JP2003073214A - Industrial bactericidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial bactericidal composition capable of exhibiting excellent antibacterial and antifungal activity in an alkaline range, having low toxicity, and capable of being stably kept for a long period. SOLUTION: This industrial bactericidal composition contains a benzisothiazoline-based compound and/or a phenylurea-based compound, a natural water-soluble gum, a salt of condensate of β-naphthalenesulfonic acid with formaldehyde, and, if desired, a nonionic surfactant.

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, algae and the like.

[0002]

2. Description of the Related Art Conventionally, various industrial waters such as paper pulp mills and cooling water circulation processes, metal working oils such as cutting oils, casein, starch paste, glue, coated paper, paper coating liquid, surface In various industrial products such as sizing agents, paints, adhesives, synthetic rubber latex, printing inks, polyvinyl alcohol films, vinyl chloride films, plastic products, cement admixtures, harmful microorganisms easily propagate,
This is a cause of deterioration of quality such as product contamination and generation of offensive odor. Therefore, bactericides that exert a bactericidal effect for controlling the growth of such microorganisms are widely used. Many of such bactericides for industrial use are highly toxic, have harmful effects on the human body, and may have environmental pollution.
It cannot be used at too high a concentration.

In addition, many industrial bactericides including conventional bactericides and antibacterial agents are generally stable in the acidic region and decomposed in the alkaline region so that long-term effects could not be expected.
That is, the above-mentioned industrial bactericidal agent is added to the sterilization target system prepared in an alkaline range according to the needs of the market, for example, coating color, cutting oil, latex compound, calcium carbonate slurry, mud water polymer, fiber oil agent, etc., at a normal concentration. In that case, since the bactericidal active ingredient decomposes with time, it is necessary to increase the addition amount in anticipation of decomposition. In addition, in some cases, the decomposition product of the bactericidal active ingredient lowers the pH of the system to be sterilized, which may impair the product value. Particularly in the case of coating colors and the like, there was a case where the pH was lowered and the viscosity increased, and the stability of the formulation was poor, so that the effect was not exhibited and continuous operation of the plant was impossible.

Conventionally, in a system to be sterilized in the alkaline range, a compound stable in the alkaline range, for example, hexahydro-1,3-5-tris (2-hydroxyethyl) -s-
Triazine, hexahydro-1,3,5-triethyl-
Triazine compounds such as s-triazine and 2-hydroxyethylaminoethanol have been commonly used. However, since the triazine-based compound itself is alkaline, it has the drawbacks of changing the pH of the system to be sterilized and decomposing in the vicinity of neutrality. Further, since the bactericidal effect is weak, it is necessary to add a large amount, which is not economical.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide an industrial bactericidal composition which exhibits excellent antibacterial and antifungal properties in an alkaline range with a small amount of addition, has low toxicity, and is stably maintained for a long period of time. It is to provide things.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned objects, the present inventors have found that a benzisothiazoline compound or / and a phenylurea compound, a natural water-soluble gum, a nonionic interface as an active ingredient. A bactericidal composition containing an active agent and a salt of a β-naphthalenesulfonic acid formalin condensate, exhibits excellent antibacterial and antifungal properties in a small amount in an alkaline range, and is particularly effective as a particulate active ingredient in an aqueous preparation. The present inventors have found that the suspended state can be stably maintained for a long period of time, and have conducted further studies to complete the present invention.

That is, the present invention is characterized by containing (1) a benzisothiazoline compound or / and a phenylurea compound, a polysaccharide, a nonionic surfactant and a salt of a β-naphthalenesulfonic acid formalin condensate. (2) a benzisothiazoline-based compound having the general formula (1);

[Chemical 3] (Wherein Y ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and the A ₁ ring represents an optionally substituted benzene ring), which is the compound represented by the above (1). An industrial bactericidal composition, (3) wherein, in the general formula (1), Y ₁ is a hydrogen atom or alkyl having 1 to 8 carbon atoms, and the benzene ring represented by the A ₁ ring is an unsubstituted benzene ring. Two
The industrial bactericidal composition described in (4), wherein the benzisothiazoline-based compound is 1,2-benzisothiazolin-3-one and Nn-butyl-benzisothiazoline-3-
The industrial bactericidal composition according to any one of the above (1) to (3), which is at least one of the ONs, (5) the phenylurea-based compound has the general formula (2);

[Chemical 4] (In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a halogen atom, and R ₃ and R ₄ are the same or different, and may be bonded to a hydrogen atom or an adjacent nitrogen atom through oxygen. An industrial bactericidal composition according to any one of the above (1) to (4), which is a compound represented by a good optionally substituted hydrocarbon group), (6) in the general formula (2), R ₁ and R ₂ are the same or different and each is a halogen atom, and R ₃ and R ₄ are the same or different and may be bonded to adjacent nitrogen atoms via oxygen; The industrial bactericidal composition according to (5) above, which is a hydrocarbon group of 8, and (7) the phenylurea compound is 3- (3,4-dichlorophenyl)-.
The industrial bactericidal composition according to any one of (1) to (6) above, which is 1,1-dimethylurea, and (8) the polysaccharide is a natural water-soluble gum, wherein any one of claims 1 to 7 is characterized. (9) The natural water-soluble gum is one or more natural water-soluble gums selected from the group consisting of xanthan gum, gum arabic, locust bean gum, guar gum, karaya gum, gaddy gum and taragant gum. The industrial sterilization composition according to (8) above,
(10) 1,2-benzisothiazolin-3-one is a benzisothiazoline-based compound, 3- (3,4-dichlorophenyl) -1,1-dimethylurea is a phenylurea-based compound, xanthan gum is a polysaccharide, and a nonionic surface active agent is used. The industrial bactericidal composition according to (1) above, wherein the agent is polyoxyethylene alkylphenyl ether and the salt of β-naphthalenesulfonic acid formalin condensate is β-naphthalenesulfonic acid formalin condensate sodium salt.
Benzisothiazoline compound 30 to 50% by weight or / and phenylurea compound 15 to 40% by weight,
Polysaccharide 0.1-1.0% by weight, nonionic surfactant 2-
It relates to an industrial bactericidal composition comprising 15% by weight and 1 to 10% by weight of a salt of a β-naphthalenesulfonic acid formalin condensate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the benzisothiazoline compound used in the present invention include compounds represented by the general formula (1).

[Chemical 5] (In the formula, Y ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and the A ₁ ring represents an optionally substituted benzene ring.) In the above formula (1), the substitution represented by Y ₁ The hydrocarbon group in the hydrocarbon group which may be formed has 1 to 2 carbon atoms.
There may be mentioned 0, preferably 1 to 14 hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups and aryl groups. An alkyl group and a cycloalkyl group are preferred, and an alkyl group is more preferred.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, sec-octyl, tert-octyl, nonyl. , Carbon number such as decyl
There may be mentioned 10 alkyl groups. Preferably methyl,
1 to 1 carbon atoms such as ethyl, propyl, butyl and octyl
8 alkyl groups can be mentioned. More preferably, for example, methyl, n-butyl, n-octyl can be mentioned.

The alkenyl group has, for example, 2 carbon atoms such as vinyl, allyl, isopropenyl, 1-propenyl, 2-propenyl and 2-methyl-1-propenyl.
~ 4 alkenyl groups. Preferably vinyl,
Examples include alkenyl groups having 2 to 3 carbon atoms such as allyl.

Examples of the alkynyl group include alkynyl groups having 2 to 5 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl and pentynyl. Preferably, it has 2 carbon atoms such as ethynyl and propynyl.
~ 3 alkynyl groups.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Preferably, it has 5 to 5 carbon atoms such as cyclopentyl and cyclohexyl.
And 6 cycloalkyl groups.

Examples of the above-mentioned aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthryl and phenanthryl.

Examples of the substituent of the optionally substituted hydrocarbon group represented by Y ₁ include a hydroxyl group, a halogen atom (eg, fluoro, chloro, bromo, etc.),
Cyano group, amino group, carboxyl group, alkoxy group (eg, alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy), aryloxy group (eg, aryloxy group having 6 to 20 carbon atoms such as phenoxy group) Groups), alkylthio groups (for example, alkylthio groups having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio and butylthio) and 6 to 2 carbon atoms.
And the arylthio group of 0 (eg, phenylthio group). Preferred are a halogen atom and an alkoxy group. These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

Of the above-mentioned optionally substituted hydrocarbon groups represented by Y ₁ , unsubstituted hydrocarbon groups are preferred, among which alkyl groups, especially methyl, ethyl, propyl, n-butyl are preferred. , N-octyl, and other alkyl groups having 1 to 8 carbon atoms are preferable, and methyl, n-butyl, and n-octyl are more preferable. Therefore, preferable examples of Y ₁ include a hydrogen atom, methyl, n-butyl and n-octyl.

In the benzisothiazoline compound represented by the above formula (1), the substituent of the benzene ring represented by A ₁ ring is a substituent of the optionally substituted hydrocarbon group represented by Y _1. Examples thereof include the same ones as described above, preferably a halogen atom and an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl). These substituents may be the same or different and may be substituted by 1 to 4, preferably 1 or 2.

Specific examples of the benzisothiazoline type compound represented by the above formula (1) include, for example, 1,2-benzisothiazolin-3-one (hereinafter abbreviated as BIT),
Nn-butyl-benzisothiazolin-3-one and the like can be mentioned.

The benzisothiazoline compounds used in the present invention are salts thereof, for example, alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, ammonia, ethylenediamine, 1,6.
It may be used in the form of a salt with an aliphatic amine such as hexamethylenediamine, an aromatic amine such as aniline, a heterocyclic amine such as pyridine, pyrrolidine, morpholine and methylpyridine. Of these salts, preferably, alkali metals such as sodium and potassium, ammonia,
Examples thereof include aliphatic amines such as ethylenediamine and heterocyclic amines such as pyridine.

In the present invention, the benzisothiazoline compound as a raw material can be produced by a known technique, but a commercially available product may be used. Examples of commercially available products include Proxel Press Paste P6 (trade name) (1, 2
-Benzisothiazolin-3-one 80% by weight, manufactured by Abyssia), Bankish 100 (trade name) (Nn-butyl-2-benzisothiazolin-3-one 95% by weight,
Manufactured by Abyssia) and the like.

Examples of the phenylurea compound used in the present invention include compounds represented by the general formula (2).

[Chemical 6] (In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a halogen atom, and R ₃ and R ₄ are the same or different, and may be bonded to a hydrogen atom or an adjacent nitrogen atom through oxygen. In the general formula (2), examples of the halogen atom represented by R ₁ and R ₂ include halogen atoms such as fluoro, chloro, and bromo. Preferred is chloro.
Examples of the hydrocarbon group represented by R ₃ and R ₄ that may be bonded to adjacent nitrogen atoms via oxygen and may be substituted include a hydrocarbon group having 1 to 18 carbon atoms. Examples thereof include an alkoxyl group, an alkyl group,
Examples thereof include an alkenyl group, an alkynyl group, a cycloalkyl group and an aryl group. Preferred is an alkyl group.

Examples of the alkoxyl group represented by R ₃ and R ₄ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, Isooctyloxy,
Examples thereof include alkoxyl groups having 1 to 10 carbon atoms such as sec-octyloxy, tert-octyloxy, nonyloxy and decyloxy. Preferably, an alkoxyl group having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, octyloxy and the like can be mentioned. More preferably, for example, methoxy, n-butoxy, n-octyloxy can be mentioned.

Examples of the alkyl group represented by R ₃ and R ₄ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, sec- Examples thereof include alkyl groups having 1 to 10 carbon atoms such as octyl, tert-octyl, nonyl and decyl.
Preferably, an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, octyl and the like can be mentioned. More preferably, for example, methyl, n-butyl, n-octyl can be mentioned.

Examples of the alkenyl group represented by R ₃ and R ₄ include alkenyl groups having 2 to 4 carbon atoms such as vinyl, allyl, isopropenyl, 1-propenyl, 2-propenyl and 2-methyl-1-propenyl. Is mentioned. Preferred are alkenyl groups having 2 to 3 carbon atoms such as vinyl and allyl.

Examples of the alkynyl group represented by R ₃ and R ₄ include alkynyl groups having 2 to 5 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl and pentynyl. Preferred are alkynyl groups having 2 to 3 carbon atoms such as ethynyl and propynyl.

Examples of the cycloalkyl group represented by R ₃ and R ₄ include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Preferred are cycloalkyl groups having 5 to 6 carbon atoms such as cyclopentyl and cyclohexyl.

Examples of the aryl group represented by R ₃ and R ₄ include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthryl and phenanthryl. Preferred is an aryl group having 6 carbon atoms such as phenyl.

Specific examples of the phenylurea compound represented by the above formula (2) include 3- (3,4-dichlorophenyl) -1,1-dimethylurea (hereinafter abbreviated as DCMU) and 3- (4 -Monochlorophenyl) -1,1-dimethylurea, 3- (4-monochlorophenyl) -1-
Methoxy-1-methylurea, 3- (4-monochlorophenyl) -1-butynyl-1-methylurea, 3-
(3,4-Dichlorophenyl) -1-methoxy-1-methylurea, 3- (3,4-dichlorophenyl) -1-
Methyl-1-propenylurea, 3- (3,4-dichlorophenyl) -1-isopropenyl-1-propynyl and the like can be mentioned. Preferably DCMU is used.

In the present invention, the phenylurea compound can be produced by a known technique, but a commercially available product may be used. Examples of commercially available products include Preventol A6 (trade name) (DCMU 98% by weight, manufactured by Bayer)
And so on.

As the polysaccharide used in the present invention, a natural water-soluble gum is preferably used. Examples of natural water-soluble gums include xanthan gum, gum arabic, locust bean gum, guar gum, karaya gum,
Gaddy gum and taragant gum, arabinogalactan, dextran and the like can be mentioned, with preference given to xanthan gum.

The natural water-soluble gum used in the present invention can be obtained, for example, by subjecting a raw material collected from a natural tree such as a leguminous plant by a known method to processing such as purification and pulverization. You may use. Examples of such commercially available products include Guarcoal (manufactured by Sanei Pharmaceutical Trading Co., Ltd.) and Karayacol (Sanei Pharmaceutical Trading Co., Ltd.).
Manufactured by Sanei Pharmaceutical Trading Co., Ltd., Locust Call manufactured by Sanei Pharmaceutical Trading Co., Ltd., and the like.

As the nonionic surfactant, a nonionic surfactant represented by the following formula (3) can be used.

[Chemical 7] (In the formula, A ₂ represents a benzene ring which may be substituted with a vinyl group or a styryl group, and n represents 1 or 2.) The number of the vinyl group or the styryl group as the substituent of the benzene ring is 1 to 3. When there are a plurality of substituents, they may be the same or different. The benzene ring in the styryl group may be substituted, and examples of such a substituent include a hydroxyl group, a halogen atom (for example, fluoro,
Chloro, bromo, etc.), cyano group, amino group, carboxyl group, alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, etc., having 1 to 4 carbon atoms), aryloxy group (eg, phenoxy group, etc.) 6-20 aryloxy groups, etc.), alkylthio groups (for example, alkylthio groups having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio, butylthio, etc.) and arylthio groups having 6 to 20 carbon atoms (eg, phenylthio group, etc.), etc. Is mentioned. Preferred are a halogen atom and an alkoxy group. These substituents are the same or different and are 1 to 5, preferably 1
~ 3 may be substituted. A nonionic surfactant having an HLB of 10 or more, more preferably about 10 to 15 can be used. Specifically, for example, polyoxyethylene alkyl phenyl ether, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid ester, Examples thereof include polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene alkyl ether. Preferably, polyoxyethylene alkylphenyl ether is used.

The nonionic surfactant used in the present invention can be easily produced by a known method, but a commercially available product may be used. Examples of such commercially available products include Emulgen A-60 (manufactured by Kao) and Emulgen A-90.
(Made by Kao), Emulgen PP-290 (made by Kao), etc. are mentioned.

The salt of the β-naphthalenesulfonic acid formalin condensate used in the present invention is, for example, β-
Naphthalenesulfonic acid formalin condensate sodium salt,
Examples thereof include β-naphthalenesulfonic acid formalin condensate potassium salt and β-naphthalenesulfonic acid formalin condensate ammonium, and preferably β-naphthalenesulfonic acid formalin condensate sodium salt.

The salt of the β-naphthalenesulfonic acid formalin condensate can be easily produced by a known method.
Moreover, you may use a commercially available thing. Examples of such commercially available products include Demol NL (manufactured by Kao), Demol N
(Made by Kao), Demol MS (made by Kao) and the like.

The industrial bactericidal composition of the present invention comprises about 30 to 50% by weight of a benzisothiazoline compound or / and about 15 to 40% by weight of a phenylurea compound.
About 0.1 to 1.0% by weight of a polysaccharide, about 1 to 15% by weight of a nonionic surfactant, and about 1 to 10% by weight of a salt of a β-naphthalenesulfonic acid formalin condensate may be blended. Preferably, the benzisothiazoline compound is about 30-40% by weight or / and the phenylurea compound is about 20-30% by weight, and the polysaccharide is about 0.2-.
It may be added in an amount of about 0.6% by weight, about 5 to 15% by weight of a nonionic surfactant, and about 1 to 5% by weight of a salt of a β-naphthalenesulfonic acid formalin condensate.

The compounding of the above compounds is not particularly limited as long as it is a solvent capable of dissolving or dispersing these compounds. Examples of such a solvent include water, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert-butanol, 3-methyl-
Alcohol-based solvent such as 3-methoxybutanol, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol solvents such as tripropylene glycol monomethyl ether, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as propylene carbonate, For example dioxane, tetrahydrofuran, Ether solvents such as Chirueteru, for example ethyl acetate, butyl acetate, isobutyl acetate,
Ester-based solvents such as 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, and dimethyl succinate, such as benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, Aromatic solvents such as ethylbiphenyl, diethylbiphenyl and solvent naphtha, for example, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform and methylene chloride, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile and N-methylpyrrolidone. And polar solvents.

Further, an industrially used aliphatic petroleum solvent or aromatic petroleum solvent may be used. Examples of the aliphatic petroleum solvent include mineral spirits. As the aromatic petroleum solvent, commercially available products such as MSP (distillation range 90 to 120 ° C., specific gravity (1
5/4 ° C) 0.820 or more, mixed aniline point 26 ° C or less, aromatic content (volume%) 70 or more), Superzole 100 (distillation range 95 to 111 ° C, specific gravity (15/4 ° C))
0.825 or more, mixed aniline point 26 ° C, aromatic content (volume%) 75 or more), Pecazole ARO-80 (distillation range 104 to 123 ° C, specific gravity (15/4 ° C) 0.832
Above, mixed aniline point 26 ℃, aromatic content (volume%) 7
5.9), Swazol 100 (distillation range 106-116)
℃, specific gravity (15/4 ℃) 0.835 or more, mixed aniline point 24.6 ℃ or less, aromatic content (volume%) 76.4),
Swazol 200 (distillation range 132-144 ° C, specific gravity (15/4 ° C) 0.844, mixed aniline point 23.8)
℃, aromatic content (volume%) 80.9), MHS (distillation range 140-170 ℃, specific gravity (15/4 ℃) 0.86-
0.88, mixed aniline point 11-12 ° C, aromatic content (volume%) 98 or more), high arom 2S (distillation range 15
2 to 187 ° C., specific gravity (15/4 ° C.) 0.816, mixed aniline point 47 ° C. or lower, aromatic content (volume%) 45 to 5
5), Swazol 310 (distillation range 153-177 ° C.,
Specific gravity (15/4 ° C.) 0.817, mixed aniline point 43.
6 ° C., aromatic content (volume%) 51.0), Supersol 150 (distillation range 153-197 ° C., specific gravity (15/4)
℃) 0.815, mixed aniline point 21.5 ℃, aromatic content (volume%) 50 or more), Shoishi Hysol (distillation range 1
53-198 ° C, specific gravity (15.6 / 15.6 ° C) 0.8
18, aromatic content (volume%) 55), HAWS (distillation range 154-190 ° C, specific gravity (15/4 ° C) 0.822,
Aromatic content (volume%) 50), Superzole 1500
(Distillation range: 155 to 171 ° C, specific gravity (15/4 ° C))
869, mixed aniline point 14.6 ° C, aromatic content (volume%) 98 or more), Nisseki Hysol 100 (distillation range 15
5 to 180 ° C, specific gravity (15/4 ° C) 0.870 to 0.8
80, mixed aniline point 15 ° C. or lower, aromatic content (volume%) 99.0 or higher), Vegasol R-100 (distillation range 156 to 174 ° C., specific gravity (15/4 ° C.) 0.874, mixed aniline point 14 ° C. , Aromatic content (volume%) 96.
4), Solvesso 100 (distillation range 158-177 ° C,
Specific gravity (15/4 ℃) 0.870, Mixed aniline point 14
℃, aromatic content (volume%) 98.0), MSS (distillation range 158-180 ℃, specific gravity (15.6 / 15.6 ℃)
0.86 to 0.89, mixed aniline point 13 to 14 ° C, aromatic content (volume%) 98 or more), SHELLSOL A
(Distillation range 160 to 182 ° C, specific gravity (15/4 ° C))
873, aromatic content (volume%) 98), Swazol 10
00 (distillation range 162-176 ℃, specific gravity (15/4 ℃)
0.878, mixed aniline point 12.7 ° C, aromatic content (volume%) 99.7), Idemitsu Ipsol 100 (distillation range 162-179 ° C, specific gravity (15/4 ° C) 0.875,
Mixed aniline point 13.5 ° C, aromatic content (volume%) 9
9.5 or more), Shoishi Tokusan Hisol (distillation range 162 to 1)
80 ° C, specific gravity (15/4 ° C) 0.881, mixed aniline point 12.6 ° C, aromatic content (volume%) 99.99), Swazol 1500 (distillation range 180-207 ° C, specific gravity (15/4 ° C) ) 0.886, mixed aniline point 16.5
℃, aromatic content (volume%) 98.8), Nisseki Hysol 150 (distillation range 182 to 216 ℃, specific gravity (15/4
C.) 0.887 to 0.904, mixed aniline point 17 ° C. or lower, aromatic content (volume%) 99.0 or higher), Supersol 1800 (distillation range 183 to 208 ° C., specific gravity (15)
/ 4 ° C) 0.889, mixed aniline point 15.7 ° C, aromatic content (volume%) 99 or more), Solvesso 150 (distillation range 185-211 ° C, specific gravity (15/4 ° C) 0.89).
6, mixed aniline point 18.3 ℃, aromatic content (volume%)
97.3), Idemitsu Ipsol 150 (distillation range 186-
205 ° C, specific gravity (15.6 / 15.6 ° C) 0.895,
Mixed aniline point 15.2 ° C, aromatic content (volume%) 9
9.5 or more), SHELLSOL AB (distillation range 18
7-213 ° C, specific gravity (15/4 ° C) 0.894, aromatic content (volume%) 99.5), Pegasol R-150 (distillation range 191-212 ° C, specific gravity (15/4 ° C) 0.89
0, mixed aniline point 18 ° C, aromatic content (volume%) 9
7.2), Swazol 1800 (distillation range 197-23
7 ° C., specific gravity (15/4 ° C.) 0.940, mixed aniline point 14.0 ° C., aromatic content (volume%) 99.6) and the like. Of these, water and / or glycol solvents are preferable. These solvents may be used alone or in combination of two or more kinds.

The industrial germicidal composition of the present invention may optionally contain a pH adjuster. Examples of pH adjusters include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, aqueous ammonia,
Triethanolamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triisopropanolamine, trisodium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, monoethanolamine, diethanolamine, diisopropanolamine, hydrochloric acid, citric acid, oxidation Examples include magnesium, nitric acid, sulfuric acid, and the like.

Further, the industrial bactericidal composition of the present invention has known additives such as other algae-proofing agents and / or fungicides, surfactants other than nonionic surfactants, and oxidizing agents depending on its purpose and use. You may add an inhibitor, a light stabilizer, a defoaming agent, etc.

Other algicides and / or fungicides include organic compounds such as 3-iodo-2-propynyl-butyl-carbamate, diiodomethyl-p-tolylsulfone and p-chlorophenyl-3-iodopropargylformal. Iodine compounds, for example thiocarbamate compounds such as tetramethylthiuram disulfide,
Nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile, such as N- (fluorodichloromethylthio) -phthalimide and N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl-
Haloalkylthio compounds such as sulfamides, pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, pyrithione compounds such as zinc pyrithione and sodium pyrithione, such as 2- (4- Thiocyanomethylthio)
Benzothiazole-based compounds such as benzothiazole, for example, methyl-2-benzimidazole carbamate, 2
Imidazole compounds such as-(4-thiazolyl) -benzimidazole, e.g. 3-benzo [b] thien-2
Oxathiazine compounds such as -yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide, for example triazine compounds such as 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine A compound, for example, a triazole compound such as α-t-butyl-α (p-chlorophenylethyl) -1H-1,2,4-triazole-1-ethanol (conventional name tebuconazole), for example, 3,3,4,4- Examples thereof include thiophene compounds such as tetrachlorotetrahydrothiophene-1,1-dioxide. These other algae and / or fungicides may be used alone or in combination of two or more. Further, the blending ratio of these is appropriately determined depending on the dosage form, purpose and use.

As the surfactant other than the nonionic surfactant, for example, known surfactants such as soaps, anionic surfactants, cationic surfactants, amphoteric surfactants and polymer surfactants. And preferably an anionic surfactant. These are used instead of or together with nonionic surfactants.

Examples of the anionic surfactants include alkylbenzene sulfonic acid metal salts, alkylnaphthalene sulfonic acid metal salts, polycarboxylic acid type surfactants, dialkylsulfosuccinic acid ester metal salts, polyoxyethylene distyrenated phenyl ether sulfate ammonium salts. , Lignin sulfonic acid metal salts and the like.
Further, as these metal salts, for example, sodium salts,
Examples thereof include potassium salt and magnesium salt.

As the antioxidant, for example, 2,6
-Di-t-butyl-4-methylphenol, 2,2'-
Phenol-based antioxidants such as methylenebis [4-methyl-6-t-butylphenol], for example, amine-based antioxidants such as alkyldiphenylamine and N, N′-di-s-butyl-p-phenylenediamine. .

These surfactants and antioxidants other than the nonionic surfactant are added in an amount of about 0.1 to 5 parts by weight per 100 parts by weight of the liquid agent, for example, in the case of the liquid agent. Examples of the light stabilizer include bis (2,2,2
Examples thereof include hindered amine light stabilizers such as 6,6-tetramethyl-4-piperidyl) sebacate. Such a light stabilizer is, for example, in the case of a liquid agent, a liquid agent 10
About 0.1 to 10 parts by weight is added to 0 parts by weight.

The industrial bactericidal composition of the present invention is a known agent such as a liquid agent (including a water suspension agent and an oil agent), a paste agent, a powder agent, a granule agent, a microcapsule, etc. depending on its purpose and use. It can be used by formulating into a mold.
In addition, it may be prepared as an inclusion compound, or may be prepared by supporting it on montmorillonite (smectites) such as layered silicate or adsorbing it on clay, silica, talc or the like.

The industrial bactericidal composition of the present invention obtained as described above can exert excellent effects as a controlling agent against bacteria, mold, yeast, algae and the like. Therefore, for example, pulp and paper mills, various industrial water such as cooling water circulation process, oil for metal processing such as cutting oil, casein, starch paste, glue, coated paper, coating liquid for paper, surface sizing agent, paint, Adhesive, synthetic rubber latex, printing ink,
Polyvinyl alcohol film, vinyl chloride film,
It can be effectively used for controlling harmful microorganisms in various industrial products such as plastic products, cement admixtures, sealing agents and jointing agents. More specifically,
For example, it is suitable for use as a slime control agent in paper pulp mills and cooling water circulation processes, metalworking oils, casein, starch coating solutions, preservatives for resin products, paints, resins, inks, and industrial germicides such as silicone sealing agents. To be

The amount of the industrial composition of the present invention to be added may be appropriately determined depending on the object of application, but it is about 10 to 10.
It is preferably used as a concentration of 20000 mg (active ingredient) / kg (product), preferably about 100 to 10000 mg (active ingredient) / kg (product). The active ingredient here means a benzisothiazoline compound or / and a phenylurea compound.

[0048]

[Example] [Example 1] Preventol A6 (trade name)
(DCMU 98% by weight, manufactured by Bayer) 20 parts by weight, demole NL (trade name) (β-naphthalenesulfonic acid formalin condensate sodium salt 41%, manufactured by Kao) 3 parts by weight, Emulgen A-60 (trade name) (polyoxy) Ethylene alkyl phenyl ether HLB12.8, manufactured by Kao) 8 parts by weight, Kojin (trade name) (xanthan gum, manufactured by Kojin)
0.5 parts by weight, 0.1 parts by weight of Nopco 8034L (trade name) (silica silicone antifoaming agent, manufactured by San Nopco) and 68.4 parts by weight of water were mixed, and T. K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was bead milled (liquid flow rate 5
L / min, bead particle size φ2 mm, number of passes 2 times) to obtain an aqueous preparation.

Example 2 30 parts by weight of Preventol A6 (trade name) (98% by weight of DCMU, manufactured by Bayer),
Demol NL (trade name) (β-naphthalenesulfonic acid formalin condensate sodium salt 41%, manufactured by Kao) 4 parts by weight, Emulgen A-90 (trade name) (polyoxyethylene alkylphenyl ether HLB14.5, manufactured by Kao) 9 Parts by weight, Eugene (trade name) (xanthan gum,
Kokijin) 0.3 parts by weight, Nopco 8034L (trade name)
(Silica-silicone defoaming agent, manufactured by San Nopco) 0.1 part by weight and 56.6 parts by weight of water were mixed, and T.I. K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was bead milled (liquid flow rate 5 L / min, bead diameter φ2 mm, number of passes 2
), And an aqueous preparation was obtained.

Example 3 Proxel Press Paste P
6 (Brand name) (BIT 80% by weight, manufactured by Abyssia) 25 parts by weight, Demol NL (Brand name) (β-naphthalenesulfonic acid formalin condensate sodium salt 41%, manufactured by Kao) 5
Parts by weight, Emulgen A-90 (trade name) (polyoxyethylene alkylphenyl ether HLB14.5, manufactured by Kao) 7 parts by weight, Kerzan (trade name) (xanthan gum, manufactured by CPI Kelco) 0.4 parts by weight, Nopco 8034
0.1 parts by weight of L (trade name) (silica silicone antifoaming agent, manufactured by San Nopco) and 62.5 parts by weight of water are mixed,
T. K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was bead milled (liquid flow rate 5 L / min, bead diameter φ2 m).
m, the number of passes was twice) to obtain an aqueous preparation.

Example 4 Proxel Press Paste P
6 (trade name) (BIT 80% by weight, manufactured by Abyssia) 37.
5 parts by weight, demole NL (trade name) (β-naphthalenesulfonic acid formalin condensate sodium salt 41%, manufactured by Kao) 5 parts by weight, Emulgen A-60 (trade name) (polyoxyethylene alkylphenyl ether HLB12.
8, made by Kao) 9 parts by weight, Kerzan (trade name) (xanthan gum, made by CPI Kelco) 0.3 parts by weight, Nopco 80
34 L (trade name) (silica silicone antifoaming agent, manufactured by San Nopco) was mixed with 0.1 part by weight of water and 48.1 parts by weight of T.I. K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was bead milled (liquid flow rate 5 L / min, bead diameter φ2
mm, the number of passes was twice) to obtain an aqueous preparation.

Comparative Example 1 Proxel Press Paste P
6 (trade name) (BIT 80% by weight, manufactured by Abyssia) 25 parts by weight, Emulgen A-90 (trade name) (polyoxyethylene alkylphenyl ether HLB14.5, manufactured by Kao) 12 parts by weight, Kerzan (trade name) (xanthan gum) , Made by CPI Kelco) 0.4 parts by weight, Nopco 8034
0.1 parts by weight of L (trade name) (silica silicone antifoaming agent, manufactured by San Nopco) and 62.5 parts by weight of water are mixed,
T. K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was bead milled (liquid flow rate 5 L / min, bead diameter φ2 m).
m, the number of passes was twice) to obtain an aqueous preparation.

Comparative Example 2 Proxel Press Paste P
6 (trade name) (BIT 80% by weight, manufactured by Abyssia) 37.
5 parts by weight, Kerzan (trade name) (xanthan gum, manufactured by CPI Kerco) 0.3 part by weight, Nopco 8034L (trade name) (silica silicone-based defoaming agent, manufactured by San Nopco)
1 part by weight and 62.1 parts by weight of water are mixed, and T. K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was pulverized with a bead mill (liquid flow rate 5 L / min, bead diameter φ2 mm, number of passes twice) to obtain an aqueous preparation.

[Comparative Example 3] 30 parts by weight of Preventol A6 (trade name) (DCMU 98% by weight, manufactured by Bayer)
Emulgen A-90 (trade name) (polyoxyethylene alkylphenyl ether HLB14.5, made by Kao) 1
3 parts by weight, Kojin (trade name) (xanthan gum, manufactured by Kojin) 0.3 parts by weight, Nopco 8034L (trade name) (silica silicone-based defoamer, manufactured by San Nopco) 0.1 part by weight and water 56.6 parts by weight Parts, and K. The mixture was stirred with a homodisper for 1 hour. Next, this solution was pulverized with a bead mill (liquid flow rate 5 L / min, bead diameter φ2 mm, number of passes twice) to obtain an aqueous preparation.

[Test Example 1] Examples 1 to 4 and Comparative Example 1
80m of each preparation obtained in ~ 3 in a 100mL glass bottle
L was placed and left in a thermostat at 40 ° C. for 30 days, and sedimentation was observed. The height of sedimentation formed was expressed as a ratio to the total height of the liquid surface of the preparation placed in a glass bottle, and the results are shown in Table 1.

[0056]

[Table 1]

[0057]

INDUSTRIAL APPLICABILITY The industrial bactericidal composition of the present invention has good fluidity and good dispersibility, the suspension state of the active ingredient in the aqueous preparation is stably maintained for a long period of time, and is excellent even when used in a small amount. Antibacterial and antifungal properties can be desired.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C02F 1/50 C02F 1/50 532C 532D 532H 532J 540 540B 550 550D C08K 5/21 C08K 5/21 5/46 5/46 C08L 5/00 C08L 5/00 (72) Inventor Junichi Miyake 2-1785, 13-33honmachi, Yodogawa-ku, Osaka-shi, Osaka Prefecture Takeda Pharmaceutical Co., Ltd. Living Environment Company F-term (reference) 4H011 AA02 BA01 BA06 BB10 BB14 BC03 BC07 BC19 DA15 DC04 DC05 DD01 DD07 DG11 DH10 4J002 AB051 ET016 EV316 FD186 FD317

Claims (10)

[Claims] 1. A benzisothiazoline compound or /
And a phenylurea-based compound, a polysaccharide, a nonionic surfactant, and a salt of a β-naphthalenesulfonic acid formalin condensate, which is an industrial germicidal composition. 2. A benzisothiazoline compound is represented by the general formula (1): (Wherein Y ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and the A ₁ ring represents an optionally substituted benzene ring). Item 1. The industrial sterilizing composition according to Item 1. 3. In the formula (1), Y ₁ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the benzene ring represented by A ₁ ring is an unsubstituted benzene ring. The industrial sterilizing composition described. 4. The benzisothiazoline compound is 1,
The industrial germicidal composition according to any one of claims 1 to 3, which is at least one of 2-benzisothiazolin-3-one and Nn-butyl-benzisothiazolin-3-one. 5. A phenylurea compound is represented by the general formula (2): (In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a halogen atom, and R ₃ and R ₄ are the same or different, and may be bonded to a hydrogen atom or an adjacent nitrogen atom through oxygen. The industrial bactericidal composition according to any one of claims 1 to 4, which is a compound represented by a good optionally substituted hydrocarbon group. 6. In the general formula (2), R ₁ and R ₂ are the same or different and are halogen atoms, and R ₃ and R ₄ are the same or different and are bonded to adjacent nitrogen atoms via oxygen. The industrial sterilizing composition according to claim 5, which is a hydrocarbon group having 1 to 8 carbon atoms which may be substituted. 7. The phenylurea compound is 3- (3,3
4-Dichlorophenyl) -1,1-dimethylurea, The industrial sterilizing composition according to any one of claims 1 to 6. 8. The polysaccharide is a natural water-soluble gum.
The industrial sterilizing composition according to any one of 1 to 7. 9. The industrial sterilizer according to claim 8, wherein the natural water-soluble gum is at least one natural water-soluble gum selected from the group consisting of xanthan gum, gum arabic, locust bean gum, guar gum, karaya gum, gaddy gum and taragant gum. Composition. 10. A benzisothiazoline compound is 1, 2
-Benzisothiazolin-3-one, phenylurea compound is 3- (3,4-dichlorophenyl) -1,1-
The industry according to claim 1, wherein dimethylurea, the polysaccharide is xanthan gum, the nonionic surfactant is polyoxyethylene alkylphenyl ether, and the salt of β-naphthalenesulfonic acid formalin condensate is β-naphthalenesulfonic acid formalin condensate sodium salt. Disinfectant composition.