JP2781835B2 - Slime control agent - Google Patents

Description

The present invention relates to a slime control agent for industrial water.

[Conventional technology]

In industrial water, for example, papermaking water and cooling water used in the pulp preparation and papermaking processes of pulp mills and paper mills, slime is formed by the propagation of microorganisms such as bacteria, yeasts, and filamentous fungi, causing various obstacles. It is known. The slime adheres to almost every part of the water-using process, such as a ruffler wall, a screen, an inlet or tie wall, a white water pit, and an inner wall of a recovered white water pipe in a papermaking process, and gradually increases in thickness, and finally comes off. For example, it mixes into pipe slurry or clogs screens and pipes. In this case, small slime lump mixed in the pulp slurry causes yellow or brown spots on the paper, so-called eyeballs, deteriorating the paper quality, and large slime lumps cause the paper to run out.
In recent years, improvement of white water recovery rate, eutrophication with additives such as starch, polyacrylamide, sediment containing inorganic filler, resin component of wood, increase of pitch-like sediment due to adhesive derived from waste paper, etc. For example, the papermaking process provides an environment more suitable for propagation of microorganisms. In particular, an improvement in the recovery rate of white water makes it easier to cause emergence of bacteria resistant to the slime control agent and a bacterial replacement phenomenon, which is a cause of a decrease in the efficacy of the control agent. For this reason, more slime control agents have been developed and used than before.

[Problems to be solved by the invention]

However, at present, there is no slime control agent capable of maintaining sufficient efficacy under such conditions, and development of a satisfactory slime control agent has been demanded.

[Means for solving the problem]

We have 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and the general formula (Wherein X represents a fluorine atom or a chlorine atom), by using the isophthalonitrile derivative represented by the formula (1) in a specific ratio, an excellent synergistic effect which could not be expected from using these compounds alone. Was obtained, and the present invention was completed based on this.

Isophthalonitrile derivatives of formula I include 2,4,5,6
-Tetrafluoroisophthalonitrile, 5-chloro-2,
4,6-trifluoroisophthalonitrile can be mentioned.

3,3,4,4-tetrachlorotetrahydrothiophene-1,1
The compounding ratio of the dioxide to the isophthalonitrile derivative of the formula I is between 30:70 and 70:30 by weight.

The slime controlling agent of the present invention is preferably used by dissolving 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and an isophthalonitrile derivative of the formula I in a solvent. In some cases, it may be a suspending or emulsifying agent. The concentration of the active ingredient is 1-95% (w / w), preferably 5-60% (w / w).

As the solvent, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and isophorone, benzene, toluene, xylene, 1,2-dimethyl-4-ethylbenzene, 1,3-dimethyl-4-ethylbenzene, and 1,4-
Aromatic hydrocarbons such as dimethyl-2-ethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, ethylene glycol dimethyl ether,
Glycol ethers such as diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate,
Glycol ester ethers such as ethylene glycol diacetate, ethyl acetate, butyl acetate, dimethyl maleate, diethyl adipate, diethyl succinate, esters such as diethyl fumarate, ethylene carbonate,
Carbonates such as propylene carbonate, halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene and chlorobenzene are used. Usually 3-methoxybutyl acetate,
Glycol ester ethers such as ethylene glycol diacetate are used. These solvents may be used alone or in combination of two or more.

The formulation of the present invention may contain a surfactant. As the surfactant, a nonionic surfactant is preferable, for example, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene alkyl phenyl ether such as polyoxyethylene nonyl phenyl ether, oxyethylene oxypropylene block polymer and the like. can give. The content of these surfactants is 0.1 to 30% (w / w) based on the whole preparation, preferably
0.5 to 10% (w / w). Further, to the slime controlling agent of the present invention, stabilizers, extenders, corrosion inhibitors, detergents and the like generally used in the production of slime controlling agents and other disinfectants can be appropriately added.

The amount of the slime control agent of the present invention added to the papermaking process varies depending on the water source, the paper, the addition method (continuous addition method, impact addition method), and the like.
00 ppm, preferably 0.5 to 50 ppm shows sufficient efficacy.

〔The invention's effect〕

Since the slime controlling agent of the present invention has an excellent slime controlling action over a long period of time, slime damage in industrial water can be prevented for a long time with a small amount of use.

 Parts in the lower formulation examples mean parts by weight.

Formulation Example 1 2,4,5,6-tetrafluoroisophthalonitrile 10 parts,
3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
10 parts of the dioxide and 80 parts of dimethyl maleate were mixed to obtain a slime control agent.

Formulation Example 2 5-chloro-2,4,6-trifluoroisophthalonitrile 20 parts, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide 10 parts and propylene carbonate 7
0 parts were mixed to obtain a slime control agent.

Formulation Example 3 8,4,5,6-tetrafluoroisophthalonitrile 8 parts,
3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
12 parts of dioxide, 77 parts of xylene and 3 parts of polyoxyethylene nonylphenyl ether (Nitsan nonion NS-210, manufactured by NOF Corporation) were mixed to obtain a slime control agent.

Formulation Example 4 10 parts of 5-chloro-2,4,6-trifluoroisophthalonitrile, 10 parts of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, propylene carbonate 40
, A 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and 10 parts of polyoxyethylene oleyl ether (Emulgen 404, manufactured by Kao Corporation) were mixed to obtain a slime control agent.

Formulation Example 5 2,4,5,6-tetrafluoroisophthalonitrile 10 parts,
3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide 10 parts, 3-methoxybutyl acetate 40 parts and diethylene glycol monoethyl ether acetate
Forty parts were mixed to obtain a slime control agent.

Test Example 1 During the newspaper production process, a test agent was added to 50 ml of white water collected from a stock inlet so that the active ingredient became 2 ppm, and the mixture was shaken at 30 ° C. for 1 hour. 10 ml of Waxman liquid medium was added to the contact white water for 1 hour, and cultured with shaking at 32 ° C. The absorbance at 660 nm of this culture was measured over time to compare the degree of inhibition of slime-forming bacteria propagation.

As reagents, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (TTD) and the following isophthalonitrile derivative were dissolved in 3-methoxybutyl acetate, and diethylene glycol It was used after diluting with ethyl ether acetate.

Isophthalonitrile derivative I-1: 2,4,5,6-tetrafluoroisophthalonitrile I-2: 5-chloro-2,4,6-trifluoroisophthalonitrile The results are shown in Table 1. The suppression time in the table is a time until the absorbance of each culture solution becomes 0.1, and the stronger the effect, the longer the suppression time. Experiment numbers 2 to 4, 7 to 9 in the table
Is a slime controlling agent of the present invention, and others are comparative examples.

Thus, the slime control agent of the present invention containing TTD and I-1 or I-2 has a longer effect at the same active ingredient concentration than the preparation containing TTD, I-1 or I-2 alone. It is known to have a time slime control action.

Test Example 2 In a stainless steel water tank having a diameter of 30 cm and a depth of 30 cm, two pieces of Lauan wood having a width of 5 cm, a length of 30 cm, and a thickness of 1.5 cm were vertically mounted as a temperature controller, a stirrer, a thermometer, and a slime measuring plate. .

Pulp 1.0% in Waxman liquid medium diluted 1000 times
And white water culture solution (culture solution obtained by culturing white water collected from the papermaking process in a Warksman liquid medium at 30 ° C. for one day) at 0.1 ml /
, And artificial white water adjusted to pH 5 with aluminum sulfate was supplied to the tank at a flow rate of 2 / hour, and the same amount of artificial white water was discharged. The same reagent agent as in Test Example 1 was added by a pump three times a day for three hours once a day so that the active ingredient became 4 ppm based on the artificial white water supplied.

The white water temperature was kept at 30 ° C., and stirring was continued. After 10 days, the slime control effect was evaluated. There are two types of white water used in the white water culture solution: white water (A) collected from the cardboard center papermaking process and white water (B) collected from the newsprint papermaking process.

For evaluation, the slime measurement plate was visually observed, and the amount of slime adhered was scored by a 10-point method.

 The outline of the scoring standard is as follows.

 0: No slime was adhered at all.

1: The slime begins to stick to a part of the measuring plate as a dot.

 2: Slime is thinly attached to about 1/3 of the measuring plate.

 3: Slime is thinly attached to about 1/2 of the measurement plate.

 4: Slime is thinly attached to about 2/3 of the measuring plate.

 5: Slime adheres thinly on the entire surface of the measurement plate.

6: Slime adheres thinly on the entire surface of the measurement plate, but partially adheres thickly.

7: Slime adheres to the entire surface of the measurement plate, and about 1/3 of the slime adheres thickly.

8: Slime adheres to the whole surface of the measurement plate, and about 1/2 is thickly adhered.

9: Slime adheres to the entire surface of the measurement plate, and about 2/3 of the slime adheres thickly.

10: Slime is thickly attached to the entire surface of the measurement plate and partially peeled off.

The amount of slime adhered is a relative and comprehensive evaluation with no slime controlling agent added and a comparative agent. Table 2 shows the results. Experiment numbers 13 to 15 and 18 to 20 in the table are slime controlling agents of the present invention, and others are comparative examples.

Thereby, the slime controlling agent of the present invention containing TTD and I-1 or I-2 is more excellent at the same active ingredient concentration than the preparation containing TTD, I-1 or I-2 alone. It is known to have a slime control action.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI // (A01N 43/10 37:34) (56) References JP-A-62-294602 (JP, A) JP-A-62-294 16401 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) A01N 43/10 A01N 37/34

Claims (1)

(57) [Claims] (1) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a compound represented by the general formula: A slime control agent comprising an isophthalonitrile derivative represented by the formula (X represents a fluorine atom or a chlorine atom) in a ratio of 30:70 to 70:30 by weight.