JP2007145720A - Industrial antimicrobial composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrial antimicrobial composition comprising 5-chloro-2,4,6-trifluoroisophthalonitrile and 2,2-dibromo-2-cyanoacetamide as active ingredients and exhibiting stable effects. <P>SOLUTION: The industrial antimicrobial composition comprises the 5-chloro-2,4,6-trifluoroisophthalonitrile and the 2,2-dibromo-2-cyanoacetamide as the active ingredients and contains propylene carbonate, a low-polar solvent and a surfactant. Both the active ingredients in the industrial antimicrobial composition have excellent storage stability and the industrial antimicrobial composition exhibits the stable effects without depositing crystals when added into water. Since the amount of the surfactant used is small, the composition can effectively be used as a slime controlling agent for papermaking. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is an industrial bactericidal composition comprising 5-chloro-2,4,6-trifluoroisophthalonitrile and 2,2-dibromo-2-cyanoacetamide as active ingredients, and a composition that exhibits a stable effect. It is about.

  In white water systems in the papermaking process and cooling water systems in chemical factories, microorganisms grow using organic substances mixed in the water as nutrients, causing unpleasant odors, slime generation and exfoliation, and product quality degradation, continuous operation for cleaning Cause troubles such as stoppages and lowering of cooling efficiency. Also, in general industrial products, many microbial failures occur depending on the raw material composition and product storage conditions, and their control is an important issue.

Conventionally, a number of bactericides have been used to prevent or sterilize the growth of these microorganisms. As these bactericides, 2,2-dibromo-2-cyanoacetamide (hereinafter abbreviated as dibromide) is well known. This drug is often stored and transported as a liquid composition for application. However, dibromide solutions generally do not necessarily have good chemical stability, and are liable to undergo decomposition such as thermal decomposition, hydrolysis, and photolysis. Therefore, there is a drawback that the active ingredient is reduced within a relatively short period of time, and the effect as an industrial disinfectant is reduced.
Various studies have been conducted on the improvement of stability to suppress the decomposition of dibromide. For example, a method of dissolving dibromide in polyalkylene glycols (Japanese Patent Laid-Open No. 47-3647 (Patent Document 1)) A composition in which dibromide is blended with propylene carbonate [JP-A-5-331006 (Patent Document 2)] has been proposed as an improved method. Furthermore, a bactericide having excellent stability in which dibromide or the like is dissolved in propylene carbonate and oxyalkylene ether has been proposed [Japanese Patent Laid-Open No. 2000-143409 (Patent Document 3)].

  Further, 5-chloro-2,4,6-trifluoroisophthalonitrile (hereinafter abbreviated as CFPN) is known as a disinfectant. CFPN is effective against filamentous fungi but is inferior in activity against bacteria, and a bactericidal agent having a bactericidal activity against filamentous fungi and bacteria by combining this with dibromide has been proposed [JP-A-62-402] (Patent Document 4)]. However, when dibromide and CFPN are dissolved in polyethylene glycols, propylene carbonate or propylene carbonate and oxyalkylene ether in a solvent having a high water solubility, CFPN is precipitated as crystals when added to water. May be reduced. Further, when polyethylene glycols or oxyalkylene ethers are used, the stability of dibromide is not sufficient, and there is a further problem that CFPN is decomposed.

  Patent Document 4 exemplifies xylene and cyclohexanone as a solvent, but xylene is not preferred as a solvent because of flammability and toxicity, and cyclohexanone cannot provide a preparation with excellent stability. If a large amount of surfactant is used, the emulsification dispersibility is improved and the problem of precipitation of active ingredient crystals is avoided. However, when used in the paper and pulp industry, the surfactant remains on the paper surface and the size properties are reduced. Therefore, it is preferable to reduce the use of the surfactant as much as possible.

  As described above, in the conventional technology, dibromide and CFPN are mixed, both components are stably stored for a long period of time, and crystals of the active ingredient are precipitated when added to water by using a small amount of surfactant. It is difficult to prevent. Industrial disinfectants are generally produced in the form of liquid compositions, and there is a need for industrial disinfectants that maintain long-term storage stability and exhibit stable effects.

JP-A-47-3647 JP-A-5-331006 JP 2000-143409 A JP-A-62-402

  The present invention provides an industrial sterilizing composition containing dibromide and CFPN as active ingredients, having excellent storage stability, and exhibiting a stable effect without addition of crystals when added to water. It was made for the purpose.

An outline of the present invention is as follows.
(1) An industrial sterilizing composition comprising CFPN and dibromide as active ingredients, and containing propylene carbonate, a low polarity solvent and a surfactant;
(2) The industrial sterilizing composition according to (1), wherein the low polarity solvent is a dialkyl carbonate;
(3) The industrial sterilizing composition according to (1) or (2), wherein the low polarity solvent is a dialkyl carbonate and the alkyl group is an alkyl group having 3 to 5 carbon atoms,
(4) The industrial sterilizing composition according to any one of (1) to (3), wherein the low-polarity solvent is 3 to 20% by mass relative to 100% by mass of the industrial sterilizing composition,
(5) The industrial sterilizing composition according to any one of (1) to (4), wherein the surfactant is 0.5 to 1% by mass relative to 100% by mass of the industrial sterilizing composition. ,
(6) The surfactant is a mixture of polyoxyethylene distyryl phenyl ether formaldehyde condensate, polyoxyethylene castor oil and calcium alkylbenzenesulfonate, described in any one of (1) to (5) An industrial sterilizing composition.

  As a result of intensive studies to solve the above problems, the present inventor rationally blended propylene carbonate and a low polarity solvent as a solvent to dissolve dibromide and CFPN, and a surfactant of 1% or less. In order to complete the present invention, it has been found that the stability of both components is improved, the dispersibility when added to water is improved, and the biological effect is stabilized, which cannot be predicted from conventional techniques. It came.

  The industrial sterilizing composition of the present invention has both excellent storage stability for both active ingredients of CFPN and dibromide, and when added to water, there is no crystal precipitation, so the synergistic effect of CFPN and dibromide is fully demonstrated. And can exhibit a stable effect. Although it can be used for various sterilization applications, it can be effectively used as a slime control agent for papermaking because the amount of surfactant used is particularly small.

Hereinafter, the present invention will be specifically described.
The industrial bactericidal composition of the present invention contains CFPN and dibromide as bactericidal active ingredients, and the blending ratio of these active ingredients is rationally selected so as to exert a sufficient effect in the applied field. Usually, CFPN may be appropriately selected from the range of 2 to 20% by mass and dibromide is 5 to 30% by mass with respect to the total amount of the industrial sterilizing composition.

  As a low polarity solvent used by this invention, the solubility with respect to water at 25 degreeC points out 0.1% or less, and a dialkyl carbonate is mentioned. Here, the alkyl group preferably has 3 to 5 carbon atoms. For example, dipropyl carbonate or dibutyl carbonate can be used. The alkyl group of the dialkyl carbonate becomes incompatible with propylene carbonate if the alkyl group has too many carbon atoms. If the amount is too small, the prevention of crystal precipitation cannot be sufficiently achieved.

  The blending ratio of propylene carbonate and low-polarity solvent is such that crystal precipitation does not occur in the preparation at −5 ° C., and when added to water at the time of use, it quickly emulsifies and disperses so that crystal precipitation does not occur for at least 24 hours. It is necessary to limit the blending amount to 20 to 80% by mass of propylene carbonate, preferably 40 to 70% by mass, and 3 to 20% by mass of the low polarity solvent with respect to the total amount of the industrial disinfectant composition. , Preferably it is the range of 5-15 mass%. What is necessary is just to select suitably from this range and to use.

  Examples of the surfactant used in the present invention include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants. Of these, nonionic surfactants and anionic surfactants are preferably used. For example, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene allyl phenyl ether, polyoxyalkylene allyl phenyl ether formaldehyde condensate, polyoxyalkylene castor oil ether, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene allyl phenyl ether phosphoric acid Examples thereof include salts and alkylbenzene sulfonates, and these surfactants can be used alone or in combination. In particular, the composition is preferably a mixture of polyoxyethylene distyryl phenyl ether formaldehyde condensate, polyoxyethylene castor oil, and calcium alkylbenzenesulfonate, and by changing the composition ratio depending on the amount of low-polar solvent used, 1 The active ingredient can be emulsified and dispersed with a use amount of% or less. The surfactant is preferably blended in an amount of 0.5 to 1% by mass. The composition ratio is adjusted in the range of 35 to 42 parts by mass of polyoxyethylene distyryl phenyl ether formaldehyde condensate, 26 to 31 parts by mass of polyoxyethylene castor oil, and 28 to 40 parts by mass of calcium alkylbenzenesulfonate. preferable.

  The industrial sterilizing composition of the present invention can be obtained by mixing two active ingredients, propylene carbonate, a low polarity solvent and a surfactant and stirring them until uniform. Moreover, it filters as needed. The order of mixing the components during production may be arbitrary and is not particularly limited.

  The industrial sterilizing composition of the present invention is mainly used for industrial water use, for example, as a microbial disorder preventing agent in a system that uses a large amount of water such as papermaking processes, industrial cooling water systems, cooling water systems for air conditioning of buildings, etc. Furthermore, it can also be used as an antimicrobial agent for general industrial products such as water-based paints for construction, paints for paper coating in paper mills, metalworking oils, starches, casein and other pastes.

  The industrial sterilizing composition of the present invention is not particularly limited in the method of use, and dripping treatment, intermittent addition treatment, coating treatment, spray treatment, immersion treatment, and the like are employed. These are appropriately selected and used according to the application scene, target, purpose, and the like.

  EXAMPLES Next, although an Example, a test example, etc. are shown and this invention is demonstrated more concretely, this invention is not limited to these. In Examples, Comparative Examples and Test Examples, “parts” means “mass parts”. Further, the surfactant A is a surfactant LO: surfactant HY 8: 2 mixture, and the surfactant B is a surfactant LO: surfactant HY 7: 3 mixture. Agent C represents a mixture of surfactant LO: surfactant HY of 1: 1, and surfactant D represents a mixture of surfactant LO: surfactant HY of 3: 7. Here, the surfactant LO contains 28% by mass of polyoxyethylene distyryl phenyl ether formaldehyde condensate, 19% by mass of polyoxyethylene castor oil, 33% by mass of calcium alkylbenzenesulfonate, and the balance kerosene-based and aromatic solvent mixture. The surfactant HY contains 35% by mass of polyoxyethylene distyryl phenyl ether formaldehyde condensate, 24% by mass of polyoxyethylene castor oil, 21% by mass of alkylbenzene sulfone calcium, and the balance kerosene and aromatic solvent mixture. It becomes.

Example 1
An emulsion was obtained by mixing 25 parts of dibromide, 3 parts of CFPN, 56 parts of propylene carbonate, 15 parts of dibutyl carbonate, and 1 part of surfactant A.

Examples 2-7
In the same manner as in Example 1, Examples 2 to 7 were blended in the proportions shown in Table 1 to obtain industrial sterilization compositions.

Comparative Example 1
25 parts of dibromide, 3 parts of CFPN, 71.3 parts of propylene carbonate and 0.7 part of surfactant A were mixed to obtain an industrial bactericidal composition.

Comparative Examples 2-10
In the same manner as in Comparative Example 1, Comparative Examples 2 to 10 could be blended at the ratios shown in Tables 2 and 3. In Table 3, Hysol SAS296 is a product of Nippon Petrochemical Co., Ltd. having phenylxylylethane as the main component. The dibasic acid ester is a mixed ester of dimethyl adipate, dimethyl glutarate, and dimethyl succinate having a mass ratio of 17:66:17, and is a product (product name: DBE) of DuPont.

Test Example 1 Stability test 100 g of each industrial sterilizing composition prepared in accordance with Examples and Comparative Examples was put in a glass container, sealed, and stored in a thermostat at 50 ° C. for 7 days. The residual amount was measured and the residual rate of each was determined. The results are shown in Table 4.

  In Comparative Example 10, propylene carbonate and dialkyl carbonate (C14 to C15) were incompatible and could not be carried out.

  As can be seen from Table 4, the fungicide containing propylene carbonate of the present invention (Examples) and dipropyl carbonate or dibutyl carbonate, etc. is the remaining active ingredients (dibromide, CFPN) after storage at 50 ° C. for 7 days. The rate was 99% or more. On the other hand, among the comparative examples, the solvent having a residual ratio of 95% or more was propylene carbonate alone or a mixed solvent of propylene carbonate and xylene, dibasic acid ester, or diethyl carbonate.

Test Example 2 Dispersibility Test Preparation of Comparative Agent A sample was prepared by replacing the surfactant A of Comparative Example 1 with the surfactant B, the surfactant C, or the surfactant D. Each sample is represented as Comparative Example 1-A, Comparative Example 1-B, Comparative Example 1-C, and Comparative Example 1-D. Comparative examples 2 to 9 were produced in the same manner.

Test Method 100 ml of clean water is put in a 100 ml beaker, 1 ml of the drug prepared according to the example and the comparative example is added to a state where a 3 cm rotor is rotated at 200 rpm, and the time until the drug is completely emulsified and dispersed is measured. . Table 5 shows the dispersion end time and the dispersion state. In the table, “a” indicates the floating of the oily substance, “b” indicates that a precipitate is formed, and “c” indicates that crystals are precipitated and not dispersed.

  As seen in Table 5, the disinfectant containing propylene carbonate of the present invention (Example) and dipropyl carbonate or dibutyl carbonate was emulsified and dispersed in about 3 minutes without crystal precipitation. Only xylene was emulsified and dispersed in about 3 minutes without crystal precipitation at 1. However, in the emulsified state using xylene, the emulsified particles were large and the xylene separated and floated over time. In the case of using only a dibasic acid ester, diethyl carbonate or propylene carbonate as a solvent in which the residual ratio of the active ingredient (dibromide, CFPN) was 99% or more, crystals precipitated and did not disperse. The only system that is stable and stable in emulsification dispersion for more than 24 hours was the fungicide of the present invention (Example).

Claims (6)

  An industry characterized by containing 5-chloro-2,4,6-trifluoroisophthalonitrile and 2,2-dibromo-2-cyanoacetamide as active ingredients, and containing propylene carbonate, a low polarity solvent and a surfactant. Bactericidal composition.   The industrial sterilizing composition according to claim 1, wherein the low polarity solvent is a dialkyl carbonate.   The industrial sterilizing composition according to claim 1 or 2, wherein the low polarity solvent is a dialkyl carbonate, and the alkyl group is an alkyl group having 3 to 5 carbon atoms.   The industrial sterilization composition according to any one of claims 1 to 3, wherein the low-polarity solvent is 3 to 20 mass% with respect to 100 mass% of the industrial sterilization composition.   Surfactant is 0.5-1 mass% with respect to 100 mass% of industrial sterilization compositions, The industrial sterilization composition of any one of Claims 1-4.   The industrial bactericidal composition according to any one of claims 1 to 5, wherein the surfactant comprises a mixture of polyoxyethylene distyryl phenyl ether formaldehyde condensate, polyoxyethylene castor oil and calcium alkylbenzenesulfonate.