HUH3566A - Space-limiting structure particularly wall or ceiling and method for producing same - Google Patents

Abstract

A wall comprising two generally parallel wallboards (1), which form a part of the surface of the wall on each side, together with a post (4) of sheet metal, preferably of galvanized sheetiron, with a flange (5) on each end of the section of the post, where each flange lies in a respective kerf (7) in the edge of a wallboard, wherein each wallboard has a groove (3) in the one edge and a respective tongue (2) at the opposite edge, in addition to the kerf for the flange of the sheet metal post in one or the other edge.

Description

The present invention relates to antimicrobial compositions comprising isothiazolone and one or more other biocides and which inhibit the growth of microorganisms in various industrial systems and household products, agricultural products, and biopharmaceuticals, in a more effective and broader range. More particularly, the present invention relates to the use of compositions comprising 2-methylisothiazolin-3-one (hereinafter referred to as 2-methyl-3-isothiazolone) and at least one of the following six compounds: sodium dichlorophene, bis (2-hydroxy-5-chloro) -phenyl) sulfide, benzyl bromoacetate, dodecylamine, 4- (2-nitrobutyl) morpholine and di-propylamine ether.

As used herein, antimicrobial (or antimicrobial or biocidal) activity is understood to include all bactericidal, fungicidal and algacidic activities.

Isothiazolones are described, inter alia, in U.S. Patent Nos. 3,761,488, 4,105,431, 4,252,694, 4,265,899, and 4,279,762. They also disclose their use as antimicrobial agents.

It has been found that formulations containing 2-methyl-3-isothiazolone and at least one of the above six compounds exhibit unexpectedly synergistic microbicidal activity against a broad spectrum of microorganisms: the combined effect of the two components on microorganisms is unexpectedly greater than the sum of the effects of each component. This synergism results neither from the expected activity of the components nor from the expected improvement in activity. As a result of synergism, the effective dose required can be reduced, which not only is economical but also increases safety margins. The synergistic compositions of the present invention exhibit more effective and broader antimicrobial activity in many systems.

Thus, the antimicrobial compositions of the present invention comprise 2-methyl-3-isothiazolone and a second component, which is sodium dichlorophene, bis (2-hydroxy-5-chlorophenyl) sulfide, phenyl bromoacetate, dodecylamine, It may be one or more compounds selected from 4- (2-nitrobutyl) morpholine and di-propylamine ether and the weight ratio of 2-methyl-3-isothiazolone to the second component is 40: 1 to 1:32.

Major uses of the synergistic antimicrobial compositions of the present invention include: inhibiting the growth of bacteria and fungi in aqueous paints and coatings, adhesives, sealants, latex emulsions and binders; wood preservation; preservation of cutting fluids; inhibition of growth of mucus-forming bacteria and fungi in pulp, paper mills and cooling towers; spray or dip treatment of textiles and leather to prevent the growth of mold; protection of paint films, in particular external paints, against fungi that appear during the degradation of the paint film; protection of processing equipment against mucus deposits during the processing of sugar cane and sugar beet; inhibiting the growth and deposition of micro-organisms in air-washing or purification systems and in fresh industrial water supply systems; preservation of fuels; inhibition of microorganism impurities and deposits in oil fields in drilling fluids and sludges and in secondary gasoline recovery processes; inhibition of bacterial and fungal growth in paper coatings and coating processes; inhibiting the growth and deposition of bacteria and fungi in the manufacture of various special boards such as cardboard and chipboard; prevention of discoloration of lichen on freshly cut trees of different species; inhibition of bacterial and fungal growth in various types of clay and pigment sludges; as a strong surface disinfectant to prevent the growth of bacteria and fungi on walls, floors, etc .; as a preservative in cosmetics and toiletries raw materials, floor polishers, industrial plasticizers, household and industrial cleaners; inhibiting the growth of harmful bacteria, fungi and yeasts on trees, plants, fruits, seeds or soil; disinfection of agricultural preparations, electroplating systems, diagnostic and reagent products, medical devices; protection of animal bath compositions against microorganisms; and inhibiting the growth of microorganisms in photographic techniques, etc.

The compositions of the invention may be added separately to any system, or the basic components may be formulated, if desired, into a simple mixture of a suitable carrier or solvent, or may be formulated in an aqueous emulsion or dispersion.

The invention further relates to a method of preventing or inhibiting the growth of bacteria, fungi or algae in a site susceptible to or exposed to the above contaminants, the method comprising applying to the site or site to be treated an amount of a composition of the invention. The invention also relates to the use of the compositions of the invention as antimicrobial agents.

The composition according to the invention can be formulated with a variety of solvents. The solutions may contain from 0.01 to 99.9% by weight, more particularly from 5 to 30% by weight, of the active compound composition. In general, it is convenient to prepare the composition in water-diluted form by adding an emulsifier to the organic solution and then diluting with water.

The weight ratio of 2-methyl-3-isothiazolone to the second component in the composition of the invention may be from about 40: 1 to about 1:32. Further specific and preferred ratios are described in the Examples.

The synergistic effect of the two-component composition was investigated on Escherichia coli (ATCC 11229) or Candida albicans (ATCC 11651), Aspergillus niger (ATCC 6275) and Aureobasidium pullulan (ATCC 9348) fungi, with a broad range of Twice serial dilutions of medium with TSB) were made with one microbicidal compound in one dimension and the other in another dimension. Each tube was inoculated with about 1 to 5 x 10 ⁷ bacteria / ml or 1 to 5 x 10 ⁵ fungi / ml microbes. The minimum inhibitory concentration (MIC) was taken as the lowest concentration of each compound or mixture of compounds that inhibited visible growth (turbidity) in E. coli at 37 ° C and in fungi at 30 ° C for 7 days. ). MIC was considered as the endpoint of activity. The endpoints of the mixture of Compound A (2-methyl-3-isothiazolone) and Compound B (the second microbicidal component) were then compared to the endpoints of Compound A alone or Compound B alone. Synergism was determined by the commonly used and accepted method of Kuli FC, Eisman PC, Sylwestrovicz HD and Mayer RL (Microbiology 9, 538-541 (1961)).

Synergic index (Ski) = Qa / QA + Qb / QB in the above equation

QA is the final concentration of Compound A in ppm used alone;

Qa is the concentration of compound in the mixture resulting in an end point in ppm;

QB is the ppm final concentration of Compound B used alone;

Qb is the final concentration of Compound B in the mixture in ppm;

If the sum of Qa / QA and Qb / QB is greater than 1, this means antagonism. If the sum is equal to 1, this means additivity, and if less than 1, synergy is proven.

To demonstrate the synergism of microbicide combinations, experimental results are shown in Figures 1-6. See Table 1. Each table refers to the combination of 2-methyl-3-isothiazolone and a second microbicide in which

1. the name of the second microbicidal compound (Compound B);

2. the results of the test against E. coli and C. albicans (C. alb);

3. end point activity in ppm as measured by MIC for Compound A alone (QA), Compound B alone (QB), Compound A in mixture (Qa) or Compound B in mixture (Qb);

4. the calculated value of the synergistic index (Si) for

Si = Qa / QA + Qb / QB and the weight ratio of 2-methyl-3-isothiazolone (Compound A) to Compound B in the combination (A: B);

5. the weight ratio range of synergism and the preferred weight ratios. Those skilled in the art will appreciate that the ratios given are only approximate.

The MICs (QA or QB) of individual compounds tested alone are endpoint activities.

1, Table

2-Methyl-3-isothiazolone (A) / sodium dichlorophene (B) combination

TSB in Escherichia coli

MIC A _____________ B _____________ A: B ______ Synergic index

250 ppm 0 ppm - * 125 16 8: 1 0.62 125 31 4: 1 0.75 62 31 2: 1 0.50 31 31 1: 1 0.37 16 31 1: 2 0.31 16 62 1: 4 0.56 8 62 1: 8 0.53 4 62 1:16 0.52 0 125 Candida albicans TSB examining MIC A B A: B Szinercfikus 250 ppm 0 ppm - 125 8 16: 1 0.75 62 16 4: 1 0.75 31 16 2: 1 0.62 16 16 1: 1 0.56 8 16 1: 2 0.53 4 16 1: 4 0.52 2 16 1: 8 0.51 1 16 1:16 0.50 0 31

Ratios (A: B) range from 16: 1 to 1:16

Table 2

Combination of 2-Methyl-3-isothiazolone (A) / bis (2-hydroxy-5-chlorophenyl) sulfide (B)

TSB in Escherichia coli

MIC THE B A: B Szinerqikus index 250 ppm 0 ppm 125 16 8: 1 0.62 125 31 4: 1 0.75 62 62 1: 1 0.75 31 62 1: 2 0.62 16 62 1: 4 0.56 8 62 1: 8 0.53 0 125 Candida albicans Examined in TSB MIC THE B A: B Szinerqikus index 250 pprn 0 ppm 125 16 8: 1 0.75

62

Ratios (A: B) range from 8: 1 to 1: 8.

* ** · · ♦ «« ·

Table 3

2-Methyl-3-isothiazolone (A) / phenylbromoacetate (B) combination

TSB in Escherichia coli

MIC THE B A: B Synaine index 250 ppm 0 ppm - 125 6 20: 1 0.53 125 12 10: 1 0.56 125 25 5: 1 0.62 62 25 2.5: 1 0.37 62 50 1.2: 1 0.50 31 50 1: 1.5 0.37 31 100 1: 3 0.62 16 100 1: 6 0.56 8 100 1:12 0.53 0 200 Candida albicans- -thread TSB examining MIC THE B A: B Szineraikus index

250 ppm 0 ppm - 125 3 40: 1 0.56 125 6 20: 1 0.62 125 6 20: 1 0.62 62 6 10: 1 0.37 31 6 5: 1 0.24

continue Table 3

MIC A

A: B Synergistic index

16 6 2.5: 1 0.18 8 6 1.2: 1 0.15 8 12 1: 1.5 0.28 4 12 1: 3 0.27 4 25 1: 6 0.52 2 25 1:12 0.51 0 50

Ratios (A: B) range from 40: 1 to 1:12.

Table 4

Combination of 2-methyl-3-isothiazolone (A) / dodecylamine (B)

TSB in Escherichia coli

MIC THE B A: B Szinerqikus index 125 ppm 0 ppm - 62 3 20: 1 0.62 62 6 10: 1 0.75 31 12 2.5: 1 0.75 16 12 1.2: 1 0.62 0 25 Candida albicans TSB examining MIC THE B A: B Szinerqikus index 250 ppm 0 ppm - 125 3 40: 1 0.75 62 3 20: 1 0.50 62 6 10: 1 0.75 31 6 5: 1 0.62 16 6 2.5: 1 0.56 0 12

Ratios (A: B) range from 40: 1 to 1.2: 1.

Table 5

2-Methyl-3-isothiazolone (A) / 4- (2-nitrobutyl) -

-morpholine (B) In TSB with Escherichia coli The combination examining A: B Szinerqikus index MIC THE B 125 ppm 0 ppm - 62 8 8: 1 0.53 62 16 4: 1 0.56 62 31 2: 1 0.62 62 62 1: 1 0.75 31 62 1: 2 0.50 16 62 1: 4 0.37 16 125 1: 8 0.62 0 250 Candida albicans thread in TSB examining MIC THE B A: B Szinerqikus index 250 ppm 0 ppm - 125 8 16: 1 0.56 125 16 8: 1 0.62 125 31 4: 1 0.75 62 31 2: 1 0.50 31 31 1: 1 0.37 31 62 1: 2 0.62 16 62 1: 4 0.56 8 62 1: 8 0.53 4 62 1:16 0.52 0 125

Ratios (A: B) range from 16: 1 to 1:16

Table 6

Combination of 2-Methyl-3-isothiazolone (A) / di (propylamine) ether (B)

TSB in Escherichia coli

MIC A B A: B Synergistic index 125 ppm 0 ppm 62 6 10: 1 0.56 62 12 5: 1 0.62 62 25 2.5: 1 0.75 31 50 1: 1.6 0.75 0 100 Candida albicans- thread Examined in TSB MIC A B A: B Synaine index 250 ppm 0 ppm 125 6 20: 1 0.56 125 12 10: 1 0.75 62 12 5: 1 0.50 62 25 2.5: 1 0.75 0 50 Ratios (A: B) 20: 1 and 1: 1.6. The compositions of the invention exhibit synergistic activity.

in most cases, it is also evident in bacteria, fungi and mixtures of bacteria and fungi. Therefore, the invention is an * * 'λ λ λ λ λ λ λ λ λ λ λ λ.

The combinations of 15 not only reduce the concentration of application of the biocidal product, but also provide a broader spectrum of activity. This is particularly advantageous in situations where, in general, no good results can be achieved with any of the individual components because of their poor activity against the particular microorganisms.

Claims (11)

A microbicidal composition, the first component of which is 2-methyl-3-isothiazolone and the second component is sodium dichloroprofen, bis (2-hydroxy-5-chlorophenyl) sulfide, benzyl bromoacetate, dodecylamine, 4-. The weight ratio of (2-nitrobutyl) morpholine or di-propylamino ether to the first component is from 40: 1 to 1:16. The composition of claim 1, wherein the ratio of the first component to the second component of sodium dichloroprofen is from 16: 1 to 1:16. The composition of claim 1, wherein the ratio of the first component to the second component of bis (2-hydroxy-5-chlorophenyl) sulfide is from 8: 1 to 1: 8. The composition of claim 1, wherein the ratio of the first component to the second component of benzyl bromoacetate is 40: 1 to 1:12. The composition of claim 1, wherein the ratio of the first component to the second component of dodecylamine is 40: 1 to 1: 1. The composition of claim 1, wherein the ratio of the first component to the second component of 4- (2-nitrobutyl) morpholine is from 16: 1 to 1:16. The composition of claim 1, wherein the ratio of the first component to the second component of the di (propylamino) ether is from 20: 1 to 1: 2. An antimicrobial composition comprising 0.01 to 99.9% by weight, preferably 5-30% by weight, of 1-7. A composition according to any one of claims 1 to 6, an organic solvent and optionally an emulsifier and water. 9. A method of preventing or inhibiting the growth of bacteria, fungi or algae in a site susceptible to or exposed to contamination by applying to said site or site an amount of a composition or composition according to any one of claims 1 to 8 that inhibits or inhibits growth. The process of claim 9, wherein the site is an aqueous medium and the composition further comprises an organic solvent, an emulsifier and water. Use of a composition according to any one of claims 1 to 7 as a microbicide.