CA1045972A - Surface-coating compositions containing substituted oxazolidines - Google Patents
Surface-coating compositions containing substituted oxazolidinesInfo
- Publication number
- CA1045972A CA1045972A CA219,138A CA219138A CA1045972A CA 1045972 A CA1045972 A CA 1045972A CA 219138 A CA219138 A CA 219138A CA 1045972 A CA1045972 A CA 1045972A
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- hydroxymethyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/025—Preservatives, e.g. antimicrobial agents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Abstract of the Disclosure Surface-coating compositions that have improved resistance to attack by bacteria and fungi contain 0.10 percent to 3.0 per-cent by weight of a biocidal component selected from the group consisting of (a) compounds having the structural formula (b) compounds having the structural formula (c) compounds having the structural formula wherein each R represents alkyl of 1 to 6 carbon atoms, hydroxy-methyl, or hydroxymethoxymethyl; R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, halophenyl, or -(CH2O)nCH2OH: each R"
represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, hydroxymethyl, or -(CH2)nCHO: each R"' represents alkyl of 1 to 6 carbon atoms:
m represents 0 to 1; and n represents a number in the range of 0 to 4; and (d) mixtures of said compounds. The substituted oxazolidines preferably contain a total of not more than six oxymethylene units (-CH2O-) in one or more ring substituents.
represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, hydroxymethyl, or -(CH2)nCHO: each R"' represents alkyl of 1 to 6 carbon atoms:
m represents 0 to 1; and n represents a number in the range of 0 to 4; and (d) mixtures of said compounds. The substituted oxazolidines preferably contain a total of not more than six oxymethylene units (-CH2O-) in one or more ring substituents.
Description
:
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I ~1 This invention relates to sur~ace-coating compo~itions
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I ~1 This invention relates to sur~ace-coating compo~itions
2 l~that have improved resistance t~ deterioration resulting ~rom
3 ¦¦ attack by bacteria, ~ungi, and other microorganisms. More
4 ~¦particularly, it relates to sur~ace-coating compo~itions that con-~ltain a biocidally-ef~ective amount of a substituted oxazolidine.
6 11 It is well known in $he art that paints and varnishes ofte 7 ¦ have inadequate resistance to the action of microorganisms. Some 8 ~ of these coating compositions, such as enamels and house paints, 9 ¦ contain as their resinous binders drying oils, oleoresinous ¦ varnish~s, or alkyd resins, which are subject to attack by fungi 11 and bacteria. Others, for example, aqueous dispersions o~ water-12 insoluble synthetic linear polymers, generally con-tain as plasti-13 cizers and thickeners materials that have their origin in animal `
14 or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating 16 compositions seriously hinders their full scale utilization, l7 particularly in those areas and in those applications that are 18 conducive to such attack.
19 Various biocidal materials have been suggested for use in sur~ace-coating compositions, but none has proven entirely satis-21 factory in this application. Some do not provide the required 22 prolonged protection against attack by microorganisms, while other 23 undergo sulfide staining and still others hydrolyze in alkaline 24 aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching once the coating has been 26 spread in a thin layer over the surface to be protected. Some 27 biocidal materials cause the coating compositions to gel or impart 28 color or odor to them.
29 This invention relates to biocides that are o~ particular ~ value in surface-coating compositions. These biocides, which are 11 ~ 3 - ` ~
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1 1lthoroug1lly compatlble with the resinous binders that commonly are 2 1~ used in surface-coating compositions and which are resistant to 3 l¦sulfide staining1 provide excellent and prolonged resistance to 4 3~deterioration resulting from attack by bacteria, fungi, and other s ¦ microorganisms without adversely a~fecting the color, p~I, viscosit , 6 ~ and other physical properties of the surface-coa-ting compositions.
7 ¦ The biocidal compounds that are used in the surface-8 ~ coating compositions of this invention include 9 ~ (a) compounds having the struc-tural formula o ~ R
11 R - f~ ClH2 l2 \ fH /
14 R~
15 (b) compounds having the s-tructural formula 2 f fH2 18 \ fH / \ fH /
R" R"
21 (c) compounds having the structural formula 22 R"'\ ~CH2(OC~I2)mO~I
23 R"' \ NHCH2OH
2~ wherein each R represents alkyl of l to 6 carbon atoms, hydroxy-methyl, or hydroxymethoxymethyl; R' represents hydrogen, alkyl of 26 l to 6 carbon atoms, phenyl, halophenyl, or -(CH2O)nCH2OH; each R"
27 represents hydrogen, alkyl of l to 6 carbon atoms, chloroalkyl of u l to 4 carbon atoms, phenyl, halophenyl, hydroxymethyl, or 29 -(CH~)nCHO; each R"'represents alkyl of l to 6 carbon atoms;
m represents 0 or l; and n represents a number in the ran~e of . .. .
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0 to ~; and 2 1 (d) mixtures o~' these compound~.
3 1 Examples of the monocycli~ biocidal compounds of this 4 ¦ invention include 4,4-dimethyloxazolidine, 4-methyl-4-hexyloxa-1 zolidine, ~,4-di-tert.butyloxazolidine, 4-methyl-4-hydroxymethyl-6 ~ oxazolidine, 4,4~di(hydroxymethyl)oxazolidine, 3-hydroxymethyl- . .
7 ! 4,4-dim0thyloxazolidine, 3-methyl-4,4-diethyloxazolidine, 3-phenyl- .
8 ~ 4-methyl-4-hydroxymethyloxazolidine, 3-p chlorophenyl-4,4-diiso-g ~ propyloxazolidine, 2-methyl-3-tert.butyl-4,4-di(hydroxymethyl)oxa-zolidinej 2-~ormyl-4,4-dimethyloxazolidine, 2-(~-chloroethyl)-4,4-11 ~ dimethyloxazolidine, 2-phenyl-4-methyl-4-hydroxymethyloxazolidine, 12 2-p-chlorophenyl-4-methyl-4-hydroxymethyloxazolidine, and 2-(2,~-13 dichlorophenyl)-4,4-dipropyloxazolidine. Examples of the bicyclic 14 oxazolidines include the following: 5-methyl-l-aza-3,7-dioxa- ~ .
bicyclo(3,3,0)octane, 5-(2-ethylbutyl)-l-aza-3,7-dioxabicyclo :
6 (3,3,0)octane, 5-hydroxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane :
17 5-hydroxymethoxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2,5-18 bis(hydroxymethyI~l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-phenyl-19 5-hydroxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-(~-ohloro-ethyl)-5-methyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(2-21 ethylbutyl)-5-methyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-phenyl-22 5-ethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(2,6-dichloro-23 phenyl)-5-isopropyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, 2-formyl-24 5-ethyl-l-aza-3,7-dio~abicyclo(3,3,0)octane, 2,5,8-trimethyl-l-aza- .
¦3,7-dioxabicyclo(3,3,0)octane, and 2,8-diethyl-5-hydroxymethyl-26 l-aza~3,7-dioxabicyclo(3,3,0)octane. Illustrative of the acyclic 27 compounds are 2-(N-hydroxymethy1amino)-2-methylpropanol-l-hemi-28 for~mal, 2-(N-hydroxymethylamino)-2-ethylbutanol-l, 2-(N-hydroxy-29 methylamino-2-hexyloctanol-l-hemiformal, 2-(N-hydroxymethylamino)-2-ethyloctanol-l, and 2-(N-hydroxymethylamino)-8-methylhexanol-l.
6 11 It is well known in $he art that paints and varnishes ofte 7 ¦ have inadequate resistance to the action of microorganisms. Some 8 ~ of these coating compositions, such as enamels and house paints, 9 ¦ contain as their resinous binders drying oils, oleoresinous ¦ varnish~s, or alkyd resins, which are subject to attack by fungi 11 and bacteria. Others, for example, aqueous dispersions o~ water-12 insoluble synthetic linear polymers, generally con-tain as plasti-13 cizers and thickeners materials that have their origin in animal `
14 or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating 16 compositions seriously hinders their full scale utilization, l7 particularly in those areas and in those applications that are 18 conducive to such attack.
19 Various biocidal materials have been suggested for use in sur~ace-coating compositions, but none has proven entirely satis-21 factory in this application. Some do not provide the required 22 prolonged protection against attack by microorganisms, while other 23 undergo sulfide staining and still others hydrolyze in alkaline 24 aqueous paint systems or separate from the applied coating by migration, volatilization, or leaching once the coating has been 26 spread in a thin layer over the surface to be protected. Some 27 biocidal materials cause the coating compositions to gel or impart 28 color or odor to them.
29 This invention relates to biocides that are o~ particular ~ value in surface-coating compositions. These biocides, which are 11 ~ 3 - ` ~
10~5!3 7Z
1 1lthoroug1lly compatlble with the resinous binders that commonly are 2 1~ used in surface-coating compositions and which are resistant to 3 l¦sulfide staining1 provide excellent and prolonged resistance to 4 3~deterioration resulting from attack by bacteria, fungi, and other s ¦ microorganisms without adversely a~fecting the color, p~I, viscosit , 6 ~ and other physical properties of the surface-coa-ting compositions.
7 ¦ The biocidal compounds that are used in the surface-8 ~ coating compositions of this invention include 9 ~ (a) compounds having the struc-tural formula o ~ R
11 R - f~ ClH2 l2 \ fH /
14 R~
15 (b) compounds having the s-tructural formula 2 f fH2 18 \ fH / \ fH /
R" R"
21 (c) compounds having the structural formula 22 R"'\ ~CH2(OC~I2)mO~I
23 R"' \ NHCH2OH
2~ wherein each R represents alkyl of l to 6 carbon atoms, hydroxy-methyl, or hydroxymethoxymethyl; R' represents hydrogen, alkyl of 26 l to 6 carbon atoms, phenyl, halophenyl, or -(CH2O)nCH2OH; each R"
27 represents hydrogen, alkyl of l to 6 carbon atoms, chloroalkyl of u l to 4 carbon atoms, phenyl, halophenyl, hydroxymethyl, or 29 -(CH~)nCHO; each R"'represents alkyl of l to 6 carbon atoms;
m represents 0 or l; and n represents a number in the ran~e of . .. .
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0 to ~; and 2 1 (d) mixtures o~' these compound~.
3 1 Examples of the monocycli~ biocidal compounds of this 4 ¦ invention include 4,4-dimethyloxazolidine, 4-methyl-4-hexyloxa-1 zolidine, ~,4-di-tert.butyloxazolidine, 4-methyl-4-hydroxymethyl-6 ~ oxazolidine, 4,4~di(hydroxymethyl)oxazolidine, 3-hydroxymethyl- . .
7 ! 4,4-dim0thyloxazolidine, 3-methyl-4,4-diethyloxazolidine, 3-phenyl- .
8 ~ 4-methyl-4-hydroxymethyloxazolidine, 3-p chlorophenyl-4,4-diiso-g ~ propyloxazolidine, 2-methyl-3-tert.butyl-4,4-di(hydroxymethyl)oxa-zolidinej 2-~ormyl-4,4-dimethyloxazolidine, 2-(~-chloroethyl)-4,4-11 ~ dimethyloxazolidine, 2-phenyl-4-methyl-4-hydroxymethyloxazolidine, 12 2-p-chlorophenyl-4-methyl-4-hydroxymethyloxazolidine, and 2-(2,~-13 dichlorophenyl)-4,4-dipropyloxazolidine. Examples of the bicyclic 14 oxazolidines include the following: 5-methyl-l-aza-3,7-dioxa- ~ .
bicyclo(3,3,0)octane, 5-(2-ethylbutyl)-l-aza-3,7-dioxabicyclo :
6 (3,3,0)octane, 5-hydroxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane :
17 5-hydroxymethoxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2,5-18 bis(hydroxymethyI~l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-phenyl-19 5-hydroxymethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-(~-ohloro-ethyl)-5-methyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(2-21 ethylbutyl)-5-methyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-phenyl-22 5-ethyl-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(2,6-dichloro-23 phenyl)-5-isopropyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, 2-formyl-24 5-ethyl-l-aza-3,7-dio~abicyclo(3,3,0)octane, 2,5,8-trimethyl-l-aza- .
¦3,7-dioxabicyclo(3,3,0)octane, and 2,8-diethyl-5-hydroxymethyl-26 l-aza~3,7-dioxabicyclo(3,3,0)octane. Illustrative of the acyclic 27 compounds are 2-(N-hydroxymethy1amino)-2-methylpropanol-l-hemi-28 for~mal, 2-(N-hydroxymethylamino)-2-ethylbutanol-l, 2-(N-hydroxy-29 methylamino-2-hexyloctanol-l-hemiformal, 2-(N-hydroxymethylamino)-2-ethyloctanol-l, and 2-(N-hydroxymethylamino)-8-methylhexanol-l.
- 5 -.,. , .. ~ ' - -, ,' ' ' ' ;
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; A pre~erred group o~ the biocidal compounds o~ this inven-2 ~tion ar0 the polyoxymethyleneoxazolidines that have the structural 3 ~ ~`ormulas 4 1(d) CH20(CH2O)ncH2oH
5 ~ CH2- C fH2
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; A pre~erred group o~ the biocidal compounds o~ this inven-2 ~tion ar0 the polyoxymethyleneoxazolidines that have the structural 3 ~ ~`ormulas 4 1(d) CH20(CH2O)ncH2oH
5 ~ CH2- C fH2
6 0 ~ ~ N \ ~ 0 8 ~ R" R"
gand (e) R
o R -C- 1H2 11 H0CH2(0CH2)n N\
14 wherein R, R", and n have the aforementioned significance.
Illustrative of the bicyclic polyoxymethyleneoxaæolidines 16 are the fol~owing: 5-[hydroxymethyl-di(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, 5-Lhydroxymethyl-tri(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-phenyl-5-[hydroxymethyl-19 tetra(oxymethylene)}-l~aza-3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(a-chloroethyl)-5-Lhydroxymethyl-penta(oxymethylene)]-l-aza-21 3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(p-chlorophenyl)-5-[hydroxy-22 methyl-tri(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, 23 2-hydroxymetl1yl-5-[hydroxymethyl-tetra(oxymethylene)]-l-aza-3,7-24 dioxabicyclo(3,3,0)octane, 2,8-bis(2-ethylbutyl)-5-[hydroxymethyl-2s tri(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, and 2,8-26 bis(hydroxymethyl)-5-[hydroxymethyl-di(oxymethylene)]-l-aza-3,7-27 dioxabicyclo(3,3,0)octane. Examples of the monocyclic polyoxy-28 methyleneoxazolidines include 3-hydroxymethyloxymethylene-4,4-29 dimethyloxazolidine, 3-[hydroxymethyl-di(oxymethylene)]-4,4 diethyloxazolidine, 3-[hydroxymethyl tri(oxymethylene)]-4,4-~ - 6 -~09LS9~Z
I ildiethyloxazolidine, 3-~hydroxymethyl-tetra(oxymethylene)]~4-methyl- .
2 1i 4-isopropyloxazolidine, 2-hexyl-3-[hydroxymethyl-tri(oxymethylene)] _ 3 ~,¦ 4,4-di(hydroxymethyl)oxazolidine, 2-phenyl-3-~hydroxymethyl-di(oxy-~ ~¦methylene)]-4-hexyl-4-hydroxymethyloxazolidine, 2-p-chlorophenyl-l~3-(hydroxymethyloxymethylene)-4,4-di(hydroxymethyl)oxazolidine, 6 ¦ 2-hydroxymethyl-3-[hydroxymethyl-di(oxymethylene)]-4,4-dibutyl-
gand (e) R
o R -C- 1H2 11 H0CH2(0CH2)n N\
14 wherein R, R", and n have the aforementioned significance.
Illustrative of the bicyclic polyoxymethyleneoxaæolidines 16 are the fol~owing: 5-[hydroxymethyl-di(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, 5-Lhydroxymethyl-tri(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, 2-phenyl-5-[hydroxymethyl-19 tetra(oxymethylene)}-l~aza-3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(a-chloroethyl)-5-Lhydroxymethyl-penta(oxymethylene)]-l-aza-21 3,7-dioxabicyclo(3,3,0)octane, 2,8-bis(p-chlorophenyl)-5-[hydroxy-22 methyl-tri(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, 23 2-hydroxymetl1yl-5-[hydroxymethyl-tetra(oxymethylene)]-l-aza-3,7-24 dioxabicyclo(3,3,0)octane, 2,8-bis(2-ethylbutyl)-5-[hydroxymethyl-2s tri(oxymethylene)]-l-aza-3,7-dioxabicyclo(3,3,0)octane, and 2,8-26 bis(hydroxymethyl)-5-[hydroxymethyl-di(oxymethylene)]-l-aza-3,7-27 dioxabicyclo(3,3,0)octane. Examples of the monocyclic polyoxy-28 methyleneoxazolidines include 3-hydroxymethyloxymethylene-4,4-29 dimethyloxazolidine, 3-[hydroxymethyl-di(oxymethylene)]-4,4 diethyloxazolidine, 3-[hydroxymethyl tri(oxymethylene)]-4,4-~ - 6 -~09LS9~Z
I ildiethyloxazolidine, 3-~hydroxymethyl-tetra(oxymethylene)]~4-methyl- .
2 1i 4-isopropyloxazolidine, 2-hexyl-3-[hydroxymethyl-tri(oxymethylene)] _ 3 ~,¦ 4,4-di(hydroxymethyl)oxazolidine, 2-phenyl-3-~hydroxymethyl-di(oxy-~ ~¦methylene)]-4-hexyl-4-hydroxymethyloxazolidine, 2-p-chlorophenyl-l~3-(hydroxymethyloxymethylene)-4,4-di(hydroxymethyl)oxazolidine, 6 ¦ 2-hydroxymethyl-3-[hydroxymethyl-di(oxymethylene)]-4,4-dibutyl-
7 i oxazolidine, and 2,3-bis(hydroxymethyloxymethylene)-4,4-dimethyl-
8 ¦ oxazolidine.
9 ~ Particularly pre~erred for use in surface-coating compo- ..
o ¦ sitions are the polyoxymethyleneoxazolidines in which the total 11 ¦ number of oxymethylene (-CH2O-) units in one or more of the sub-12 ~ stituents on the oxazolidine ring is not greater than Six. While 13 ~ compounds having more than six oxymethylene units in their ring 14 substituents are very ef~ective in controlling the growth o~
bacteria and ~ungi, they tend to be somewhat unstable in surface-16 coating compositions and to impart to them the odor o~ ~ormaldehyd~ .
17 Examples of the particularly preferred bicyclic compounds include }B polyoxymethyleneoxazolidines in which 19 (i) the substituent in the 5-position is -(CH2O(CH2O)l_~- f CH2OH and the substituents in the 2- and 8-positions are 21 hydrogen, alkyl, phenyl, or halophenyl;
22 (ii) the substituent in the 5-position is CH2OCE2OCHaOH, 23 that in the 2-position is -(CH2O)o 2CH2OH, and that in the 24 8-position is hydrogen, alkyl, phenyl, or halophenyl;
2S (iii) the substituent ln the 5-position is -CH2O(CH2O)1_2-26 l CH2OH and the substituents in the 2- and 8-positions are 27 -CH20H .
28 Examples of the particularly pre~erred monocyclic compounds includ~
29 polyoxymethyleneoxazvlidines in which (i) the substituent in the 2-position is hydrogen, alkyl, il - 7 -- . ... . : :. : .
75~
1 j~ phenyl, or halophenyl, that in the 3-position is -(CH2O)1_4-2 ~j CH20H, and those in the 4-position are alkyl;
3 i~ (ii) the substituent in the 2-position i~ -(C~2O)0_3CH20H, 4 that in the 3-posltion is -CHaOCH20H, and those in the s ~ 4-position are alkyl;
6 ¦ (iii) the substituent in the 2-position is -CH20H, that ~ ~ in the 3-position is -(C~20)1_2CH20H, and one or both of 8 those in the 4-position are -C~20H.
g The biocidal compounds of this invention may be prepared o by any suitable and convenient procedure. For example, they may be prepared by the reaction of an aminoalcohol with an aldehyde at a ..
12 temperature between about 20C. and 100C. The reaction is pre-13 ferably carried out in aqueous solution at ambient temperature.
Illustrative of the aminoalcohols that can be used in the reaction are 2-amino-2-methylpropanol-1 J 2-amino-2-methyl-1,3-propanediol, 16 2-amino-2-ethyl-1,3-propanediol, and tris(hydroxymethyl)amino-17 methane. The aldehyde may be an aliphatic aldehyde, such as form-la aldehyde, acetaldehyde, butyraldehyde, a-chloroacetaldehyde, or 19 2-ethylbutyraldehyde; an aromatic aldehyde, such as benzaldehyde, p-chlorobenzaldehyde, or 2,~-dichlorobenzaldehyde; or a dialdehyde, Zl such as glyoxal, succinaldehyde, or glutaraldehyde. A single 22 aldehyde or a mixture of aldehydes may be used. Alternatively, 23 the polyoxymethyleneoxazolidines may be prepared by the reaction 24 of the appropriate oxazolidine with formaldehyde and/or paraform-aldehyde.
26 The substituted oxazolidines are preferably prepared by 27 mixing an aminoalcohol with an aqueous solution that contains 28 formaldehyde and optionally another aldehyde at ambient temperatur~
29 to form an aqueous solution that contains 20 percent to 80 percent by weight, and preferably 40 percent to 60 percent by weight, of 10459'7Z
1 ~¦one or more o~ the ~'orementioned substituted oxazolidines. The 2 ~I aqueous solution may then be used without purification or addi-3 ~tional treatment other than adj~lstment o-f the concentration o~ the 4 il reaction product to the desired level to protect surface-coating l~compositions ~rom attack by bacteria and fungi. In addition to 6 ¦ costing less than the purified oxazolidlnes and being easier to 7 ~ incorporate in the aqueous surface-coating compositions, the 8 ~ aqueous oxazolidine solutions provide better biocidal activity for g ~ a given concentration of the oxa~olidine in the surface-coating ~ composition. Unlike most other aqueous surface-coating composi-11 -tions that contain a biocide, the surface-coating compositions to 12 which the aqueous polyo~ymethyleneoxazolidine solutions have been 13 added tend to become lighter in color on aging.
14 The substitu*ed oxazolidines of this invention can be used to impart bacterial and fungal resistance to a wide variety of 16 surface-coating compositions including both water-based and organi 17 solvent-based coating systems.
In a preferred embodiment of the invention, the substitute 19 oxazolidines are used as the biocide in aqueous sur~ace-coating compositions that contain about lO percent to 60 percent by weight 21 of a water-insoluble, film-forming resinous binder that is an oleo 2~ resinous binder, a synthetic linear addition polymer, or a mixture 23 of these binders. The useful aqueous dispersions of synthetic 24 linear addition polymers are ordinarily prepared by the emulsion polymerization o~ ethylenically-unsaturated monomers. Illustrativ 26 of these polymers are polyvinyl acetate; polyvinyl butyrate; poly-z7 ¦ vinyl chloride; copolymers of vinyl acetate with vinyl chloride 28 1 or acrylonitrile; copolymers of vinyl chloride with vinylidene 29 chloride; polyethylene; polyisobutylene; polys-tyrene; copolymers of styrene with maleic anhydride or butadiene; copolymers of ~:
I -g ~ ~ .
o ¦ sitions are the polyoxymethyleneoxazolidines in which the total 11 ¦ number of oxymethylene (-CH2O-) units in one or more of the sub-12 ~ stituents on the oxazolidine ring is not greater than Six. While 13 ~ compounds having more than six oxymethylene units in their ring 14 substituents are very ef~ective in controlling the growth o~
bacteria and ~ungi, they tend to be somewhat unstable in surface-16 coating compositions and to impart to them the odor o~ ~ormaldehyd~ .
17 Examples of the particularly preferred bicyclic compounds include }B polyoxymethyleneoxazolidines in which 19 (i) the substituent in the 5-position is -(CH2O(CH2O)l_~- f CH2OH and the substituents in the 2- and 8-positions are 21 hydrogen, alkyl, phenyl, or halophenyl;
22 (ii) the substituent in the 5-position is CH2OCE2OCHaOH, 23 that in the 2-position is -(CH2O)o 2CH2OH, and that in the 24 8-position is hydrogen, alkyl, phenyl, or halophenyl;
2S (iii) the substituent ln the 5-position is -CH2O(CH2O)1_2-26 l CH2OH and the substituents in the 2- and 8-positions are 27 -CH20H .
28 Examples of the particularly pre~erred monocyclic compounds includ~
29 polyoxymethyleneoxazvlidines in which (i) the substituent in the 2-position is hydrogen, alkyl, il - 7 -- . ... . : :. : .
75~
1 j~ phenyl, or halophenyl, that in the 3-position is -(CH2O)1_4-2 ~j CH20H, and those in the 4-position are alkyl;
3 i~ (ii) the substituent in the 2-position i~ -(C~2O)0_3CH20H, 4 that in the 3-posltion is -CHaOCH20H, and those in the s ~ 4-position are alkyl;
6 ¦ (iii) the substituent in the 2-position is -CH20H, that ~ ~ in the 3-position is -(C~20)1_2CH20H, and one or both of 8 those in the 4-position are -C~20H.
g The biocidal compounds of this invention may be prepared o by any suitable and convenient procedure. For example, they may be prepared by the reaction of an aminoalcohol with an aldehyde at a ..
12 temperature between about 20C. and 100C. The reaction is pre-13 ferably carried out in aqueous solution at ambient temperature.
Illustrative of the aminoalcohols that can be used in the reaction are 2-amino-2-methylpropanol-1 J 2-amino-2-methyl-1,3-propanediol, 16 2-amino-2-ethyl-1,3-propanediol, and tris(hydroxymethyl)amino-17 methane. The aldehyde may be an aliphatic aldehyde, such as form-la aldehyde, acetaldehyde, butyraldehyde, a-chloroacetaldehyde, or 19 2-ethylbutyraldehyde; an aromatic aldehyde, such as benzaldehyde, p-chlorobenzaldehyde, or 2,~-dichlorobenzaldehyde; or a dialdehyde, Zl such as glyoxal, succinaldehyde, or glutaraldehyde. A single 22 aldehyde or a mixture of aldehydes may be used. Alternatively, 23 the polyoxymethyleneoxazolidines may be prepared by the reaction 24 of the appropriate oxazolidine with formaldehyde and/or paraform-aldehyde.
26 The substituted oxazolidines are preferably prepared by 27 mixing an aminoalcohol with an aqueous solution that contains 28 formaldehyde and optionally another aldehyde at ambient temperatur~
29 to form an aqueous solution that contains 20 percent to 80 percent by weight, and preferably 40 percent to 60 percent by weight, of 10459'7Z
1 ~¦one or more o~ the ~'orementioned substituted oxazolidines. The 2 ~I aqueous solution may then be used without purification or addi-3 ~tional treatment other than adj~lstment o-f the concentration o~ the 4 il reaction product to the desired level to protect surface-coating l~compositions ~rom attack by bacteria and fungi. In addition to 6 ¦ costing less than the purified oxazolidlnes and being easier to 7 ~ incorporate in the aqueous surface-coating compositions, the 8 ~ aqueous oxazolidine solutions provide better biocidal activity for g ~ a given concentration of the oxa~olidine in the surface-coating ~ composition. Unlike most other aqueous surface-coating composi-11 -tions that contain a biocide, the surface-coating compositions to 12 which the aqueous polyo~ymethyleneoxazolidine solutions have been 13 added tend to become lighter in color on aging.
14 The substitu*ed oxazolidines of this invention can be used to impart bacterial and fungal resistance to a wide variety of 16 surface-coating compositions including both water-based and organi 17 solvent-based coating systems.
In a preferred embodiment of the invention, the substitute 19 oxazolidines are used as the biocide in aqueous sur~ace-coating compositions that contain about lO percent to 60 percent by weight 21 of a water-insoluble, film-forming resinous binder that is an oleo 2~ resinous binder, a synthetic linear addition polymer, or a mixture 23 of these binders. The useful aqueous dispersions of synthetic 24 linear addition polymers are ordinarily prepared by the emulsion polymerization o~ ethylenically-unsaturated monomers. Illustrativ 26 of these polymers are polyvinyl acetate; polyvinyl butyrate; poly-z7 ¦ vinyl chloride; copolymers of vinyl acetate with vinyl chloride 28 1 or acrylonitrile; copolymers of vinyl chloride with vinylidene 29 chloride; polyethylene; polyisobutylene; polys-tyrene; copolymers of styrene with maleic anhydride or butadiene; copolymers of ~:
I -g ~ ~ .
10~597Z
acrylonitrile with butadiene; copolymers of methacrylic acid ~ ~ esters of ~lcohols having 1 to 8 carbon ~toms with vinyl acetate, 3 vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic 4 acid esters of alcohols having 1 to 8 carbon atoms with vinyl s acetate, vinyl chloride, acrylonitrile, or styrene; and mi~tures 6 thereof. Suitable oleoresinous binders include drying oils, such 7 as linseed oil, tung oil, soybean oil, dehydrated castor oil, 8 sa~flower oil, or fish oil; bodied drying oils; blends o~ drying g oils or bodied drying oils with a resin component such as limed o rosin, an ester gum, or phenolic resin; oleoresinous varnishes Il formed by heating one of the a~orementioned resins with one or 12 more drying oils or bodied drying oils; alkyd resins, which are 13 resinous products resulting from the reaction of a polyhydric 14 alcohol, such as pentaerythritol or glycerol, with a dicarbo~ylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.
The substituted oxazolidines can also be used as the 1~ biocide in organic solvent-based systems that contain an oleo-19 resinous binder as hereinbefore defined.
The addition to surface-coating compositions of as little 21 as 0.10 percent by weight of one or more of the biocidal compounds 22 of this invention will bring about an appreciable improvement in 23 the resistance of the composition to attack by fungi and bacteria.
24 Three percent or more of the biocidal compounds can be used, but these larger amounts ordinarily do not provide further improvement 26 in the properties of the surface-coating compositions and for this 27 reason are not usually used. The amount of the biocidal compound 28 that will provide optimum protection for surface-coating composi-29 tions depends upon such factors as the choice of the biocidal ¦compound, the choice of resinous binder and other ingredients of - 10_ lO~S9~Z
1 the composition and the amount o~ each o~ these ~aterials that is 2 ¦used, and the application ~or which ~he coa~ing composition is 3 j intended. In most cases l percent to 2 percent of an oxazolidine, 4 based on the weight o~ the composition, is used to protect surface-s coating compositions from attack by ~ungi. From O.l perce~t to 6 O. 5 percent of the oxazolidines, based on the weight o~ the compo-7 sition, is pre~erably incorporated into aqueous sur~ace-coating 8 compositions to protect them from attack by bacteria.
g In addition to the resinous binder and the biocidal compound, the sur~ace-coating compnsitions may contain various
acrylonitrile with butadiene; copolymers of methacrylic acid ~ ~ esters of ~lcohols having 1 to 8 carbon ~toms with vinyl acetate, 3 vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic 4 acid esters of alcohols having 1 to 8 carbon atoms with vinyl s acetate, vinyl chloride, acrylonitrile, or styrene; and mi~tures 6 thereof. Suitable oleoresinous binders include drying oils, such 7 as linseed oil, tung oil, soybean oil, dehydrated castor oil, 8 sa~flower oil, or fish oil; bodied drying oils; blends o~ drying g oils or bodied drying oils with a resin component such as limed o rosin, an ester gum, or phenolic resin; oleoresinous varnishes Il formed by heating one of the a~orementioned resins with one or 12 more drying oils or bodied drying oils; alkyd resins, which are 13 resinous products resulting from the reaction of a polyhydric 14 alcohol, such as pentaerythritol or glycerol, with a dicarbo~ylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.
The substituted oxazolidines can also be used as the 1~ biocide in organic solvent-based systems that contain an oleo-19 resinous binder as hereinbefore defined.
The addition to surface-coating compositions of as little 21 as 0.10 percent by weight of one or more of the biocidal compounds 22 of this invention will bring about an appreciable improvement in 23 the resistance of the composition to attack by fungi and bacteria.
24 Three percent or more of the biocidal compounds can be used, but these larger amounts ordinarily do not provide further improvement 26 in the properties of the surface-coating compositions and for this 27 reason are not usually used. The amount of the biocidal compound 28 that will provide optimum protection for surface-coating composi-29 tions depends upon such factors as the choice of the biocidal ¦compound, the choice of resinous binder and other ingredients of - 10_ lO~S9~Z
1 the composition and the amount o~ each o~ these ~aterials that is 2 ¦used, and the application ~or which ~he coa~ing composition is 3 j intended. In most cases l percent to 2 percent of an oxazolidine, 4 based on the weight o~ the composition, is used to protect surface-s coating compositions from attack by ~ungi. From O.l perce~t to 6 O. 5 percent of the oxazolidines, based on the weight o~ the compo-7 sition, is pre~erably incorporated into aqueous sur~ace-coating 8 compositions to protect them from attack by bacteria.
g In addition to the resinous binder and the biocidal compound, the sur~ace-coating compnsitions may contain various
11 auxiliary materials, such as pigments, extenders, solvents, dyes,
12 defoaming agents, driers, thickeners, emulsi~iers, plasticizers, and the like in the ~mounts ordinarily used for these purposes.
14 The biocidal compounds may be incorporated into the lS sur~ace-coating compositions by any convenient procedure. As has 16 been indicated hereinbe~ore, aqueous solutions containing the 17 oxazolidines can be mixed with the aqueous surface-coating compo-1~ sition, Alternatively, the biocidal compounds can be combined 19 with the pigments and other components to form a pigment phase 20 that is mixed with the resinous binder and water or organic 21 solvent to form the surface-coating composition, 22 The invention is further illustrated by the following ..
23 examples, 2~ Example l A. A polyvinyl acetate latex paint was prepared by 26 mixing together the ~ollowing materials: .:
27 Parts by Weight 28 Water 481.5 29 25% Aqueous solution o~ sodium salt of 2 maleic anhydride/diisobutylene copolymer ~11-I
104~972 ¦I Parts by Weight ~ I Potassium pyrophosphate 3 3 Long chain ~atty acid alkanolamide 9 4 Defoamer 6 Ethylene glycol 75 1-1/4% Aqueous solution of Hydroxyethyl-6 cellulose 7 Aqueous emulsion containing 55% of 1299 8 polyvinyl acetate g Diethyl ether of diethylene glycol 30 o Titanium dioxide 690 ll Talc 345 12 Calcium metasilicate 150
14 The biocidal compounds may be incorporated into the lS sur~ace-coating compositions by any convenient procedure. As has 16 been indicated hereinbe~ore, aqueous solutions containing the 17 oxazolidines can be mixed with the aqueous surface-coating compo-1~ sition, Alternatively, the biocidal compounds can be combined 19 with the pigments and other components to form a pigment phase 20 that is mixed with the resinous binder and water or organic 21 solvent to form the surface-coating composition, 22 The invention is further illustrated by the following ..
23 examples, 2~ Example l A. A polyvinyl acetate latex paint was prepared by 26 mixing together the ~ollowing materials: .:
27 Parts by Weight 28 Water 481.5 29 25% Aqueous solution o~ sodium salt of 2 maleic anhydride/diisobutylene copolymer ~11-I
104~972 ¦I Parts by Weight ~ I Potassium pyrophosphate 3 3 Long chain ~atty acid alkanolamide 9 4 Defoamer 6 Ethylene glycol 75 1-1/4% Aqueous solution of Hydroxyethyl-6 cellulose 7 Aqueous emulsion containing 55% of 1299 8 polyvinyl acetate g Diethyl ether of diethylene glycol 30 o Titanium dioxide 690 ll Talc 345 12 Calcium metasilicate 150
13 This paint had the following properties as determined by
14 standard paint testing procedures:
Viscosity 65 K.U.
6 Brookfield Viscosity 800 c s (No. 4 spindle, 60 rpm) P
17 pH 7.8 .
18 f Yellowness index 3.0 Sma~l amounts of the biocidal compounds of this invention .
21 or comparative biocides were added to portions of this paint.
22 B, An acrylic latex paint was prepared by mixing together 23 the following materials:
24 Parts by Weight :
Water 168 26 Alkyl aryl ether surfactant 6 27 25% Aqueous solution of sodium salt of a7 28 1 maleic anhydride/diisobutylene copolymer 29 1 Defoamer 12 l 2% Aqueous solution o~ hydroxyethyl- 300 30 1 cellulose 1 ¦¦ Parts by Wei~ht 2 I Ethylene grlycol 60 3 ¦ Titanium dioxide 750 4 ¦ Mica (waterground) 90 .
s Calcium carbonate 375 6 ¦ Ammonium hydroxide (28%) 7 ¦ Aqueous dispersion containing 46% acrylic ester copolymer (66% ethyl acrylate, 32,5% 1642 8 methyl acrylate, and 1,5% acrylic acid) 9 ¦ This paint had the following properties:
o ¦ Viscosity 72 K,U, .
¦ Brookfield Viscosity . 3 spindle, 60 rpm) 1250 cps, 13 I pH 9,2 1~ I Yellowness index 2,6
Viscosity 65 K.U.
6 Brookfield Viscosity 800 c s (No. 4 spindle, 60 rpm) P
17 pH 7.8 .
18 f Yellowness index 3.0 Sma~l amounts of the biocidal compounds of this invention .
21 or comparative biocides were added to portions of this paint.
22 B, An acrylic latex paint was prepared by mixing together 23 the following materials:
24 Parts by Weight :
Water 168 26 Alkyl aryl ether surfactant 6 27 25% Aqueous solution of sodium salt of a7 28 1 maleic anhydride/diisobutylene copolymer 29 1 Defoamer 12 l 2% Aqueous solution o~ hydroxyethyl- 300 30 1 cellulose 1 ¦¦ Parts by Wei~ht 2 I Ethylene grlycol 60 3 ¦ Titanium dioxide 750 4 ¦ Mica (waterground) 90 .
s Calcium carbonate 375 6 ¦ Ammonium hydroxide (28%) 7 ¦ Aqueous dispersion containing 46% acrylic ester copolymer (66% ethyl acrylate, 32,5% 1642 8 methyl acrylate, and 1,5% acrylic acid) 9 ¦ This paint had the following properties:
o ¦ Viscosity 72 K,U, .
¦ Brookfield Viscosity . 3 spindle, 60 rpm) 1250 cps, 13 I pH 9,2 1~ I Yellowness index 2,6
15 I Small amounts of the biocidal compounds of this invention :
or comparative biocides were added to portions of this paint. ~ :
17 . C, An exterior house paint was prepared by mixing together the following materials: ;:
19 Parts by Weight Basic lead carbonate ~88 21 Zinc oxide 232 22 Titanium dioxide (rutile) 149 23 Talc 260 24 Linseed oil 242 2s Bodied linseed oil 11~
26 Mineral splrlts 114 27 Antiskinning agent 2 28 Manganese naphthenate (6%) 2,27 29 Lead naphthenate (24%) 11,3 Small amounts of the biocidal compounds of this invention 31 or comparative biocides were added to portions of this paint, ~0~972 1 ~ D. The polyvinyl acetate latex paint, the acrylic latex 2 paint, and the oll-based paint were evaluated by means o~ an agar 3 diffusion assay. In this test, agar is inoculated with the test 4 organism, the treated palnt is placed in a well cut from the agar, s and after incubation at 28C. and 85-95% relative humidity, the 6 activity of the biocide is measured by zones of inhibition. The 7 biocidal compounds tested and the results obtained are given in 8 Table I. In this table g ZO = Zone of inhibited growth in mm.
O = No zone of inhibition; no growth Tr = Trace zone of inhibited growth -- = Not tested Bacteria A - Mixed paint spoilage strains 14 B - Pseudomonas aeruginosa C - Aerobacter aerogenes
or comparative biocides were added to portions of this paint. ~ :
17 . C, An exterior house paint was prepared by mixing together the following materials: ;:
19 Parts by Weight Basic lead carbonate ~88 21 Zinc oxide 232 22 Titanium dioxide (rutile) 149 23 Talc 260 24 Linseed oil 242 2s Bodied linseed oil 11~
26 Mineral splrlts 114 27 Antiskinning agent 2 28 Manganese naphthenate (6%) 2,27 29 Lead naphthenate (24%) 11,3 Small amounts of the biocidal compounds of this invention 31 or comparative biocides were added to portions of this paint, ~0~972 1 ~ D. The polyvinyl acetate latex paint, the acrylic latex 2 paint, and the oll-based paint were evaluated by means o~ an agar 3 diffusion assay. In this test, agar is inoculated with the test 4 organism, the treated palnt is placed in a well cut from the agar, s and after incubation at 28C. and 85-95% relative humidity, the 6 activity of the biocide is measured by zones of inhibition. The 7 biocidal compounds tested and the results obtained are given in 8 Table I. In this table g ZO = Zone of inhibited growth in mm.
O = No zone of inhibition; no growth Tr = Trace zone of inhibited growth -- = Not tested Bacteria A - Mixed paint spoilage strains 14 B - Pseudomonas aeruginosa C - Aerobacter aerogenes
16 Fungi D - Pullularia pullulans E - Penicillium crustosum 8 F - Aspergillus niger 19 Example 2 A series of the biocidal compounds o-f this invention were 21 evaluated at the level of 2C/o in a po}yvinyl acetate latex paint, 22 an acrylic latex palnt, and an oil-based paint by the procedure 23 described in Example lD. The results obtained are given in 24 Table II.
Example 3 26 A series of aqueous solutions of the biocides o-f this 27 invention was prepared by mixing an aminoalcohol with a 37%
28 aqueous ~ormaldehyde solution at room temperature. The amino-29 alcohols used, the amounts of formaldehyde added, and the com-position of the resulting solutions are given in Table III.
1045g7Z
Example 4 ~ a) The aqueous solutions described in Example 3 were 3 evaluated as biocides ~or paints by the procedure described in ~ Example lD. The results obtained are given in Table I~.
b) The paints containing the aqueous solutions of 6 Example 3 were ~tored for 4 weeks at 120F, a~d then evaluated.
7 The results obtained, which are given in Table V 7 indicate that ~ the solutions had lost little or none of their biocidal activity 9 on storage.
o Example 5 11 To portions o~ the polyvinyl acetate latex paint whose 12 preparation is described in Example lA were added small amounts 13 of the aqueous biocidal solutions whose preparation is described 14 in Example 3. The resulting treated paints were evaluated by the following procedure:
16 A mixed bacterial inoculum consisting of Pseudomonas aeruginosa ATCC 10145, Aerobacter aerogenes ATCC 7256, Bacillus subtilis, Bacillus _egsterium and Bacillus licheniformis was pre-19 pared by incubation of inoculated (0.5 ml) milk dilution bottles 20 containing 50 ml. of solidi~ied Trypticase-Soy Agar.
21 After incubation for 18 to 24 hours at 35C., the cultures 22 were removed ~rom the agar surface, diluted to an appropriate 23 volume in phosphate buffer (0.05 M, pH 7.0), and inoculated into 24 300 gram portions of the test paints. The amount of the culture added to the paint was such that the final level of bacteria was 26 between 0.5 X 106 and 3 X 106 per gram of paint. After thorough 27 mixing, the paints were incubated at 35C. under 90 percent 28 relative humidity. At intervals during the incubation, measure-29 ments of viability of the bacteria and viscosity of the paint were made. The viability test was carried out by adding an aliquot of lQ~
l the palnt to Trypticase-Soy Broth, incubating for 48 hours a-t 2 35C., and then streaking it on a Trypticase-Soy Agar plate. After 3 a 34 hour incubation period at 35C., the plates were examined for 4 ¦ growth along the streak. The results obtained are reported in S ¦ Table ~I as -~ (growth present) or - (growth absent). The viscosity 6 ¦ of the paint samples was measured with a Brookfield Viscometer 7 ¦ using a No. 3 spindle at 60 rpm. The percentage decrease of the 8 ¦ viscosity of each of the treated paints during the incubation 9 ¦ period is reported in Table VI.
o ¦ Example 6 Il ¦ A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)-12 ¦aminomethane, 121.5 grams (1.5 moles) of 37% aqueous formaldehyde 13 ¦solution, and 31.6 grams (1.0 mole) of 95% para~ormaldehyde was 14 ¦stirred and heated at its reflux temperature until a homogeneous ¦solution was obtained. The solution was cooled and fil-tered.
16 ¦There was obtained 213 grams o~ a clear yellow solution that con-
Example 3 26 A series of aqueous solutions of the biocides o-f this 27 invention was prepared by mixing an aminoalcohol with a 37%
28 aqueous ~ormaldehyde solution at room temperature. The amino-29 alcohols used, the amounts of formaldehyde added, and the com-position of the resulting solutions are given in Table III.
1045g7Z
Example 4 ~ a) The aqueous solutions described in Example 3 were 3 evaluated as biocides ~or paints by the procedure described in ~ Example lD. The results obtained are given in Table I~.
b) The paints containing the aqueous solutions of 6 Example 3 were ~tored for 4 weeks at 120F, a~d then evaluated.
7 The results obtained, which are given in Table V 7 indicate that ~ the solutions had lost little or none of their biocidal activity 9 on storage.
o Example 5 11 To portions o~ the polyvinyl acetate latex paint whose 12 preparation is described in Example lA were added small amounts 13 of the aqueous biocidal solutions whose preparation is described 14 in Example 3. The resulting treated paints were evaluated by the following procedure:
16 A mixed bacterial inoculum consisting of Pseudomonas aeruginosa ATCC 10145, Aerobacter aerogenes ATCC 7256, Bacillus subtilis, Bacillus _egsterium and Bacillus licheniformis was pre-19 pared by incubation of inoculated (0.5 ml) milk dilution bottles 20 containing 50 ml. of solidi~ied Trypticase-Soy Agar.
21 After incubation for 18 to 24 hours at 35C., the cultures 22 were removed ~rom the agar surface, diluted to an appropriate 23 volume in phosphate buffer (0.05 M, pH 7.0), and inoculated into 24 300 gram portions of the test paints. The amount of the culture added to the paint was such that the final level of bacteria was 26 between 0.5 X 106 and 3 X 106 per gram of paint. After thorough 27 mixing, the paints were incubated at 35C. under 90 percent 28 relative humidity. At intervals during the incubation, measure-29 ments of viability of the bacteria and viscosity of the paint were made. The viability test was carried out by adding an aliquot of lQ~
l the palnt to Trypticase-Soy Broth, incubating for 48 hours a-t 2 35C., and then streaking it on a Trypticase-Soy Agar plate. After 3 a 34 hour incubation period at 35C., the plates were examined for 4 ¦ growth along the streak. The results obtained are reported in S ¦ Table ~I as -~ (growth present) or - (growth absent). The viscosity 6 ¦ of the paint samples was measured with a Brookfield Viscometer 7 ¦ using a No. 3 spindle at 60 rpm. The percentage decrease of the 8 ¦ viscosity of each of the treated paints during the incubation 9 ¦ period is reported in Table VI.
o ¦ Example 6 Il ¦ A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)-12 ¦aminomethane, 121.5 grams (1.5 moles) of 37% aqueous formaldehyde 13 ¦solution, and 31.6 grams (1.0 mole) of 95% para~ormaldehyde was 14 ¦stirred and heated at its reflux temperature until a homogeneous ¦solution was obtained. The solution was cooled and fil-tered.
16 ¦There was obtained 213 grams o~ a clear yellow solution that con-
17 ¦tained 43.1% of water and 56.9% of solids. The pH of an 0.1 M
18 ¦solution of the product was 6.6. The product was shown by NMR,
19 IR, and GC analysis of its silyl ethers to be a mixture of 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, 5-hydroxy-21 methoxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, and 5-hydroxy-22 methylpolyox~methylene-1-aza-3,7-dioxabicyclo(3,3,0)octanes having 23 the structural formula 24 fH20(cH20)xcH2oH
fH2 f-- fH2 26 0 ~ N \ / 0 28 wherein x represents numbers in the range of 1 to 3.
29 Example 7 A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)-. , ., 10~5g7z 1 amlnomethane, 121.5 grams (1.5 moles) of 37% aqueous ~ormaldehyde t solution, and 47.3 grams (1.5 moles) of 95% paraformaldehyde was 3 stirred and heated at its re~lux temperature until a homogeneous 4 solution was obtained. The solution was cooled and filtered.
s There was obtained 229.3 grams of a clear yellow solution that 6 ¦contained 40.1% of water and 59.9% of solids. The pH o~ an 0.1 M
7 ~solution of the product was 6.6. The product was shown by NMR, IR ?
8 ¦and GC analysis of its silyl ethers to be a mixture containing 9 ¦ about 20% o~ 5-hydroxymethyl-1-aza-397-dioxablcyclo(3,3,0)octane, ¦ 37% of 5-hydroxymethoxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, ¦14% of 5-Lhydroxymethyl-di(oxymethylene)~-1-aza-3,7-dioxabicyclo-l~ ¦(3,3,0)octane, 21% of 5-Lhydroxymethyl-tri(oxymethylene)]-1-aza-l3 ¦3,7-dioxabicyclo(3,3,0)octane, and 8% of 5-[hydroxymethyl-tetra-14 ¦(oxymethylene)]-1-aza-3,7-dioxabicyclo(3,3,0)octane.
lS Example 8 A mixture of 29.0 grams (0.2 mole) of 5-hydroxymethyl-1-17 a~a-3,7-dioxabicyclo(3,3,0)octane and 32.4 grams (0.4 mole) of 37%
18 aqueous ~ormaldehyde solution was stirred at ambient temperature 19 ¦ until a homogeneous solution was obtained. The product was an I aqueous solution that contained 26.1% of water and 73.9% of 21 ¦ 5-[hydroxymethyl-di(oxymethylene)~-1-aza-3,7-dioxabicyclo(3,3,0)-2~ ¦ octane. The pH of an 0.1 M solution of the product was 6.9.
23 ¦ Example 9 24 ¦ A mixture of 20.2 grams (0.2 mole) of 4,4-dimethyloxa-2s ¦ zolidine and 32.4 grams (0.4 mole) of 37% aqueous formaldehyde 26 ¦ solution was stirred at ambient temperature until a homogeneous 27 ¦ solution was obtained. The product was an aqueous solution that 28 ¦ contained 31.5% of water and 68.5% of 3-hydroxymethyloxymethylene-29 14,4-dimethyloxazolidine. The pH of an 0.1 M solution of the ¦ product was 9.8.
, . ~ .; ,. . .
I Example lO
2 A mixture o~` 20.2 grams (0.2 mole) of 4,4-dimethyloxa-3 zolidine, 32.4 grams (0.4 mole) of 37% aqueous formaldehyde 4 solution, and 6.3 grams (0.2 mole) of 95% paraformaldehyde was s stirred and heated at its reflux temperature until a homogeneous 6 1 solution was obtained. The solution was cooled and filtered.
7 ¦ The resulting clear solution contained 36.6% of water and 63.4%
8 of solids. The pH of an O.l M solution of the product was 10.7.
9 The product was shown by NMR analysis to be a mixture of poly(o~y-o methylene)-4,4-dimethyloxazolidines containing a major amount of 1l 3-LhYdroxymethyl-di(oxymethylene)~-4,4-dimethyloxazolidine~
12 Example ll 13 A mixture of 20.2 grams (0.2 mole) of 4,4-dimethyloxa-14 zolidine, 48.7 grams (0.6 mole) of 37% aqueous ~ormaldehyde s solution, and 6.3 grams (0.2 mole) of 95% para~ormaldehyde was 16 stirred and heated at its reflux temperature until a homogeneous 17 solution was obtained. The solution was cooled and filtered. It 18 contained 40.4% of water and 59.6% of solids. The pH of an O.l M
19 solution o~ the product was 10.3. The product was shown by
fH2 f-- fH2 26 0 ~ N \ / 0 28 wherein x represents numbers in the range of 1 to 3.
29 Example 7 A mixture of 60.5 grams (0.5 mole) of tris(hydroxymethyl)-. , ., 10~5g7z 1 amlnomethane, 121.5 grams (1.5 moles) of 37% aqueous ~ormaldehyde t solution, and 47.3 grams (1.5 moles) of 95% paraformaldehyde was 3 stirred and heated at its re~lux temperature until a homogeneous 4 solution was obtained. The solution was cooled and filtered.
s There was obtained 229.3 grams of a clear yellow solution that 6 ¦contained 40.1% of water and 59.9% of solids. The pH o~ an 0.1 M
7 ~solution of the product was 6.6. The product was shown by NMR, IR ?
8 ¦and GC analysis of its silyl ethers to be a mixture containing 9 ¦ about 20% o~ 5-hydroxymethyl-1-aza-397-dioxablcyclo(3,3,0)octane, ¦ 37% of 5-hydroxymethoxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane, ¦14% of 5-Lhydroxymethyl-di(oxymethylene)~-1-aza-3,7-dioxabicyclo-l~ ¦(3,3,0)octane, 21% of 5-Lhydroxymethyl-tri(oxymethylene)]-1-aza-l3 ¦3,7-dioxabicyclo(3,3,0)octane, and 8% of 5-[hydroxymethyl-tetra-14 ¦(oxymethylene)]-1-aza-3,7-dioxabicyclo(3,3,0)octane.
lS Example 8 A mixture of 29.0 grams (0.2 mole) of 5-hydroxymethyl-1-17 a~a-3,7-dioxabicyclo(3,3,0)octane and 32.4 grams (0.4 mole) of 37%
18 aqueous ~ormaldehyde solution was stirred at ambient temperature 19 ¦ until a homogeneous solution was obtained. The product was an I aqueous solution that contained 26.1% of water and 73.9% of 21 ¦ 5-[hydroxymethyl-di(oxymethylene)~-1-aza-3,7-dioxabicyclo(3,3,0)-2~ ¦ octane. The pH of an 0.1 M solution of the product was 6.9.
23 ¦ Example 9 24 ¦ A mixture of 20.2 grams (0.2 mole) of 4,4-dimethyloxa-2s ¦ zolidine and 32.4 grams (0.4 mole) of 37% aqueous formaldehyde 26 ¦ solution was stirred at ambient temperature until a homogeneous 27 ¦ solution was obtained. The product was an aqueous solution that 28 ¦ contained 31.5% of water and 68.5% of 3-hydroxymethyloxymethylene-29 14,4-dimethyloxazolidine. The pH of an 0.1 M solution of the ¦ product was 9.8.
, . ~ .; ,. . .
I Example lO
2 A mixture o~` 20.2 grams (0.2 mole) of 4,4-dimethyloxa-3 zolidine, 32.4 grams (0.4 mole) of 37% aqueous formaldehyde 4 solution, and 6.3 grams (0.2 mole) of 95% paraformaldehyde was s stirred and heated at its reflux temperature until a homogeneous 6 1 solution was obtained. The solution was cooled and filtered.
7 ¦ The resulting clear solution contained 36.6% of water and 63.4%
8 of solids. The pH of an O.l M solution of the product was 10.7.
9 The product was shown by NMR analysis to be a mixture of poly(o~y-o methylene)-4,4-dimethyloxazolidines containing a major amount of 1l 3-LhYdroxymethyl-di(oxymethylene)~-4,4-dimethyloxazolidine~
12 Example ll 13 A mixture of 20.2 grams (0.2 mole) of 4,4-dimethyloxa-14 zolidine, 48.7 grams (0.6 mole) of 37% aqueous ~ormaldehyde s solution, and 6.3 grams (0.2 mole) of 95% para~ormaldehyde was 16 stirred and heated at its reflux temperature until a homogeneous 17 solution was obtained. The solution was cooled and filtered. It 18 contained 40.4% of water and 59.6% of solids. The pH of an O.l M
19 solution o~ the product was 10.3. The product was shown by
20 analysis to be a mixture of poly(oxymethylene~-4,4-dimethyl-
21 oxazolidines containing a major amount of 3-[hydroxymethyl-
22 tri(oxymethylene)]-4,4-dimethyloxazolidine.
23 Example 12
24 The products of Examples 6-ll were evaluated as biocides
25 ~or paints by the procedure described in Example lD. The results
26 obtained are given in Table VII.
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1 ~ The superioIity as biocides for sur~ace-coating composi-z ¦tions o~ the pre~erred polyoxymethyleneoxazolidines over a 3 ¦closely-related substituted oxazolidine is apparent ~rom a com-4 ¦parison of the biocidal data for the products of Examples 6-9 with s ¦those ~or 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane 6 ~The products o~ Examples 6 and 7, which are mixtures of substi-7 ¦ tuted oxazolidines that contain the comparator 5 hydroxymethyl-l-8 ¦ aza-3,7-dioxabicyclo(3,3,0)octane as well as the 5-hydroxymethyl-g ¦polyoxymethylene-l-aza-3,7-dioxabicyclo(3,3,0)octanes were o ¦substantially more e~fective against bacteria and fungi than the ll ¦comparator. Similarly, it is shown in Table VII that the product 12 ¦of Example 8 is more active at the 0.5% level in the PVA paint 13 ¦and at the 1% level in the acrylic paint than the comparator at 14 ¦the 2% level.
¦ Each of the other substituted oxazolidines disclosed 6 ¦herein can be used in a similar way to protect surface-coating ~ ¦compo91tio irom attack by bacteria anl ~ungi.
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1 ~ The superioIity as biocides for sur~ace-coating composi-z ¦tions o~ the pre~erred polyoxymethyleneoxazolidines over a 3 ¦closely-related substituted oxazolidine is apparent ~rom a com-4 ¦parison of the biocidal data for the products of Examples 6-9 with s ¦those ~or 5-hydroxymethyl-1-aza-3,7-dioxabicyclo(3,3,0)octane 6 ~The products o~ Examples 6 and 7, which are mixtures of substi-7 ¦ tuted oxazolidines that contain the comparator 5 hydroxymethyl-l-8 ¦ aza-3,7-dioxabicyclo(3,3,0)octane as well as the 5-hydroxymethyl-g ¦polyoxymethylene-l-aza-3,7-dioxabicyclo(3,3,0)octanes were o ¦substantially more e~fective against bacteria and fungi than the ll ¦comparator. Similarly, it is shown in Table VII that the product 12 ¦of Example 8 is more active at the 0.5% level in the PVA paint 13 ¦and at the 1% level in the acrylic paint than the comparator at 14 ¦the 2% level.
¦ Each of the other substituted oxazolidines disclosed 6 ¦herein can be used in a similar way to protect surface-coating ~ ¦compo91tio irom attack by bacteria anl ~ungi.
23 ~ ~
26 .
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Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A surface-coating composition having improved resistance to attack by bacteria and fungi that comprises (a) a water-insoluble, film-forming resinous binder selected from the group consisting of synthetic linear addition polymers prepared by the emulsion polymerization of ethylenically-unsaturated monomers, oleorisin-ous binders, and mixtures thereof, and (b) 0.10 percent to 3.0 percent, based on the weight of the composition of a biocidal component selected from the group consisting of (i) compounds having the structural formula (ii) compounds having the structural formula (iii) compounds having the structural formula wherein R represents alkyl of 1 to 6 carbon atoms, hydroxymethyl, or hydroxymethoxymethyl;
R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, or halophenyl;
each R" represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, hydroxy-methyl, or -(CH2)nCHO;
each R"' represents alkyl of 1 to 6 carbon atoms;
m represents 0 or 1; and n represents a number in the range of 0 to 4; and (iv) mixtures thereof.
R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, or halophenyl;
each R" represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, hydroxy-methyl, or -(CH2)nCHO;
each R"' represents alkyl of 1 to 6 carbon atoms;
m represents 0 or 1; and n represents a number in the range of 0 to 4; and (iv) mixtures thereof.
2. A surface-coating composition as defined in claim 1 that comprises an aqueous composition that contains about 10 percent to 60 percent by weight of a synthetic linear addition polymer prepared by the emulsion polymerization of ethylenically-unsaturated monomers.
3. A surface-coating composition as defined in claim 2 wherein the synthetic linear addition polymer is polyvinyl acetate.
4. A surface-coating composition as defined in claim 2 wherein the synthetic linear addition polymer is an acrylate polymer.
5. A surface-coating composition as defined in claim 2 that contains 0.1 percent to 0.5 percent of said biocidal component.
6. A surface-coating composition as defined in claim 1 wherein the biocidal component comprises 4,4-dimethyloxazolidine.
7. A surface-coating composition as defined in claim 1 wherein the biocidal component comprises 5-hydroxymethyl-1-aza-3,7-dioxabicyclo-(3,3,0)octane.
8. The method of controlling the growth of fungi and bacteria in a surface-coating composition that comprises a water-insoluble, film-forming, resinous binder selected from the group consisting of synthetic linear addition polymers prepared by the emulsion polymerization of ethylenically-unsaturated monomers, oleoresinous binders, and mixtures thereof that com-prises incorporating in said composition 0.1 percent to 3.0 percent, based on the weight of said composition, of a biocidal component selected from the group consisting of (a) compounds having the structural formula (b) compounds having the structural formula (c) compounds having the structural formula wherein each R represents alkyl of 1 to 6 carbon atoms, hydroxymethyl, or hydroxymethoxymethyl;
R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, or halophenyl;
each R" represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, -(CH2)nCHO, or hydroxymethyl;
each R"' represents alkyl of 1 to 6 carbon atoms;
m represents 0 or 1; and n represents a number in the range of 0 to 4; and (d) mixtures thereof.
R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, or halophenyl;
each R" represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, -(CH2)nCHO, or hydroxymethyl;
each R"' represents alkyl of 1 to 6 carbon atoms;
m represents 0 or 1; and n represents a number in the range of 0 to 4; and (d) mixtures thereof.
9. The method of claim 8 wherein 0.1 percent to 0.5 percent of the biocidal component is incorporated into the aqueous surface-coating composition.
10. The method of claim 8 wherein the biocidal component is added as an aqueous solution that contains 20 percent to 80 percent by weight of said biocidal component.
11. The method of claim 8 wherein the biocidal component is added as an aqueous solution that contains 40 percent to 60 percent by weight of said biocidal component.
12. A biocidal composition for use in controlling the growth of bacteria and fungi in aqueous surface-coating compositions that is an aqueous solution containing 20 percent to 80 percent by weight of a biocidal component selected from the group consisting of (a) compounds having the structural formula (b) compounds having the structural formula (c) compounds having the structural formula wherein each R represents alkyl of 1 to 6 carbon atoms, hydroxymethyl, or hydroxymethoxymethyl;
R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, or halophenyl;
each R" represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, -(CH2)nCHO, or hydroxymethyl;
each R"' represents alkyl of 1 to 6 carbon atoms;
m represents 0 or 1; and n represents a number in the range of 0 to 4; and (d) mixtures thereof.
R' represents hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, or halophenyl;
each R" represents hydrogen, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 4 carbon atoms, phenyl, halophenyl, -(CH2)nCHO, or hydroxymethyl;
each R"' represents alkyl of 1 to 6 carbon atoms;
m represents 0 or 1; and n represents a number in the range of 0 to 4; and (d) mixtures thereof.
13. A biocidal composition as defined in claim 12 that contains 40 percent to 60 percent by weight of said biocidal compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA224,433A CA1002526A (en) | 1974-02-15 | 1975-04-11 | Surface-coating compositions containing polyoxymethyleneoxazolidines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44304474A | 1974-02-15 | 1974-02-15 | |
| US447797A US3890264A (en) | 1974-03-04 | 1974-03-04 | Surface-coating compositions containing polyoxymethyleneoxazolidines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1045972A true CA1045972A (en) | 1979-01-09 |
Family
ID=27033373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA219,138A Expired CA1045972A (en) | 1974-02-15 | 1975-01-31 | Surface-coating compositions containing substituted oxazolidines |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5927321B2 (en) |
| AT (1) | AT342734B (en) |
| BR (1) | BR7500832A (en) |
| CA (1) | CA1045972A (en) |
| CH (1) | CH619730A5 (en) |
| DE (1) | DE2506310A1 (en) |
| ES (1) | ES434734A1 (en) |
| FR (3) | FR2279737A1 (en) |
| IL (1) | IL46544A (en) |
| IT (1) | IT1029706B (en) |
| MX (1) | MX3134E (en) |
| NL (1) | NL178084C (en) |
| NO (1) | NO143029C (en) |
| SE (2) | SE414940B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3019356A1 (en) * | 1980-05-21 | 1981-11-26 | Sika AG, vorm. Kaspar Winkler & Co., 8048 Zürich | NEW COMPOUNDS HAVING ADIMINE AND OXAZOLIDINE GROUPS, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS HARDENERS FOR POLYISOCYANATES |
| BR112013014873B8 (en) * | 2010-12-17 | 2019-08-06 | Angus Chemical | A method for inhibiting the growth or spread of microorganisms, exterminating microorganisms, disinfecting and / or preventing the growth of new microorganisms in an aqueous or water-containing system. |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2448890A (en) * | 1948-09-07 | Condensation products of polyht | ||
| US3062710A (en) * | 1959-02-18 | 1962-11-06 | Dow Chemical Co | Treating compositions containing nitrogenous condensation products |
| US3759942A (en) * | 1970-06-08 | 1973-09-18 | Sun Chemical Corp | Crosslinking monomers containing the 1-aza-3,7-dioxabicyclo {8 3.3.0{9 {11 octane structure |
| US3773730A (en) * | 1971-03-06 | 1973-11-20 | Comm Solvents Corp | Polymers from oxazolidines and urea |
| US3738992A (en) * | 1972-02-07 | 1973-06-12 | Commercial Solvents Corp | 1-aza-5-hydroxymethyl-3,7-dioxabicyclo-(3.3.0)-octann |
| DE2218417A1 (en) * | 1972-04-15 | 1973-10-25 | Henkel & Cie Gmbh | USE OF SUBSTITUTED OXAZOLIDINS AS ANTIMICROBIAL ACTIVE INGREDIENTS |
| DE2218348A1 (en) * | 1972-04-15 | 1973-10-31 | Henkel & Cie Gmbh | USE OF BICYCLIC OXAZOLIDINES AS ANTIMICROBIAL ACTIVE INGREDIENTS |
| DE2337755B2 (en) * | 1973-07-25 | 1976-10-07 | Schülke & Mayr GmbH, 2000 Norderstedt | PRESERVATIVES AND DISINFECTANTS |
| DE2454740A1 (en) * | 1974-11-19 | 1976-05-20 | Bayer Ag | NEW N-PHENYLCARBAMATES |
-
1975
- 1975-01-28 CH CH98275A patent/CH619730A5/en not_active IP Right Cessation
- 1975-01-31 CA CA219,138A patent/CA1045972A/en not_active Expired
- 1975-02-03 IL IL46544A patent/IL46544A/en unknown
- 1975-02-07 BR BR832/75A patent/BR7500832A/en unknown
- 1975-02-12 AT AT102975A patent/AT342734B/en not_active IP Right Cessation
- 1975-02-12 MX MX100227U patent/MX3134E/en unknown
- 1975-02-12 IT IT48142/75A patent/IT1029706B/en active
- 1975-02-13 SE SE7501609A patent/SE414940B/en not_active IP Right Cessation
- 1975-02-13 SE SE7713651A patent/SE434051B/en not_active IP Right Cessation
- 1975-02-14 ES ES434734A patent/ES434734A1/en not_active Expired
- 1975-02-14 JP JP50018069A patent/JPS5927321B2/en not_active Expired
- 1975-02-14 DE DE19752506310 patent/DE2506310A1/en active Granted
- 1975-02-14 FR FR7504730A patent/FR2279737A1/en active Granted
- 1975-02-14 NO NO75750490A patent/NO143029C/en unknown
- 1975-02-14 NL NLAANVRAGE7501762,A patent/NL178084C/en not_active IP Right Cessation
- 1975-10-20 FR FR7532028A patent/FR2279828A1/en active Granted
- 1975-10-20 FR FR7532027A patent/FR2283138A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2279828A1 (en) | 1976-02-20 |
| SE414940B (en) | 1980-08-25 |
| JPS50116641A (en) | 1975-09-12 |
| NL178084C (en) | 1986-01-16 |
| NL7501762A (en) | 1975-08-19 |
| FR2279737B1 (en) | 1979-04-13 |
| NO143029B (en) | 1980-08-25 |
| JPS5927321B2 (en) | 1984-07-05 |
| FR2283138A1 (en) | 1976-03-26 |
| FR2279828B1 (en) | 1978-10-06 |
| DE2506310A1 (en) | 1975-08-21 |
| FR2283138B1 (en) | 1979-06-22 |
| MX3134E (en) | 1980-04-28 |
| SE7713651L (en) | 1977-12-01 |
| BR7500832A (en) | 1975-12-02 |
| AU7750075A (en) | 1976-07-22 |
| FR2279737A1 (en) | 1976-02-20 |
| IL46544A (en) | 1978-06-15 |
| CH619730A5 (en) | 1980-10-15 |
| SE434051B (en) | 1984-07-02 |
| SE7501609L (en) | 1975-08-18 |
| ATA102975A (en) | 1977-08-15 |
| DE2506310C2 (en) | 1989-12-28 |
| IT1029706B (en) | 1979-03-20 |
| ES434734A1 (en) | 1977-04-01 |
| NO750490L (en) | 1975-08-18 |
| AT342734B (en) | 1978-04-25 |
| IL46544A0 (en) | 1975-04-25 |
| NO143029C (en) | 1980-12-03 |
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