TW589143B - Industrial microbicide and method for stabilizing nitroalcohol compound and isothiazolone type compound - Google Patents
Industrial microbicide and method for stabilizing nitroalcohol compound and isothiazolone type compound Download PDFInfo
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- TW589143B TW589143B TW090114119A TW90114119A TW589143B TW 589143 B TW589143 B TW 589143B TW 090114119 A TW090114119 A TW 090114119A TW 90114119 A TW90114119 A TW 90114119A TW 589143 B TW589143 B TW 589143B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
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- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
589143 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(i ) [本發明之工業領域] 本發明為有關一種工業用殺菌劑,包括:作為有效成 分之硝基醇化合物及異噻唑酮型化合物。詳古 ° ’本發明 為有關一種經安定化處理之工業用殺菌劑,包括硝基醇化 合物及異噻唑酮型化合物,及一種使包括硝基醇化2物及 異噻唑酮型化合物之工業用殺菌劑安定化之方法。 [先前技藝] 有害微生物容易繁殖於造紙紙漿工業領域之造紙過程 所用之水中,各種工業領域如循環冷卻水所用之水中,"以 及用於製造水性塗料組成物、紙之塗料溶液、膠乳液、織 物乳液、紡絲油、切削油、織物印染漿、皮革等之水中 有微生物繁殖之水,變成惡臭之源,使該工業之工作環境 劣化,且降低生產力及產品之品質。於是,為防止微= 繁殖並予以消毒淨化,各種防腐劑及殺菌劑已用於工 上。 ’、 一種異噻唑酮型化合物已知為能夠在工業水中制約或 =止有害微生物產生之藥劑之一,且作工業用殺菌劑及抗 菌劑均顯示優異效果。然而,異噻唑_型化合物具有在實 用濃度中之抗菌譜狹窄,於是化合物難以應付各種型微生 物之問題。再者,呈自由型之異噻唑酮型化合物,極易感 受水、濕氣、溫度等之影響而被分解,因此,通常溶於無 水有機溶劑中貯存。 為擴大工業用殺菌劑之抗菌譜,已研究混合使用各種 抗細菌劑、防黴劑、及除藻劑。使用作為抗菌劑時,已建 ^紙張尺ϋ用中國國家標準(CNS)A4規格(21〇 χ 297公楚) 1 312663 (請先閲讀背面之注意事項再填寫本頁各攔)589143 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (i) [Industrial Field of the Invention] The present invention relates to an industrial bactericide, which includes a nitro alcohol compound and isothiazole as active ingredients. Ketone compounds. Detailed description ° 'The present invention relates to a stabilized industrial bactericide, including a nitro alcohol compound and an isothiazolone type compound, and an industrial sterilization agent including a nitro alcohol compound and an isothiazolone type compound. Agent stabilization method. [Previous technology] Harmful microorganisms easily multiply in the water used in the papermaking process of the paper and pulp industry, water used in various industrial fields such as circulating cooling water, " and used to manufacture water-based coating compositions, paper coating solutions, latex, The water of fabric emulsions, spinning oils, cutting oils, fabric printing and dyeing pastes, leather, etc. contains water for microbial reproduction, which becomes a source of foul odors, which deteriorates the industrial working environment and reduces productivity and product quality. Therefore, in order to prevent micro-proliferation and disinfection and purification, various preservatives and fungicides have been used in the industry. ', An isothiazolone compound is known as one of the agents capable of controlling or preventing harmful microorganisms from being produced in industrial water, and has shown excellent effects as both industrial bactericides and antibacterial agents. However, isothiazolyl-type compounds have a narrow antibacterial spectrum in practical concentrations, making it difficult for the compounds to cope with the problems of various types of microorganisms. In addition, free-type isothiazolone compounds are extremely susceptible to decomposition by the effects of water, moisture, temperature, etc., and are therefore usually dissolved in anhydrous organic solvents for storage. In order to expand the antibacterial spectrum of industrial bactericides, various combinations of antibacterial agents, antifungal agents, and algicides have been studied. When used as an antibacterial agent, the paper size has been established in accordance with the Chinese National Standard (CNS) A4 specification (21 × 297 gongchu) 1 312663 (Please read the precautions on the back before filling in the blocks on this page)
589143 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 Α7 Β7 五、發明説明(2 ) 議混合例如:2-溴-2-硝基-1,3-丙二醇(日本專利公報 4682/1983)。然而,有效成分之安定性仍不足,若與乳液 混合,會引起乳液形態破壞,所謂之乳液敗形。此處,溶 解異噻唑酮型化合物之合宜有機溶劑,通常使用二醇型有 機溶劑。然而,殺細菌製劑溶於二醇型有機溶劑,根據The Fire Services Act標示乃危險物質,需特別小心處理或貯 存此溶液,且製劑溶於二醇型有機溶劑,有難以安全且容 易處理之問題。因此,曾建議一種安全性製劑,包括異噻 唑酮型化合物,以水稀釋,減少有機溶劑。然而,當溶於 二醇型有機溶劑之製劑以水稀釋得適當濃度之工業用殺菌 劑時,製劑有異噻唑酮型化合物有時於短時間内會分解或 沈殿之問題。 為解決此問題,例如日本專利公開221813/1993號、 日本專利公開170608Π993號、日本專利公開286815/|993 號等揭示含溴酸或碘酸之鹼金屬鹽作安定劑之異噻唑_型 化合物水溶液之組成物,並揭示異噻唑酮型化合物於該組 成物中能安定長期存在不會分解。 然而,即使包括水及異噻唑酮型化合物之製劑,於溴 酸或碘酸之鹼金屬鹽例如溴酸鉀中能夠使之安定,但仍有' 異噻唑酮型化合物之熱安定性變得不足,且若溴酸鉀濃度 降低,異噻唑酮型化合物變成容易分解等問題。 & 而且,含高濃度溴酸或碘酸之鹼金屬鹽之製劑,若製 劑溫度降低至攝氏數度時,鹼金屬鹽會沈澱,則製劑效果 降低。亦即,因鹼金屬鹽之固體沈澱物難再度溶解,若一 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ四7公釐 2 312663 (請先閲讀背面之注意事項再塡寫本頁各攔)589143 Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Consumer Affairs Agency A7 B7 V. Description of the invention (2) Suggested mixing example: 2-bromo-2-nitro-1,3-propanediol (Japanese Patent Gazette 4682/1983). However, the stability of the active ingredient is still insufficient. If it is mixed with the emulsion, it will cause the emulsion form to be destroyed, so-called emulsion failure. Here, as a suitable organic solvent for dissolving the isothiazolone type compound, a glycol type organic solvent is usually used. However, bactericidal preparations are soluble in diol-based organic solvents and are dangerous substances according to The Fire Services Act. This solution needs to be handled or stored with special care, and the preparations are soluble in diol-based organic solvents, which is difficult and safe to handle. . Therefore, it has been suggested that a safe formulation, including an isothiazolone compound, be diluted with water to reduce organic solvents. However, when a formulation dissolved in a diol-type organic solvent is diluted with water to a suitable concentration of an industrial bactericide, the formulation has a problem that the isothiazolone compound sometimes decomposes or sinks in a short time. To solve this problem, for example, Japanese Patent Publication No. 22181/1993, Japanese Patent Publication No. 170608Π993, Japanese Patent Publication No. 286815 / | 993 and the like disclose an aqueous solution of an isothiazole-type compound containing an alkali metal salt of bromic acid or iodic acid as a stabilizer. The composition, and revealed that the isothiazolone compound can be stable in the composition for a long time without decomposing. However, even if formulations including water and isothiazolone compounds are stabilized in an alkali metal salt of bromic acid or iodic acid such as potassium bromate, the thermal stability of isothiazolone compounds is still insufficient, and If the concentration of potassium bromate is decreased, the isothiazolone compound becomes liable to be decomposed. & Moreover, if the preparation contains a high concentration of an alkali metal salt of bromic acid or iodic acid, if the temperature of the preparation is lowered to a few degrees Celsius, the alkali metal salt will precipitate and the effect of the preparation will be reduced. That is, because the solid precipitate of the alkali metal salt is difficult to dissolve again, if a paper size applies the Chinese National Standard (CNS) A4 specification (21 × 4 7 mm 2 312663 (please read the precautions on the back before writing) (Blocks on this page)
589143 A7 B7 i、發明説明( 經濟部智慧財產局員工消費合作社印製 旦驗金屬鹽沈澱,結果造成溴酸或块酸驗金屬之濃度降 低,使得異噻嗤酮型化合物不安定。 [本發明所要解決之問題] 於此等情況下,本發明所要解決之問題,乃提供一種 具廣大抗菌譜之工業用殺菌劑,含有之有效成分,即使不 用有機溶劑,仍能長期安定,且不引起乳液敗形。 [解決問題之方式] 本案發明人為解決上述問題,進行各種研究,發現一 種具廣大抗菌譜之優異工業用殺菌組成物,含有即使不用 有機溶劑仍能長期安定之有效成分,不引起乳液敗形,可 由硝基醇化合物及異噻唑酮型化合物作有效成分,加驗金 屬石肖酸鹽,並且視需要添加鹼金屬氣化物作為此等有效成 分之安定劑。 亦即,本發明包括: (1) 一種工業用殺菌劑,包括:硝基醇化合物(a)、異 噻唑_型化合物(b)、以及鹼金屬硝酸鹽(C)者; (2) 如上述(1)之工業用殺菌劑,又含有鹼金屬氯化物 ⑷者; (3) 如上述(1)或(2)之工業用殺菌劑,更含有水溶性二 醇型溶劑(e)者; (4) 如上述(1)之工業用殺菌劑,其中化合物 通式⑴者 卜 I紙張尺度賴 210 χ 297 公釐) 3 312663 (請先閲讀背面之注意事項再填寫本頁各攔)589143 A7 B7 i. Description of the invention (The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a metal salt precipitation test, resulting in a decrease in the concentration of bromic acid or bulk acid test metal, making the isothiazolone type compound unstable. [The present invention The problem to be solved] Under these circumstances, the problem to be solved by the present invention is to provide an industrial bactericide with a broad antibacterial spectrum. The effective ingredients contained in it can be stable for a long time even without the use of organic solvents without causing emulsion. [Solutions to solve the problem] In order to solve the above problems, the inventors of the present case conducted various studies and found that an excellent industrial bactericidal composition with a broad antibacterial spectrum contains an effective ingredient that can be stable for a long time even without an organic solvent without causing emulsion. Failure, the nitroalcohol compound and isothiazolone compound can be used as the active ingredient, metal stone stearate can be added, and alkali metal vapor can be added as a stabilizer for these active ingredients if necessary. That is, the present invention includes: (1) An industrial bactericide, comprising: a nitro alcohol compound (a), an isothiazole-type compound (b), And alkali metal nitrates (C); (2) Industrial bactericides as described in (1) above, and those containing alkali metal chlorides; (3) Industrial bactericides as described in (1) or (2) above (4) Industrial bactericides as described in (1) above, in which the general formula of the compound is the paper size of 210 χ 297 mm. 3 312663 (please first (Read the notes on the back and fill in the blocks on this page)
•訂 -線 589143 A7 B7 五、發明説明(4 ) OH X1 Y1 —CH—C—Y2 N〇2 (1) (式中,X1為具羥基之i至4個碳之烷基或鹵原子;γΐ為 氫原子、1至4個碳之烷基、或2至4個碳之烯基;γ2為 氫原子、鹵原子、具羥基之1至4個碳之烷基、或任意具 羥基之2至4個碳之烯基); (5) 如上述(1)之工業用殺菌劑,其中化合物(a)為2_ 漠-2 -石肖基丙院-1,3 -二醇或2,2 -二溴-2 -石肖基乙醇者。 (6) 如上述(1)之工業用殺菌劑,其中化合物(b)具通式 (2)者: (請先閲讀背面之注意事項再填寫本頁各攔)• Order-line 589143 A7 B7 V. Description of the invention (4) OH X1 Y1 —CH—C—Y2 N〇2 (1) (where X1 is an alkyl or halogen atom of i to 4 carbons having a hydroxyl group; γΐ is a hydrogen atom, an alkyl group of 1 to 4 carbons, or an alkenyl group of 2 to 4 carbons; γ2 is a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbons having a hydroxyl group, or any 2 of a hydroxyl group Alkenyl to 4 carbons); (5) The industrial fungicide as described in (1) above, wherein the compound (a) is 2_ Mo-2-Shi Xiaoji Cingyuan-1, 3-diol or 2, 2-2 Bromine-2-Shishothyl alcohol. (6) The industrial bactericide as described in (1) above, in which the compound (b) has the general formula (2): (Please read the precautions on the back before filling in the blocks on this page)
經濟部智慧財產局員工消費合作社印製 (式中,X2及X3為相同或不同之氫原子、鹵原子、或j至 6個碳之烧基;Y3為氫原子或任意具取代基之}至8個碳 之烴基); (7)如上述(1)之工業用殺菌劑,其中化合物(b)為2· 甲基-4-異噻嗤啉—3-或5 -氣基-2 -甲基-4-異噻唑啉酮 者; 如上述(1)之工業用殺菌劑,其中化合物(c)為确酸 鈉或硝酸鉀者; (9)如上述(2)之工業用殺菌劑,其中化合物(d)為氣化 鈉或氣化鉀者; 本紙張尺度適用中國國家標準(CNS)A4規格(21〇x297公釐) "' ------ 4 312663 589143 A7Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where X2 and X3 are the same or different hydrogen atom, halogen atom, or j to 6 carbons; Y3 is a hydrogen atom or any substituent)} to (8-carbon hydrocarbon group); (7) The industrial bactericide as described in (1) above, wherein the compound (b) is 2. methyl-4-isothiazoline-3 or 5-amino-2-methyl Those based on 4-isothiazolinone; industrial fungicides as described in (1) above, wherein compound (c) is sodium or potassium nitrate; (9) industrial fungicides as described in (2) above, where Compound (d) is sodium gaseous or potassium gaseous; this paper size applies to China National Standard (CNS) A4 (21 × 297 mm) " '------ 4 312663 589143 A7
經濟部智慧財產局員工消費合作社印製 (10) 如上述(3)之工業用殺菌劑,其中化合物(e)為乙一 醇、丙二醇、二乙二醇、二丙二醇、或二乙二醇單甲喊者^ (11) 如上述(1)之工業用殺菌劑,包括:〇 至4〇重量%化合物⑷、0.01至20重量%化合物(b)、及〇 〇ι至^ 重量%化合物((:)者; (12) 如上述(11)之工業用殺菌劑,又含有至$ 量%化合物(d)者; (13) 如上述(11)及(12)中任一項之工業用殺菌劑,又含 有0.1至90重量%化合物者; (14) 如上述(1)至(13)中任一項之工業用殺菌劑,係用 於膠乳、合成樹脂乳液、或塗料者。 (15) 種使硝基醇化合物(a)及異噻嗤酮型化合物(b) 女疋之方法,係添加鹼金屬硝酸鹽(c)之化合物(a)及(b)中 者;以及 (16) 如上述(1 5)使硝基醇化合物(a)及異噻唑酮型化合 物(b)安定之方法,其中又添加鹼金屬氣化物者。 [本發明之實施具體例] 本發明所用之硝基醇化合物(a)為已知化合物,例如, 以通式(1)表示之化合物, X1 T , Y1 —CH—C—Y2 N〇2 ⑴ (式中,X1為具羥基之1至4個碳之烷基或鹵原子;…為 氫原子、1至4個碳之烧基、或2至4個碳之烯基;γ2表 本紙張尺度適用中國國家標準(CNS)A4規格(21〇><297公釐) 5 312663 (請先閲讀背面之注意事項再填寫本頁各攔) 訂 •線 589143 五、發明説明(6 ) 示氫原子、齒原子、具羥基之1至4個碳之烷基、或具經 基之2至4個碳之烯基 於通式(1)中,X1及Y2所示具羥基之個碳之烷 基實例,係表示在1至4個碳之烷基(例如,甲基 '乙基、 丙基、異丙基、丁基、異丁基等)之任何位置,具至少一個 羥基之基。X1及Y2所示鹵原子之實例,包含··氟、氣、 漠、攝等。 、 Y1所不2至4個碳之烯基,包含乙烯基、烯丙基、異 丙烯基、2-甲基-i-丙烯基等。γ2所示任意具羥基之二至* 個碳之烯基,包含至少一個羥基於任何位置取代之2至4 個碳之稀基。 通式(1)所定義之硝基醇化合物,包含: 2-溴基-2-碗基丙烧·ι,3_二醇(BNPD), -溴基-2 _硝基丁烧-1,3-二醇, -漠基-3-硝基戊烧_2,4-二醇, 2,2_溴基-2-硝基-1-乙醇(DBNE), 經濟部智慧財產局員工消費合作社印製 2 -石肖基-1,3·丙二醇, 參(羥甲基)確基甲烷, 3,3··一漠基-3-墙基-2-丙醇, 2-氣基-2-硝乙醇, 2_氣基-2-石肖基-1,3-丙二醇, -氣基-3 -石肖基-2-丙醇。 本發明所用之異噻唑酮型化合物,, 之化合物, 為例如具通式⑺ 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公楚) 312663 6 589143 A7 B7 五、發明説明(7 )Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (10) The industrial bactericide as described in (3) above, in which the compound (e) is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, or diethylene glycol monomethyl Shout ^ (11) The industrial bactericide as described in (1) above, including: 0 to 40% by weight of compound 至, 0.01 to 20% by weight of compound (b), and 00 to ^% by weight of compound ((: ); (12) The industrial bactericide as described in (11) above, and containing up to $% by weight of the compound (d); (13) The industrial bactericide as described in any one of (11) and (12) above Those containing 0.1 to 90% by weight of the compound; (14) The industrial bactericide according to any one of the above (1) to (13), used for latex, synthetic resin emulsion, or coating. (15) species The method for making the nitroalcohol compound (a) and the isothione compound (b) son-in-law is adding one of the compounds (a) and (b) of the alkali metal nitrate (c); and (16) as described above (15) A method for stabilizing a nitroalcohol compound (a) and an isothiazolone compound (b), in which an alkali metal vapor is further added. Specific Examples] The nitro alcohol compound (a) used in the present invention is a known compound, for example, a compound represented by the general formula (1), X1 T, Y1 —CH—C—Y2 N0 2 ⑴ (wherein, X1 is an alkyl or halogen atom of 1 to 4 carbons having a hydroxyl group; ... is a hydrogen atom, an alkyl group of 1 to 4 carbons, or an alkenyl group of 2 to 4 carbons; γ2 table paper size applies to Chinese national standards (CNS) A4 specification (21〇 > < 297 mm) 5 312663 (Please read the precautions on the back before filling in the blocks on this page) Order • 589143 V. Description of the invention (6) Hydrogen atom, tooth atom , An alkyl group having 1 to 4 carbons having a hydroxyl group, or an alkylene having 2 to 4 carbons having a hydroxyl group is based on the example of an alkyl group having a carbon group with a hydroxyl group represented by X1 and Y2 in the general formula (1), and represents A group having at least one hydroxyl group at any position of an alkyl group of 1 to 4 carbons (for example, methyl'ethyl, propyl, isopropyl, butyl, isobutyl, etc.). Halides shown by X1 and Y2 Examples of atoms include fluorine, gas, molybdenum, photo, etc., Alkenyl groups of 2 to 4 carbons, Y1, including vinyl, allyl, isopropenyl, 2-methyl-i-propenyl Etc. γ2 Any alkenyl group having two to * carbons having a hydroxyl group, including a dilute group of 2 to 4 carbons having at least one hydroxyl group substituted at any position. A nitro alcohol compound as defined by the general formula (1), comprising: 2-bromo group -2-bowlyl propane, 3,3-diol (BNPD), -bromo-2_nitrobutan-1,3-diol, -molyl-3-nitropentan_2,4 -Diol, 2,2-bromo-2-nitro-1-ethanol (DBNE), printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 2-Shi Xiaoji-1,3-propanediol, ginseng (hydroxymethyl) Methane, 3,3 · monomolyl-3-wallyl-2-propanol, 2-gasyl-2-nitroethanol, 2-gasyl-2-stone-based stilky-1,3-propanediol, -gasyl -3-Shishoki-2-propanol. The isothiazolone compound used in the present invention is, for example, a compound having the general formula ⑺ The paper size applies the Chinese National Standard (CNS) A4 specification (210x297) 312663 6 589143 A7 B7 V. Description of the invention (7)
(2) (請先閲讀背面之注意事項再塡寫本頁各攔) (式中’X及X3為相同或不同之氫原子、鹵原子或 個碳之烷基;Y3為氫原子或任意具取代基之u 8個碳之 烴基)。 於通式(2)中’ X2、X3所示之鹵素,為例如氟、氯、溴、 碘等,其中,以氣較佳。具丨至6個碳之烷基實例,為甲 基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第 三丁基、戊基等。於烷基中,以丨至4個碳之烷基例如甲 基、乙基、丙基等較佳。於上述取代基中,X2以氫或氣較 佳’以氣更佳。而且,X3以氫或氣較佳,以氫更佳。 Y3所示任意具取代基之i至8個碳之烴基中,取代基 之實例為羥基、鹵素(例如氯、氟、溴、碘等)、氰基、胺 基、羧基、1至4個碳之烷氧基(例如甲氧基、乙氧基等)、 經濟部智慧財產局員工消費合作社印製 6至10個碳之芳氧基(例如苯氧基等)、1至4個碳之烷硫 基(例如甲硫基、乙硫基等)、6至1 〇個碳之芳硫基(例如苯 硫基等)等。於此等取代基中,以鹵原子、1至4個碳之烷 氧基等較佳。烴基之氫原子可由該等取代基取代,取代基 為1至5個、較佳1至3個,且該等取代基可彼此相同或 不同。 Y3所示任意具取代基之烴基中,烴基實例為1至1 〇 個碳之烷基、2至6個碳之烯基、2至6個碳之炔基、3至 10個碳之環烷基、6至14個碳之芳基等,於此等烴基中, 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 7 312663 589143 Α7Μ 五、發明説明(8 以1至10個碳之燒基及 暴及至10個碳之環烷基較佳,又以 1至10個碳之烷基更佳。 該1至10個碳之院基,例如甲基、乙基、丙基、異丙 基、丁基、異丁基、第二丁基、第三丁基戊基己基、 庚基、辛基、異辛基、第二辛美 〒暴第二辛基、壬基、癸基 等。於烧基中,更佳為U3個燒基,例如,甲基、乙基 等’及7至9個碳之烷基,例如辛基、第三辛基等。 該2至6個碳之稀基,例如乙稀基、稀丙基、異丙稀 基、1-丙稀基、2-丙稀基、2_甲基·卜丙稀基等。於稀基中, 以乙烯基及烯丙基較佳。 該2至6個碳之炔基,例如乙炔基、1-丙炔基、2·丙 快基、丁炔基、戊炔基等,其中,以乙炔基及丙块基較佳。 該3至10個碳之環院基實例,為環丙基、環丁基環 戊基、ί衣己基、%庚基、環辛基等。纟中,以環戊基及環 己基較佳。 經濟部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁各攔) 該6至14個碳之芳基實例,為苯基、萘基、蒽基、菲 基等。其中,以苯基較佳。 如上述,各種基可例舉為任意經取代之烴基,且以Υ3 表示’其中’以甲基及辛基較佳,又以甲基更佳。 通式(2)所定義之異噻唑酮型化合物,包含:5_氣_2_ 甲基-4-異噻唑啉-3-酮、2-甲基-4-異噻唑啉_3_酮、2_正辛 基-4·異噻唑啉·3-明、4,5-二氣基-2-正辛基_4_異噻唑啉_3_ 酮、2-乙基_4_異噻唑啉_3_酮、4,5_二氯_2_環己基_4_異噻 唑琳-3-酮、5-氯_2_乙基-4-異噻唑啉-3-酮、5_氣_2_第三辛 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 8 312663 3 4 1X 9 8 A7 B7 五、發明説明(9 ) 經濟部智慧財產局員工消費合作社印製 基-4-異噻唑啉-3-酮等。 於該化合物中,較佳為5-氯-2-甲基_4_異噻唑琳_3_ 酮、2-甲基-4-異噻唑琳-3-酮、2-正辛基_4_異噻唑啉_3__、 及4,5·二氣-2-正辛基-4-異噻嗤啉,更佳為5氯 基-4·異噻唑啉-3-酮及2-甲基-4-異噻唑啉_3_網。 該通式(2)所定義之異噻唑酮型化合物,可單獨或二赛 以上混合使用。因此,該混合物二種以上可混合使用。 所有異噻唑酮型化合物,均為周知化合物,可依下述 說明書所揭示之方法或其類似方製得:例如,美國專利 3761488號、美國專利3849430號、美國專利387〇795號、 美國專利4067878號、美國專利415〇〇26號、美國專= 4241214號、美國專利3517022號、美國專利3〇65123號、 美國專利3761489號等。 記述鹼金屬硝酸鹽(C)作安定劑,加至本發明所用之硝 基醇化合物(a)及異噻嗤酮型化合物(b)。 鹼金屬硝酸鹽中,鹼金屬之實例為鋰、鈉、鉀、铷等, 其中’以納及較佳。 鹼金屬氣化物(d)中,鹼金屬實例為鋰、鈉、鉀、铷等, 其中,以鈉及鉀較佳,又以鈉更佳。 若此等鹼金屬硝酸鹽及鹼金屬氣化物溶於水中,可合 宜加入適當溶劑。該溶劑之較佳實例,為水溶性二醇型溶 劑類,例如乙二醇、二乙二醇、丙二醇、二丙二醇等。岭 本發明所用之水溶性二醇型溶劑(e),實例包含:2至 6個碳之伸烷二醇型溶劑類,例如:乙二醇、二乙二醇、 本紙張尺度It財關家標準(CNS)A4規格(21Gx297公梦「 9 312663 〈請先聞讀背而之沣意事項存塡寫本頁各攔)(2) (Please read the precautions on the back before writing the descriptions on this page) (where 'X and X3 are the same or different hydrogen atom, halogen atom or alkyl group of carbon; Y3 is hydrogen atom or any Substituent group of 8 carbons). The halogen represented by X2 and X3 in the general formula (2) is, for example, fluorine, chlorine, bromine, iodine, etc. Among them, gas is preferred. Examples of alkyl groups having from 1 to 6 carbons are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl and the like. Among the alkyl groups, alkyl groups of 4 to 4 carbons such as methyl, ethyl, propyl and the like are preferred. Among the above substituents, X2 is more preferably hydrogen or gas, and more preferably gas. Moreover, X3 is preferably hydrogen or gas, and more preferably hydrogen. Among the hydrocarbon groups of i to 8 carbons having substituents shown in Y3, examples of the substituents are a hydroxyl group, a halogen (such as chlorine, fluorine, bromine, iodine, etc.), a cyano group, an amine group, a carboxyl group, and 1 to 4 carbons. Alkoxy groups (such as methoxy, ethoxy, etc.), aryloxy groups (such as phenoxy, etc.) of 6 to 10 carbons printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and alkoxy groups of 1 to 4 carbons Thio (such as methylthio, ethylthio, etc.), arylthio of 6 to 10 carbons (such as phenylthio, etc.) and the like. Among these substituents, a halogen atom, an alkoxy group of 1 to 4 carbons, and the like are preferable. The hydrogen atom of the hydrocarbyl group may be substituted by these substituents. The substituents are 1 to 5, preferably 1 to 3, and the substituents may be the same as or different from each other. Among the hydrocarbyl groups having substituents shown in Y3, examples of the hydrocarbyl group are an alkyl group of 1 to 10 carbons, an alkenyl group of 2 to 6 carbons, an alkynyl group of 2 to 6 carbons, and a cycloalkane of 3 to 10 carbons. Base, aryl groups of 6 to 14 carbons, etc. Among these hydrocarbon bases, the paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 7 312663 589143 Α7M 5. Description of the invention (8 to 1 to An alkyl group of 10 carbons and a cycloalkyl group of up to 10 carbons are preferred, and an alkyl group of 1 to 10 carbons is more preferred. The 1-10 carbon group such as methyl, ethyl, and propyl Base, isopropyl, butyl, isobutyl, second butyl, third butylpentylhexyl, heptyl, octyl, isooctyl, second octyl, second octyl, nonyl, Decyl, etc. Among the alkyl groups, more preferably U3 alkyl groups, such as methyl, ethyl, and the like, and alkyl groups of 7 to 9 carbons, such as octyl, third octyl, etc. The 2 to 6 Diluted groups of one carbon, such as ethylene, propyl, isopropyl, 1-propenyl, 2-propenyl, 2-methyl · propenyl, etc. In the dilute group, ethylene And allyl are preferred. The alkynyl of 2 to 6 carbons, such as acetylene Radicals, 1-propynyl, 2-propynyl, butynyl, pentynyl, etc., of which ethynyl and propidyl are preferred. The example of a cycloalkyl radical of 3 to 10 carbons is cyclopropane Base, cyclobutylcyclopentyl, hexyl,% heptyl, cyclooctyl, etc. In the middle, cyclopentyl and cyclohexyl are preferred. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the back first) Please note that you need to fill in this page.) Examples of aryl groups of 6 to 14 carbons are phenyl, naphthyl, anthracenyl, phenanthryl, etc. Among them, phenyl is preferred. As mentioned above, various groups can be exemplified. For example, it is any substituted hydrocarbon group, and Υ3 represents 'wherein' is preferably methyl and octyl, and more preferably methyl. An isothiazolone compound as defined by the general formula (2) includes: _2_methyl-4-isothiazoline-3-one, 2-methyl-4-isothiazoline_3_one, 2_n-octyl-4 · isothiazoline · 3-min, 4,5- Dioxo-2-n-octyl_4_isothiazoline_3_one, 2-ethyl_4_isothiazoline_3_one, 4,5_dichloro_2_cyclohexyl_4_isothiazole Lin-3-one, 5-chloro_2_ethyl-4-isothiazolin-3-one, 5_gas_2_ third octane paper standard applicable to China Standard (CNS) A4 specification (210 X 297 mm) 8 312663 3 4 1X 9 8 A7 B7 V. Description of the invention (9) Printed base 4-isothiazolin-3-one by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Among the compounds, 5-chloro-2-methyl_4_isothiazoline_3_one, 2-methyl-4-isothiazoline-3-one, 2-n-octyl_4 are preferred. _Isothiazoline_3__, and 4,5 · digas-2-n-octyl-4-isothiazoline, more preferably 5chloro-4 · isothiazolin-3-one and 2-methyl- 4-isothiazoline_3_net. The isothiazolone compound defined by the general formula (2) can be used alone or in combination of two or more. Therefore, two or more of these mixtures can be mixed and used. All isothiazolone compounds are well-known compounds and can be prepared according to the methods disclosed in the following specification or their analogues: for example, U.S. Patent No. 3761488, U.S. Patent No. 3849430, U.S. Patent No. 3870795, U.S. Patent No. 4067878 No., US Patent No. 41502, US Patent No. 4241214, US Patent No. 3517022, US Patent No. 3,065,123, US Patent No. 3761489, etc. The alkali metal nitrate (C) is described as a stabilizer, and it is added to the nitro alcohol compound (a) and the isothione compound (b) used in the present invention. Among the alkali metal nitrates, examples of the alkali metal are lithium, sodium, potassium, rhenium, and the like, and among them, Na is more preferred. In the alkali metal gaseous substance (d), examples of the alkali metal are lithium, sodium, potassium, rhenium, etc. Among them, sodium and potassium are preferred, and sodium is more preferred. If these alkali metal nitrates and alkali metal vapors are dissolved in water, appropriate solvents may be suitably added. Preferable examples of the solvent are water-soluble glycol-type solvents such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and the like. Examples of the water-soluble diol-based solvents (e) used in the present invention include: 2 to 6 carbons of butanediol-based solvents, such as ethylene glycol, diethylene glycol, and this paper. Standard (CNS) A4 specification (21Gx297 public dream "9 312663 (please read the intent of the back and save it, write each block on this page)
•訂· -線 )• order · -line)
、發明説明(10 經濟部智慧財產局員工消費合作社印製 inZ —丙一醇、丁二醇、15•戊二醇等;二醇謎变 各劑類’例如:醇 醉早甲醚、乙二醇單乙醚、乙二醇單 J醚、二乙二醇單甲醚'-一抑 触豐 —乙—酵早乙醚、三丙二醇單甲 ^ 饭1甲烷一醇中,較佳為二丙二酵,於 一醇醚型化合物中,較佳A — 平乂1主馬一乙二醇單甲醚。 於本發明工業用殺菌劑令,除了水以外,各別成分之 ,和比率’為化合物⑷0.01至40重量%,較佳〇1蓋25 重量%;化合物(1))〇.〇1至20重量%,較佳〇1至1〇重量0/〇; 化合物⑷0·01至30重量%,較佳〇」至Η重量% ;若用 化合物(d) ’則化合物(d)(M至5重量%,較佳〇 $至3重 量%;若用化合物⑷,則化合物⑷〇」至9〇重量%,較佳 5至70重量%。 若本發明之殺菌劑被製成含水之組成物,則組成物之 pH值可調至較佳範圍。較佳ipH值為3至石。 用作該pH值調節劑之物質,例如,酸如無機酸、含 羧基之有機化合物、績酸、酚型化合物等。該無機酸之實 例,為鹽酸、硫酸、磷酸、硝酸、硼酸、亞硝酸' 碳酸、 氫氟酸、硫化氫等。含羧基之有機化合物,包含:乙酸、 三氟乙酸、酿酸、檸檬酸、甲酸、草酸、酒石酸、苯甲酸、 乙二胺四乙酸(EDTA)、酞酸氫鉀等。此外,胺基酸類例如 麩胺酸、甘胺酸等。磺酸之實例,為對-甲苯磺酸、甲磺酸 等,該酚型化合物之實例,為苯酚。 再則,於細調pH值時,可與該酸類同時使用例如無 機鹼及鹼如含氮有機化合物及胺基酸型化合物。該無機鹼 (請先閱讀背面之注意事項再填寫本頁各攔)Description of the invention (10 inZ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as glycerol, butanediol, 15-pentanediol, etc .; diol mysterious agents, such as early methyl ether, ethylene glycol Alcohol monoethyl ether, ethylene glycol mono-J ether, diethylene glycol monomethyl ether'-Yiyifengfeng-B-fermented early ether, tripropylene glycol monomethyl ^ rice 1 methane monoalcohol, dipropylene glycol is preferred Among monoalcohol-type compounds, A—Pingxi 1 main horse monoethylene glycol monomethyl ether is preferred. In the industrial bactericide of the present invention, in addition to water, the sum of the components, and the ratio 'is compound ⑷0. .01 to 40% by weight, preferably 〇1 cover 25% by weight; compound (1)) 0.001 to 20% by weight, preferably 〇1 to 10% by weight 0 / 〇; compound ⑷01 to 30% by weight , Preferably 0 ″ to Η% by weight; if compound (d) ′ is used, then compound (d) (M to 5% by weight, preferably 0 to 3% by weight; if compound ⑷ is used, then compound ⑷ ″ to 9 0% by weight, preferably 5 to 70% by weight. If the fungicide of the present invention is made into a water-containing composition, the pH value of the composition can be adjusted to a preferred range. A preferred ipH value is 3 to 10 A substance used as the pH adjuster, for example, an acid such as an inorganic acid, an organic compound containing a carboxyl group, an acid, a phenolic compound, etc. Examples of the inorganic acid are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, and Nitric acid 'carbonic acid, hydrofluoric acid, hydrogen sulfide, etc. Organic compounds containing carboxyl groups include: acetic acid, trifluoroacetic acid, lactic acid, citric acid, formic acid, oxalic acid, tartaric acid, benzoic acid, ethylenediaminetetraacetic acid (EDTA), Potassium hydrogen phthalate, etc. In addition, amino acids such as glutamic acid, glycine, etc. Examples of the sulfonic acid are p-toluenesulfonic acid, methanesulfonic acid, etc., and examples of the phenolic compound are phenol. When finely adjusting the pH value, you can use inorganic bases and bases such as nitrogen-containing organic compounds and amino acid-type compounds together with the acid. The inorganic base (please read the precautions on the back before filling in the blocks on this page)
-訂. •線 本紙張尺度適用中國國家標準(CNS)A4規格 312663 297公釐) 4 1X 9 8-Order. • Thread This paper size applies Chinese National Standard (CNS) A4 specification 312663 297 mm 4 1X 9 8
五、發明説明(U ) 經濟部智慧財產局員工消費合作杜印製 之實例,為氫氧化鈉、氫氧化鉀、氨、氫氧化鈣、氧化鎂、 碳酸鈉、碳酸氫鈉等。 該含氮有機化合物之實例,為苯胺、六氫吡畊、六氫 D比咬 '二乙胺、D比啶等。該胺基酸型化合物之實例,為組 胺酸、麩胺酸等。 雖然’本發明工業用殺菌劑(產物製劑)之製法未予特 別限制’且各別成分可以任何次序加入,但建議下述方法: 將硝基醇化合物、異噻唑酮型化合物、鹼金屬硝酸鹽、以 及視需要之鹼金屬氣化物加至水中,以混合器予以混合, 直至此合物完全均勻。所要加入之鹼金屬硝酸鹽及鹼金屬 氣化物’可溶於水中,或水及如上述有機溶劑之液體混合 物中,然後,與水混合。 該水溶性一醇型溶劑,可加至本發明之異噻唑酮型化 合物组成物中。 右用水溶性二醇溶劑,液劑之製法與不用溶劑之製法 類似加入規疋量之硝基醇化合物、異噻唑酮型化合物, 及其他之各別成分後,以授拌器予以授掉及混合,直至混 合物均勻即獲得製劑。 根據本發明之工業用殺菌製劑,可又與另一殺菌劑混 合。殺菌劑之實例,為2,2.n氮基丙醯胺、3务2_ 丙炔丁胺甲酸酯、2-笨并咪唑胺甲酸曱酯、3,3,4,4_四氯四 虱噻吩-ι,ι-二氧化物、4,5_二氣」,2_二酼_3_酮、四氣異酞 腈、亞甲雙硫氰酸醋、苯并異噻唑啉_3_嗣、哦硫鋅(_V. Description of the Invention (U) Examples of consumer cooperation printed by the Intellectual Property Bureau of the Ministry of Economy include sodium hydroxide, potassium hydroxide, ammonia, calcium hydroxide, magnesium oxide, sodium carbonate, sodium bicarbonate, and the like. Examples of the nitrogen-containing organic compound are aniline, hexahydropyrine, hexahydro D-diethylamine, D-pyridine, and the like. Examples of the amino acid type compound are histidine, glutamic acid, and the like. Although 'the manufacturing method of the industrial bactericide (product preparation) of the present invention is not particularly limited' and the respective ingredients can be added in any order, the following method is recommended: a nitro alcohol compound, an isothiazolone compound, an alkali metal nitrate And, if necessary, an alkali metal gaseous substance is added to water and mixed with a mixer until the compound is completely homogeneous. The alkali metal nitrate and alkali metal vapor to be added are soluble in water, or a liquid mixture of water and an organic solvent as described above, and then mixed with water. This water-soluble monoalcohol-type solvent can be added to the isothiazolone-type compound composition of the present invention. The right method uses a water-soluble diol solvent. The preparation method of the liquid agent is similar to the method without a solvent. After adding the specified amount of nitro alcohol compound, isothiazolone compound, and other individual ingredients, use a blender to teach and mix. , Until the mixture is homogeneous to obtain a formulation. The industrial germicidal preparation according to the present invention may be mixed with another germicidal agent. Examples of bactericides are 2,2.n aziridinamide, 3 × 2-propargyl carbamate, 2-benzimidazolium formate, 3,3,4,4_tetrachlorotetrac Thiophene-ι, ι-dioxide, 4,5_digas ", 2_difluorene_3_one, tetragas isophthalonitrile, methylene dithiocyanate, benzoisothiazoline_3_ 嗣, Oh zinc sulphide (_
Py thione)#此等殺菌劑之添加量,較佳對·重量份 &張心適时_家標準----- 11 312663 (請先閲讀背面之注意事項再填寫本頁各攔)Py thione) # The amount of these fungicides added is better. · Parts by weight & Zhang Xinshi timely _ home standard ----- 11 312663 (please read the precautions on the back before filling in this page)
43 五、發明説明(12 異噻唑酮型化合物,為約0.1至20重量份。 再則’根據目的及用途,周知之添加物, 性劑、抗氧化劑等,可加至本發明之工業用殺菌劑。活 表面活性劑之實例,包含:習知之表面活性劑,例如 肥皁、非離子表面活性劑、陰離子表面活性劑、陽離子 面活性劑、兩性離子表面活性劑、聚合物表面活性劑等, 其中,以非離子表面活性劑、以及陰離子表面活性劑較佳。 非離子表面活性劑之實例,為聚氧烯芳苯趟、聚氧乙 烯壬苯醚、環氧乙烷、以及環氧丙烷之嵌段共聚物等。 一而且,陰離子表面活性劑之實例,為烷苯磺酸金屬鹽、 烷萘磺酸金屬鹽、聚羧酸金屬鹽、二烷磺丁二酸酯金屬鹽、 聚氧乙烯二苯乙烯一修飾之苯醚硫酸銨鹽、木質素磺酸金 屬鹽、木質素磺酸金屬鹽等。再者,金屬鹽類之實例,為 納鹽類、鉀鹽類、鎂鹽類等。 經濟部智慧財產局員工消費合作社印製 抗氧化劑之實例,為酚型抗氧化劑類,例如:2,6_二 第二丁基_4_甲酚、2,2,_亞甲雙(4-甲基_6_第三丁酚)等;以 及胺型抗氡化劑類,例如_·烷基二苯胺、N,N、二第二丁基 -對-苯二胺等。 此等表面活性劑及抗氧化劑之添加量,對液體製劑而 言’較佳為01至5重量份至1〇〇重量份。 右加上述之其他添加劑,例如:另一殺菌劑、表面活 性劑、抗氧化劑等,較佳者為對應添加物種類改變驗金屬 墙酸鹽、鹼金屬氣化物、水溶性二醇型溶劑、水等之混合 比率。 本紙張尺度適用中國國家標準(CNS)A4規格(21〇x297公釐) 12 312663 589143 A7 B7 五、發明説明(l3 ) 本發明之工業用殺菌劑,可用於已習用殺菌劑之各種 工業領域’其中’工業用殺囷劑特別施用於造紙過程白水 處理工業、膠乳、聚合物乳液、顏料、塗料、印刷板處理 液、吸附劑、冷卻水、印墨、切削油、化粧品、不織布、 紡絲油、皮革等,更適合於合成聚合物乳液、紡絲油、切 削油、印墨等。 使用本發明工業用殺菌劑時,可應用下述習知方法; 例如滴定法、間歇式添加法、塗覆法、喷霧法、浸潰法等。 此等方法可對應處理目標及用途目的實施。於此例,工業 用殺菌劑之添加量,控制成有效成分於目標含水組成物之 最後總濃度,較佳約1至5000ppm,更佳5至l〇〇〇ppm。 例如,若為膠乳,較佳為以所加之工業用殺菌劑量控制有 效成分(靖基醇化合物及異噻嗤_型化合物)之最後濃度為 5 至 500ppm。 [操作例] 茲由實施例、比較例及試驗例,詳述本發明。 實施例1 經濟部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再塡寫本頁各攔) 溶液A之製備係溶解0.75克2-甲基-4-異噻唑啉_3_酮 (]^11>2.2 5克5-氣基-2-甲基-4-異噻唑啉-3-_((:1-]^1丁)、 15克2-溴基_2_硝基丙烧- 二醇(BNPD)、4·3克石肖酸納 (NaN03)、以及1.3克氣化鈉(NaCl)於7 5.4克水中,再加j 克水而獲得製劑(100克)。 實施例2 於實施例1獲得之溶液A,加1 ·0克硝酸鉀(κΝ03), 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 13 312663 / Φ 4 9 8 5 A7 _ B7 五、發明説明(14 ) 獲得製劑(100克)° 實施例3 溶液B之製備係溶解〇·75克MIT、2.25克C1-MIT、 1·0克2,2-二溴基-2-硝基乙醇(DBNE)、4.3克硝酸鈉、及 1.3克氣化鈉,於40克二乙二醇及49·4克水之混合液中, 再加1克水而獲得製劑(100克)。 實施例4 施實施例3獲得之溶液β中,加1 〇克硝酸鉀,獲得 製劑(100克)。 比較例1 添加 0.75 克 ΜΙΤ、2.25 克 C1-MIT、15 克 BNPD、及 〇·3克5 -溴基-5-石肖基_ 1,3-二曙烧(Bronidiox Κ ;羅門哈斯 (Rohm & Haas)公司製造)至18克二丙二醇及63.7克水之 混合液中,並使之溶解於此混合液中,獲得製劑(1 〇〇克)。 比較例2 經濟部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再塡寫本頁各攔) 添加 0.27 克 MIT、2.73 克 C1-MIT、15 克 BNPD、及 〇·3克溴酸鉀,至22克乙二醇及59.7克水之混合液中,並 使之溶解於此混合液中,獲得製劑(100克)。 比較例3 溶解 0.21 克 MIT、2.79 克 C1-MIT、15 克 BNPD、3.2 克硝酸鎂[Mg(N03)2]及1.9克氣化鎂(MgCl2),於76.9克水 中,獲得製劑(100克)。 比較例4 添加 0.27 克 MIT、2.73 克 C1-MIT、及 15 克 BNPD、 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 14 312663 589143 A7 B7 五、發明説明(l5 ) 以及0.3克5 -漠基-5-石肖基-1,3-二曙燒(BronidioxK; 哈斯公司製造)至81·7克水中,並使之溶解於水中, 製劑(100克)。 比較例6 添加 0.27 克 MIT、2.73 克 CH-MIT、1 克 、 0.3克溴酸鉀,於22克乙二醇、21克二乙二醇及 羅門獲轉 水之混合液中,並使之溶解於此混合液中’獲得製 及走 克) 劑(1〇 上述實施例1至4及比較例1至6之製劑成分, 如表1所述。 [表1] 實施例及比較例之製劑成分43 5. Description of the invention (12 Isothiazolone compounds, about 0.1 to 20 parts by weight. Then, according to the purpose and application, well-known additives, sex agents, antioxidants, etc., can be added to the industrial sterilization of the present invention Examples of active surfactants include conventional surfactants such as soaps, non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, polymer surfactants, etc. Among them, nonionic surfactants and anionic surfactants are preferred. Examples of nonionic surfactants are polyoxyalkylene benzene, polyoxyethylene nonyl ether, ethylene oxide, and propylene oxide. Block copolymers, etc. Moreover, examples of the anionic surfactant are metal alkane sulfonic acid metal salt, metal alkane naphthalene sulfonic acid metal salt, polycarboxylic acid metal salt, dioxane succinate metal salt, polyoxyethylene Stilbene-modified phenyl ether ammonium sulfate, ligninsulfonic acid metal salt, ligninsulfonic acid metal salt, etc. Furthermore, examples of metal salts are sodium salts, potassium salts, magnesium salts and the like. through Examples of antioxidants printed by the Consumer Cooperatives of the Ministry of Economics and Intellectual Property of the Ministry of Finance are phenolic antioxidants, such as 2,6_disecond butyl_4_cresol, 2,2, _methylenebis (4- Methyl-6-tert-butylphenol), etc .; and amine-type anti-antioxidants, such as-alkyldiphenylamine, N, N, disecond butyl-p-phenylenediamine, etc. These surface activities The addition amount of the agent and the antioxidant is preferably from 01 to 5 parts by weight to 100 parts by weight for the liquid preparation. The other additives mentioned above are added to the right, for example: another bactericide, surfactant, antioxidant, etc. It is better to change the mixing ratio of metal wall acid salt, alkali metal vapor, water-soluble diol-type solvent, water, etc. according to the type of additive. This paper size is applicable to China National Standard (CNS) A4 specification (21〇x297) (Mm) 12 312663 589143 A7 B7 V. Description of the invention (l3) The industrial fungicide of the present invention can be used in various industrial fields in which fungicides have been used. Among them, the industrial fungicide is especially applied to the white water treatment industry in the papermaking process, Latex, polymer emulsion, pigment, coating, printing plate treatment fluid , Adsorbent, cooling water, printing ink, cutting oil, cosmetics, non-woven fabrics, spinning oil, leather, etc., are more suitable for synthetic polymer emulsions, spinning oil, cutting oil, printing ink, etc. Use of the industrial bactericide In this case, the following conventional methods can be applied; for example, the titration method, batch addition method, coating method, spray method, dipping method, etc. These methods can be implemented according to the treatment goals and application purposes. In this example, industrial applications The added amount of the fungicide is controlled to the final total concentration of the active ingredient in the target aqueous composition, preferably about 1 to 5000 ppm, and more preferably 5 to 1000 ppm. For example, if it is a latex, it is preferable to use the added industrial The final concentration of the active ingredients (the Yasyl alcohol compound and the isothiazolyl-type compound) is controlled by a bactericidal dose to be 5 to 500 ppm. [Operation Examples] The present invention will be described in detail by way of examples, comparative examples, and test examples. Example 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before writing the descriptions on this page) Solution A was prepared by dissolving 0.75 g of 2-methyl-4-isothiazoline_3_ Ketone () ^ 11 > 2.2 5 g 5-amino-2-methyl-4-isothiazoline-3 -_ ((: 1-) ^ 1 butan), 15 g 2-bromo-2-nitro Propane-diol (BNPD), 4.3 grams of sodium schottate (NaN03), and 1.3 grams of sodium gasification (NaCl) in 7 5.4 grams of water, followed by j grams of water to obtain a preparation (100 grams). Example 2 The solution A obtained in Example 1 was added with 1.0 g of potassium nitrate (κΝ03). The paper size is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 13 312663 / Φ 4 9 8 5 A7 _ B7 V. Description of the invention (14) Obtained preparation (100 g) ° Example 3 The preparation of solution B was dissolved in 0.75 g MIT, 2.25 g C1-MIT, 1.0 g 2,2-dibromo-2 -Nitroethanol (DBNE), 4.3 g of sodium nitrate, and 1.3 g of sodium vaporization, in a mixture of 40 g of diethylene glycol and 49.4 g of water, and then adding 1 g of water to obtain a preparation (100 g) Example 4 To the solution β obtained in Example 3, 10 g of potassium nitrate was added to obtain a preparation. 100 grams). Comparative Example 1 0.75 grams of MIT, 2.25 grams of C1-MIT, 15 grams of BNPD, and 0.3 grams of 5-bromo-5-stoneshoeki_ 1,3-diosynchodine (Bronidiox K; Rohm and Haas (Manufactured by Rohm & Haas)) to a mixed solution of 18 g of dipropylene glycol and 63.7 g of water and dissolved in this mixed solution to obtain a preparation (1000 g). Comparative Example 2 Intellectual Property Office, Ministry of Economic Affairs Printed by the employee consumer cooperative (please read the precautions on the back before writing this page) Add 0.27 grams of MIT, 2.73 grams of C1-MIT, 15 grams of BNPD, and 0.3 grams of potassium bromate to 22 grams of ethylene glycol and 59.7 g of a mixed solution of water was dissolved in the mixed solution to obtain a preparation (100 g). Comparative Example 3 0.21 g of MIT, 2.79 g of C1-MIT, 15 g of BNPD, 3.2 g of magnesium nitrate [Mg ( N03) 2] and 1.9 g of MgCl2 in 76.9 g of water to obtain a preparation (100 g). Comparative Example 4 Added 0.27 g of MIT, 2.73 g of C1-MIT, and 15 g of BNPD. This paper is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) 14 312663 589143 A7 B7 V. Description of the Invention (l5) and 0. 3 g of 5-molyl-5-stone-shoky-1,3-dishuyan (Bronidiox K; manufactured by Haas company) to 81.7 g of water and dissolved in water to prepare a preparation (100 g). Comparative Example 6 0.27 g of MIT, 2.73 g of CH-MIT, 1 g, and 0.3 g of potassium bromate were added to a mixed solution of 22 g of ethylene glycol, 21 g of diethylene glycol, and roman's distilling water, and dissolved therein. In the mixed solution, the agent (10) of the formulation components of Examples 1 to 4 and Comparative Examples 1 to 6 is as described in Table 1. [Table 1] Formulation components of Examples and Comparative Examples
(請先閱讀背面之注意事項再填寫本頁各攔J(Please read the notes on the back before filling in this page.
AA
經濟部智慧財產局員工消費合作社印製 成分 實施例 比較ί歹ί 1 2 3 4 1 2 3 4 MIT 0.75 0.75 0.75 0.75 0.75 0.27 0.21 "〇! C1-MIT 2.25 2.25 2.25 2.25 2.25 2.73 2.79 2.7 BNPD 15 15 15 15 15 Π DBNE 1 1 乙二醇 22 2l 二乙二醇 40 40 二丙二醇 18 水 76.4 75.4 50.4 49.4 63.7 59.7 76.9 60' NaNO, 4.3 4.3 4.3 4.3 KNO, 1.0 1.0 NaCl 1.3 1.3 1.3 1.3 KbrO, 0.3 Bronidiox K 0.3 Mg(NO 丄 3.2 MgCl, 1.9Ί 〇Comparison of printed examples of employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2 3 4 1 2 3 4 MIT 0.75 0.75 0.75 0.75 0.75 0.27 0.21 " 〇! C1-MIT 2.25 2.25 2.25 2.25 2.25 2.73 2.79 2.7 BNPD 15 15 15 15 15 Π DBNE 1 1 ethylene glycol 22 2l diethylene glycol 40 40 dipropylene glycol 18 water 76.4 75.4 50.4 49.4 63.7 59.7 76.9 60 'NaNO, 4.3 4.3 4.3 4.3 KNO, 1.0 1.0 NaCl 1.3 1.3 1.3 1.3 KbrO, 0.3 Bronidiox K 0.3 Mg (NO 丄 3.2 MgCl, 1.9Ί 〇
Bronidiox K : 5_ 溴基-5-石肖基-1,3-二曙烧 試驗例1 經貯存4週後,有效成分之殘存率及外觀變化. 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)Bronidiox K: 5_ Bromo-5-stone-shoky-1,3-erosine firing test example 1 After 4 weeks of storage, the residual rate and appearance change of the active ingredients. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)
312663 ;訂· 線 15 4 1X 9 8 A7 ____ B7 五、發明説明(l6 ) 實施例1至4及比較例1至6之製劑,分別置於玻璃 弃瓦中予以费封’然後於6 0 C恒溫浴中貯存4週。測定2 _ 甲基-4-異噻嗤啉-3-酮(MIT)、5-氣基-2-甲基·4·異噻嗤啉_ 3-酮(CI-MIT)' 2·溴基-2-硝基丙烷-1,3-二醇(BNPD)、及 2,2· 溴基-2-梢基乙醇(DBNE)之殘存率(%),並目測外觀變化。 依下述標準進行判定,結果示於表2。 外觀未混濁或沈激:〇 未沈澱形成,但見混濁:△ 均見混濁或沈澱:X [表2] 經貯存4週後,有效成分之殘存率及外觀變化 i效 實拍 L例 比較例 成分 名稱 1 2 3 4 1 2 3 4 5 6 殘存 率 (%) MIT 70.0 70.7 70.1 70.3 36.4 0 47.6 0 41.0 60.0 Cl-· MIT 95.1 95.6 95.1 95.0 0 0 22. 1 0 0 80.0 BNPD 99.4 99.6 87.7 80.0 74.6 76.2 89.0 DBNE 98.5 96.5 76 6 外觀 〇 〇 〇 Ο X X X X X / w . V-l Δ 經濟部智慧財產局員工消費合作社印製 由表2可知,於實施例丨至4之製劑,其中已加鹼金 屬石肖酸鹽及亂化納’不拘有否加二醇類,製劑均安定。於 任何例中MIT之殘存率均超過7〇0/〇,ci_MIT、BNPD及 DBNE之殘存率,均為95%以上。另一方面,於比較例1 至6之製劑,其中鹼金屬硝酸鹽及氣化鈉均未加,ΜΙτ之 殘存率顯示60%以下’任何ci-MlT、BNPD及DBNE之殘 存率顯示90%以下。由此等結果知,含硝基醇化合物(a) 及異噻唑酮型化合物(b)二者作為活性成分之工業用殺菌 ^紙張尺度適用中國國家標準(CNS)A4規格---- 312663 (請先閲讀背面之注意事項再填寫本頁各攔) 16 589143 A7 B7 五、發明説明(17 ) 劑’證明加驗金屬硝酸鹽及氣化鈉,能明顯使活性成分安 定。 試驗 SBR膠乳之相容性試驗 實施例1至4及比較例1至6之製劑,分別於載玻片 上’以1 : 1之容量比與SBR膠乳(S A-22)混合,由目測觀 察膠乳之膠凝情形。依下述標準進行判定。結果示於表3。 未膠凝:〇 微膠凝:△ 膠凝:X [表3] 與SBR膠乳之相容性 實施例 比較例 ------ 1 2 3 4 1 2 3 4 5 6 SBR膠乳 〇 〇 〇 〇 Δ Δ X △ Δ Δ 由表3可知,雖然内容物彼此些許不同,於實施例1 至4之製劑,未引起所謂之乳液敗形,而比較例1至6之 製劑,均引起乳液敗形。 經濟部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再塡寫本頁各攔) [本發明之功效] 本發明之工業用殺菌劑,即使成不含有機溶劑如水溶 性二醇等之液體製劑,仍能長期安定,具與如膠乳等乳液 之優異相容性,不會引起所謂之乳液敗形。312663; order · line 15 4 1X 9 8 A7 ____ B7 V. Description of the invention (l6) The preparations of Examples 1 to 4 and Comparative Examples 1 to 6 were placed in glass discarded tiles to be sealed, then at 60 C Stored in a constant temperature bath for 4 weeks. Determination of 2_methyl-4-isothiazoline-3-one (MIT), 5-amino-2-methyl · 4 · isothiazoline_ 3-one (CI-MIT) '2 · bromo group Residual ratio (%) of 2-nitropropane-1,3-diol (BNPD) and 2,2 · bromo-2-pentyl ethanol (DBNE), and visual changes were observed. The determination was performed according to the following criteria, and the results are shown in Table 2. Appearance without turbidity or irritation: 〇No precipitation was formed, but turbidity was observed: △ All turbidity or precipitation was seen: X [Table 2] After 4 weeks of storage, the residual rate of the active ingredients and the appearance of the product were changed. Ingredient name 1 2 3 4 1 2 3 4 5 6 Survival rate (%) MIT 70.0 70.7 70.1 70.3 36.4 0 47.6 0 41.0 60.0 Cl- · MIT 95.1 95.6 95.1 95.0 0 0 22. 1 0 0 80.0 BNPD 99.4 99.6 87.7 80.0 74.6 76.2 89.0 DBNE 98.5 96.5 76 6 Appearance 00 × 00 XXXXX / w. Vl Δ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs It can be seen from Table 2 that the formulations of Examples 1-4 have been added with alkali metal stone oxalic acid Salt and randomized sodium 'are free from the addition of glycols, and the preparations are stable. In any case, the residual rate of MIT exceeds 70 / 〇, and the residual rates of ci_MIT, BNPD and DBNE are all above 95%. On the other hand, in the preparations of Comparative Examples 1 to 6, in which neither the alkali metal nitrate nor sodium gasification was added, the residual rate of MIτ showed less than 60%, and the residual rate of any ci-MlT, BNPD, and DBNE showed less than 90%. . From these results, it is known that industrial bactericidal compounds containing both the nitro alcohol compound (a) and the isothiazolone compound (b) as active ingredients ^ The paper size applies the Chinese National Standard (CNS) A4 specification ---- 312663 ( Please read the precautions on the back before filling in this page) 16 589143 A7 B7 V. Description of the invention (17) The agent 'certifies that the addition of metal nitrate and sodium gas can significantly stabilize the active ingredients. Test the compatibility of SBR latex. The formulations of Examples 1 to 4 and Comparative Examples 1 to 6 were mixed on a glass slide with a SBR latex (S A-22) at a volume ratio of 1: 1, and the latex was visually observed. The gelling situation. Judgment is based on the following criteria. The results are shown in Table 3. Ungelling: 〇Gelting: △ Gelling: X [Table 3] Compatibility Examples with SBR Latex Comparative Examples-1 2 3 4 1 2 3 4 5 6 SBR Latex 〇〇〇 〇Δ Δ X Δ Δ Δ As can be seen from Table 3, although the contents are slightly different from each other, the preparations of Examples 1 to 4 did not cause so-called emulsion failure, while the preparations of Comparative Examples 1 to 6 all caused emulsion failure. . Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Such liquid preparations can still be stable for a long time, have excellent compatibility with emulsions such as latex, and will not cause so-called emulsion failure.
本紙張尺度適用中國國家標準(cNs)A4^^7i77iT 17 312663This paper size applies to China National Standard (cNs) A4 ^^ 7i77iT 17 312663
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JP5101826B2 (en) * | 2006-02-28 | 2012-12-19 | 日本曹達株式会社 | Water-soluble preparation containing isothiazolone compound and method for stabilizing isothiazolone compound |
JP5431291B2 (en) * | 2009-12-18 | 2014-03-05 | ダウ・イタリア・ディビジョン・コマーシャル・ソシエテ・ア・レスポンサビリテ・リミテ | Disinfectant formulation suitable for use at low temperatures |
JP5431292B2 (en) * | 2009-12-18 | 2014-03-05 | ダウ・イタリア・ディビジョン・コマーシャル・ソシエテ・ア・レスポンサビリテ・リミテ | Disinfectant formulations that remain liquid at low temperatures |
JP5680368B2 (en) * | 2010-10-26 | 2015-03-04 | 丸三化学産業株式会社 | Industrial disinfectant composition stabilized against light |
EP2594133B1 (en) * | 2011-11-16 | 2014-03-19 | Rohm and Haas Company | Hindered primary chlorinated amine in a latex formulation |
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GB8416314D0 (en) * | 1984-06-27 | 1984-08-01 | Rohm & Haas | Stabilization of aqueous solutions |
JP2740554B2 (en) * | 1989-08-08 | 1998-04-15 | 株式会社日本触媒 | Brine composition |
IL96820A (en) * | 1990-12-28 | 1995-06-29 | Bromine Compounds Ltd | Stabilized isothiazolinone formulations |
JP3139167B2 (en) * | 1992-09-11 | 2001-02-26 | 北興化学工業株式会社 | Stable liquid antibacterial and antifungal preparation |
JP3604173B2 (en) * | 1994-04-01 | 2004-12-22 | 日本エンバイロケミカルズ株式会社 | Disinfectant and disinfection method using the same |
JPH08133913A (en) * | 1994-11-08 | 1996-05-28 | Katayama Chem Works Co Ltd | Long-acting 3-isothiazolone-based industrial germicidal preservative |
US5910503A (en) * | 1997-10-28 | 1999-06-08 | Rohm And Haas Company | Stable microbicide formulation |
JPH11180806A (en) * | 1997-12-22 | 1999-07-06 | Kurita Water Ind Ltd | Antimicrobial composition |
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KR20000017371A (en) * | 1998-08-31 | 2000-03-25 | 마크 에스. 아들러 | Stable microbicide formulation |
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