CA2278288A1 - Reduction of emissions of volatile compounds by additives - Google Patents
Reduction of emissions of volatile compounds by additives Download PDFInfo
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- CA2278288A1 CA2278288A1 CA002278288A CA2278288A CA2278288A1 CA 2278288 A1 CA2278288 A1 CA 2278288A1 CA 002278288 A CA002278288 A CA 002278288A CA 2278288 A CA2278288 A CA 2278288A CA 2278288 A1 CA2278288 A1 CA 2278288A1
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- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/45—Inorganic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
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Abstract
This application relates to the use of isothiazolone compounds, mercapto compounds, cyclodextrin compounds, iodopropynyl butylcarbamate, diiodomethyl p-tolyl sulphone, zinc oxide, hydrogen peroxide or mixtures of two or more such compounds as additive for the reduction of emissions of volatile compounds which are potentially hazardous or cause unpleasant odour from compositions which comprise constituents which form such compounds which are potentially hazardous or cause unpleasant odour.
Description
Reduction of emissions of volatile compounds by additives The invention relates to the use of special additives for reducing the emission of volatile compounds from compos i ti ons and p roducts whi ch comp ris a cons ti tuents whi ch can form or release such volatile compounds. In particular, the invention relates to the provision of additives for the reduction of emissions of volatile compounds which are potentially hazardous or cause unpleasant odour, such as HCN, l0 amines and thio compounds.
The re a re many s ubs tances and compos i ti ons whi ch f o rm or release volatile compounds which have unpleasant odour and are potentially hazardous on accumulation. Depending on the extent of the release or emission of volatile compounds, the unpleasant odour or the potential hazard occurs in a range whi ch extends f rom "not pe rceptible" o r "not p res ent" to "predominant". In particular, a decrease of the emission is desirable in the case of substances or compositions which release the compounds in question to a relatively great extent. Howeve r, even i n the cas a o f s ubs tances and compounds whi ch releas a thes a s ubs tances i n amounts whi ch a re ve ry small and are basically negligible, so that in the case of correct handling, there is no question with regard to odour pollution or safety hazard, a decrease in emissions can also be desirable, however, in order to keep the safety margin, until the individual MAK values are reached, as high as possible.
Fo r exampl e, the re a re compos i ti ons f rom whi ch, unde r ce rtai n condi ti ons , compounds s uch as H Q~1, ami nes s uch as NH3 and CH3NH2 o r thi o compounds s uch as HZ S, fo r example, a re releas ed. In this cas e, a decreas a in the releas e, in particular, of HCN is of interest, which can proceed in highly variable extents from, for example, cyanide or thi ocyanate i ons o r compounds havi ng cyani de o r thi ocyanate 3 5 s ubs ti tuents o r compos i ti ons comp ris i ng s uch compounds .
In addi ti on to the i no rgani c compounds , i n pa rti -cula r, o rganothi ocyanates , whi ch i nclude a romati c and aliphati c o rganothi ocyanates , a re potenti al H CN s ou rces .
Examples of aliphatic and aromatic organothiocyanates are thi ocyanate-s ubs ti tuted thi azoles , 3-thi ocyanato-N-octylacrylamide and methylenebisthiocyanate (MSI') . They frequently have a characteristic unpleasant odour and, under certain conditions, also release volatile compounds such as, for example, thio compounds and HCN. The emission values in this cas a are, at leas t in the cas a of approved comme rci al p roducts , wi thi n the pe rmi tted limi t values (MAK values ) , but, in principle, can also lie above these. Emissions of this type and, in particular, elevated emissions, represent a potenti al hazard to pe rs ons handli ng o r us i ng the p roducts contai ni ng thes a cons ti tuents .
The contents of the i ndi vi dual compounds i n ques ti on in the surrounding atmosphere serve, for example, as measured parameter for the emission of a product, e. g. , for the emission of HCN, the HCN content in the surrounding ai r serves as indicator, in which case this can be determined using an appropriate test tube (e. g. a Drager tube: prussic acid 2/a (hydrogen cyanide) (CH 25701) ).
Quantitative determination of emissions such as HCN
is comparatively complex and frequently cannot be carried out i n p cacti ce. To remedy this , the refo re, s ubj ecti ve organoleptic tests, which give highly meaningful results, are currently customarily also carried out. In this case, the odour impression of the tested compositions is determined, a reference sample being tested in conjunction.
The object therefore underlying the invention is to reduce emissions of volatile compounds such as HCN, thio 3 0 compounds and ami nes , fo r example, whi ch a re potenti ally hazardous or cause unpleasant odour, from compositions and p roducts whi ch comp ris a cons ti tuents whi ch fo rm s uch compounds which are potentially hazardous or cause unpleasant odour, and, in this regard, to provide low-emission 3 5 compos i ti ons .
This object is achieved by means of the fact that is othi azolone compounds s uch as N-octylis othi azolone and benzis othi azolone, me rcapto compounds , cyclodext ri n compounds, iodopropynyl butylcarbamate and diiodomethyl p-tolyl sulphone, zinc oxide, hydrogen peroxide, oz mixtures o f two o r mo re s uch compounds , a re us ed as addi ti ve f o r the reduction of emissions of volatile compounds which are potenti ally hazardous o r caus a unpleas ant odou r f rom ' compos i ti ons whi ch comp ris a cons ti tuents whi ch fo rm s uch compounds whi ch a re potenti ally haza rdous o r caus a unpleas ant odou r.
Preferred embodiments are the subject-matter of the l0 subclaims.
According to the invention, it has been found that emissions which are potentially hazardous or have unpleasant odour may be greatly reduced or eliminated by addition of the abovementioned additive compounds. The extent of the emission reducti on may be s et vi a the concept rati on of the addi ti ves .
In the case of products which already comply with the legally prescribed limit values (MAK values ) , according to the i nventi on, a fu rthe r reducti on o r a limi nati on o f s uch emissions can increase the safety margin until the MAK values 2 0 a re reached, whe reas i n the cas a o f s ubs tances and compos i -tions whose emission lies above this, a decrease or elimination of the emissions can lead to the corresponding comme rci al p roducts bei ng app roved o r bei ng abl a to be put on the market.
The reduction can appear in advantages with respect to odou r ve rs us a compa ris on p roduct whi ch contai ns no additive according to the invention. The advantage achieved is, for example, a reduction of the odour strength and/or a change of the odour note or type of odour.
The following description, to illustrate the invention, is essentially concerned with reducing the emission of HCN from organothiocyanate compounds. However, the i nventi on is not res t ri cted the reto, as the furthe r qualitative results for emissions of thio compounds show. To illustrate the reduction of HCN emissions, the test s ubs tances s elected we re fi rs tly an a romati c thiocyanatothiazole or 3-thiocyanato-N-octylacrylamide and secondly aliphatic methylenebisthiocyanate (MBT).
The re a re many s ubs tances and compos i ti ons whi ch f o rm or release volatile compounds which have unpleasant odour and are potentially hazardous on accumulation. Depending on the extent of the release or emission of volatile compounds, the unpleasant odour or the potential hazard occurs in a range whi ch extends f rom "not pe rceptible" o r "not p res ent" to "predominant". In particular, a decrease of the emission is desirable in the case of substances or compositions which release the compounds in question to a relatively great extent. Howeve r, even i n the cas a o f s ubs tances and compounds whi ch releas a thes a s ubs tances i n amounts whi ch a re ve ry small and are basically negligible, so that in the case of correct handling, there is no question with regard to odour pollution or safety hazard, a decrease in emissions can also be desirable, however, in order to keep the safety margin, until the individual MAK values are reached, as high as possible.
Fo r exampl e, the re a re compos i ti ons f rom whi ch, unde r ce rtai n condi ti ons , compounds s uch as H Q~1, ami nes s uch as NH3 and CH3NH2 o r thi o compounds s uch as HZ S, fo r example, a re releas ed. In this cas e, a decreas a in the releas e, in particular, of HCN is of interest, which can proceed in highly variable extents from, for example, cyanide or thi ocyanate i ons o r compounds havi ng cyani de o r thi ocyanate 3 5 s ubs ti tuents o r compos i ti ons comp ris i ng s uch compounds .
In addi ti on to the i no rgani c compounds , i n pa rti -cula r, o rganothi ocyanates , whi ch i nclude a romati c and aliphati c o rganothi ocyanates , a re potenti al H CN s ou rces .
Examples of aliphatic and aromatic organothiocyanates are thi ocyanate-s ubs ti tuted thi azoles , 3-thi ocyanato-N-octylacrylamide and methylenebisthiocyanate (MSI') . They frequently have a characteristic unpleasant odour and, under certain conditions, also release volatile compounds such as, for example, thio compounds and HCN. The emission values in this cas a are, at leas t in the cas a of approved comme rci al p roducts , wi thi n the pe rmi tted limi t values (MAK values ) , but, in principle, can also lie above these. Emissions of this type and, in particular, elevated emissions, represent a potenti al hazard to pe rs ons handli ng o r us i ng the p roducts contai ni ng thes a cons ti tuents .
The contents of the i ndi vi dual compounds i n ques ti on in the surrounding atmosphere serve, for example, as measured parameter for the emission of a product, e. g. , for the emission of HCN, the HCN content in the surrounding ai r serves as indicator, in which case this can be determined using an appropriate test tube (e. g. a Drager tube: prussic acid 2/a (hydrogen cyanide) (CH 25701) ).
Quantitative determination of emissions such as HCN
is comparatively complex and frequently cannot be carried out i n p cacti ce. To remedy this , the refo re, s ubj ecti ve organoleptic tests, which give highly meaningful results, are currently customarily also carried out. In this case, the odour impression of the tested compositions is determined, a reference sample being tested in conjunction.
The object therefore underlying the invention is to reduce emissions of volatile compounds such as HCN, thio 3 0 compounds and ami nes , fo r example, whi ch a re potenti ally hazardous or cause unpleasant odour, from compositions and p roducts whi ch comp ris a cons ti tuents whi ch fo rm s uch compounds which are potentially hazardous or cause unpleasant odour, and, in this regard, to provide low-emission 3 5 compos i ti ons .
This object is achieved by means of the fact that is othi azolone compounds s uch as N-octylis othi azolone and benzis othi azolone, me rcapto compounds , cyclodext ri n compounds, iodopropynyl butylcarbamate and diiodomethyl p-tolyl sulphone, zinc oxide, hydrogen peroxide, oz mixtures o f two o r mo re s uch compounds , a re us ed as addi ti ve f o r the reduction of emissions of volatile compounds which are potenti ally hazardous o r caus a unpleas ant odou r f rom ' compos i ti ons whi ch comp ris a cons ti tuents whi ch fo rm s uch compounds whi ch a re potenti ally haza rdous o r caus a unpleas ant odou r.
Preferred embodiments are the subject-matter of the l0 subclaims.
According to the invention, it has been found that emissions which are potentially hazardous or have unpleasant odour may be greatly reduced or eliminated by addition of the abovementioned additive compounds. The extent of the emission reducti on may be s et vi a the concept rati on of the addi ti ves .
In the case of products which already comply with the legally prescribed limit values (MAK values ) , according to the i nventi on, a fu rthe r reducti on o r a limi nati on o f s uch emissions can increase the safety margin until the MAK values 2 0 a re reached, whe reas i n the cas a o f s ubs tances and compos i -tions whose emission lies above this, a decrease or elimination of the emissions can lead to the corresponding comme rci al p roducts bei ng app roved o r bei ng abl a to be put on the market.
The reduction can appear in advantages with respect to odou r ve rs us a compa ris on p roduct whi ch contai ns no additive according to the invention. The advantage achieved is, for example, a reduction of the odour strength and/or a change of the odour note or type of odour.
The following description, to illustrate the invention, is essentially concerned with reducing the emission of HCN from organothiocyanate compounds. However, the i nventi on is not res t ri cted the reto, as the furthe r qualitative results for emissions of thio compounds show. To illustrate the reduction of HCN emissions, the test s ubs tances s elected we re fi rs tly an a romati c thiocyanatothiazole or 3-thiocyanato-N-octylacrylamide and secondly aliphatic methylenebisthiocyanate (MBT).
Suitable emission-reducing additives according to the invention are, for example, the following isothiazolones and mixtures of the same: N-octylisothiazolone, 5-chloro-N-methylisothiazolone, N-methylisothiazolone, a mixture of 5-chloro-N-methylisothiazolone and N-methylisothiazolone, 1, 2-benzisothiazolone, 5, 6-dihydro-2-methyl-2H-cyclopent(d)isothiazol-3(4H)-one. A suitable mercapto compound is, for example, Pyrion disulphide. Suitable cyclodextrins are, for example, a-, Vii- or y-cyclodextrin (cyclohexaamylose, methylcycloheptaamylose or cyclooctaamylose). In addition, iodopropynyl butylcarbamate, diiodomethyl p-tolyl sulphone, zi nc oxi de and hydrogen pe roxi de a re s ui table.
The preferred emission-reducing additive is N-octylis othi azolone. In the examples , the embodiments acco rdi ng to the i nventi on p repa red a re p repa rati ons whi ch comprise the emission-reducing additive, in particular an isothiazolone, which reduces the emission of the preparations and, i nte r ali a, als o acts as an HCN t rap.
The invention makes it possible to reduce the release of HCN both i n aqueous s ys terns ove r a wi de pH range, s uch as pH 1 to pH 12, e. g. by adding Ovate r-s oluble is othi azolones , s uch as N-methylis othi azolone, benzis othi azolone o r 5 , 6-dihydro-2-methyl-2H-cyclopent(d)isothiazol-3(4H)-one, zinc oxi de and hyd rogen pe roxi de, and i n li pophi li c medi a, e. g. by adding N-octylisothiazolone.
According to the invention, therefore, in particular HC~1 emissions can be reduced from primarily liquid products (solutions, dispersions, preferably aqueous dispersions ) .
Si nce s ubs tances and compos i ti ons havi ng hi gh H CN
emissions are not suitable for the market, according to the i nventi on, the pos s i bi li ty i s p rovi ded o f reduci ng thei r emissions so greatly that marketing is thus possible.
Moreover, according to the invention, by adding the emission-reducing additives, emissions which are already acceptable and comply with current safety regulations can further be dec reas ed, fo r example the o rganolepti c p rope rti es can als o be imp roved, whi ch can lead to an i nc yeas ed ma rk et acceptance.
WO 98/32473 PCT/IB98~0063 Furthermore, it is important that the action, e. g. a biocidal action, ascribed to the treated compositions is not impaired by the emission-reducing additives.
The invention can be used, for example, in the area of solutions or dispersions for a fungicidal and algistatic ' finishing of materials and technical preservation. Concrete areas of application and user products are, for example, preservatives, disinfectants, impregnating agents, paints, sizings and adhesives, primers, coatings, lubricants and plasters.
The emission-reducing additives according to the invention are used at least in a total amount of 0. O1 ~ by weight, preferably 0.01 to 10.0 by weight, in particular 0.1 to 7.5 ~ by weight, and preferably 0.5 to 5. 0 ~ by weight, based on the composition. When a plurality of emission-reduci ng compounds a re us ed, the p ropo rti on o f each o f thes a addi ti ve components can be s et acco rdi ng to the s peci fi c product requi cements.
Experimental results are given below which indicate the HCI~1 emission from aromatic organothiocyanate-containing compositions or which confirm the emission-reducing action of the s ai d addi ti ve compounds .
Aromatic organothiocyanate + HCN trap Example I
Aqueous dispersions which comprised 7. 8 $ by weight of aromatic organothiocyanate (in the form of 26~ by weight of a 30~ strength dispersion), based on the weight of the dispersions, were admixed with various amounts of different cyclodextrins ( 0. 5 °s, 1. 0 ~, 2. 0 ~, 3. 0 ~ and 5. 0 ~, bas ed on the weight of the dispersions, of cyclodextrin (CD) alpha (Example Ia) or CD beta (Example Ib) or CD gamma (Example Ic) t and we re tes ted fo r compati bi li ty and s tabi li ty. The procedure and the results of "HCN" measurements are reported below.
WO 98!32473 PCT/iB98/00063 Appearance after storage at room temperature for 12 days or ~ n ~..oov~.
The dis pe rs i ons contai ni ng CD alpha and gamma (Examples Ia and Ic) were unchanged with respect to homogeneity and yellowish-white colour. In the case of the dispersions containing CD beta (Example Ib), slightly inhomogeneous, unstable brownish dispersions formed, in pa rti cul a r at the hi ghe r content rati ons .
to Result:
Cyclodextrin alpha and cyclodextrin gamma lead to homogeneous a romati c-o rganothi ocyanate-contai ni ng and comparatively stable compositions. Cyclodextrin beta impai rs the s tabi li ty and homogenei ty of aromati c-o rganothi ocyanate-contai ni ng compos i ti ons .
Example II
Aqueous dispersions which comprised 7. 8 % by weight of aromatic organothiocyanate (in the form of 26% by weight of a % strength dispersion) , based on the weight of the dispersions, were admixed with various amounts of N-octylis othi azolone ( 45 % s t rength s oluti on) ( 0. 5 %, 1. 0 %, 2. 0 %, 3. 0 % o r 5 . 0 %, bas ed on the wei ght o f the dis pe rs i on ) and we re 25 tes ted for compatibi li ty and s tabi li ty. The procedure and results of "HCt~T' measurements are reported below.
Appearance after storage at room temperature for 7 days:
After 7 days, homogeneous yellowish-white dispersions 3 o we re p res ent unchanged.
Example III
HCN measurements using a Draper test tube for HGN (see above) (5 strokes ) for the dispersions of Examples I and II:
In this tes t, the Drape r tes t tube was us ed togethe r wi th a pump. 8th ti ps o f the tube we re b rok en o f f and one end o f the tube was then i ns a rted ti ght ly i nto the pump. The W(~ 98/32473 PCT/1B98/00063 _ 7 _ HCN content was tested by holding the other end of the tube in the air space over the surface of the respective sample in a 50 ml wide-neck sample vial which was filled with 50 g of the s ample. The tempe nature was 23. 5 ° C. The s ample vi als had been sealed for 4 weeks. For measurement, the ai r was sucked ' through the tube. The measurement period was about 60 seconds for 5 strokes and correspondingly about 24 seconds for 2 strokes. The result was then determined on the basis of the coloration (reaction of HGN with HgCl2 and methyl red). The meas a cement method co r res ponds to the Drage r i ns t ructi on 234-257 of 1995.) Blank value (without additive, aromatic organo-thi ocyanate-contai ni ng aqueous di s pe rs i ons ) --~ app rox. 1. 5 ppm.
Example Ia:+ 5 CD alpha --> approx. 1.5 o ppm Example Ib:+ 5 CD beta -~ 1 - 1.5 ppm o Example Ib:+ 5 CD gamma ~ approx. 1.5 ppm ~
Example I + 5 N-octylis othi azolone-~ 0 ppm I: ~
( 45 s t rength s oluti o on ) HCN measurements using Drager tubes for HCN (see above) (5 strokes ) for the dispersions according to Example II in a 250 ml wide-neck bottle which contained approximately 40 g of the respective dispersion:
Blank value: approximately 1 - 2 ppm All other samples: no HCN detectable! !
Result:
An addition of cyclodextrin somewhat decreases the HCN emission of aromatic-organothiocyanate-containing dispersions.
An addi ti on of N-octylis othi azolone ( 45 % s t rength z solution) significantly decreases the HCN emission of a xomati c-o rganothi ocyanate-contai ni ng dis pe rs i ons .
_ g _ Example IV
Aqueous dispersions were produced which comprised 7. 8 % by weight of aromatic organothiocyanate (in the form of 13 % by wei ght o f a 60 % s t rength di s pe rs i on ) bas ed on the wei ght o f the dis pe rs i ons . The dis pe rs i ons we re homogeneous and whi tis h-yellow (ve ry hi gh quali ty) .
Example V
HCN measurements using Drager tubes (5 strokes) of the dispersions of Example IV (aromatic organothiocyanate without and wi th 1. 0 %, 2. 0 %, 3. 0 % and 5. 0 % N-octylis othi azolone ( 45 %
s t rength s oluti on ) The dispersions were measured after storage at room temperature for 24 hours in a 250 ml wide-neck bottle which contained approximately 100 g of the respective s ample:
Zero value After1 week at room temperature Blank: without 30 ppm > ppm additive 3o + 1% Kathon 893 approx. 25 ppm 8 ppm + 2% Kathon 893 approx. 10 ppm 5 ppm + 3% Kathon 893 approx. 5 ppm 2-3 ppm + 5% Kathon 893 approx. 2 ppm 2 ppm The dispersions remained unchanged with respect to homogeneity and whitish-yellow colour. There was a marked odour improvement with respect to the blank value.
The aromatic organothiocyanate content of the dispersions containing 0 or 1 % N-octylisothiazolone (45 %
strength solution) was:
wi thout N-octylis othi azolone 7. 1 %
wi th 1 % N-octylis othi azolone 7. 1 %
WQ 98/32473 PCTIIB98~063 _ g _ Res a 1 t:
An addi ti on of N-octylis othi azolone s i gni fi cantly decreases the HCt~ emission of aromatic-organothiocyanate-containing dispersions. The odour of such dispersions is improved in this case. There is no decomposition of the organothiocyanate active compound.
Example VI
Solutions containing aromatic organothiocyanate +
N-octylisothiazolone:
Li qui d p repa rati ons bas ed on a romati c o rgano-thi ocyanate ( 60 o s t rength s oluti on) and N-octylis othi azolone ( 45 ~ s t rength s o luti on ) ( data i n pa its by wei ght ) , H CN
emission measurement (see above):
N-octylisothiazolone 0 90 80 70 60 50 40 30 20 10 ( 45 s s t rength s oluti on ) Organothiocyanate 100 10 20 30 40 50 60 70 80 90 60 ~ s t rength s oluti on ) HCN emission in ppm, measured using Drager tubes at 22°C, measurement vessel 100 ml wide-neck bottle filled with 100 g of solution:
After 48 h < < < < 2 After 96 h < < < <
After 1 < < 1 1 2 week The s oluti ons had not changed afte r s to rage at room ' 25 temperature for 2 months.
Example VII
Solutions containing aromatic organothiocyanate +
N-oct~lisothiazolone:
Li qui d p repa rati ons bas ed on a romati c o rgano-thi ocyanate ( 60 % s t rength s oluti on) and N-octylis othi azolone 45 % s t rength s oluti on ) ( data i n pa its by wei ght ) , H CN
emission measurement (see above):
N-octylisothiazolone8 6 4 2 ( 45 % s t rength solution) Organothiocyanate 92 94 96 98 ( 60 % s t rength s oluti on) HCN emission in ppm, measured using Drager tubes at l0 22 ° C, measurement vess el 100 ml wide-neck bottle fi lled wi th 100 g of solution:
After 48 h 1-3 4-5 17 > 30a After 1 week 2-3 5 7 17-18 2 s t rok es Result:
B,~ addi ng N-octylis othi azolone to a romati c-thiocyanate-containing solutions, homogeneous mixtures which have a significantly decreased HCN emission are obtained in all mixing ratios.
Further additives decreasing the HCN emission of aromatic organothiocyanate In the s tud_i es , furthe r H CN t raps we re found, whe re i n each cas a homogeneous dis pe rs i on comp ri s i ng 7. 8 % by wei ght of aromatic organothiocyanate was prepared containing 2% by weight of active compound of the respective additive (in the cas a of H202 ( 30 % s trength) i t was therefore 6. 66 % by weight) , and the HCN emission was measured as a function of time using a Drager tube.
HCL~T emission in ppm, measured using Drager tubes at 22 ° C, meas urement vess el 5 0 ml wi de-neck bottle fi lled wi th 25 g of dispersion:
WO 98/32473 PCT/IB98l00063 HCN trap HCN after pH
after 1 week after 48 h ppm 1 i n week ppm Wi thout addi ti on > 3 2 0 4 .
A) Cyclodextrin alpha 20 20 4.5 B) Cyclodextrin beta 25 20 4.5 C) Cyclodextrin beta 25 20 4.5 D) Cyclodextrin gamma 25 20 4.5 E ) Zi nc py ri thi one 25 25 4 .
F) 1, 2- Hsnzisothiazolone 5 < 1 4. 6 G) Pyrion disulphide 8 1-2 4.2 H) N-Methylisothiazolone 2-3 2 4.0 I) Iodopropynyl butylcarbamate 10-12 10 4.6 J) Hydrogen peroxide (30 s) 10 7 2. 7 K) Zi nc oxi de 6 8 7. 1 L) Henzothiophene-2-cyclohexyl- 20 20 4.1 ca rbami de S, S-di oxi de' M) 5,6-Dihydro-2-methyl-2H-cyclo- 0 0 4.1 pent (d)isothiazol-3 (9H)-one"
N) PVP 25 25 4.0 O) PVP + hydrogen peroxide (30 ~) 18 720 2.5 "' ' 5 0 o acti ve content, i ni ti al content rati on = 4 ~
" 5 0 ~ acti ve content, i ni ti al content rati on = 4 0 "' 12 $ HZO2; i ni ti al content rati on = 16. 6 ~
Res ult: The fu rthe r addi ti ves s tudi ed lead to a reducti on o f the H CN emis s i on, whi ch reducti on, i n comps ris on wi th the isothiazolones, is somewhat lesser.
Preferred examples of these further additives lead to a comparatively high reduction (to < 20 ppm) of the HCN
emission of aromatic-organothiocyanate-containing compos i ti ons .
HCN emission and stability of commercial compositions which - comprise aromatic organothiocyanate and N-.octylisothiazoione:
A tes t was made o f whethe r i ns tabi li ti es o r reducti ons i n acti ve compound occu r du ri ng s to rage o f i WO 98!32473 PCT/IB98/00063 comme rci al compos i ti ons whi ch comp ris a a romati c o rgano-thiocyanate and N-octylisothiazolone.
Res a 1 t:
An addition of N-octylisothiazolone to, for example, fi lm p res a rvati ves bas ed on compos i ti ons whi ch contai ned aromatic organothiocyanate, led to optically clear, homogeneous solutions. The HCN emission was significantly reduced. The active compound content is virtually unchanged after storage at room temperature or +40°C for 1 month.
The same applies to the HCN emission of pure acrylic mas on ry pai nt whi ch was t reated i n a co r res pondi ng manne r.
Res a 1 t:
At the application concentration, no HCN is detectable and the s tabi li ty was excellent.
Example VIII
3-Thiocvanato-N-octvlacrvlamide:
Preparation of 3-thiocyanato-N-octylacrylamide and N-octyl-3-thiocyanatoacrylamide from N-octylisothiazolone (NOITZ, ext racted f rom N-octylis othi azolone ( 45 $ s t rength s oluti on ) by s haki ng wi th toluene and wate r ) and KCN:
213 g (1 mol) of NOITZ + 65 g (1 mol) of KCN were sti rred together in 600 ml of water. 10 $ strength HzS09 was added dropwise with sti rring and cooling (maximum temperature 30°C). The mixture was stirred for 3 hours. The precipitate was filtered off by suction, taken up in 500 ml of warm DIPE, dried over Na2S09 and crystallized out with addition of approximately 1.5 1 of PE. The crystals were filtered off by s ucti on and was hed wi th PE. Af to r dryi ng, 145 . 4 g o f N-octyl-3-thiocyanatoacrylamide (60.5 $ yield) resulted, in the form of yellowish crystals, F: 81°C.
The 3-thiocyanato-N-octylacrylamide which was isolated in crystalline form is vi rtually insoluble in water (< 0. 01 $) and dissolves at about 2. 5 to 10 $ in glycols or glycol ethe rs . The 2. 5 to 10 $ s t rength s oluti ons o f WO 98J324~3 PCT/IB98/00063 3-thiocyanato-N-octylacrylamide in glycols or glycol ethers emit HCN, that is to say approximately 30 ppm (1 stroke) after storage at room temperature for 1 week, whereas the crystalline material had an HC'N emission of approximately 25 ppm at 5 strokes (Drager tube, see above).
Solvent: HC~T ( 1 stroke) 1,2-Propyl glycol approx. completely 2.5 $ soluble Dipropyl glycol 10$ completely > = 40 soluble Triethylene glycol 8$ completely approx. 30 s oluble Phenoxypropanols 10$ completely approx. 30 s oluble Phenoxyethanol 10$ completely approx. 30 s oluble 1-Methoxy-2- 10$ completely approx. 30 propanol soluble Hityl diglycol 10 $ completely approx. 30 s oluble Ethylene glycol 1$ completely approx. 30 soluble Deioni zed water vi rtually insoluble (< 0.
O1 $) All s oluti ons , afte r s to rage at room tempe rature fo r 2 months were without change, clear and slightly yellowish.
A 5 $ s t rength aqueous dis pe rs i on of 3-thi ocyanato-N-octylacrylamide is almost white, homogeneous and has an HCN
emission of 13 ppm (5 strokes ) (Draper tube, see above) .
Adding, for example, N-octylisothiazolone considerably decreased the HCN emission. The results were roughly as fo r the o rganothi ocyanate tes ted.
Example IX
Emission of thio compounds:
An aqueous Pyri on dis ulphi de s oluti on ( contai ni ng 0. 84 $ active compound) was prepared from 7. 46 g (0. 02 mol) Pyrion-Na (40 $ strength in water) , 1 g (0. O1 mol) of sulphuric acid 96~ and 1.18 g (0.011 mol) of H20Z 30$
strength in 100 g of deionized water. It was clear and slightly yellow. A marked odour of thio compounds was noted.
If this solution was admixed with 10 g of a mixture of 5-chloro-N-methylisothiazolone and N-methylisothiazolone ( app roximately 14 ~ by wei ght acti ve compound content ) , the "thio odour" disappeared.
The preferred emission-reducing additive is N-octylis othi azolone. In the examples , the embodiments acco rdi ng to the i nventi on p repa red a re p repa rati ons whi ch comprise the emission-reducing additive, in particular an isothiazolone, which reduces the emission of the preparations and, i nte r ali a, als o acts as an HCN t rap.
The invention makes it possible to reduce the release of HCN both i n aqueous s ys terns ove r a wi de pH range, s uch as pH 1 to pH 12, e. g. by adding Ovate r-s oluble is othi azolones , s uch as N-methylis othi azolone, benzis othi azolone o r 5 , 6-dihydro-2-methyl-2H-cyclopent(d)isothiazol-3(4H)-one, zinc oxi de and hyd rogen pe roxi de, and i n li pophi li c medi a, e. g. by adding N-octylisothiazolone.
According to the invention, therefore, in particular HC~1 emissions can be reduced from primarily liquid products (solutions, dispersions, preferably aqueous dispersions ) .
Si nce s ubs tances and compos i ti ons havi ng hi gh H CN
emissions are not suitable for the market, according to the i nventi on, the pos s i bi li ty i s p rovi ded o f reduci ng thei r emissions so greatly that marketing is thus possible.
Moreover, according to the invention, by adding the emission-reducing additives, emissions which are already acceptable and comply with current safety regulations can further be dec reas ed, fo r example the o rganolepti c p rope rti es can als o be imp roved, whi ch can lead to an i nc yeas ed ma rk et acceptance.
WO 98/32473 PCT/IB98~0063 Furthermore, it is important that the action, e. g. a biocidal action, ascribed to the treated compositions is not impaired by the emission-reducing additives.
The invention can be used, for example, in the area of solutions or dispersions for a fungicidal and algistatic ' finishing of materials and technical preservation. Concrete areas of application and user products are, for example, preservatives, disinfectants, impregnating agents, paints, sizings and adhesives, primers, coatings, lubricants and plasters.
The emission-reducing additives according to the invention are used at least in a total amount of 0. O1 ~ by weight, preferably 0.01 to 10.0 by weight, in particular 0.1 to 7.5 ~ by weight, and preferably 0.5 to 5. 0 ~ by weight, based on the composition. When a plurality of emission-reduci ng compounds a re us ed, the p ropo rti on o f each o f thes a addi ti ve components can be s et acco rdi ng to the s peci fi c product requi cements.
Experimental results are given below which indicate the HCI~1 emission from aromatic organothiocyanate-containing compositions or which confirm the emission-reducing action of the s ai d addi ti ve compounds .
Aromatic organothiocyanate + HCN trap Example I
Aqueous dispersions which comprised 7. 8 $ by weight of aromatic organothiocyanate (in the form of 26~ by weight of a 30~ strength dispersion), based on the weight of the dispersions, were admixed with various amounts of different cyclodextrins ( 0. 5 °s, 1. 0 ~, 2. 0 ~, 3. 0 ~ and 5. 0 ~, bas ed on the weight of the dispersions, of cyclodextrin (CD) alpha (Example Ia) or CD beta (Example Ib) or CD gamma (Example Ic) t and we re tes ted fo r compati bi li ty and s tabi li ty. The procedure and the results of "HCN" measurements are reported below.
WO 98!32473 PCT/iB98/00063 Appearance after storage at room temperature for 12 days or ~ n ~..oov~.
The dis pe rs i ons contai ni ng CD alpha and gamma (Examples Ia and Ic) were unchanged with respect to homogeneity and yellowish-white colour. In the case of the dispersions containing CD beta (Example Ib), slightly inhomogeneous, unstable brownish dispersions formed, in pa rti cul a r at the hi ghe r content rati ons .
to Result:
Cyclodextrin alpha and cyclodextrin gamma lead to homogeneous a romati c-o rganothi ocyanate-contai ni ng and comparatively stable compositions. Cyclodextrin beta impai rs the s tabi li ty and homogenei ty of aromati c-o rganothi ocyanate-contai ni ng compos i ti ons .
Example II
Aqueous dispersions which comprised 7. 8 % by weight of aromatic organothiocyanate (in the form of 26% by weight of a % strength dispersion) , based on the weight of the dispersions, were admixed with various amounts of N-octylis othi azolone ( 45 % s t rength s oluti on) ( 0. 5 %, 1. 0 %, 2. 0 %, 3. 0 % o r 5 . 0 %, bas ed on the wei ght o f the dis pe rs i on ) and we re 25 tes ted for compatibi li ty and s tabi li ty. The procedure and results of "HCt~T' measurements are reported below.
Appearance after storage at room temperature for 7 days:
After 7 days, homogeneous yellowish-white dispersions 3 o we re p res ent unchanged.
Example III
HCN measurements using a Draper test tube for HGN (see above) (5 strokes ) for the dispersions of Examples I and II:
In this tes t, the Drape r tes t tube was us ed togethe r wi th a pump. 8th ti ps o f the tube we re b rok en o f f and one end o f the tube was then i ns a rted ti ght ly i nto the pump. The W(~ 98/32473 PCT/1B98/00063 _ 7 _ HCN content was tested by holding the other end of the tube in the air space over the surface of the respective sample in a 50 ml wide-neck sample vial which was filled with 50 g of the s ample. The tempe nature was 23. 5 ° C. The s ample vi als had been sealed for 4 weeks. For measurement, the ai r was sucked ' through the tube. The measurement period was about 60 seconds for 5 strokes and correspondingly about 24 seconds for 2 strokes. The result was then determined on the basis of the coloration (reaction of HGN with HgCl2 and methyl red). The meas a cement method co r res ponds to the Drage r i ns t ructi on 234-257 of 1995.) Blank value (without additive, aromatic organo-thi ocyanate-contai ni ng aqueous di s pe rs i ons ) --~ app rox. 1. 5 ppm.
Example Ia:+ 5 CD alpha --> approx. 1.5 o ppm Example Ib:+ 5 CD beta -~ 1 - 1.5 ppm o Example Ib:+ 5 CD gamma ~ approx. 1.5 ppm ~
Example I + 5 N-octylis othi azolone-~ 0 ppm I: ~
( 45 s t rength s oluti o on ) HCN measurements using Drager tubes for HCN (see above) (5 strokes ) for the dispersions according to Example II in a 250 ml wide-neck bottle which contained approximately 40 g of the respective dispersion:
Blank value: approximately 1 - 2 ppm All other samples: no HCN detectable! !
Result:
An addition of cyclodextrin somewhat decreases the HCN emission of aromatic-organothiocyanate-containing dispersions.
An addi ti on of N-octylis othi azolone ( 45 % s t rength z solution) significantly decreases the HCN emission of a xomati c-o rganothi ocyanate-contai ni ng dis pe rs i ons .
_ g _ Example IV
Aqueous dispersions were produced which comprised 7. 8 % by weight of aromatic organothiocyanate (in the form of 13 % by wei ght o f a 60 % s t rength di s pe rs i on ) bas ed on the wei ght o f the dis pe rs i ons . The dis pe rs i ons we re homogeneous and whi tis h-yellow (ve ry hi gh quali ty) .
Example V
HCN measurements using Drager tubes (5 strokes) of the dispersions of Example IV (aromatic organothiocyanate without and wi th 1. 0 %, 2. 0 %, 3. 0 % and 5. 0 % N-octylis othi azolone ( 45 %
s t rength s oluti on ) The dispersions were measured after storage at room temperature for 24 hours in a 250 ml wide-neck bottle which contained approximately 100 g of the respective s ample:
Zero value After1 week at room temperature Blank: without 30 ppm > ppm additive 3o + 1% Kathon 893 approx. 25 ppm 8 ppm + 2% Kathon 893 approx. 10 ppm 5 ppm + 3% Kathon 893 approx. 5 ppm 2-3 ppm + 5% Kathon 893 approx. 2 ppm 2 ppm The dispersions remained unchanged with respect to homogeneity and whitish-yellow colour. There was a marked odour improvement with respect to the blank value.
The aromatic organothiocyanate content of the dispersions containing 0 or 1 % N-octylisothiazolone (45 %
strength solution) was:
wi thout N-octylis othi azolone 7. 1 %
wi th 1 % N-octylis othi azolone 7. 1 %
WQ 98/32473 PCTIIB98~063 _ g _ Res a 1 t:
An addi ti on of N-octylis othi azolone s i gni fi cantly decreases the HCt~ emission of aromatic-organothiocyanate-containing dispersions. The odour of such dispersions is improved in this case. There is no decomposition of the organothiocyanate active compound.
Example VI
Solutions containing aromatic organothiocyanate +
N-octylisothiazolone:
Li qui d p repa rati ons bas ed on a romati c o rgano-thi ocyanate ( 60 o s t rength s oluti on) and N-octylis othi azolone ( 45 ~ s t rength s o luti on ) ( data i n pa its by wei ght ) , H CN
emission measurement (see above):
N-octylisothiazolone 0 90 80 70 60 50 40 30 20 10 ( 45 s s t rength s oluti on ) Organothiocyanate 100 10 20 30 40 50 60 70 80 90 60 ~ s t rength s oluti on ) HCN emission in ppm, measured using Drager tubes at 22°C, measurement vessel 100 ml wide-neck bottle filled with 100 g of solution:
After 48 h < < < < 2 After 96 h < < < <
After 1 < < 1 1 2 week The s oluti ons had not changed afte r s to rage at room ' 25 temperature for 2 months.
Example VII
Solutions containing aromatic organothiocyanate +
N-oct~lisothiazolone:
Li qui d p repa rati ons bas ed on a romati c o rgano-thi ocyanate ( 60 % s t rength s oluti on) and N-octylis othi azolone 45 % s t rength s oluti on ) ( data i n pa its by wei ght ) , H CN
emission measurement (see above):
N-octylisothiazolone8 6 4 2 ( 45 % s t rength solution) Organothiocyanate 92 94 96 98 ( 60 % s t rength s oluti on) HCN emission in ppm, measured using Drager tubes at l0 22 ° C, measurement vess el 100 ml wide-neck bottle fi lled wi th 100 g of solution:
After 48 h 1-3 4-5 17 > 30a After 1 week 2-3 5 7 17-18 2 s t rok es Result:
B,~ addi ng N-octylis othi azolone to a romati c-thiocyanate-containing solutions, homogeneous mixtures which have a significantly decreased HCN emission are obtained in all mixing ratios.
Further additives decreasing the HCN emission of aromatic organothiocyanate In the s tud_i es , furthe r H CN t raps we re found, whe re i n each cas a homogeneous dis pe rs i on comp ri s i ng 7. 8 % by wei ght of aromatic organothiocyanate was prepared containing 2% by weight of active compound of the respective additive (in the cas a of H202 ( 30 % s trength) i t was therefore 6. 66 % by weight) , and the HCN emission was measured as a function of time using a Drager tube.
HCL~T emission in ppm, measured using Drager tubes at 22 ° C, meas urement vess el 5 0 ml wi de-neck bottle fi lled wi th 25 g of dispersion:
WO 98/32473 PCT/IB98l00063 HCN trap HCN after pH
after 1 week after 48 h ppm 1 i n week ppm Wi thout addi ti on > 3 2 0 4 .
A) Cyclodextrin alpha 20 20 4.5 B) Cyclodextrin beta 25 20 4.5 C) Cyclodextrin beta 25 20 4.5 D) Cyclodextrin gamma 25 20 4.5 E ) Zi nc py ri thi one 25 25 4 .
F) 1, 2- Hsnzisothiazolone 5 < 1 4. 6 G) Pyrion disulphide 8 1-2 4.2 H) N-Methylisothiazolone 2-3 2 4.0 I) Iodopropynyl butylcarbamate 10-12 10 4.6 J) Hydrogen peroxide (30 s) 10 7 2. 7 K) Zi nc oxi de 6 8 7. 1 L) Henzothiophene-2-cyclohexyl- 20 20 4.1 ca rbami de S, S-di oxi de' M) 5,6-Dihydro-2-methyl-2H-cyclo- 0 0 4.1 pent (d)isothiazol-3 (9H)-one"
N) PVP 25 25 4.0 O) PVP + hydrogen peroxide (30 ~) 18 720 2.5 "' ' 5 0 o acti ve content, i ni ti al content rati on = 4 ~
" 5 0 ~ acti ve content, i ni ti al content rati on = 4 0 "' 12 $ HZO2; i ni ti al content rati on = 16. 6 ~
Res ult: The fu rthe r addi ti ves s tudi ed lead to a reducti on o f the H CN emis s i on, whi ch reducti on, i n comps ris on wi th the isothiazolones, is somewhat lesser.
Preferred examples of these further additives lead to a comparatively high reduction (to < 20 ppm) of the HCN
emission of aromatic-organothiocyanate-containing compos i ti ons .
HCN emission and stability of commercial compositions which - comprise aromatic organothiocyanate and N-.octylisothiazoione:
A tes t was made o f whethe r i ns tabi li ti es o r reducti ons i n acti ve compound occu r du ri ng s to rage o f i WO 98!32473 PCT/IB98/00063 comme rci al compos i ti ons whi ch comp ris a a romati c o rgano-thiocyanate and N-octylisothiazolone.
Res a 1 t:
An addition of N-octylisothiazolone to, for example, fi lm p res a rvati ves bas ed on compos i ti ons whi ch contai ned aromatic organothiocyanate, led to optically clear, homogeneous solutions. The HCN emission was significantly reduced. The active compound content is virtually unchanged after storage at room temperature or +40°C for 1 month.
The same applies to the HCN emission of pure acrylic mas on ry pai nt whi ch was t reated i n a co r res pondi ng manne r.
Res a 1 t:
At the application concentration, no HCN is detectable and the s tabi li ty was excellent.
Example VIII
3-Thiocvanato-N-octvlacrvlamide:
Preparation of 3-thiocyanato-N-octylacrylamide and N-octyl-3-thiocyanatoacrylamide from N-octylisothiazolone (NOITZ, ext racted f rom N-octylis othi azolone ( 45 $ s t rength s oluti on ) by s haki ng wi th toluene and wate r ) and KCN:
213 g (1 mol) of NOITZ + 65 g (1 mol) of KCN were sti rred together in 600 ml of water. 10 $ strength HzS09 was added dropwise with sti rring and cooling (maximum temperature 30°C). The mixture was stirred for 3 hours. The precipitate was filtered off by suction, taken up in 500 ml of warm DIPE, dried over Na2S09 and crystallized out with addition of approximately 1.5 1 of PE. The crystals were filtered off by s ucti on and was hed wi th PE. Af to r dryi ng, 145 . 4 g o f N-octyl-3-thiocyanatoacrylamide (60.5 $ yield) resulted, in the form of yellowish crystals, F: 81°C.
The 3-thiocyanato-N-octylacrylamide which was isolated in crystalline form is vi rtually insoluble in water (< 0. 01 $) and dissolves at about 2. 5 to 10 $ in glycols or glycol ethe rs . The 2. 5 to 10 $ s t rength s oluti ons o f WO 98J324~3 PCT/IB98/00063 3-thiocyanato-N-octylacrylamide in glycols or glycol ethers emit HCN, that is to say approximately 30 ppm (1 stroke) after storage at room temperature for 1 week, whereas the crystalline material had an HC'N emission of approximately 25 ppm at 5 strokes (Drager tube, see above).
Solvent: HC~T ( 1 stroke) 1,2-Propyl glycol approx. completely 2.5 $ soluble Dipropyl glycol 10$ completely > = 40 soluble Triethylene glycol 8$ completely approx. 30 s oluble Phenoxypropanols 10$ completely approx. 30 s oluble Phenoxyethanol 10$ completely approx. 30 s oluble 1-Methoxy-2- 10$ completely approx. 30 propanol soluble Hityl diglycol 10 $ completely approx. 30 s oluble Ethylene glycol 1$ completely approx. 30 soluble Deioni zed water vi rtually insoluble (< 0.
O1 $) All s oluti ons , afte r s to rage at room tempe rature fo r 2 months were without change, clear and slightly yellowish.
A 5 $ s t rength aqueous dis pe rs i on of 3-thi ocyanato-N-octylacrylamide is almost white, homogeneous and has an HCN
emission of 13 ppm (5 strokes ) (Draper tube, see above) .
Adding, for example, N-octylisothiazolone considerably decreased the HCN emission. The results were roughly as fo r the o rganothi ocyanate tes ted.
Example IX
Emission of thio compounds:
An aqueous Pyri on dis ulphi de s oluti on ( contai ni ng 0. 84 $ active compound) was prepared from 7. 46 g (0. 02 mol) Pyrion-Na (40 $ strength in water) , 1 g (0. O1 mol) of sulphuric acid 96~ and 1.18 g (0.011 mol) of H20Z 30$
strength in 100 g of deionized water. It was clear and slightly yellow. A marked odour of thio compounds was noted.
If this solution was admixed with 10 g of a mixture of 5-chloro-N-methylisothiazolone and N-methylisothiazolone ( app roximately 14 ~ by wei ght acti ve compound content ) , the "thio odour" disappeared.
Claims (8)
1. Us a of isothiazolone compounds, mercapto compounds, cyclodextrin compounds, iodopropynyl butylcarbamate, diiodomethyl p-tolyl sulphone, zinc oxide, hydrogen peroxide or mixtures of two or more such compounds as additive for the reduction of emissions of volatile compounds which are potentially hazardous or cause unpleasant odour from compositions which comprise constituents which form such compounds which are potentially hazardous or cause unpleasant odour.
2. Us a according to Claim 1, characterized in that, as emission-reducing additive, use is made of N-octylisothiazolone, 5-chloro-N-methylisothiazolone, N-methylisothiazolone, a mixture of 5-chloro-N-methyl-isothiazolone and N-methylisothiazolone, 1,2-benziso-thiazolone, 5,6-dihydro-2-methyl-2H-cyclopent(d)isothiazol-3(4H)-one, Pyrion disulphide and/or alpha-, beta- or gamma-cyclodextrin.
3. Use according to Claim 1 or 2, characterized in that, as emission-reducing additive, use is made of N-octylisothiazolone.
4. Use according to one of Claims 1 to 3, characterized in that the emission of HCN, amines or thio compounds and, in particular, of HCN, is reduced.
5. Use according to Claim 4, characterized in that the emission of HCN is reduced from compositions which comprise compounds which have cyanide or thiocyanate ions or cyanide or thiocyanate substituents, in particular organothiocyanate ions or organothiocyanate substituents.
6. Use according to one of the preceding claims, characterized in that the emission is reduced from liquid compositions, in particular from solutions and dispersions, preferably from aqueous dispersions.
7. Use according to Claim 6, characterized in that the emission is reduced from cleaning agents, disinfectants, preservatives, lubricants, impregnating agents, paints, coatings and plasters.
8. Use according to one of the preceding claims, characterized in that the emission-reducing additive is used at least in an amount of 0.01 % by weight, preferably 0.01 to 10.0% by weight, in particular 0.1 to 7.5 % by weight and especially 0.5 to 5.0 % by weight, based on the composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19703711A DE19703711C2 (en) | 1997-01-23 | 1997-01-23 | Reduction of HCN emissions by additives |
| DE19703711.9 | 1997-01-23 | ||
| PCT/IB1998/000063 WO1998032473A2 (en) | 1997-01-23 | 1998-01-16 | Reduction of emissions of volatile compounds by additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2278288A1 true CA2278288A1 (en) | 1998-07-30 |
Family
ID=7818974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002278288A Abandoned CA2278288A1 (en) | 1997-01-23 | 1998-01-16 | Reduction of emissions of volatile compounds by additives |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0968005B1 (en) |
| JP (1) | JP2001521411A (en) |
| AU (1) | AU5336598A (en) |
| BR (1) | BR9807087A (en) |
| CA (1) | CA2278288A1 (en) |
| DE (2) | DE19703711C2 (en) |
| ES (1) | ES2235309T3 (en) |
| WO (1) | WO1998032473A2 (en) |
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| AU5991401A (en) * | 2000-08-18 | 2002-02-21 | Procter & Gamble Company, The | Reduction of odors from coating material |
| DE10340829A1 (en) * | 2003-09-04 | 2005-04-07 | Schülke & Mayr GmbH | Low-salt or salt-free microbicidal composition based on isothiazolone derivatives and pyrion disulfide |
| US20100189811A1 (en) * | 2009-01-29 | 2010-07-29 | Thor Gmbh | Biocide compositions comprising 3-methylisothiazolin-3-one and a haloalkyl sulphone |
| ES2705088B2 (en) | 2017-09-20 | 2020-03-30 | Liderkit S L | NEW GEL-COAT ADDITIVATED WITH PARTICLES OF TITANIUM DIOXIDE AND ALUMINA |
| JP7415104B2 (en) * | 2019-06-03 | 2024-01-17 | 三井化学株式会社 | Method for producing aqueous solution of diiodomethane compound |
| WO2022246218A1 (en) * | 2021-05-21 | 2022-11-24 | Troy Technology Ii, Inc. | Boosted ipbc for wet-state bacterial control |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3996346A (en) * | 1975-03-18 | 1976-12-07 | Dominic Thomas Staffier | Composition for reducing bodily odor and perspiration |
| LU81802A1 (en) * | 1978-10-20 | 1980-01-25 | Metallurg Ct Voor Res Metallur | PROCESS FOR PURIFYING WASTEWATER |
| JPS63209798A (en) * | 1987-02-24 | 1988-08-31 | Tokyo Met Gov Gesuidou Service Kk | Sludge deodorizer |
| JPH01204940A (en) * | 1988-02-12 | 1989-08-17 | Asada Seifun Kk | Polypropylene resin molding composition |
| JPH01224098A (en) * | 1988-03-02 | 1989-09-07 | Tokyo Met Gov Gesuidou Service Kk | Deodorizing method for dehydrated sludge cake |
| JPH0683720B2 (en) * | 1990-06-19 | 1994-10-26 | 日本曹達株式会社 | Circulating toilet treatment agent |
| JPH05139918A (en) * | 1991-11-22 | 1993-06-08 | Nikka Chem Co Ltd | Antimicrobial and deodorant agent |
| JPH0623345A (en) * | 1992-07-09 | 1994-02-01 | Hokko Chem Ind Co Ltd | Excretion purifying agent |
| US5284649A (en) * | 1992-09-29 | 1994-02-08 | The Procter & Gamble Company | Deodorant gel sticks containing 1-hydroxy pyridinethione active |
| US5415785A (en) * | 1992-12-11 | 1995-05-16 | Nalco Chemical Company | Method for removing a cyanide contaminant from refinery waste water streams |
| JP3252239B2 (en) * | 1992-12-15 | 2002-02-04 | コニカ株式会社 | Processing method and processing solution for silver halide photographic material |
| US5292776A (en) * | 1993-03-26 | 1994-03-08 | Betz Laboratories, Inc. | Microbial inhibiting compositions and their use |
| JP2747880B2 (en) * | 1993-12-27 | 1998-05-06 | 株式会社工生研 | Deodorant for dehydrated cake |
-
1997
- 1997-01-23 DE DE19703711A patent/DE19703711C2/en not_active Expired - Fee Related
-
1998
- 1998-01-16 DE DE69828492T patent/DE69828492T2/en not_active Expired - Fee Related
- 1998-01-16 EP EP98900123A patent/EP0968005B1/en not_active Expired - Lifetime
- 1998-01-16 CA CA002278288A patent/CA2278288A1/en not_active Abandoned
- 1998-01-16 ES ES98900123T patent/ES2235309T3/en not_active Expired - Lifetime
- 1998-01-16 JP JP53177398A patent/JP2001521411A/en active Pending
- 1998-01-16 BR BR9807087-8A patent/BR9807087A/en not_active IP Right Cessation
- 1998-01-16 AU AU53365/98A patent/AU5336598A/en not_active Abandoned
- 1998-01-16 WO PCT/IB1998/000063 patent/WO1998032473A2/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| DE19703711A1 (en) | 1998-07-30 |
| WO1998032473A3 (en) | 1998-09-11 |
| DE19703711C2 (en) | 1999-07-01 |
| WO1998032473A2 (en) | 1998-07-30 |
| ES2235309T3 (en) | 2005-07-01 |
| AU5336598A (en) | 1998-08-18 |
| JP2001521411A (en) | 2001-11-06 |
| DE69828492D1 (en) | 2005-02-10 |
| EP0968005A2 (en) | 2000-01-05 |
| EP0968005B1 (en) | 2005-01-05 |
| DE69828492T2 (en) | 2005-12-15 |
| BR9807087A (en) | 2000-04-18 |
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