JP2003238318A - Industrial microbicidal composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrial microbicidal composition sufficiently developing excellent controlling effect on bacteria, fungi, yeast, alga, etc., over a long period. <P>SOLUTION: The industrial microbicidal composition contains 1 pt.wt. of 5-chloro-2-methyl-4-isothiazolin-3-one, 1.05-30 pts.wt. of 2-methyl-4-isothiazolin-3- one and 1.25-30 pts.wt. of 2-bromo-2-nitropropane-1,3-diol. The industrial microbicidal composition develops stable controlling effect on bacteria, fungi, yeast, alga, etc., over a long period and is suitable as a controlling agent for the organisms. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial bactericidal composition, and more particularly to an industrial bactericidal composition suitable for use as a control agent for bacteria, fungi, yeasts and algae.

[0002]

2. Description of the Related Art Conventionally, various industrial waters such as a pulp and paper mill, a cooling water circulation process, an oil agent for metal processing such as cutting oil, casein, starch paste, glue, coated paper, coating liquid for paper, size Various industrial products such as adhesives, paper strengthening agents, paints, adhesives, synthetic rubber latex, inks, polyvinyl alcohol films, vinyl chloride films, resin products, cement admixtures, sealing agents, jointing agents, bacteria, fungi,
Harmful microorganisms such as yeast and algae are liable to propagate, which causes deterioration of productivity and quality and generation of malodor. Therefore, industrial bactericides are widely used to control the growth of such microorganisms.

Compounds such as isothiazoline compounds and nitroalcohol compounds have been conventionally known as such industrial bactericides, and synergistic control is achieved by combining these isothiazoline compounds and nitroalcohol compounds. Various proposals have been made to realize the effect.

For example, JP-A-60-54281 discloses an isothiazolone derivative and a halogenated aliphatic nitroalcohol (however, 2-bromo-2-nitropropane-1,3-diol is not described). Weight ratio 1:
It is described that an excellent synergistic effect can be exhibited by using together in a ratio of 10 to 10: 1.

Further, for example, in Japanese Patent Application Laid-Open No. 8-133913, a 3-isothiazolone compound and a halogenated aliphatic nitro alcohol are contained in a weight ratio of 1: 11.5 to.
It is described that the combined use at a ratio of 1: 500 can produce a stable synergistic effect over a long period of time.

[0006]

However, the industrial fungicides described in any of the above publications are still not practically sufficient for obtaining a stable control effect over a long period of time, and further long-term stability Is required.

Therefore, the present invention has been made in view of the above circumstances, and its purpose is to prevent bacteria, fungi,
An object of the present invention is to provide an industrial bactericidal composition capable of sufficiently exhibiting an excellent controlling effect on yeast, algae and the like for a long period of time.

[0008]

In order to achieve the above object, the present inventors have combined an isothiazoline compound and a nitroalcohol compound to produce an excellent synergistic effect stably for a long period of time. As a result of diligent study on a sterilizing composition for use in the field, 5-chloro-2-methyl-4-isothiazoline-3 which is an isothiazoline compound
-One and 2-methyl-4-isothiazolin-3-one to 5-chloro-2-methyl-4-isothiazolin-
2-Methyl-4-isothiazoline-3 for 3-one
-One was used as an excess amount, and 2-bromo-2-nitropropane-1, as a nitroalcohol-based compound,
The present inventors have completed the present invention as a result of discovering the knowledge that excellent long-term stability can be expressed by selecting 3-diol and using it in a predetermined amount.

That is, the present invention provides (1) 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1. , 3-diol to 1.0 part by weight of 5-chloro-2-methyl-4-isothiazolin-3-one, 1.05 to 30 parts by weight of 2-methyl-4-isothiazolin-3-one, 2- (2) 5-Chloro-2-methyl-, an industrial germicidal composition, characterized in that it contains bromo-2-nitropropane-1,3-diol in a proportion of 1.25 to 30 parts by weight. The above-mentioned (1), which contains 2-methyl-4-isothiazolin-3-one in a proportion of 1.2 to 8 parts by weight with respect to 1 part by weight of 4-isothiazolin-3-one. Industrial sterilizing composition described in (3) - chloro-2-methyl-4-
2 to 12 parts of 2-bromo-2-nitropropane-1,3-diol is added to 1 part by weight of isothiazolin-3-one.
(4) The industrial sterilizing composition as described in (1) or (2) above, characterized in that it is contained in a proportion of parts by weight.
5-chloro-2-methyl-4-isothiazoline-3-
2-bromo-2-nitropropane-1,3-diol in an amount of 0.14 to 5 parts by weight based on 1 part by weight of the total amount of one- and 2-methyl-4-isothiazolin-3-one. (1) to (3), characterized in that
(5) A sterilizing composition for industrial use according to any one of (1) to (4), which is prepared as a solution with a solvent, and contains 1 to 4 of 5-chloro-2-methyl-4-isothiazolin-3-one in the solution.
% By weight, 2-methyl-4-isothiazolin-3-one 5-30% by weight, 2-bromo-2-nitropropane-
The industrial sterilizing composition according to any one of (1) to (3), which contains 1,3-diol in an amount of 5 to 30% by weight, (6) diethylene glycol or the solvent. And / or propylene glycol is used, (7) The industrial sterilizing composition according to (5), (7) which is added to a system to be sterilized having a pH of 7 to 10. ) To (6), the industrial sterilizing composition is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial bactericidal composition of the present invention comprises 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin- as active ingredients.
3-one and 2-bromo-2-nitropropane-1,
The 3-diol was added to 2-methyl-4 with respect to 1 part by weight of 5-chloro-2-methyl-4-isothiazolin-3-one.
1.05 to 30 parts by weight of isothiazolin-3-one,
It contains 2-bromo-2-nitropropane-1,3-diol in a proportion of 1.25 to 30 parts by weight.

In the present invention, 5-chloro-2-methyl-4-isothiazolin-3-one has been conventionally used as an industrial bactericide and is a commercially available compound.

Further, in the present invention, 2-methyl-4-
Similarly, isothiazolin-3-one is a compound that has been conventionally used as an industrial fungicide and is commercially available.

Incidentally, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are commercially available products prepared in advance as a mixture. Good.

In the present invention, 2-bromo-2-
Nitropropane-1,3-diol is also a compound that has been conventionally used as an industrial fungicide and is commercially available.

And, in the industrial sterilization composition of the present invention,
1.05 to 30 parts by weight of 2-methyl-4-isothiazolin-3-one per 1 part by weight of 5-chloro-2-methyl-4-isothiazolin-3-one, preferably 1.
2 to 8 parts by weight, more preferably 1.25 to 2.5 parts by weight, and 1.25 to 30 parts by weight of 2-bromo-2-nitropropane-1,3-diol. Preferably 2 to 12 parts by weight, more preferably 4 to 8
It is compounded in a ratio of parts by weight.

By blending 2-chloro-4-methyl-4-isothiazolin-3-one with 5-chloro-2-methyl-4-isothiazolin-3-one in such a range, sterilization in the alkaline range is achieved. It is possible to improve the control effect against bacteria, mold, yeast, algae, etc. in the target system. Further, by adding 2-bromo-2-nitropropane-1,3-diol to 5-chloro-2-methyl-4-isothiazolin-3-one in such a range, a further control effect can be obtained. Further, it is possible to improve the stabilization.

Further, in such a blend, 2 parts per 1 part by weight of the total amount of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one is 2 parts. -Bromo-2-nitropropane-
0.14 to 5 parts by weight of 1,3-diol, preferably
0.5-3 parts by weight, more preferably 1.05-2.
It is preferable to add 5 parts by weight. By blending in such a range, to stabilize the industrial sterilization composition in the sterilization target system, improve the sustainability of the control effect, in particular, in the sterilization target system in the alkaline region, bacteria, fungus, The control effect on yeast, algae, etc. can be improved.

The industrial bactericidal composition of the present invention contains these 5-chloro-2-methyl-4-isothiazoline-3.
-One, 2-methyl-4-isothiazolin-3-one, and 2-bromo-2-nitropropane-1,3-diol can be prepared by appropriately blending them by a known method.

The industrial bactericidal composition of the present invention was previously prepared with 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 2-bromo-2-. A formulation containing nitropropane-1,3-diol may be added to the system to be sterilized.
-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol were individually added to the sterilization target system. And may be allowed to act in the system to be sterilized.

The industrial bactericidal composition of the present invention may be formulated according to the purpose and use, and its dosage form is not particularly limited, but it is prepared as a liquid agent (including a water suspension agent and an oil agent). Is preferred.

To prepare a liquid preparation, for example, 5-chloro-2-methyl-4-isothiazolin-3-one is contained in an amount of 1 to 4% by weight, and further 1.5 to 3 with respect to the total amount of the preparation.
%, 2-methyl-4-isothiazolin-3-one 5-30% by weight, and further 5-20% by weight 2-bromo-2-nitropropane-1,3-diol 5-30%.
It may be dissolved or dispersed in a solvent as appropriate so that the weight ratio is 10% to 20% by weight.

The solvent is not particularly limited as long as it can dissolve or disperse these compounds.
Water, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert.
-Alcoholic solvents such as butanol, 3-methyl-3-methoxybutanol, eg ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5
A glycol solvent such as pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or tripropylene glycol monomethyl ether is used. Of these solvents, glycol is preferably used in order to further stabilize both 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol. A system solvent, more preferably diethylene glycol or propylene glycol is used. These solvents may be used alone or in combination of two or more.

Further, the industrial bactericidal composition of the present invention may contain known additives such as surfactants, antioxidants and light stabilizers, depending on the purpose and application, of the industrial bactericidal composition of the present invention. You may add suitably in the range which does not inhibit the outstanding effect.

The industrial bactericidal composition of the present invention thus obtained exerts a stable controlling effect on bacteria, fungi, yeasts, algae, etc. for a long period of time, and is therefore suitably used as a controlling agent for these. To be

Therefore, the industrial sterilizing composition of the present invention is
For example, pulp and paper mills, various industrial water such as cooling water circulation process, metal working oil such as cutting oil, casein,
Starch glue, glue, coated paper, paper coating liquid, sizing agent, paper strength enhancer, paint, adhesive, synthetic rubber latex, ink,
Polyvinyl alcohol film, vinyl chloride film,
Various industrial products such as resin products, cement admixtures, sealants, and jointing agents can be effectively used for the control of sterilization target harmful microorganisms.

In particular, the industrial germicidal composition of the present invention comprises:
Even when added to a sterilization target system in the alkaline region, more specifically, for example, a sterilization target system having a pH of 7 to 10, a stable control effect can be exhibited for a long period of time. Therefore, among the above industrial products, among others, ink,
It is preferably used as an antibacterial agent such as paints and resin emulsions, a fungicide and an algae inhibitor.

The amount of the industrial sterilizing composition of the present invention to be added may be appropriately determined depending on the system to be sterilized.
It is preferably used as a concentration of 10000 mg (total amount of active ingredient) / kg (product), and more preferably 50 to 5000 mg (total amount of active ingredient) / kg (product).

[0028]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

The abbreviations used in the following examples are shown below.

Cl-MIT: 5-chloro-2-methyl-
4-Isothiazolin-3-one MIT: 2-Methyl-4-isothiazolin-3-one BNPD: 2-Bromo-2-nitropropane-1,3-
Diol BIT: 1,2-benzisothiazolin-3-one DBNE: 2,2-dibromo-2-nitro-1-ethanol DEG: diethylene glycol PG: propylene glycol DPG: dipropylene glycol MCT: methyl carbitol (diethylene glycol monomethyl ether) ( 1) Preparation example 1 of industrial sterilization composition Cl-MIT was 1.5% by weight and MIT was 5.
Sonnen FP (Cl-MIT / MIT = 10/1 (weight ratio), active ingredient concentration 11% by weight, manufactured by Chemiclea) so that 0% by weight and BNPD are 15.0% by weight.
g, Codec 50C (MIT: 50% by weight, manufactured by Rohm and Haas) 9.7 g, and Myside AS
(BNPD: 99.9% by weight, manufactured by Nagase & Co., Ltd.) 15.2
g to 100 g of the amount of DEG remaining in the formulation,
100 g of liquid preparation was prepared by stirring and dissolving at room temperature.

Examples 2 to 19 Zonen FP, Codec 50C and Myaside AS were added to the respective solvents shown in Tables 1 and 2 so that the weight ratio in the liquid preparations would be the ratios shown in Tables 1 and 2. Liquid agents were prepared in the same manner as in Example 1 except for the above.

Comparative Examples 1 to 4 The Sonnen FP, the codec 50C and the Myaside AS are adjusted so that the weight ratio in the liquid agent is the ratio shown in Table 1.
A liquid agent was prepared in the same manner as in Example 1 except that was added to each solvent shown in Table 1.

Comparative Example 5 In the liquid formulation, Cl-MIT was 2.5% by weight and BIT was 5.
0% by weight and BNPD at 15.0% by weight, 25 g of Sonnen FP, Proxel Press Paste D (BI
T: 80% by weight, manufactured by Abyssia) 6.25 g, and
15.2 g of Myaside AS was added to an amount of the amount of the remaining amount of 100 g of the formulation, and the mixture was stirred and dissolved at room temperature to prepare 100 g of liquid agent. In Table 1, the MIT content derived from Sonnen FP is omitted because it is a very small amount.

Comparative Example 6 In the liquid formulation, Cl-MIT was 2.5% by weight and MIT was 5.
Zonen FP 25 g, codec 50C 9.5 g, and divenirol A-75 (DBNE: 75 wt%, manufactured by Keiai Kasei Co., Ltd.) 20 g so that the amount of 0% by weight and DBNE becomes 15.0% by weight, the remaining amount of 100 g of the preparation In addition to a sufficient amount of DEG, 100 g of liquid formulation was prepared by stirring and dissolving at room temperature.

(2) Antiseptic test ink (manufactured by Sakata Inx, preservative-free product, pH 8.
To 5), the industrial germicidal compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were added so that the concentration in the ink would be 0.1% by weight. Then, after leaving it sealed at 60 ° C for 2 weeks, putrefactive seeds were added and cultured at 33 ° C, and after 3 months (1
Spoilage was added weekly. ), In broth medium,
The number of bacteria other than the gelled one was measured. The results are shown in Table 1.

(3) Stability Test The industrial sterilizing compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were added to water having a pH of 9 (phosphate buffer solution) at 0.25% by weight at 40 ° C. Sealed for 7 days, then allowed to cool to room temperature and by liquid chromatography, Cl-
The residual rate of MIT was measured. The results are shown in Table 1.

Similarly, 0.25% by weight of the industrial sterilizing composition of each of Examples and Comparative Examples was added to water having a pH of 9 (phosphate buffer solution), and the mixture was left to seal at 40 ° C. for 4 days. ,
Then, the mixture was allowed to cool and returned to room temperature, and the residual ratio of BNPD (DBNE in Comparative Example 6) was measured by liquid chromatography. The results are shown in Table 1.

[0038]

[Table 1] (4) Formulation heat resistance test The industrial sterilization compositions of Examples 2 and 12 to 19 were left sealed at 60 ° C. for 14 days, and then the residual ratios of Cl-MIT and BNPD were measured by liquid chromatography. The results are shown in Table 2.

[0039]

[Table 2]

INDUSTRIAL APPLICABILITY As described above, the industrial bactericidal composition of the present invention exerts a stable control effect on bacteria, fungi, yeasts, algae, etc. for a long period of time and is therefore suitable as a control agent for these Can be used for. In particular, the industrial sterilization composition of the present invention exhibits a stable control effect over a long period of time even when added to a sterilization target system in an alkaline region, more specifically, for example, a pH 7 to 10 sterilization target system. be able to. Therefore, it can be suitably used as an antibacterial agent such as ink, paint, resin emulsion, antifungal agent, and antialgal agent.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C02F 1/50 C02F 1/50 520K 520Z 532 532C 532D 532H 532J 540 540B (72) Inventor Akira Tanaka Osaka Osaka City, Yodogawa-ku 13-85 Takeda Pharmaceutical Co., Ltd. Living environment company (72) Inventor Takayuki Sugiyama 2-chome 17-85, Yodogawa-ku Osaka, Osaka Takeda Pharmaceutical Co., Ltd. F-term in environment company (reference) 4H011 AA02 BA06 BB03 BB10 DA13 DD01 DF04

Claims (7)

[Claims] 1. 5-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-
3-one and 2-bromo-2-nitropropane-1,
For 3-diol, 1.05-30 parts by weight of 2-methyl-4-isothiazolin-3-one, and 2-bromo for 1 part by weight of 5-chloro-2-methyl-4-isothiazolin-3-one. -2-
An industrial sterilizing composition comprising nitropropane-1,3-diol in a proportion of 1.25 to 30 parts by weight. 2. Methyl 2-methyl-4-isothiazolin-3-one to 1 part by weight of 5-chloro-2-methyl-4-isothiazolin-3-one.
The industrial bactericidal composition according to claim 1, which contains isothiazolin-3-one in a ratio of 1.2 to 8 parts by weight. 3. 2-Bromo-2-, based on 1 part by weight of 5-chloro-2-methyl-4-isothiazolin-3-one.
The industrial sterilizing composition according to claim 1 or 2, which contains 2 to 12 parts by weight of nitropropane-1,3-diol. 4. 2-Bromo-2-nitropropane based on 1 part by weight of the total amount of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. The industrial sterilizing composition according to any one of claims 1 to 3, which contains 0.14 to 5 parts by weight of -1,3-diol. 5. A liquid preparation prepared by using a solvent, wherein 1 to 4% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one is contained in the liquid preparation, and 2-methyl-4-isothiazolin-3-one is added. 5 to 30
The industrial sterilizing composition according to any one of claims 1 to 3, which comprises 5% to 30% by weight of 2-bromo-2-nitropropane-1,3-diol. 6. The industrial bactericidal composition according to claim 5, wherein diethylene glycol and / or propylene glycol is used as the solvent. 7. The industrial sterilizing composition according to any one of claims 1 to 6, which is added to a system to be sterilized having a pH of 7 to 10.