condition, and the antibacterial effect was determined by measuring the number of viable cells over time by TGC agar plate pour method. After measuring the number of viable bacteria, putrefused latex was added to 1
Inoculated 1% weekly. "Test Results" The results are shown in Table 4 in accordance with the results of the determination of Test Example 1. [Discussion] As shown in Table 3, the evaluation results on the 28th day of the preparations containing one active ingredient in Comparative Examples 1 to 3 and the two active ingredients in Comparative Examples 4 to 6 were obtained. + To ++++, whereas the first embodiment
The evaluation results of the preparations containing the three types of active ingredients are as follows:
++, it was confirmed that the preparation of the three kinds of active ingredients showed a remarkable antibacterial effect on latex as compared with the preparation of each of the active ingredients alone or in combination of two kinds.

【0020】[0020]

【表4】表4 ラテックスに対する抗菌評価 Table 4 Antibacterial evaluation for latex

【0021】[0021]

【発明の効果】以上説明したように本発明を適用した場
合、従来の単独または、2種混合の組み合わせでは不充
分であった強力な抗菌力をもった工業用抗菌組成物また
は抗菌方法の提供が可能である。
As described above, when the present invention is applied, the present invention provides an industrial antibacterial composition or an antibacterial method having a strong antibacterial activity, which was insufficient with the conventional single or combination of two. Is possible.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C02F 1/50 520 C02F 1/50 520A 520K 532 532C 532D 540 540B ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C02F 1/50 520 C02F 1/50 520A 520K 532 532C 532D 540 540B

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 グルタルアルデヒド及びオルトフタルア
ルデヒド及び2−メチル−4−イソチアゾリン−3−オ
ンを含有することを特徴とする工業用抗菌組成物。
1. An industrial antibacterial composition comprising glutaraldehyde, orthophthalaldehyde and 2-methyl-4-isothiazolin-3-one.
【請求項2】 請求項1記載の工業用抗菌組成物を工業
用水系組成物または、製紙工程白水または、工業用冷却
水に添加することを特徴とする抗菌方法。
2. An antibacterial method comprising adding the industrial antibacterial composition according to claim 1 to an industrial waterborne composition, papermaking process white water, or industrial cooling water.
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JP2008007408A (en) * 2006-06-27 2008-01-17 K I Chemical Industry Co Ltd Sterilization composition having lowered tinting property and method for lowering tinting property
WO2009053325A2 (en) * 2007-10-25 2009-04-30 Lanxess Deutschland Gmbh Stable, synergistic mixtures

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JPH07116669A (en) * 1993-10-20 1995-05-09 Permachem Asia Ltd Slime control agent for paper making
JPH0925205A (en) * 1995-07-11 1997-01-28 Kurita Water Ind Ltd Antibacterial agent for industrial use
JPH10287511A (en) * 1997-04-09 1998-10-27 K I Kasei Kk Antimicrobial and algicidal agent for nonmedical use and prevention of microorganism and alga

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Publication number Priority date Publication date Assignee Title
FR2736572B1 (en) * 1995-07-13 1997-10-03 Facom PLIERS

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH07116669A (en) * 1993-10-20 1995-05-09 Permachem Asia Ltd Slime control agent for paper making
JPH0925205A (en) * 1995-07-11 1997-01-28 Kurita Water Ind Ltd Antibacterial agent for industrial use
JPH10287511A (en) * 1997-04-09 1998-10-27 K I Kasei Kk Antimicrobial and algicidal agent for nonmedical use and prevention of microorganism and alga

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008007408A (en) * 2006-06-27 2008-01-17 K I Chemical Industry Co Ltd Sterilization composition having lowered tinting property and method for lowering tinting property
WO2009053325A2 (en) * 2007-10-25 2009-04-30 Lanxess Deutschland Gmbh Stable, synergistic mixtures
DE102007051006A1 (en) 2007-10-25 2009-04-30 Lanxess Deutschland Gmbh Stable, synergistic mixtures
WO2009053325A3 (en) * 2007-10-25 2010-04-01 Lanxess Deutschland Gmbh Stable, synergistic mixtures
JP2011500754A (en) * 2007-10-25 2011-01-06 ランクセス・ドイチュランド・ゲーエムベーハー Stable synergistic mixture

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