JP2000086413A - Slime-controlling agent composition and slime control - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a slime-controlling agent composition capable of exerting a high effect under any of acid, neutral and alkaline paper-making conditions by including a specific hydantoin-based compound, dibromo-nitrilopropionamide, and a specific isophthalonitrile-based compound. SOLUTION: This composition is obtained by including as an active ingredient (A) a hydantoin-based compound (pref., e.g. 1-bromo-3-chloro-5,5- dimethylhydantoin) of formula I (R1 and R2 are each Cl or Br; and R3 and R4 are each H or an 1-12C alkyl), (B) 2,2-dibromo-3-nitrilopropionamide, and (C) an isophthalonitrile-based compound (e.g. 2,4,5,6-tetrachloroisophthalonitrile) of formula II (R5 to R8 are each F or Cl). Preferably, the weight ratio of A to (B+C) is (1 to 0.05) to (1 to 20) and the weight ratio of B to C is (1 to 0.1) to (1 to 4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slime control agent composition and a slime control method, and more particularly, to a slime control agent for effectively suppressing obstacles caused by slime generated in process water of pulp mills and paper mills. The present invention relates to a composition and a slime control method.

[0002]

2. Description of the Related Art It is well known that in a pulp mill and a paper mill, the growth of microorganisms in the water used in the process causes various problems.
For example, white water in a paper machine of a paper mill contains a large amount of a substance that is a nutrient source of microorganisms, and various chemicals and fillers are added thereto. In a very favorable environment for the propagation of When microorganisms proliferate in white water, the microorganisms and their metabolites aggregate to form sticky substances, so-called slime. , Causing stains, spots, eyeballs, etc. on the paper, which may impair the quality of the product, and cause other obstacles in the process such as paper breakage, clogging of wires or blankets, corrosion, odor, etc. Becomes The white water as the direct contact with the products of the paper, also because they are incorporated into some paper, where resulting slime often present serious problems than those in the general cooling water or process water.

[0003] Papermaking methods include an acid papermaking method in which papermaking is carried out at a pH of 4 to 6, a neutral papermaking method and an alkaline papermaking method in which papermaking is carried out at a pH of 6 to 8, and recently, an in-process apparatus. Neutral and alkaline papermaking methods are increasing because of low corrosion, the ability to use inexpensive calcium carbonate as a filler, and the excellent quality of the paper produced. On the other hand, in the papermaking process, the recycling and reuse of white water has progressed, and it has come to be operated in a condition close to closed. As the recycling and reuse of white water proceeds with the alkaline papermaking method,
In addition to the concentration of nutrients in the water, the water temperature rises, and the optimal pH for the growth and growth of microorganisms is in the range of 6 to 8, making the system extremely convenient as a habitat for microorganisms. The slime problem has become more serious than that of the acidic papermaking method. On the other hand, the rate of paper recycling is increasing due to environmental issues such as the protection of forest resources. Recycled waste paper is added with a large amount of various chemicals in order to improve the quality and yield of paper, making it a more favorable condition for the growth of microorganisms.
Slime control has become increasingly important.

Various slime control agents have been proposed for controlling microorganisms and preventing slime damage in process water of pulp mills and paper mills. For example, 2,2-dibromo-3-nitrilopropionamide,
Organic bromine-based compounds represented by 2-bromo-4-hydroxyacetophenone, 1-bromoacetoxy-2-propanol, 1,4-bisbromoacetoxy-2-butene and the like (JP-B-52-12247, JP-B-52-12247) −46
285, JP-A-8-198715), 5-
Α-chlorobenzaldoxime, an isothiazolone-based compound represented by a mixture of chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (JP-A-6-49797) hydantoin-based compound (JP-B 51-33171 and JP-Hei 8-176996) have been proposed.

Further, a combination of a hydantoin compound and 2,2-dibromo-3-nitrilopropionamide (JP-A-9-31675) and a combination of 2,2-dibromo-3-nitrilopropionamide and isophthalonitrile ( JP-A-62-402) has also been proposed.

[0006] However, most of the conventional slime control agents have a pH of 4 to 6 which has conventionally been the mainstream.
And the pH is from 6 to 8.
Under the conditions of neutral papermaking and alkaline papermaking, these slime control effects are not always sufficiently high. Furthermore, recently, the usage ratio of waste paper has increased and slime disorders have been diversified, and it has not been satisfactory from the viewpoint of slime control. When a conventional slime control agent is applied to a neutral papermaking / alkali papermaking system, it is difficult to obtain the same effect as that of an acidic papermaking system. The disadvantage was inevitable.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a paper
An object of the present invention is to provide a slime control agent composition and a slime control method that are not affected by changes in operating conditions of the pulp industry and exhibit high effects not only in acidic papermaking but also in neutral papermaking and alkali papermaking conditions.

[0008]

SUMMARY OF THE INVENTION The inventor of the present invention has taken into account the conditions of neutral papermaking and alkaline papermaking, and newly emerging problems such as an increase in the ratio of waste paper, and has endured such an environment.
As a result of studying a slime control agent exhibiting an effect, a specific hydantoin-based compound was further added to 2,2-dibromo-3-nitrilopropionamide (hereinafter abbreviated as “DBNPA”) and a specific isophthalonitrile-based compound. It has been found that a synergistic effect is exerted by combining and applying the present invention, and it has been found that this object can be sufficiently achieved, and the present invention has been completed.

That is, the invention of claim 1 is a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ and R ² may be the same or different from each other, and at least one is a chlorine or bromine atom;
The other represents any of chlorine, bromine and hydrogen atoms, and R ³ and R ⁴ may be the same or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). Hydantoin-based compound and DBNPA
And the general formula (II)

Embedded image (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a fluorine or chlorine atom) and an isophthalonitrile-based compound represented by the following formula: It is a slime control agent composition characterized by containing, wherein the invention of claim 2 is characterized in that the hydantoin-based compound is 1-bromo-3-chloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5. A slime control agent composition which is at least one selected from -dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin. The invention of claim 3 provides a hydantoin-based compound, DBNPA and isophthalonitrile. Weight ratio of 1: 0.05 to 1:20, and the weight ratio of DBNPA and isophthalonitrile compound is 1: 0. A slime control agent composition which is combined so as to be 1: 4, and the invention of claim 4 is a slime control method comprising adding the slime control agent composition to process water in a pulp mill or a paper mill. The invention according to claim 5 is a slime control method in which process water in a pulp mill or a paper mill is white water discharged from an alkaline paper machine.

[0010]

In hydantoin compound of the general formula (I) in DETAILED DESCRIPTION OF THE INVENTION The present invention, wherein R ¹ and R ² may be independently identical or different from each other, at least one of chlorine or bromine atom And the other represents any of chlorine, bromine and hydrogen atoms, and R ³ and R ⁴ may be the same or different from each other, and each represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
2 represents an alkyl group. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, n-hexyl group, 2-
Examples include an ethylhexyl group, an n-octyl group, and an n-dodecyl group. An alkyl group having 13 or more carbon atoms is not preferable because the water solubility of the hydantoin-based compound becomes poor. Specific examples of the hydantoin-based compound represented by the general formula (I) include 1-bromo-3-chloro-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-diethylhydantoin, Bromo-3-chloro-hydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin and the like can be mentioned.

In the isophthalonitrile compound of the general formula (II) according to the present invention, R ⁵ , R ⁶ , R ⁷ and R ⁸
May be the same or different, and each represents a fluorine atom or a chlorine atom. Specific examples of the isophthalonitrile-based compound represented by the general formula (II) include 2,4,5,6-tetrachloroisophthalonitrile and 5-chloro-2,4,6-trifluoroisophthalonitrile. Is mentioned.

[0012] slime control agent composition of the present invention, the hydantoin compound of formula (I), those containing isophthalonitrile compound of DBNPA and formula (II). In the present invention, in order to express a synergistic effect by blending these three components, the hydantoin compound of the general formula (I) and [the total amount of the DBNPA and the isophthalonitrile compound of the general formula (II)] The weight ratio is 1:
0.05 to 1:20, preferably 1: 0.5 to 1: 8, and the weight ratio of DBNPA to the isophthalonitrile compound of the general formula (II) is 1: 0.1 to 1: 1. : 4,
Preferably it is 1: 0.2 to 1: 2.

As described above, by using the hydantoin compound of the general formula (I), DBNPA and the isophthalonitrile compound of the general formula (II) in combination, each of them can be used alone or any of them. It has been found that excellent effects not exhibited by the combination of the two components are exhibited.

The slime control agent composition of the present invention is particularly applied to process water in pulp mills and paper mills.

The process water in the pulp mill and the paper mill in the present invention includes process water generally called so-called white water, such as a wood chipping process, a paper making process, a screen process, and a bleaching process, and other processes in a pulp mill and a paper mill. Includes all water handled. In particular, the slime control agent composition of the present invention is characterized by exhibiting a remarkable slime control effect even in white water discharged from an alkaline paper machine having a pH of 6 to 8.

The amount of the slime control agent composition of the present invention added to the aqueous system depends on the process to be applied and the operating conditions of the process, the water quality of the target aqueous system, the type and number of living microorganisms in the aqueous system, and the amount of slime. Although it depends on the degree of occurrence, the components of the slime control agent composition and the compounding ratio thereof, the frequency of addition of the slime control agent composition, etc., it is not limited, but usually, the hydantoin system of the general formula (I) The total amount of the compound, DBNPA and the isophthalonitrile compound of the general formula (II) is 0.1 to 100 ppm, preferably 0.5 to 100 ppm based on the aqueous water.
-50 ppm, more preferably 1-20 ppm. If the amount is less than 0.1 ppm, the effect is small and the object of the present invention is not sufficiently achieved. If it is more than 100 ppm, the effect of suppressing slime is sufficient, but the effect is not so large for the added amount, and it is often disadvantageous from an economic viewpoint. The above concentration that kills and inhibits the growth of slime-constituting bacteria has no effect on the process and does not impair the quality of the product.

The method of adding the slime control agent composition of the present invention to an aqueous system is not particularly limited, but is generally dissolved in water or a suitable organic solvent and added to the target aqueous system. The hydantoin-based compound of the general formula (I) is solid at ordinary temperature and generally has a solubility of about 0.1 to 0.2% by weight in water. When adding the compound to an aqueous system, the hydantoin-based compound is powdered and added to the aqueous system, or water and / or a water-soluble organic solvent (a hydrophilic organic solvent or a solvent having an appropriate solubility in water). Good) and then adding. Examples of the hydrophilic organic solvent include acetone, dioxane, dimethylformamide, γ-butyrolactone,
Examples include N-methylpyrrolidone, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, propylene carbonate, and the like. Considering the easiness of addition to the process water, it can be said that it is preferable to dissolve in water and inject it into a necessary part of the process using a pump or the like. In addition, when the compound is used by dissolving it in water or an organic solvent, it is preferable to add the compound into the system as soon as possible after dissolution in consideration of stability of the hydantoin compound. The DBNAP and the isophthalonitrile compound of the general formula (II) used in the present invention are added by dissolving in a hydrophilic organic solvent as described above when adding to an aqueous system. However, the mixing of an iso-solvent into an aqueous system can also be a nutrient source for microorganisms, and therefore it is preferable to minimize it when used.

Hydantoin compound of the general formula (I), DB
The addition of NPA and the isophthalonitrile compound of the general formula (II) to the aqueous system may be carried out separately for each component compound, or may be carried out by mixing them.

The addition to the aqueous system is carried out by a method of impact addition at a high concentration at a constant interval, a method of intermittent addition, or a method of continuous addition to always maintain a constant concentration, and is not particularly limited. The microorganisms may be added so that the number of surviving microorganisms is maintained at a level not more than -quantity and slime damage does not occur.

[0020]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

[Compounds used for the test] Hydantoin compounds of the general formula (I) H-1 ... 1-bromo-3-chloro-5,5-dimethylhydantoin H-2 ... 1,3-dichloro-5,5 -Dimethylhydantoin H-3 ... 1,3-dibromo-5,5-dimethylhydantoin DBNPA Isophthalonitrile compound of the general formula (II) CFIPN ... 5-chloro-2,4,6-trifluoroisophthalonitrile TPN ... 2,4,5,6-tetrachloroisophthalonitrile

[Test Method] White water (pH = 7.5, viable cell count: 9 × 10 8) of neutral neutral paper manufacturing machine in a paper mill
(Ml / mL) was collected in a 300 mL Erlenmeyer flask in 100 mL increments, a predetermined amount of a slime control agent was added, and the mixture was brought into contact with a shaker for 30 minutes. This was followed by inoculation on a TGY agar medium (medium in which tryptone, yeast extract and glucose were dissolved in pure water and the pH was adjusted to 7), and then inoculated into the medium.
C. for 3 days, and the number of viable bacteria per 1 mL of white water was measured. The culture temperature of 32 ° C. used here is the temperature at which bacterial propagation is considered to be most active.

In the same manner, the white water
(pH = 5.5, viable cell count: 8.times.10.sup.7 cells / mL) were collected, and the viable cell count after the same treatment as above was measured.

The results are summarized in Table 1. From the table, the hydantoin compound and DBNPA, the hydantoin compound and isophthalonitonyl compound, D
Compared with the two-component combination of BNPA and isophthalonitrile compound, the hydantoin-based compound of the present invention, DBNPA, and three-component combination of isophthalonitrile have a large effect of killing and inhibiting the growth of microorganisms, and a synergistic effect of the combination. It can be seen that the bactericidal effect is particularly remarkable even in a high pH range of 7.5.

[0025]

[Table 1]

[0026]

EFFECT OF THE INVENTION As a slime control agent, a general formula
Hydantoin compound (I), DBNPA and general formula (II)
The bactericidal effect is large by using in combination with the isophthalonitrile-based compound of the formula (1). Particularly, it exerts a sufficient effect not only on the acidic side having a pH of 4 to 6, but also in a high pH range having a pH of 6 to 8. . However, it is possible to eradicate or inhibit the growth of slime-constituting bacteria that grow in process water of a pulp mill or a paper mill, and prevent slime damage occurring in the process.

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[Procedure amendment]

[Submission date] October 13, 1998 (1998.10.
13)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

That is, the invention of claim 1 is a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ and R ² may be the same or different from each other, and at least one is a chlorine or bromine atom;
The other represents any of chlorine, bromine and hydrogen atoms, and R ³ and R ⁴ may be the same or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). Hydantoin-based compound and DBNPA
And the general formula (II)

Embedded image (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a fluorine or chlorine atom) and an isophthalonitrile-based compound represented by the following formula: It is a slime control agent composition characterized by containing, wherein the hydantoin-based compound is 1-bromo-3-chloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5 A slime control agent composition which is at least one selected from -dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin. The invention of claim 3 provides a hydantoin-based compound, [DBNPA and isophthaloin Weight ratio of 1: 0.05 to 1:20, and the weight ratio of DBNPA and isophthalonitrile compound is 1: 1. : A slime control composition combined to be from 0.1 to 1: 4, wherein
The invention of claim 5 is a slime control method comprising adding such a slime control agent composition to process water in a pulp mill or a paper mill. This is a slime control method that is white water discharged from a paper machine.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

The slime control composition of the present invention comprises a hydantoin compound of the general formula (I), DBNPA and an isophthalonitrile compound of the general formula (II). In the present invention, in order to produce a synergistic effect by combining these three components, a hydantoin-based compound of the general formula (I) and [total amount of DBNPA and an isophthalonitrile-based compound of the general formula (II)] Weight ratio of 1:
0.05 to 1:20, preferably 1: 0.5 to 1: 8, and the weight ratio of DBNPA to the isophthalonitrile compound of the general formula (II) is 1: 0.1 to 1 : 4, preferably 1: 0.2 to 1: 2.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

As described above, the three components of the hydantoin-based compound of the general formula (I), DBNPA and the isophthalonitrile-based compound of the general formula (II) can be used alone or in any combination thereof. It has been found that excellent effects not exhibited by the combination of the two components are exhibited.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

The method of adding the slime control agent composition of the present invention to an aqueous system is not particularly limited, but is generally dissolved in water or a suitable organic solvent and added to the target aqueous system. The hydantoin compound of the general formula (I) is solid at ordinary temperature and generally has a solubility of about 0.1 to 0.2% by weight in water. When adding the compound to an aqueous system, the hydantoin-based compound is powdered and added to the aqueous system. Good) and then adding. Examples of the hydrophilic organic solvent include acetone, dioxane, dimethylformamide, γ-butyrolactone,
Examples include N-methylpyrrolidone, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, propylene carbonate, and the like. Considering the easiness of addition to the process water, it can be said that it is preferable to dissolve the compound in water and inject it into a necessary part of the process using a pump or the like. When the compound is used by dissolving it in water or an organic solvent, it is preferable to add the compound to the system as soon as possible after dissolution in consideration of the stability of the hydantoin compound. The DBNAP and the isophthalonitrile compound of the general formula (II) used in the present invention are added by dissolving in a hydrophilic organic solvent as described above when adding to an aqueous system. But,
Since the mixing of the ariso solvent into the water system can be a nutrient source for microorganisms, it is preferable to minimize it when it is used.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

[Test Method] White water (pH = 7.5, viable cell count: 9 × 10 ⁸⁾ of neutral neutral paper manufacturing machine in a paper mill
(Ml / mL) was collected in a 300 mL Erlenmeyer flask in 100 mL increments, a predetermined amount of a slime control agent was added, and the mixture was brought into contact with a shaker for 30 minutes. This was followed by inoculation on a TGY agar medium (medium in which tryptone, yeast extract and glucose were dissolved in pure water and the pH was adjusted to 7), and then inoculated into the medium.
C. for 3 days, and the number of viable bacteria per 1 mL of white water was measured. The culture temperature of 32 ° C. used here is the temperature at which bacterial propagation is considered to be most active.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

Similarly, white water (pH = 5.5, viable cell count: 8 × 10 ⁷ cells / mL) from the acid medium paper manufacturing machine was collected, and the viable cells were subjected to the same treatment as above. The number was measured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 1/50 520 C02F 1/50 520J 532 532C 532D 532H 540 540B 540D D21H 21/04 D21H 21/04

Claims (5)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ and R ² may be the same or different from each other, and at least one is a chlorine or bromine atom;
The other represents any of chlorine, bromine and hydrogen atoms, and R ³ and R ⁴ may be the same or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). Hydantoin compound, 2,2-dibromo-3-nitrilopropionamide, and a compound represented by the general formula (II): (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a fluorine or chlorine atom) and an isophthalonitrile-based compound represented by the following formula: A slime control agent composition comprising: 2. The method according to claim 1, wherein the hydantoin compound is 1-bromo-3.
1 selected from -chloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin
The slime control composition according to claim 1, which is at least one species. 3. The weight ratio of the hydantoin compound and [total amount of 2,2-dibromo-3-nitrilopropionamide and isophthalonitrile compound] is 1: 0.05 to
The combination according to claim 1 or 2, wherein the ratio is 1:20, and the weight ratio of 2,2-dibromo-3-nitrilopropionamide to the isophthalonitrile compound is 1: 0.1 to 1: 4. 3. The slime control agent composition according to 2. 4. A slime control method comprising adding the slime control agent composition according to claim 1 to process water in a pulp mill or a paper mill. 5. The slime control method according to claim 4, wherein the process water in the pulp mill and the paper mill is white water discharged from an alkaline paper machine.