JPH0347105A - Bactericidal composition and aqueous dispersion containing same - Google Patents

Abstract

PURPOSE:To provide a composition comprising a 2-methylisothiazoling-3-one- based compound, an alcohol, ethylene oxide adduct-contg. nonionic and/or anionic surfactant and a metallic ion blocking agent. and a polymeric aqueous dispersion containing said composition. CONSTITUTION:The objective bactericidal composition comprising (A) 2-10wt.: of a compound of the formula (X and Y are each H or halogen). (B) 85-90wt.% of a mono to trihydric <=3C alcohol, (C) 4-6wt.% of ethylene oxide adduct-contg. nonionic and/or anionic surfactant (e.g. polyoxyethylene alkyl ether sulfate) and (D) a metallic ion blocking agent (e.g. sodium salt of EDTA). And the other objective aqueous dispersion with a solid content of esp. <=45wt.%, containing said composition and an anionic polymer aqueous dispersion (of rubbery or resinous material) so as to be 100 pts.wt. for the latter and 0.001-0.1 pts.wt. for the compound of the formula. The present aqueous dispersion is ensured to have preservative effect, also being inexpensive.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a sterilizing composition for preventing an aqueous dispersion from being contaminated with microorganisms, and an aqueous dispersion containing the sterilizing composition. [Prior Art] Conventionally, many compounds have been used as industrial preservatives. Among these many preservatives, 2-methylisothiazolin-3-one compounds represented by the following general formula are listed as one of the most cost effective. In the formula, X and Y are the same or different and represent hydrogen or a halogen atom. Anionic polymer aqueous dispersions such as natural rubber latex, synthetic rubber latex, acrylic emulsion, vinyl acetate emulsion, and mixtures thereof, which are conventionally used in various industrial fields such as adhesives, paints, paper, fibers, and building materials, are During storage and preservation, it may be subject to microbial contamination such as putrefaction and coloring, which is characteristic of aqueous dispersions, resulting in quality deterioration. In order to prevent these problems, a 2-methylisothiazolin-3-one compound may be added. However, such 2-methylisothiazolin-3-one compounds have poor stability and are therefore used as stabilizers.
Various salts of metals such as Oa'' Zn++ are added and are widely used as sterilizing compositions. Although the above sterilizing compositions have excellent antiseptic effects, when added to anionic polymer aqueous dispersions, they do not sterilize. A fatal problem arises in that the aqueous anionic polymer dispersion becomes unstable due to the above-mentioned metal salts coexisting in the composition, resulting in the formation of aggregates. No. 80-96652 describes a method of adding an anionic surfactant to the above-mentioned sterilizing composition, but in order to suppress the generation of the above-mentioned aggregates in this method, the sterilizing composition must be diluted more than 4 times. The reality is that it has to be added after diluting with water. However, adding it after diluting it with water lowers the solids concentration of the aqueous dispersion, which is a major hindrance in terms of productivity and quality. In addition, when the metal salt is removed from a sterilizing composition of 2-methylisothiazolin-3-one type compound, the generation of such aggregates is not observed, but the stability as a sterilizing composition is very poor. The isothiazolin-3-one compound decomposes and has a drawback that it cannot be put to practical use. [Problem to be solved by the invention] The conventional bactericidal composition containing a metal salt stabilizer of a 2-methylisothiazolin-3-one compound If 7 is added to an aqueous anionic polymer dispersion without diluting with water, aggregates will occur, which will pose a serious problem in terms of the quality of the anionic polymer aqueous dispersion.To avoid this, the above-mentioned bactericidal composition is Since dilution with water is an essential condition, the solid concentration of the aqueous anionic polymer dispersion decreases, which poses an obstacle to productivity.In view of this situation, the present inventors have conducted extensive research. As a result of repeated research, we found that the active ingredient is a 2-methylisothiazolin-3-one compound that does not contain conventional stabilizer metal salts, and at least one type of mono- to trihydric alcohol having 3 or less carbon atoms as a solvent. , at least one selected from nonionic and anionic surfactants containing ethylene oxide adducts, and a sequestering agent, which solves the conventional drawbacks and has excellent stability and preservative effects. [Means for solving Section I!] The present invention provides a method for solving problem I! The present invention is based on the general formula (wherein X and Y are the same or different and represent hydrogen or halogen atoms). -IIl' of the compound
ft as an active ingredient, at least one selected from mono- to trivalent alcohol-μ having 3 or less carbon atoms, and at least one selected from nonionic and anionic surfactants containing ethylene oxide adducts. A disinfectant composition containing a metal ion sequestrant and a metal ion sequestering agent. Moreover, the non-invention is (4) in a composition consisting of the above-mentioned sterilizing composition and (B) anionic polymer aqueous dispersion, the general formula ( The present invention will be described in detail below. ] The 2-methylisothiazoline compound used is a bactericidal and fungicidal substance, and X and Y in the general formula tlj are
are the same or the same and represent hydrogen or halogen atoms. Examples of the halogen atom include chlorine, bromine, and iodine atoms, but chlorine is the best because of its bactericidal and microcidal power. A typical example is 2-methylisothiazoline-3-
on, 2-methyon, 4-chloroisothiapurin-3-one, 2-methy/v-5-chloroisothiazolin-3-one, and 2-methyA/-4,5-dichloroisothiazolin-3-one. One kind or a mixture of two or more of these can be used in the disinfectant composition. Generally, disinfectant compositions are used in the form of a solution for ease of handling, but since the 2-methylisothiazolin-3-one compound is a solid, it is used after being dissolved in a solvent. The solvent that can be used at this time is preferably one that does not have an adverse effect on the aqueous anionic polymer dispersion described below and one that does not decompose the 2-methylisothiazolin-3-one compound. It has been found that mono- to trihydric alcohols having 3 or less alcohols are excellent. Specific examples of these solvents include methano-μ, ethanol-IV,
Examples include hydrophilic solvents such as H-propatol, 1ao-propatol, ethylene glycol, propylene geficol, and glycerin. Solvents other than these, such as hydrophilic solvents such as Cellosopes, Carpitols, polyethylene glycols, and polypropylene glycols, cause large decomposition of 2-methylisothiazolin-3-one compounds, and butanol and pentanol. , a lipophilic solvent such as benzyl alcohol is used to prepare an anion-containing polymer aqueous dispersion t-
It is not preferred because it has the disadvantage of causing agglomeration. The mono- to trihydric alcohol solvent having 3 or less carbon atoms used in the present invention may be used alone or in a mixture of two or more thereof. The surfactant used in the disinfectant composition of the present invention is a nonionic surfactant with an ethylene oxide adduct added for the same purpose as the solvent described above, and anionic surfactant is an ethylene oxide adduct. It has been found to have a better effect than surfactants that do not have a long shelf life. Specific examples thereof include polyoxyethylene 7μ kyl ether/I/sulfate ester, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl phenyl ether, polyoxyethylene alV'flW phenyl condensate ether, etc. It will be done. Since the anionic polymer aqueous dispersion to which the sterilizing composition of the present invention is added is aqueous, aggregation may be observed at low addition moles, so the ethylene oxide addition number is preferably 6 or more. . These surfactants may be used alone or in a mixture of two or more in the sterilizing composition. The sequestering agent used in the disinfectant composition of the present invention deactivates the activity of heavy metal ions that may be contained in trace amounts in the disinfectant composition and prevents the decomposition of 2-methylisothiazolin-3-one compounds. Add for this purpose. Specific examples thereof include sodium salt of ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 0-phenanthroline. The 2-methylisothiazolin-3-one compound represented by the above-mentioned general name in the bactericidal composition of the present invention is important for improving the stability of the bactericidal composition and its addition to the anionic polymer aqueous dispersion described below. From the point of view of preventing agglomeration, 0.5 to 20 in the sterilizing composition! ! The content is preferably 2% to 10% by weight, more preferably 2 to 10% by weight. The alcohol solvent used in the above-mentioned method is preferably contained in the sterilizing composition in an amount of 80 to 97% by weight, more preferably 85 to 90% by weight. The nonionic and anionic surfactants used in the present invention described above are preferably contained in the disinfectant composition in an amount of 1 to 10% by weight, more preferably 4 to 6% by weight. In addition, the above-mentioned sequestering agent may be present in the disinfectant composition in an amount of 0.0
It is preferably added in a proportion of 0.01 to o, 5 weight fi of 1%, more preferably 0.01 to 0.1% by weight. The anionic polymer aqueous dispersion to which the antiseptic effect can be obtained by adding the above-mentioned disinfectant composition of the present invention has a polymer substance dispersed in an aqueous medium, and the dispersed particles have an anionic charge. It is something that exists. Examples of such polymeric substances include rubbery substances such as natural rubber, polybutadiene, styrene-butadiene copolymers, acrylic/I/based rubbers, vinyl acetate polymers, acrylic copolymers, vinyl acetate polymers, and styrene copolymers. Resin-like substances such as polymers are used, and these are used in the form of -N or a mixture of two or more types. Examples of substances imparting anionic charges include sulfate ester salts of higher alcohols, amylbenzene sulfonates,
Anionic surfactants such as aliphatic sulfone salts, dialky/L'nulphosuccinic salts, alkynaphthalene μphonates, rosinates, and fatty acid salts. Also, copolymerizable monomers such as acrylic acid, methacrylic acid, crotonic acid, fuma A'ugly, itaconic acid, maleic acid, and salts thereof are used during copolymerization, and later acalytic acid is used. Anionic charges can also be imparted by adding: or by using a radical initiator such as sodium persulfate, potassium persulfate, or ammonium persulfate for copolymerization. The above-mentioned polymer substance was added to the anionic polymer aqueous dispersion.
It also includes those obtained by forcibly dispersing in an aqueous medium in the presence of an ionic surfactant, those obtained by known emulsion polymerization techniques, and those obtained from nature. The ratio of the above-mentioned sterilizing composition (N) to the above-mentioned anionic polymer aqueous dispersion is based on 100 parts solids of the anionic polymer aqueous dispersion (B). The compound represented by general formula (I) is 0.0001 to 0
．． When blended in an amount of 5 parts by weight, preferably 0.001 to 0.1 part by weight, an effective antiseptic effect can be obtained as shown in the examples below. If the compound of the general formula + However, it is not preferable because the same antiseptic effect cannot be expected. [Examples] Next, examples and comparative examples of the present invention will be explained.
The present invention is not limited to these. All compounding ratios shown below are weight %. In addition, the sterilizing compositions of each example are prepared by stirring the components shown in each example at room temperature in the proportions shown. Example 1 1-Propyl alcohol 89.98% Total 100.00% Example Ethylenegutuicol 86.95% Nitricitriacetic acid 0.05% Total 100.00% Example 2-MethiA/-5-chloroisothiazoline-3 -one 5.00% 2-methylisothiazolin-3-one ethylene glycol A 1.00'% 88.99% polyoxyethylene nonylphenyl condensate ether (X, O, 133 mol), 00% ethylenediaminetetraacetic acid @2 Sodium 0.01% Total 100.00% Example ethylene glycol 86.99% Polyoxyethylene nonylphenyl ether (E, 0.12 mol) 3.00% Ethylenediaminetetraacetic acid i1!2 Sodium 0.01% Total 100.00% Example 2 - Methyl/v-5-chloroisothiazolin-3-one Ethyleneguzicol 1000% 84.97% Polyoxyethylene furyl ether M acid ester/L/(K, O, 12 morph 5. 00% Nitrilotriacetic acid 0.03% Total 100.00% Comparative example Magnesium nitrate 410.00% Water SO, OO% Total 100.00% Comparative example Telv (Methyl Cello Sog 89.98% Ethylenediaminetetraacetic acid rM2 sodium 0.00%) 02% Total 100.00% Comparative example Ethylene glycol nonylphenyl ether phosphate ethylene diamine tetra vinegar!! 22 Sodium Total 89.98% 5.00% 0.02% 100.00% Comparative example 2-Methi A/-5 -chloroisothiazolin-3-one
5.00% n-butano
/' 89.98% polyoxyethylene nony phenyl condensate? fi7 (E, 0.13 mo/L')
5.00% ethylenediaminetetraacetic acid @ disodium 0.02% total 100.00% Comparative example 5 2-Methyl/v-5-chloroisothiazolin-3-one
5.00% ethylene glyco-iv 90.00% polyoxyethylene furyl ether sulfurized ester, /L/(x, o, 12 mol)
5.00% total 100.00% each 5iI! The stability test method for the sterilizing compositions obtained in the Examples and Comparative Examples and the coagulum generation rate test method when added to these all anionic polymer aqueous dispersions are as follows.
The results are shown in Table-1 and Table-2. [IJ stability test method The sterilizing composition was left in a thermostat at 45°C, and after 2 weeks
-Methylisothiazolin-3-one Thread compound was measured by high performance liquid chromatography to determine the residual rate. (2) Test method for determining the generation of coagulum Add to the following 7-ionic polymer aqueous dispersion 1002, which has been previously filtered through a 120-mesh wire mesh, a sterilizing composition diluted with water at the ratio shown in Table 2 below or undiluted. Add the stock solution so that the amount of the stock solution of the sterilizing composition is 5f, and add the stock solution for 5 minutes using Labo Star Two. This was filtered through a 120-mesh wire mesh, dried at 100° C. for 2 hours, and then collected on the wire mesh and the weight of the solidified product was measured. Examples of anionic polymer aqueous dispersions used in this test are shown below. Example 1 Example 4 Carboxylated SBR latex (solid content 50%) 002 Example 5 Example 6 Carboxylated SBR latex (solid content 50%) 91 Anti-aging agent

[Solid content 20%] 2 Example 2 Example 3 Table 1 In the comparative example of the residual rate of the disinfectant composition, the stability of the 2-methylisothiazolin-3-one compound and the time of addition to the anionic polymer aqueous dispersion are shown. There was no product that satisfied both coagulation properties, and there was a significant difference from the examples according to the present invention.〇 [Effects of the Invention] The sterilizing composition of the present invention has excellent stability, so a reliable preservative effect can be obtained. Also, there is no need to store it in a low-temperature warehouse, so there is a cost advantage. In addition, the aqueous dispersion containing the sterilizing composition of the present invention has excellent productivity in that it can be produced without a significant decrease in solids content when the sterilizing composition is added, and in particular, the anionic dispersion has a solid content of t-45% or more. Suitable for producing aqueous polymer dispersions.

Claims (1)

[Claims] 1. At least one compound represented by the general formula (I) ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (wherein X and Y are the same or different and represent a hydrogen or halogen atom) as a component, at least one selected from mono- to trihydric alcohols having 3 or less carbon atoms, at least one selected from nonionic and anionic surfactants containing ethylene oxide adducts, and a metal. A sterilizing composition comprising an ion sequestering agent. 2. In a composition comprising (A) the sterilizing composition according to claim 1 and (B) an anionic polymer aqueous dispersion, (B)
The composition of (A) is blended so that the amount of the compound represented by general formula (I) in the composition of (A) is 0.0001 to 0.5 parts by weight based on 100 parts by weight of solid content. An aqueous dispersion containing a sterilizing composition characterized by: