(19) J

(12)

~ ™ llll I I I II II II III 1 1 I I I II 1 1 European Patent Office

Office europeen des brevets (11) E P 0 4 7 6 9 4 3 B 1

EUROPEAN PATENT S P E C I F I C A T I O N

(45) Date of publication and mention of the grant of the patent: 23.10.1996 Bulletin 1996/43

(21) Application number: 91308405.9

(22) Date of filing : 1 3.09.1 991

(51) int. CI.6: A01N 43/80, A01 N 25/04, A01 N 2 5 / 0 2

(54) Water-dilutable isothiazolone composit ions Wasserverdunnbare Isothiazolonzusammensetzungen Compositions d'isothiazolones diluables dans I'eau

(84) Designated Contracting States: AT BE CH DE DK ES FR GB GR IT LI LU NL SE

(30) Priority: 21.09.1990 US 586063

(43) Date of publication of application: 25.03.1992 Bulletin 1992/13

(73) Proprietor: ROHM AND HAAS COMPANY Philadelphia Pennsylvania 19105 (US)

(72) Inventor: Mattox, John Robert Perkasie, Pennsylvania 18944 (US)

(74) Representative: Angell, David Whilton et al ROHM AND HAAS (UK) LTD. European Operations Patent Department Lennig House 2 Mason's Avenue Croydon CR9 3NB (GB)

CO CO

CO

o Q_ LU

(56) References cited: EP-A- 0 174 086 US-A- 4 062 946

DE-A- 2 256 757 US-A- 4 252 694

• PETROLE INFORMATIONS, no. 1646, 1988, PARIS FR pages 14 - 15; 'UN BIOCIDE EFFICACE POUR LA PROTECTION DES FUELS'

• WORLD PATENTS INDEX LATEST Section Ch, Week 9045, 16 January 1991 Derwent Publications Ltd., London, GB; Class C, AN 90- 3401 1 5/45 & JP-A-2 247 1 32

• DATABASE WPI, Derwent Publications Ltd., London, GB; accession no. 67-01 746H (00), week 6800; & JP-A-43005029

• PESTICIDE SCIENCE, vol. 26, no. 1, 1989, BARKING GB pages 51 - 77; T.F.TADROS: 'Colloidal Aspects of Pesticidal and Pharmaceutical Formulations - An Overview'

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).

Printed by Rank Xerox (UK) Business Services 2.13.8/3.4

EP 0 476 943 B1

Description

This invention relates to a water-dilutable preservative concentrate and to an emulsion prepared therefrom suitable for preserving fabric, wood, timber, leather, and various films generated from polymer latices.

5 Preservatives are often used in conjunction with the manufacture of fabrics, wood products, leather, and other sub- strates subject to microbial attack. Attack by fungi and bacteria can lead to discoloration and/or degradation of the sub- strate. Often the preservative is applied by diluting it in water and subsequently dipping the article to which the preservative is to be applied into the solution. In addition, the preservative can be prediluted in water or added directly to a liquid matrix to preserve subsequent films formed upon drying of the matrix, i.e., polymer emulsions or paints.

10 If the preservative is water insoluble it is often combined with water immiscible solvents and emulsifiers so that on addition to water an emulsion forms in which the preservative is, at least initially, uniformly dispersed in the aqueous medium. It is known to incorporate such preservatives, e.g., isothiazolones with fungicidal properties such as those marketed by Rohm and Haas Company as Kathon biocides, into the treatment mixture.

A problem which has been noted in applications which involve dipping a substrate, such as fabric, wood, leather, 15 and the like, into emulsions of isothiazolone fungicides, is that the isothiazolone may be taken up by the substrate in a

non-uniform manner due to poor homogeneity of the emulsion. Related problems occur where emulsions are used to impregnate wood. This is usually accomplished by introducing the isothiazolone emulsion into a vessel containing the wood to be impregnated, and applying pressure and vacuum according to various defined procedures. The emulsion not taken up by the wood is pumped into a storage tank where is remains, with little or no agitation, until reused to

20 impregnate subsequent batches. Often the stored emulsion must remain unagitated during non-use periods, or over- night, weekends, etc. Emulsions which are prepared and held unagitated, before addition to polymer laticies or paints, have similar homogeneity problems. The problem is especially acute in situations where the emulsion is prepared and used over a period of weeks with little or no agitation. Separation of emulsions can lead to overdosing or underdosing the preservative.

25 One approach to solving the problem of inhomogeneity caused by separation of the oil phase with time is to formu- late a microemulsion, such as described in U.S.-A-4,954,338. The small particle size (<100nm) of the microemulsion precludes phase separation but typically requires five to ten times the amount of emulsif ier needed to form macroemul- sions. It has been observed that high emulsifier levels can sometimes be detrimental to retention of isothiazolone on the preserved substrate when the substrate (fabric, wood, leather, and the like) subsequently comes into contact with

30 water during use or storage. High levels of emulsifier can cause solubilization of the water insoluble preservative during subsequent contact with water, resulting in loss of some of the isothiazolone and consequently a lesser degree of pres- ervation than expected from a given initial concentration of isothiazolone. The degree of post solubilization is dependent upon the amount of emulsifier present: thus it is usually desirable to minimize the amount of emulsifier present in order to minimise the loss of preservation on subsequent exposure to water.

35 It is known to use a mixture of isothiazolones, emulsifiers, and organic solvents to prepare emulsive concentrates of isothiazolones for dilution into aqueous systems. However, these emulsive concentrates do not possess good "phase stability" (lack of phase separation) upon dilution; one factor contributing to the tendency of these mixtures to undergo phase separation is the large density differential that exists between the isothiazolone/solvent phase and the aqueous phase.

40 It is known to use a mixture of agricultural pesticides/insecticides/herbicides, emulsifier, and organic solvents for dispersal and/or dilution into aqueous solutions for applications to crops, plants, soil, and the like. Commercially used pesticide emulsive concentrates are usually considered satisfactory and adequate if they do not phase separate within one to two hours after dilution, because agitation is usually present during application.

In the case where solvents alone are used to dissolve the isothiazolone preservative, to form an "isothiazolone con- 45 centrate", the concentrate is diluted on site into the aqueous treatment solution for dipping of a substrate or impregna-

tion of wood. Solvents used to make up conventional isothiazolone concentrates are typically of the low density (specific gravity <0.9), aromatic hydrocarbon type, e.g., xylene. These solvents possess the necessary solubility characteristics to dissolve significant amounts of water-insoluble isothiazolones such as 4,5-dichloro-2-n-octyl-3-isothiazolone. These particular isothiazolone concentrates also contain a small amount of emulsifier in order to produce a dispersion/emul-

50 sion once the concentrate is diluted into the aqueous solution to be used to treat the wood. Due to the large density differential between the solvent concentrate and the aqueous solution in which the concentrate is being diluted, the resultant emulsion of isothiazolone very often is unstable in terms of homogeneity, i.e., phase separation occurs between the bulk aqueous phase (specific gravity of approximately 1 .00 for water) and the solvent-isothiazolone phase (specific gravity of approximately 0.95). This tendency to phase separate causes problems in repeated use of the aque-

55 ous emulsions to treat substrates with isothiazolone preservatives in that within a short time the uptake of isothiazolone into the substrate becomes non-uniform due to non-homogeneous exposure to the isothiazolone. The dip tank method of treating substrates such as fabric, wood, leather, and the like, requires a significant degree of solution/emulsion homogeneity for an extended period of time in order to treat with a precise amount of preservative. Other situations

2

EP 0 476 943 B1

where emulsions of isothiazolones are prepared, used intermittently, and stored without agitation, such as preemulsifi- cation before adding to latex, or impregnation of wood, have similar homogeneity requirements.

We have now surprisingly found that by incorporation of a certain class of organic solvents into the formulation of the isothiazolone emulsive concentrate, the tendency of the isothiazolone-containing treatment solution (emulsion) to

5 remain homogeneous (stable to phase separation) is greatly enhanced, increasing the period of stability from a few hours to many weeks, allowing a high degree of utilization of the isothiazolone "charged" to the system with a uniform uptake by the substrate being treated.

Accordingly in a first aspect the invention provides a isothiazolone concentrate comprising:

10 (a) from 1 to 35% by weight of an isothiazolone, preferably having a water solubility of less than 1% by weight, of the formula:

15

20

R O

N -Y

FT

wherein

Y is an alkyl group of 2 to 18 carbon atoms optionally substituted with one or more of hydroxy, halo, 25 cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, carbalkoxy, alkoxy, ary-

loxy, morpholino, piperidino, pyrrolidonyl, carbamoxy, or isothiazolonyl, wherein the total number of carbon atoms in the substituted alkyl group does not exceed 18; an unsubstituted or halo-substi- tuted alkenyl group of 4 to 18 carbon atoms; an unsubstituted or halo-substituted alkynyl group of to 18 carbon atoms; an unsubstituted or alkyl-substituted cycloalkyl group having a four to six car-

30 bon atom ring and up to 1 2 carbon atoms; an unsubstituted or a halo-, lower alkyl-, or lower alkoxy- substituted aralkyl group wherein the total number of carbon atoms in the aralkyl group does not exceed 10; or an unsubstituted or a halo-, nitro-, lower alkyl-, or lower carbalkoxy-, substituted aryl group wherein the total number of carbon atoms in the aryl group does not exceed 10; and

R and R1 are each independently hydrogen, halogen, or a (C1-C4) alkyl group; 35

(b) a first organic solvent comprising one or more aromatic hydrocarbons having a kauri-butanol value >70, a boil- ing point or range at one atmosphere between 1 10°C and 360°C, and a specific gravity of <0.95; (c) an emulsifier; characterised in that the concentrate further comprises; (d) a second organic solvent capable of dissolving at least 20% by weight of said isothiazolone and having a spe-

40 cif ic gravity of >0.95, comprising one or more of lower-alkyl substituted naphthalene, tetralin, lower-alkyl substituted tetralins, indane, or lower-alkyl substituted indanes, whereby said concentrate is capable of forming a stable mac- roemulsion in water.

By "stable macroemulsion" is meant a macroemulsion (typically having an emulsion particle size of at least 1^m) 45 which is phase stable for at least 24 hours, preferably for at least one week.

Another aspect of the invention comprises a stable macroemulsion of said concentrate in a medium, usually water. Generally the concentrate is prepared such that the final specific gravity of the concentrate matches the specific gravity of the medium to which it is added within the limits +0.02 units. For dilution in water, the specific gravity range of the emulsive concentrate would be 0.98-1.02, preferably 0.995-1.005. For dilution in water containing dissolved salts or

so other solids, the midpoint of the concentrate range would be higher in order to match the specific gravity of the salt solu- tion. For solutions of low density organic materials in water, the midpoint of the range could be less than 1 .000.

Another aspect of the invention comprises a method of producing a stable macroemulsion of an isothiazolone con- centrate in a medium, comprising adding an effective amount of a concentrate as defined above to a medium in which said concentrate is to be diluted, said concentrate preferably having a specific gravity of within +/- 0.02 units, more pref-

55 erably with +0.01 units, and most preferably within +0.005 units of the specific gravity of said medium. Another aspect of the invention comprises treating a substrate such as fabric, wood, leather and the like with a pre-

servative composition in an amount effective to inhibit microbial growth, said composition comprising either the isothia- zolone concentrate or a macroemulsion thereof. This treatment may involve a dilution of the concentrate into dip tanks,

3

EP 0 476 943 B1

or into a precaution tank to be used in wood impregnation or for addition to water based materials such as latex, paints, and the like.

The invention will now be described in more detail by way of example with reference to the accompanying drawings, in which

5 Figure 1 is a plot of data from Example 1 , and Figure 2 is a plot of data from Example 4.

Suitable 3-isothiazolones include those as defined above. 10 Generally the water-solubility of the isothiazolones will be less than 1% by weight. One skilled in this art will recog-

nize that the water solubility of the isothiazolones depends on the type of substituent (i.e., R, R1 and Y). For example, when R=R1=halo, the alkyl group can be as low as two carbon atoms and the water solubility will be less than 1%. When only one of the R or R1 is halo and the other hydrogen, an alkyl group of at least four carbon atoms will result in a water- solubility of less than 1%, and when both R and R1 is hydrogen such low solubility occurs when the alkyl group has at

15 least six carbon atoms. Particularly preferred isothiazolones are 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and

4,5-dichloro-2-n-octyl-3-isothiazolone. Suitable first organic solvents capable of dissolving the above isothiazolone (solubility of isothiazolone >20% by

weight, specific gravity <0.95) are xylene, Aromatic 100, Aromatic 150, Solvesso 100, Solvesso 150, Shell Sol A, 20 Cyclosol 53, psuedocumene, Panasol AN-2K, Panasol AW-2L, Panasol AN-3N, Cyclosol 27 and Chartersol 1 solvents.

Especially preferred are xylene, Solvesso 100 and Solvesso 150 solvent. The Panasol solvents are high boiling point aromatics containing mono- and di-alkylnaphthalenes. Chartersol 1 contains 96% C8+ aromatics: the Aromatic solvents contain 96% C8+ aromatics: Cyclosols are 78% + toluene/ethylbenzene, 22% or less saturates. The Aromatic and Solvesso solvents are supplied by Exxon, the Cyclosol solvents by Shell, the Panasol solvents by Amoco, and the Char-

25 tersol solvent by Charter. Aromatic, Solvesso, Cyclosol, Panasol and Chartersol are trade marks. The kauri-butanol value is a standard measure of aromatic content where values of 80-105 are typical of aromatic compounds (Hawley's Condensed Chemical Dictionary. 1 1th Edition, Von Nostrand Reinhold Co., NY, page 670).

Suitable second organic solvents capable of dissolving the above isothiazolones (>20% by weight) and having spe- cific gravities of >0.95 are lower-alkyl substituted naphthalenes where lower-alkyl refers to (Ci-C3)alkyl, tetralin, methyl

30 and dimethyl substituted tetralin, indane, methyl and dimethyl substituted indane. These substituted solvents may con- tain more than the lower-alkyl substituent so long as the specific gravity of the resultant solvent is >0.95. Desirably the solvents should also have a water solubility of less than 0.1% by weight. A preferred solvent is the commercially avail- able mixture of methyl, dimethyl, trimethyl, ethyl, and methyl ethyl substituted naphthalenes known as "methyl naphtha- lene", hereinafter referred to as methylnaphthalene.

35 Suitable emulsifiers are those conventionally used in concentrates of isothiazolones and include octyl phenol ethoxylates, nonyl phenol ethoxylates, primary or secondary alcohol ethoxylates, sorbitan esters, ethoxylated sorbitan esters, ethylene oxide propylene oxide block polymers, ethoxylated fatty acids, ethoxylated castor oil, alkyl sulfates, alkyl aryl sulfonates, sulfonates and sulfates of ethoxylated alkyl phenols, sulfates and sulfonates of oils and fatty acids, phosphates, olefin sulfonates, diphenyl sulfonates, and alkyl benzyl or alkylaryl substituted quaternary ammonium com-

40 pounds. Examples are anionic surfactants such as sodium dodecylbenzene sulfonate, calcium dodecyl benzene sul- fonate and ethanolamine dodecyl benzene sulfonate. Preferred emulsifiers are selected from commercially available anionic, nonionic blends sold under trade names such as Sponto, Toximul, T-Mulz, and Triton emulsifiers. Sponto emul- sifiers are supplied by Witco, Toximul emulsifiers by Stepan, T-Mulz emulsifiers by Thompson-Hayward, and Triton emulsifiers by Rohm and Haas Co. These are especially useful when emulsions must be prepared in a wide range of

45 water hardness. In the preparation of the emulsive concentrate compositions of this invention, the isothiazolone is present at 1-35%

of the total weight of the concentrate, preferably 5-30%, and most preferably 15-25%. The emulsifiers may be present at 1-12%, preferably 2-10% and most preferably at 3-7%. The amounts of the first (Solvent 1) and second solvent (Sol- vent 2) are chosen to prepare a concentrate which has a specific gravity to match that of the dilution medium to within

so +0.02, preferably +0.01 , and most preferably + 0.005. The Formulations Table shown below indicates typical ranges for each component of the composition of the inven-

tion. The ranges given for Solvent 1 and Solvent 2 represent the various combinations which may be required to most closely match the specific gravity of the dilution medium, given a certain concentration of isothiazolone and emulsifier. The ranges listed in the Formulations Table are capable of matching dilution media specific gravities of up to 1 .1 , typi-

55 cally 1 .05 or less, and most typically 1 .02 or less.

4

EP 0 476 943 B1

FORMULATIONS TABLE

Isothiazolone Solvent 1 Solvent 2 Emulsifier

1-35% 0-50% 5-98% 1-12%

Preferred 5-30% 3-45% 15-90% 2-10%

Most Preferred 15-25% 5-32% 35-77% 3-7% 10

It is not necessary for the specific gravity of a given composition of the invention to match exactly that of the solution into which it is to be diluted, but it should be close enough, i.e., within about 0.02 specific gravity units, in order to pro-

15 duce a stable isothiazolone emulsion, i.e., no phase separation after several weeks, after dilution of the isothiazolone emulsive concentrate. The density differentials of prior art formulations for isothiazolone emulsive concentrates using only solvents selected from the group represented by Solvent 1 are typically about 0.05 or greater, thus resulting in poor phase separation resistance, i.e., phase separation after a few hours.

The following examples are illustrative of the invention but are not intended to limit it in any way. Examples 1 and 4 20 illustrate the wide range of concentrations for each solvent component at 2 different levels of isothiazolone that would

be consistent with matching the specific gravities of dilution media in the range of 0.995 to 1.02. Example 2 presents emulsion stability data on isothiazolone emulsive concentrate compositions of the invention prepared to match the spe- cific gravity of the dilution medium to within +/- 0.005 units. Example 3 presents a comparison of the composition of the invention with 2 compositions, one representative of prior art isothiazolone emulsive concentrates in which only solvent

25 selected from the Solvent 1 group is used, and the other representative of an isothiazolone emulsive concentrate using the components of the present invention but not in the ratios required to give a density differential of approximately 0.02 or less specific gravity units relative to the dilution medium being tested.

The following examples refer to concentrations by percent; in all cases this term refers to percent by weight of a given component relative to the total weight of the solution or mixture involved. Isothiazolone A refers to 4,5-dichloro-2-

30 n-octyl-3-isothiazolone. The term active ingredient (designated Al) refers to the isothiazolone component, in this case, Isothiazolone A. The solvents designated Solvesso 100 and 150 are supplied by Exxon UK. The Emulsifier Blends are described in each example and the components are supplied by Witco Co.

EXAMPLE 1 35

SOLVENT COMPOSITION AND SPECIFIC GRAVITY At 25% Al

The following compositions containing 25% active ingredient were prepared and their specific gravities were meas- ured using a pycnometer in a thermostated bath at 25° C. The Emulsifier Blend is composed of 85% Sponto 232T and

40 1 5% Sponto 234T emulsifiers.

I II III IV V VI VII

Isothiazolone A 26.5(25.0) 26.5(25.0) 26.5(25.0) 26.5(25.0) 26.5(25.0) 26.5(25.0) 26.5(25.0) (94% tech) (As Al) Solvesso 100 34.5 33.5 32.5 28.5 26.0 23.5 21.0

Methylnaphtha- 34.0 35.0 36.0 40.0 42.5 45.0 47.5 lene

Emulsifier Blend 5.0 5.0 5.0 5.0 5.0 5.0 5.0

100.0 100.0 100.0 100.0 100.0 100.0 100.0

Specific gravity 0.9954 0.9967 0.9997 1.0044 1.0071 1.0125 1.013 (25/4) The data are plotted and the best fit line is shown in Fig. 1 .

5

EP 0 476 943 B1

Example 2

STABILITY OF ISOTHIAZOLONE A EMULSIONS TOWARD PHASE SEPARATION

In a manner similar to that described in Example 1, Formulation II was prepared except that the Emulsifier Blend used was composed of 80% Sponto 232T and 20% Sponto 234T, hereinafter referred to as formulation 1 1 A. To each of three 100 ml glass stoppered graduated cylinders was added 99 ml of deionized water (Dl), 342 ppm hardness water, and 1 000 ppm hardness water, respectively. The two hard water samples were prepared by standard procedures for preparing "standard hard water" (Specifications for Pesticides. World Health Organization, p 304 (1973)). To each of the graduated cylinders was added one ml of Formulation MA (described above). After capping the graduated cylinders they were inverted slowly 30 times and then placed on a level surface with no further agitation. The 3 samples were then observed for phase separation at 2 and 24 hours.

Observation DIH20 Sample

342 ppm 1000 ppm hardness hardness

2-hour + + + 24-hour + + + 8-week + + + 12-week +

"+" = no visible separation = separation of a cream or oil layer

Emulsion showed excellent stability in a wide range of water hardness for up to 8 weeks. Phase separation occured in the two hard water samples between 8 and 12 weeks.

The emulsion of formulation IIA in Dl water contained in a 100 ml graduated cylinder was sampled after standing 12 weeks unagitated. Samples were taken from the top and bottom 5 mis and analyzed for Al by HPLC. The concen- tration at the top was 2300 ppm Al and 2600 ppm at the bottom (nominal value expected was 2500 ppm). This demon- strated the visual observation of lack of creaming, i.e., no phase separation.

EXAMPLE 3

COMPARATIVE EMULSION STABILITY USING SINGLE SOLVENTS

In a manner similar to that described in Example 1, formulations IIA, VIII and IX were prepared using the same Emulsifier Blend composition described in Example 2.

VIII IX

Isothiazolone A (94% tech) (as Al) 26.5 (25.0) 26.5 (25.0) Solvesso 100 68.5

Methylnaphthalene 68.5

Emulsifier Blend 5.0 5.0

100.0 100.0

These formulations were subjected to the emulsion stability test as described in Example 2 by diluting with Dl water (0 ppm hardness).

EP 0 476 943 B1

Observation Sample IIA VIII IX

2-hour + + + 24-hour +

10 Both VIII and IX underwent phase separation of the oil phase between 2 and 24 hours, whereas formulation IIA

showed no separation and would be expected to maintain stability for at least 12 weeks (as shown in Example 2). The specific gravities of formulations IIA, VIII, and IX are 1 .00, 0.94 and 1 .04 respectively. Only formulation IIA is

capable of a density differential of <0.02 units relative to the dilution water, thus accounting for its excellent phase sta- rs bility relative to the other formulations.

Example 4

SOLVENT COMPOSITION AND SPECIFIC GRAVITY 20

Compositions containing 20% Al Isothiazolone A were prepared containing 3% Emulsifier Blend (same as Example 2) and varying the solvent ratio. Specific gravities were measured as in Example 1 .

25 X XI XII XIII XIV XV

Isothiazolone A (95% 21.0(20.0) 21.0(20.0) 21.0 (20.0) 21.0(20.0) 21.0 (20.0) 21.0(20.0) tech) (as Al) Solvesso 150 26.0 20.0 16.0 13.5 11.0 8.5

in Methylnaphthalene 50.0 56.0 60.0 62.5 65.0 67.5

Emulsifier Blend 3.0 3.0 3.0 3.0 3.0 3.0

100.0 100.0 100.0 100.0 100.0 100.0

35 Specif ic Gravity (25/4) 0.998 1.008 1.011 1.012 1.017 1.018

The data are plotted and shown in Figure 2.

40 Claims

1 . A isothiazolone concentrate composition comprising:

45 (a) from 1 to 35% by weight of an isothiazolone, preferably having a water solubility of less than 1% by weight, of the formula:

R O

50

55 R'

N-Y

wherein

7

EP 0 476 943 B1

Y is an alkyl group of 2 to 1 8 carbon atoms optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, carbalkoxy, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoxy, or isothiazolonyl, wherein the total number of carbon atoms in the substituted alkyl group does not exceed 18; an unsubstituted or halo-substituted alkenyl group of 4 to 1 8 carbon atoms; an unsubstituted or halo-substituted alkynyl group of to 18 carbon atoms; an unsubstituted or alkyl-substituted cycloalkyl group having a four to six carbon atom ring and up to 12 carbon atoms; an unsubstituted or a halo-, lower alkyl-, or lower alkoxy-substituted aralkyl group wherein the total number of carbon atoms in the aralkyl group does not exceed 10; or an unsubstituted or a halo-, nitro-, lower alkyl-, or lower carbalkoxy-, substituted aryl group wherein the total number of carbon atoms in the aryl group does not exceed 10; and

R and R1 are each independently hydrogen, halogen, or a (C1-C4) alkyl group;

(b) a first organic solvent comprising one or more aromatic hydrocarbons having a kauri-butanol value >70, a boiling point or range at one atmosphere between 1 10°C and 360°C, and a specific gravity of <0.95; (c) an emulsifier; characterised in that the concentrate further comprises; (d) a second organic solvent capable of dissolving at least 20% by weight of said isothiazolone and having a specific gravity of >0.95, comprising one or more of lower-alkyl substituted naphthalene, tetralin, lower-alkyl substituted tetralins, indane, or lower-alkyl substituted indanes, whereby said concentrate is capable of forming a stable macroemulsion in water.

2. Composition according to claim 1 wherein said second organic solvent is one or more of (Ci-C3)alkyl substituted naphthalenes, tetralin, methyl/dimethyl substituted tetralin, indane, or methyl or dimethyl substituted indane.

3. Composition according to claim 2 wherein said second organic solvent is a mixture of methyl, dimethyl, trimethyl, ethyl, and methyl ethyl substituted naphthalene known as "methyl naphthalene".

4. Composition according to any of claims 1 to 3 wherein the emulsifier is one or more of octyl phenol ethoxylates, nonyl phenol ethoxylates, primary or secondary alcohol ethoxylates, sorbitan esters, ethoxylated sorbitan esters, ethylene oxide propylene oxide block polymers, ethoxylated fatty acids, ethoxylated castor oil, alkyl sulfates, alkyl aryl sulfonates, sulfonates and sulfates of ethoxylated alkyl phenols, sulfates and sulfonates of oils and fatty acids, phosphates, olefin sulfonates, diphenyl sulfonates, or alkyl benzyl or alkylaryl substituted quaternary ammonium compounds.

5. Composition according to any preceding claim wherein the isothiazolone is 2-n-octyl-3-isothiazolone, 4,5-dichloro- 2-cyclohexyl-3-isothiazolone, or 4,5-dichloro-2-n-octyl-3-isothiazolone.

6. Composition according to any preceding claim, having a specific gravity range of from 0.995 to 1 .005.

7. Composition according to claim 1 wherein said first organic solvent is one or more of xylene, Aromatic 100, Aro- matic 150, Solvesso 100, Solvesso 150, Shell Sol A, Cyclosol 53, psuedocumene, Panasol AN-2K, Panasol AW- 2L, Panasol AN-3N, Cyclosol 27 or Chartersol 1.

8. Composition according to any preceding claim, wherein the isothiazolone is present in an amount of from 1 to 35%, preferably from 5 to 30% and most preferably 1 5 to 25% by weight of the total concentrate, and the emulsifiers are present at 1 to 1 2%, preferably 2 to 1 0%, more preferably 3 to 7 %.

9. A stable macroemulsion of an isothiazolone concentrate in a medium, wherein said concentrate is as defined in any of claims 1 to 8, and preferably has a specific gravity within +0.02, more preferably within +0.01 and most preferably within +0.005 units of that of the medium.

10. Method of producing a stable macroemulsion of an isothiazolone concentrate in a medium, comprising adding an effective amount of a concentrate as defined in any one of claims 1 to 8 to a medium in which said concentrate is to be diluted, said concentrate preferably having a specific gravity of within +/- 0.02 units, more preferably with +0.01 units, and most preferably within +0.005 units of the specific gravity of said medium.

11. A stable macroemulsion or a method according to claims 9 or 10 wherein said medium is water.

8

EP 0 476 943 B1

1 2. Method of inhibiting or preventing the growth of bacteria, fungi, or algae in a locus subject or susceptible to contam- ination thereby, which comprises incorporating onto or into the locus, in an amount effective to adversely affect said growth, a concentrate according to any of claims 1 to 8 or a macroemulsion according to claims 9 or 1 1 .

13. Method according to claim 12 wherein the locus is an aqueous medium, or a solid protective or decorative film, or fabric, leather, paper, or wood.

Patentanspruche

1. Isothiazolonzusammensetzungskonzentrat, enthaltend:

(a) von 1 bis 35 Gew.-% eines Isothiazolons, das vorzugsweise eine Wasserloslichkeit von weniger als 1 Gew.- % aufweist und der Formel geniigt:

Y ist in der Formel eine Alkylgruppe mit 2 bis 18 Kohlenstoffatomen, gegebenenfalls substituiert mit einem oder mehreren von Hydroxy, Halogen, Cyano, Alkylamino, Dialkylamino, Phenylamino, Halophenylamino, Carboxy, Carbalkoxy, Alkoxy Aryloxy, Morpholino, Piperidino, Pyrrolidonyl Carbamoxy oder Isothiazolonyl wobei die Gesamtzahl der Kohlenstoffatome in der substituierten Alkylgruppe 18 nicht iiberschreitet, eine nichtsubstitu- ierte oder mit Halogen substituierte Alkenylgruppe mit 4 bis 18 Kohlenstoffatomen, eine nichtsubstituierte oder mit Halogen substituierte Alkynylgruppe mit bis zu 18 Kohlenstoffatomen, eine nichtsubstituierte oder mit Alkyl substituierte Cycloalkylgruppe mit 4 bis 6 Kohlenstoffatomen im Ring und bis zu 12 Kohlenstoffatomen, eine nichtsubstituierte oder mit Halogen, niederem Alkyl oder niederem Alkoxy substituierte Aralkylgruppe, wobei die Gesamtzahl der Kohlenstoffatome in der Aralkylgruppe 1 0 nicht iiberschreitet, oder eine nichtsubstituierte oder mit Halogen, Nitro, niederem Alkyl oder niederem Carbalkoxy substituierte Arylgruppe, wobei die Gesamtzahl der Kohlenstoffatome in der Arylgruppe 10 nicht iiberschreitet, und R und R1 jeweils unabhangig voneinander Wasserstoff, Halogen oder eine (Ci-C4)-Alkylgruppe sind, (b) ein erstes organisches Losemittel, enthaltend einen oder mehrere aromatische Kohlenwasserstoffe mit einem Kauributanolwert >70, einem Siedepunkt oder Siedebereich bei einer Atmosphare zwischen 1 10°C und 360°C und einer relativen Dichte von <0,95, (c) einen Emulgator, dadurch gekennzeichnet, daB das Konzentrat weiterhin enthalt: (d) ein zweites organisches Losemittel das in der Lage ist, mindestens 20 Gew.-% des Isothiazolons aufzulo- sen, mit einer relativen Dichte von >0,95, enthaltend eines oder mehrere von mit niederem Alkyl substituiertem Naphtalin, Tetralin, mit niederem Alkyl substituierte Tetraline, Indan oder mit niederem Alkyl substituierte Ind- ane, wobei das Konzentrat in Wasser eine stabile Makroemulsion ausbilden kann.

2. Zusammensetzung nach Anspruch 1 , dadurch gekennzeichnet, daB das zweite organische Losemittel eines oder mehrere von mit (Ci-C3)-Alkyl substituierten Naphtalinen, Tetra- lin, mit Methyl/Dimethyl substituiertem Tetralin, Indan oder mit Methyl oder Dimethyl substituiertem Indan ist.

3. Zusammensetzung nach Anspruch 2, dadurch gekennzeichnet, daB das zweite organische Losemittel eine Mischung von mit Methyl, Dimethyl, Trimethyl, Ethyl und Methylethyl substituiertem Naphthalin, auch bekannt als "Methylnaphtalin", ist.

4. Zusammensetzung nach einem der Anspriiche 1 bis 3, dadurch gekennzeichnet,

R 0

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daB der Emulgator eines oder mehrere ist von Octylphenolethoxylaten, Nonylphenolethoxylaten, primaren oder sekundaren Alkoholethoxylaten, Sorbitanestern, ethoxylierten Sorbitanestern, Ethylenoxidpropylenoxid-Blockcop- olymeren, ethoxylierten Fettsauren, ethoxyliertem Rizinusol, Alkylsulfaten, Alkylarylsulfonaten, Sulfonaten und Sul- faten von ethoxylierten Alkylphenolen, Sulfaten und Sulfonaten von Olen und Fettsauren, Phosphaten,

5 Olefinsulfonaten, Diphenylsulfonaten oder mit Alkylbenzyl oder Alkylaryl substituierten quaternaren Ammonium- verbindungen.

5. Zusammensetzung nach einem der vorstehenden Anspriiche, dadurch gekennzeichnet,

10 daB das Isothiazolon 2-n-Octyl-3-isothiazolon, 4,5-Dichlor-2-cyclohexyl-3-isothiazolon oder 4,5-Dichlor-2-n-octyl- 3-isothiazolon ist.

6. Zusammensetzung nach einem der vorstehenden Anspriiche, dadurch gekennzeichnet,

15 daB sie eine relative Dichte im Bereich von 0,995 bis 1 ,005 aufweist.

7. Zusammensetzung nach Anspruch 1 , dadurch gekennzeichnet, daB das erste organische Losemittel eines oder mehrere ist von Xylol, Aromatic 100, Aromatic 150, Solvesso 100,

20 Solvesso 150, Shell Sol A, Cyclosol 53, Psuedocumene, Panasol AN-2K, Panasol AW-2L, Panasol AN-3N, Cyclo- sol 27 oder Chartersol 1 .

8. Zusammensetzung nach einem der vorstehenden Anspriiche, dadurch gekennzeichnet,

25 daB das Isothiazolon vorhanden ist in einer Menge von 1 bis 35 Gew.-%, vorzugsweise von 5 bis 30 Gew.-% und ganz besonders bevorzugt von 1 5 bis 25 Gew.-% des gesamten Konzentrats, und die Emulgatoren vorhanden sind mit 1 bis 12 Gew.-%, vorzugsweise 2 bis 10 Gew.-%, ganz besonders bevorzugt 3 bis 7 Gew.-%.

9. Stabile Makroemulsion eines Isothiazolonkonzentrats in einem Medium, 30 dadurch gekennzeichnet,

daB das Konzentrat eines gemaB einem der vorstehenden Anspriiche 1 bis 8 ist und vorzugsweise eine relative Dichte innerhalb +0,02, vorzugsweise innerhalb +0,01 und ganz besonders bevorzugt innerhalb +0,005 Einheiten von denen des Mediums aufweist.

35 1 0. Verfahren zum Herstellen einer stabilen Makroemulsion eines Isothiazolonkonzentrats in einem Medium durch Hin- zufiigen einer wirksamen Menge eines Konzentrats gemaB einem der vorstehenden Anspriiche 1 bis 8 zu einem Medium, in dem das Konzentrat verdiinnt werden soil wobei das Konzentrat vorzugsweise eine relative Dichte innerhalb +0,02 Einheiten, vorzugsweise innerhalb +0,01 Einheiten und ganz besonders bevorzugt innerhalb +0,005 Einheiten der relativen Dichte des Mediums aufweist.

40 11. Stabile Makroemulsion oder Verfahren nach Anspriichen 9 oder 10,

dadurch gekennzeichnet, daB das Medium Wasser ist.

45 12. Verfahren zum Hemmen oder Verhindern des Wachstums von Bakterien, Pilzen oder Algen an einem Ort, der damit befallen oder anfallig dafiir ist, durch Einbringen auf oder in den Ort einer das Wachstum wirksam gegenteilig beeinflussenden Menge eines Konzentrats nach einem der Anspriiche 1 bis 8 oder einer Makroemulsion nach Anspriichen 9 oder 1 1 .

so 13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daB der Ort ein waBriges Medium oder ein fester Schutz- oder Dekorf ilm oder ein Gewebe, Leder, Papier oder Holz ist.

55 Revendications

1 . Composition concentree d'isothiazolone comprenant:

10

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(a) de 1 a 35% en poids d'une isothiazolone, de preference ayant une solubilite dans I'eau inferieure a 1% en poids, de formule:

10

R O

R

N-Y

dans laquelle,

15 Y est un groupe alkyle de 2 a 1 8 atomes de carbone, eventuellement substitue par un ou plusieurs subs- tituants parmi les groupes hydroxy, halogeno, cyano, alkylamino, dialkylamino, phenylamino, halogenophenylamino, carboxy, carbalcoxy, alcoxy, aryloxy, morpholino, piperidino, pyrrolidonyle, carbamoxy, ou isothiazolonyle.ou le nombre total d'atomes de carbone dans le groupe alkyle subs- titue n'excede pas 18; un groupe alcenyle non substitue ou a substitution halogeno, ayant de 4 a

20 1 8 atomes de carbone; un groupe alcynyle non substitue ou a substitution halogeno, ayant jusqu'a 1 8 atomes de carbone; un groupe cycloalkyle non substitue ou a substitution alkyle, ayant un cycle de quatre a six atomes de carbone et jusqu'a 12 atomes de carbone; un groupe aralkyle non subs- titue ou a substitution halogeno, alkyle inferieur, ou alcoxy inferieur, dans lequel le nombre total d'atomes de carbone dans le groupe aralkyle n'excede pas 10; ou un groupe aryle non substitue

25 ou a substitution halogeno, nitro, alkyle inferieur ou carbalcoxy inferieur, dans lequel le nombre total d'atomes de carbone dans le groupe aryle n'excede pas 10; et

R et R1 represented chacun independamment I'hydrogene, un atome d'halogene, ou un groupe alkyle en Ci-C4;

30 (b) un premier solvant organique comprenant un ou plusieurs hydrocarbures aromatiques ayant un indice kauri-alcool butylique >70, un point d'ebullition ou un domaine d'ebullition, a un atmosphere, compris entre 1 10°C et 360°C, et un poids volumique <0,95; (c) un emulsifiant; caracterisee en ce que le concentre comprend en outre:

35 (d) un second solvant organique capable de dissoudre au moins 20% en poids de ladite isothiazolone et ayant un poids volumique >0,95, comprenant un ou plusieurs solvants choisis parmi le naphtalene a substitution alk- yle inferieur, la tetraline, les tetralines a substitution alkyle inferieur, lindane, ou les indanes a substitution alk- yle inferieur, ce qui fait que ledit concentre est capable de former une macroemulsion stable dans I'eau.

40 2. Composition selon la revendication 1 , dans laquelle ledit second solvant organique est un ou plusieurs solvants choisis parmi les naphtalenes a substitution alkyle en C1-C3, la tetraline, la tetraline a substitution methyle/dime- thyle, lindane, ou lindane a substitution methyle ou dimethyle.

3. Composition selon la revendication 2, dans laquelle ledit second solvant organique est un melange de naphtalene 45 a substitution methyle, dimethyle, trimethyle, ethyle, et methylethyle, connu sous le nom de "methylnaphtalene".

4. Composition selon I'une quelconque des revendications 1 a 3, dans laquelle I'emulsif iant est un ou plusieurs emul- sifiants choisis parmi les ethoxylates d'octylphenol, les ethoxylates de nonylphenol, les ethoxylates d'alcool pri- maire ou secondaire, les esters de sorbitan, les esters de sorbitan ethoxyles, les polymeres sequences d'oxyde

so d'ethylene et d'oxyde de propylene, les acides gras ethoxyles, I'huile de ricin ethoxylee, les alkylsulfates, les alky- larylsulfonates, les sulfonates et les sulfates d'alkylphenols ethoxyles, les sulfates et les sulfonates d'huiles et d'aci- des gras, les phosphates, les olefinesulfonates, des diphenylsulfonates, ou les derives d'ammonium quaternaire substitues par un alkylbenzyle ou un alkylaryle.

55 5. Composition selon I'une quelconque des revendications precedentes, dans laquelle I'isothiazolone est la 2-n-octyl- 3-isothiazolone, la 4,5-dichloro-2-cyclohexyl-3-isothiazolone ou la 4,5-dichloro-2-n-octyl-3-isothiazolone.

6. Composition selon I'une quelconque des revendications precedentes, ayant un poids volumique compris dans le domaine de 0,995 a 1 ,005.

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. Composition selon la revendication 1 , dans laquelle ledit premier solvant organique est un ou plusieurs solvants choisis parmi le xylene, I'Aromatic 100, 1'Aromatic 150, le Solvesso 100, le Solvesso 150, le Shell Sol A, le Cyclosol 53, le pseudocumene, le Panasol AN-2K, le Panasol AW-2L, le Panasol AN-3N, le Cyclosol 27 ou le Chartersol 1 .

. Composition selon Tune quelconque des revendications precedentes, dans laquelle I'isothiazolone est presente a raison de 1 a 35%, de preference de 5 a 30%, et plus particulierement de 15 a 25% en poids du concentre total, et les emulsifiants sont presents a raison de 1 a 12%, de preference de 2 a 10%, et plus particulierement de 3 a 7%.

. Macroemulsion stable d'un concentre d'isothiazolone dans un milieu, dans laquelle ledit concentre est tel que defini selon I'une quelconque des revendications 1 a 8, et de preference, possede un poids volumique dans les limites de +0,02, plus particulierement, dans les limites de +0,01 et mieux encore, dans les limites de +0,005 unite de celui du milieu.

0. Procede de production d'une macroemulsion stable d'un concentre d'isothiazolone dans un milieu, qui consiste a ajouter une quantite efficace d'un concentre tel que defini selon I'une quelconque des revendications 1 a 8 dans un milieu dans lequel ledit concentre doit etre dilue, ledit concentre ayant, de preference, un poids volumique dans les limites de +0,02 unite, plus particulierement dans les limites de +0,01 unite, et mieux encore dans les limites de +0,005 unite du poids volumique dudit milieu.

1. Macroemulsion stable ou procede selon les revendications 9 ou 10, ou ledit milieu est de I'eau.

2. Procede d'inhibition ou de prevention de la croissance des bacteries, champignons ou algues dans un lieu expose ou sujet a la contamination par ceux-ci, qui consiste a incorporer sur ou dans le lieu, un concentre selon I'une quel- conque des revendications 1 a 8 ou une macroemulsion selon la revendication 9 ou 1 1 , en une quantite efficace pour affecter negativement ladite croissance.

3. Procede selon la revendication 12, dans lequel le lieu est un milieu aqueux, ou un film protecteur ou decoratif solide, ou du textile, du cuir, du papier ou du bois.

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E F F E C T O F S O L V E N T O N

S P E C I F I C G R A V I T Y ( 2 5 % A l ) 1.02 -i

I ' r ̂ 1 | ■ ■ 1 I I I I I I | 30 40 50

% M ETHYLNAPHTHALENE

FIGURE 1

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FIGURE 2

14