TW589143B - Industrial microbicide and method for stabilizing nitroalcohol compound and isothiazolone type compound - Google Patents

Abstract

The object of the present invention is to widen the anti-microbial spectrum of an isothiazolone type compound-based industrial microbicide and to provide an industrial microbicide that is stable in storage for a long duration and has excellent compatibility to emulsions, namely, does not cause emulsion shock, and the object can be attained by adding an alkali metal nitrate (c) as a stabilizing agent to a nitroalcohol compound (a) and an isothiazolone type compound (b) as effective components and further adding an alkali metal chloride (d) and a water-soluble glycol type solvent (e).

Description

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 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. 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)

• 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)

Printed 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

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) (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)

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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)

-Order. • Thread This paper size applies Chinese National Standard (CNS) A4 specification 312663 297 mm 4 1X 9 8

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) # 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 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

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A

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_ 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; 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.

This paper size applies to China National Standard (cNs) A4 ^^ 7i77iT 17 312663

Claims (1)

No. 901141 19 Patent application Blind scope amendment (January 20, 1993) Composition of alcohol compound (a) and isothiazolone salt (c). A fungicide, wherein the fungicide is an industrial fungicide, which is composed of a nitro-type compound (b) and an alkali metal nitric acid, such as the one in the scope of the patent application, and contains an alkali metal chloride (d). Female patent application scope 丨 and ^ φ ^ Brother 2 of any of the industrial sterilization month J of which the industrial bactericide is again right ~ ~ correct 3 water > glutadiol type The solvent (e) is an industrial bactericide of one member as shown in the general formula (1), and the compound (a) oh x1 y1 ~ ch-c_Y2 IN〇2 ⑴ (in the formula, X] is an alkyl or halogen atom having 1 to 4 carbons having a hydroxyl group; γ]: an alkyl having 1 to 4 carbons or an alkenyl having 2 to 4 carbons having a hydroxyl group, and Υ2 is a hydrogen atom or an insect An atom, an alkyl group having 1 to 4 carbons having a hydroxyl group, or an alkenyl group having 2 to 4 carbons having any hydroxyl group). For example, the industrial bactericide of the scope of application for the patent, wherein the compound (a) is 2- > 2-nitropropane-13, diol or 2,2-dibromo · 2 • nitroethanol. Shi Shen. The industrial bactericide of item 1 of the monthly patent scope, in which the compound (b) is as shown by the general formula (2): 1 3 12663 (revised edition) 589143 \ γ3 (2) € In the formula, X2 and X3 are the same Or a different hydrogen atom, * atom, or an alkyl group of 1 to 6 carbons is a hydrogen atom or any i to 8 carbon hydrocarbon group having a substituent). 7. The industrial bactericide, such as the scope of the patent application, where the compound is 2-methyl-4-isothiazoline-3_one or called 5-loose_2-fluorenyl_4_isothiazoline. 3-keto. 8 · Gongfeng # 1 < Industrial fungicides, such as those in which the compound is sodium petrosate or potassium nitrate. 9. If the work in item 2 of the patent application is for sodium gasification or potassium gasification. Industrial-tinctures, where compound ⑷ 10. If the work # 3 of the scope of patent application # is ethylene glycol, propylene glycol, diethyl-salvage, where compound ⑷ monomethyl ether. Xizi, propylene glycol, or diethylene glycol 11. For industrial fungicides such as those in the scope of application for patents, i Zhongxi Fungicides are from 0.01 to 40 weight "4 compounds (a) , QW amount% compound ㈨, and 〇〇). 01 to 20 weight. To reset% compound (C) constitutes 12 · as the scope of application for patents u, foot industrial bactericides, straight piridine bactericides It also contains 0.1 to 1%, and the medium μ industry 13. Such as the scope of application for patents No. 11 and No. 12 =: ⑷ ⑷. Bactericides, in which the industrial fungicide and eight = any-item industrial killing s There are 0.1 to 90% by weight of the compound 2 3] 2663 (revised version) 589143 (e). 14 • For industrial applications such as any of the patent application scopes 1, 2, 4 to 9, U, 12 Bactericide 'Wherein the industrial fungicide is used for latex, synthetic resin emulsion, or paint. 15 · —A method for stabilizing the nitro alcohol compound (a) and isothiazole type 1 compound (b), which is added Alkali metal nitrates (c) to compounds (a) and (b) 16. Compounding a nitro alcohol as described in the scope of patent application No. 15 (A) and isothiazolone type compound (b) stabilization method, in which alkali metal chloride (d) is added. 312663 (revised edition)