WO2000022930A1 - Procede de prevention de la putrefaction d'une pate aqueuse contenant un epaississant a base de polysaccharide - Google Patents

Procede de prevention de la putrefaction d'une pate aqueuse contenant un epaississant a base de polysaccharide Download PDF

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Publication number
WO2000022930A1
WO2000022930A1 PCT/JP1999/003855 JP9903855W WO0022930A1 WO 2000022930 A1 WO2000022930 A1 WO 2000022930A1 JP 9903855 W JP9903855 W JP 9903855W WO 0022930 A1 WO0022930 A1 WO 0022930A1
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WO
WIPO (PCT)
Prior art keywords
preservative
formaldehyde
compound
aqueous slurry
pyridinethiol
Prior art date
Application number
PCT/JP1999/003855
Other languages
English (en)
Japanese (ja)
Inventor
Munetoshi Yamaji
Shinji Yoshizawa
Masa Taniguchi
Original Assignee
Somar Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Somar Corporation filed Critical Somar Corporation
Publication of WO2000022930A1 publication Critical patent/WO2000022930A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to a novel method of preserving an aqueous slurry containing a polysaccharide thickener. More specifically, polysaccharide thickeners such as carboxymethylcellulose (hereinafter abbreviated as CMC) and various natural gums are used in civil engineering work involving drilling of oil wells and soil, or in the manufacturing process of various industrial materials.
  • CMC carboxymethylcellulose
  • the present invention relates to a novel preservative method capable of preventing decay and deterioration of an aqueous slurry which has been added and thickened, and which can impart long-term storage stability to the slurry. Background art
  • Excavated mud generated in civil works, construction works, dredging works, etc. has a high water content and is often in a slurry state, so it is difficult to handle it in a solid form like solid materials. After excavation of such mud, it is often very difficult to carry out and transport it using ordinary dump trucks and trucks. For this reason, handling has been conventionally performed by adding a consolidation agent such as lime or cement, or by adding a water-soluble polymer compound or a superabsorbent resin to increase the consistency. .
  • a consolidation agent such as lime or cement
  • a water-soluble polymer compound or a superabsorbent resin to increase the consistency.
  • excavated earth and sand generated by various types of force turtles is once received in a chamber behind the power turret and then The soil is discharged from the screw conveyor.
  • a water-soluble polysaccharide thickener such as xanthan gum or CMC
  • xanthan gum or CMC water-soluble polysaccharide thickener
  • CMC water-soluble polysaccharide thickener
  • water-soluble polymer compounds including natural water-soluble polymer compounds, semi-synthetic water-soluble polymer compounds and synthetic water-soluble polymer compounds are used as modifiers to reduce the fluidity of excavated mud. A substance is added and dissolved (see JP-A-8-283717).
  • natural gums may contain endogenous microorganisms in their own right, and when used as an aqueous solution, the endogenous microorganisms immediately start growing and reduce the viscosity of the aqueous solution. As time passes, the viscosity drops sharply. Since there is a certain correlation between the growth of endogenous microorganisms and the decrease in viscosity, the use of gums in civil engineering and various industrial material manufacturing processes as described above is avoided. Absent.
  • an aqueous slurry of formalin ie, formaldehyde, which has a bactericidal action
  • formalin when used, it is effective against a wide range of microbial spectrum, but has a very low effect on inhibiting the growth of molds and yeasts.
  • the sterilizing effect is instantaneously exerted, on the other hand, it is not possible to prevent the decay of the slurry for a long period of time. To be lost Become.
  • products made using such altered slurries are also susceptible to spoilage. Disclosure of the invention
  • the present invention prevents the spoilage deterioration of an aqueous slurry containing a water-soluble polysaccharide compound such as CMC and natural gums as a thickener, and improves the viscosity and water retention of the slurry.
  • Preservation method for aqueous slurries that can maintain performance such as fluidity and plastic fluidity, does not generate putrefaction odor, maintains its rot effect over a long period of time, and does not adversely affect the environment. It is intended to provide.
  • the present inventors have conducted various studies to develop an antiseptic method for the aqueous slurry containing the thickening polysaccharide compound, which does not have the above-mentioned problems.
  • the alkali metal salt of 2-pyridinethiol-1-oxide or Zinc salts (hereinafter sometimes referred to as antimicrobial compounds) or, if desired, a combination of these and a formaldehyde-releasing compound are added to an aqueous slurry to effectively prevent decay thereof.
  • antimicrobial compounds 2-pyridinethiol-1-oxide or Zinc salts
  • a combination of these and a formaldehyde-releasing compound are added to an aqueous slurry to effectively prevent decay thereof.
  • the present inventors have found that the slurries can be produced and that the rot preventing effect can be maintained for a long period of time without deteriorating the preferable properties of the slurry, and based on this finding, the present invention has been completed.
  • the method for preventing spoilage of an aqueous slurry comprises a polysaccharide thickener containing an antimicrobial compound selected from alkali metal salts and zinc salts of 2-pyridinthiol-1-oxide as an antiseptic active ingredient.
  • a preservative method characterized by being added to an aqueous slurry containing a polysaccharide thickener as a composite antiseptic active ingredient, wherein the combination of the antimicrobial compound and a formaldehyde releasing compound is added to an aqueous slurry containing An antiseptic method characterized by being added.
  • the alkali metal salt of 2-pyridinethiol-1-oxide used as an antimicrobial compound in the preservative method of the present invention has a general formula: ⁇ (.
  • the alkali metal represented by ⁇ in the above general formula (I) includes sodium, potassium, lithium and the like, and sodium is preferred industrially.
  • one of the alkali metal salt and zinc salt of 2-pyridinethiol-1-oxide may be used alone, or two or more thereof may be used in combination.
  • the metal salt or zinc salt of 2-pyridinethiol-1-oxide may be added to the aqueous slurry as a preservative active ingredient, but the polysaccharide thickener may be added.
  • a combination of the above-mentioned alkali metal salt or zinc salt of 2-pyridinethiol-1-oxide and a formaldehyde releasing compound should be added as a composite active ingredient. Is desirable.
  • formaldehyde-releasing compound for example, 13-dimethylolone-5,5-dimethylhydantoin, 1- (3-chloroallyl) -3,57-triaza-1-azoniaadamantank
  • the mixing ratio thereof is not particularly limited and may be appropriately selected depending on the situation. 10: 1 to 1:50, preferably 10: 1 to 1:15. If the proportion of the formaldehyde-releasing compound is less than this range, the long-lasting effect of the preservative action will not be sufficiently exerted. If the proportion of the formaldehyde-releasing compound is greater than this range, the viscosity of the slurry, ⁇ ⁇ It is not preferable because physical properties such as appearance are adversely affected.
  • the amount of the above-mentioned antiseptic active ingredient to be added to the aqueous slurry in the preservative method of the present invention should be appropriately selected according to conditions such as the type of the target aqueous slurry, the use, the type of microorganism, and the density of the microorganism.
  • the amount of the antiseptic active ingredient is generally 0.002 to 2% by weight, preferably 0.01 to 1% by weight based on the total amount of the aqueous slurry containing the polysaccharide thickener. It is good to choose so that it becomes weight%.
  • the concentration of the active ingredient is from 0.1 to 0.1% by weight. It may be added so that the concentration of the active ingredient is 0.1 to 0.5% by weight when it relates to a general industrial material production process.
  • the amount of the preservative active ingredient is too small, the desired preservative effect is not sufficiently exhibited, but if it is too large, various metals contained as impurities in the 2-pyridinethiol-1-oxide salt and slurry.
  • a colored chelate compound is formed between the components and the aqueous slurry is colored, thereby deteriorating the appearance or not obtaining the desired consistency or ⁇ ⁇ .
  • Polysaccharide that can be contained in an aqueous slurry to which the preservative method of the present invention is applied ⁇
  • the thickener include natural gums such as CMC, guar gum, glucone gum, xanthan gum, and arabia gum, but these may contain only one kind or two or more kinds at the same time. It may be contained.
  • the concentration of these polysaccharide thickeners in the slurry is not particularly limited, and may be an appropriate amount depending on the use of the aqueous slurry.
  • DMDMH 1,3-Dimethylol-5,5-dimethylhydantoin
  • Each aqueous solution inoculated with the spoilage bacteria was kept in a thermostat at 35 ° C for 21 days, during which the viscosity, pH and the number of microorganisms were measured.
  • Table 1 shows the measurement results of the aqueous solution viscosity
  • Table 2 shows the measurement results of the pH.
  • the conditions for measuring the viscosity are as follows. In other words, after shaking for 5 minutes, the sample aqueous solution was allowed to stand for 24 hours at a measurement temperature of 30 ° C, and the rotor was rotated using a rotary viscometer (No. 3 ports, rotation speed: 12 rpm). The viscosity after 2 minutes of rotation was read.
  • the measurement result of the microorganism density did not reach 1 ONZm 1 in all the measurements for the viper, but did not reach 10 N / m 1 in the whole measurement for the bacteria when ZPT was added. 1, 8, 14 and After 21 they were 3.1 x 10 5 , 6.4 x 10 1.4xl 09 and 7.7 x 10 7 N / m 1 respectively.
  • An aqueous slurry of bentonite was prepared as the equivalent of a drilling mat. That is, 100 parts by weight of water, 6 parts by weight of bentonite, 0.2 parts by weight of CMC, and 0.1 parts by weight of sodium humate as a dispersant were placed in a beaker, and the mixture was homogenized. The mixture was sufficiently stirred to obtain a homogeneous bentonite slurry. For this slurry
  • the inoculum was inoculated in the same manner as in Example 1 to each of the slurry containing 0.01, 0.02, and 0.05% by weight of ZPT and the slurry to which no ZPT was added, and then kept at 35 ° C for 21 days. , PH and microbial count were measured. To clarify the persistence of the preservative effect, the bacteria were re-inoculated after 7 days and 14 days later. Table 3 shows changes in viscosity of these slurries, and Table 4 shows changes in pH. As can be seen from these measurement results, the effect of preventing the decrease in viscosity and pH for bentonite slurry was almost the same as in the case of the CMC aqueous solution.
  • Example 2 The experimental conditions were largely the same as in Example 2 above, except that the use of ZPT alone was replaced by 0.001 or 0.005% by weight of ZPT and 0.009 or 0.005% by weight of formaldehyde releasing compounds (DMDMH, Dowicil 75 and BNP). Combinations (all in total 0.01% by weight) were used.
  • DMDMH formaldehyde releasing compounds
  • Table 5 shows the change in viscosity of the bentonite slurry up to the date of 21 and Table 6 shows the change in pH.
  • Microbial density measurement results did not reach 10 NZm1 for all tests on power vines, but for bacteria, ZPT (0.005%) + DMDMH (0.005%), ZPT (0.005%) + Dowicil 75 (0.005%), ZPT (0.001%) + BNP (0.009%) and the combination of ZPT (0.005%) + BNP (0.005%), the measured results after 21 were 3.2 X 10 1.3xl 0 2 , respectively. Except for 2.0 ⁇ 10 3 and 3.8 ⁇ 10 6 NZm 1, it did not reach 10 NZm 1 in all measurements. 1
  • Example 2 The experimental conditions were almost the same as in Example 2 above, except that only DMD MH, Dowicil 75 or BNP as a formaldehyde releasing compound was used in place of ZPT so that the concentration was 0.01% by weight, respectively. It was added to the bentonite slurry. Table 7 shows the change in viscosity of the slurry, and Table 8 shows the change in pH. Table 7
  • ZPT was used under almost the same conditions as in Example 1 except that a homogeneous aqueous solution prepared from 100 parts by weight of city water and 1.7 parts by weight of xanthan gum was used instead of the CMC aqueous solution.
  • Table 10 shows the change in viscosity up to and after
  • Table 11 shows the change in pH.
  • the change in microbial density was measured for bacteria and bacteria, and when ZPT was used in combination with a formaldehyde-releasing compound, the bacterial density after one day was increased when 0.01% ZPT and 0.09% Dowicil 75 were used together. Except for 1.5 ⁇ 10 2 N ml, 1 ONZml was not reached in all measurements. Table 12 shows the change in microbial density when only DMDMH was added and when no preservative was added.
  • the preservative method of the present invention It is clear that even when the gum is a water-soluble polysaccharide thickener, an extremely excellent preservative effect can be obtained as compared with the use of a formaldehyde-releasing compound alone.
  • the preservative method of the present invention characterized in that ZPT or the like is added as a preservative, is applied to an aqueous slurry containing a perishable polysaccharide thickener to reduce the odor of the slurry and the odor associated with the putrefaction. Generation can be prevented and a decrease in slurry viscosity can be suppressed. Therefore, it is possible to improve the work efficiency of civil engineering work, especially work involving excavation of mud.
  • a formaldehyde-releasing compound is used as a preservative in combination with, for example, ⁇ ⁇ , it is possible to impart long-term storage stability to a slurry containing a polysaccharide thickener.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé destiné à empêcher la putréfaction d'une pâte aqueuse contenant un épaississant à base de polysaccharide soluble dans l'eau (carboxyméthylcellulose, caoutchouc naturel, etc.) et à doter la pâte aqueuse d'une stabilité élevée au stockage pendant une longue durée. Le procédé selon l'invention consiste à ajouter un sel de métal alcalin ou un sel de zinc de 2-pyridinethiol-1-oxyde éventuellement combiné à un composé de libération de formaldéhyde à une pâte aqueuse contenant un épaississant à base de polysaccharide.
PCT/JP1999/003855 1998-10-16 1999-07-16 Procede de prevention de la putrefaction d'une pate aqueuse contenant un epaississant a base de polysaccharide WO2000022930A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10295341A JP2000119111A (ja) 1998-10-16 1998-10-16 増粘多糖類含有スラリー用防腐剤
JP10/295341 1998-10-16

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WO2000022930A1 true WO2000022930A1 (fr) 2000-04-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4197332A1 (fr) * 2021-12-15 2023-06-21 Sika Technology AG Agent biocide

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1583420A4 (fr) * 2002-12-19 2006-04-26 Arch Chem Inc Biocides pyrithione renforces par des ions metalliques de zinc et par des amines organiques
EP2042489A1 (fr) * 2007-09-26 2009-04-01 Straetmans high TAC GmbH Elimination et prévention du changement de couleur de matières contenant du pyrithione
AR076348A1 (es) * 2009-04-22 2011-06-01 Dow Global Technologies Inc Composiciones biocidas y metodos de uso
JP5364935B2 (ja) * 2010-11-09 2013-12-11 ダウ グローバル テクノロジーズ エルエルシー フルメツラムまたはジクロスラムとジンクピリチオンとの相乗的組み合わせ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6468304A (en) * 1987-09-10 1989-03-14 Kurita Water Ind Ltd Antiseptic agent
JPH06179294A (ja) * 1992-12-11 1994-06-28 Takeda Chem Ind Ltd 印刷版処理液用防腐防かび剤、印刷版用処理液および防腐防かび方法
WO1996023850A1 (fr) * 1995-02-03 1996-08-08 Olin Corporation Procede de prevention de la decoloration de compositions pour revetement contenant de la pyrithione
JPH0987110A (ja) * 1995-09-20 1997-03-31 Yoshitomi Pharmaceut Ind Ltd ２−チオシアノピリジン−１−オキシドを含有する組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6468304A (en) * 1987-09-10 1989-03-14 Kurita Water Ind Ltd Antiseptic agent
JPH06179294A (ja) * 1992-12-11 1994-06-28 Takeda Chem Ind Ltd 印刷版処理液用防腐防かび剤、印刷版用処理液および防腐防かび方法
WO1996023850A1 (fr) * 1995-02-03 1996-08-08 Olin Corporation Procede de prevention de la decoloration de compositions pour revetement contenant de la pyrithione
JPH0987110A (ja) * 1995-09-20 1997-03-31 Yoshitomi Pharmaceut Ind Ltd ２−チオシアノピリジン−１−オキシドを含有する組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4197332A1 (fr) * 2021-12-15 2023-06-21 Sika Technology AG Agent biocide

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