CA2047225A1 - Marine dye composition - Google Patents
Marine dye compositionInfo
- Publication number
- CA2047225A1 CA2047225A1 CA 2047225 CA2047225A CA2047225A1 CA 2047225 A1 CA2047225 A1 CA 2047225A1 CA 2047225 CA2047225 CA 2047225 CA 2047225 A CA2047225 A CA 2047225A CA 2047225 A1 CA2047225 A1 CA 2047225A1
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- dye composition
- marine
- water soluble
- dispersible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 6
- -1 polyethylene Polymers 0.000 claims abstract description 5
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims abstract 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical group O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 239000000975 dye Substances 0.000 description 31
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MBMCXZDQYBABNM-UHFFFAOYSA-N 2-(2-hydroxy-9h-fluoren-1-yl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=C(CC=2C3=CC=CC=2)C3=CC=C1O MBMCXZDQYBABNM-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention concerns a marine dye composition. The composition comprises a water soluble or dispersible dye, a water soluble or dispersible binding agent and a means for adjusting the relative density of the composition by variation of its content in the composition. Microballoons of a plastics material such as polyethylene or phenol formaldehyde exemplify such means.
Description
2 ~ ~ 7 2 2 3 PCT/AU90/00005 , ,.,~ ~ " .
,;-. ". . . ~ , :
.
: . - . .
:: . . .
MARINE~ C MPOSITION
~: . 5 The present invention relates to marine dye compositlons. Marine dye composi~ions have been used in a number of applications to mark the location of crashed aircrat, life rafts and military equipment, for example ~ : rockets. :
;~ ~ 10 Life preservers used in aircraft in particular have-been provided with a 1uorescein dye placed in a ~ , , cotton bag. The~bag was sufficiently porous to allow water to seep through and dissolve the fluorescein dye. :~
. ~The disadvantages associated with using this system are ~: 15 as follows: .
~ :: : j : . . .
WO 90/10044 Pcl`/AU9o/oooo5 2~7225 - 2 - ~1 1. The bag could be easily ripped and the dye lost prematurely~
2. Once sufficient water had been absorbed by the bag and it became detached, it could float below the 5 surface of the water.
,;-. ". . . ~ , :
.
: . - . .
:: . . .
MARINE~ C MPOSITION
~: . 5 The present invention relates to marine dye compositlons. Marine dye composi~ions have been used in a number of applications to mark the location of crashed aircrat, life rafts and military equipment, for example ~ : rockets. :
;~ ~ 10 Life preservers used in aircraft in particular have-been provided with a 1uorescein dye placed in a ~ , , cotton bag. The~bag was sufficiently porous to allow water to seep through and dissolve the fluorescein dye. :~
. ~The disadvantages associated with using this system are ~: 15 as follows: .
~ :: : j : . . .
WO 90/10044 Pcl`/AU9o/oooo5 2~7225 - 2 - ~1 1. The bag could be easily ripped and the dye lost prematurely~
2. Once sufficient water had been absorbed by the bag and it became detached, it could float below the 5 surface of the water.
3. The dye often caked due to moisture being absorbed by the bag from the air. Furthermore the rate of diffusion of the dye through the cotton bag could not be controlled.
The specification of U.S. Patent No. 3,263,012 discloses a composition which purports to overcome these problems. The composition dlsclosed comprises a fluorescein compound bound in a matrix of polyvinyl alcohol resin containing glycerine and borax. The 15 composition is pressed into a cake and made into a relatively thin plate like object. The principal object of the invention disclosed in this U.S. patent is to supply a composition that provides a controlled release of dye into water over an extended period of time, for 20 example up to 45 days. The purpose of the glycerine is said to be to swell the polyvinyl alcohol resin and to dissolve the dye thereby permitting the dye to diffuse -into the resin and to be encapsulated in the resin matrix. In ad~ition, the specification states that the 25 glycerine partially controls the rate of diffusion of the dye from the polyvinyl alcohol matrix into the water when the device is ejected into the sea. The more glycerine the greater the rate of emission of dye into the water.
The presence of borax appears to be for the purpose of 30 maintaining the cohesive strength of the resin matrix.
As distinct from the objects of earlier inventions the Royal Australian Navy identified the need for a marine dye composition which could be used to locate a submarine launched pyrotechnic signal (SLMPS).
35 The dye needed to be observable for approximately thirty minutes thereby aiding in the recovery of any message -- , ' ~ ~ ~ 3 ~ 2Q~72~5 carried by the signal or to locate the submarine that fired the signal. Previously, such signals were provided with a flare that had a duration of seventy-five seconds to two minutes. `
An object of the present invention is to provide a composition that is capable of releasing dye on the surface of water for a period up to thirty minutes.
Accordingly, the present invention provides a marine dye composition comprising a water soluble or 10 dispersible dye, a density controlling means that enables the relative density of the composition to be adjusted by variation of its content in the composition and a water soluble or dispersible binding agent for binding the composition together.
Suitable dyes include Fluorescein LT marketecl by ICI Australia. It is described in the colour index as CI acid yellow 73 Constitution No. 5350 and is essentially the sodium salt of hydroxy-ortho-carboxy-phenyl fluorene. Fluorescein is 20 visible at concentrations in water above 25 p.p.m..
Below this it appears to be colourless.
Another suitable dye composition is known as "Seamarker Dye Composition" and consists of a mixture of three dye CI acids; Red 51, Red 50 and Yellow 73. The 25 predominantly red colouration of this marker comes from the sodium salt of rhodamine disulphonic acid. The sodium salt of fluorescein may also be used.
Suitable density controlling means may comprise any means for introducing permanent air pockets into the 30 composition. This may be achieved with microballoons of a plastics material such as polyethylene or- phenol formaldehyde. Microballoons ha~ing a bulk density of approximately .01 g/cc are pr~ferred. Microballoons made from polyethylene are particularly preferred.
~
: .
4 7 2 ~ 5 Preferred binding agents include water soluble derivatives of cellulose such as sodium carboxy methyl cellulose. Grades of sodium carboxy methyl cellulose are available with varying degrees of solubility. This is 5 regulated by the degree of substitution oE the polar groups by carboxy methyl groups. The rate at which the dye dissolves in sea water can therefore be determined by selecting an appropriate grade of sodium carboxy methyl cellulose.
Polyvinyl alcohol may also be used as a binder.
However, polyvinyl alcoho] is not a preferred binder because it was found to be rather messy and time consuming to use.
The relative density of the compositions of the 15 present invention can be adjusted such that it is about l. Such compositions float at the surface and maximize the aerial visibility of dye dissolved from the composition. Compositions that rapidly provide a patch of dissolved dye on the water surface can also be 20 produced. This can be particularly useful when trying to attract the attention of aircraft especially from a life raft. Dye spots can be produced within lO minutes that are visible from a distance of up to 5 km.
The composition of the present invention may be 25 packaged and displayed in a variety of ways depending on the proposed use. Small granules or pellets may be inserted into a vial for attachment to a lift jacket.
For use as an aerial marker the composition may be formed into larger pellets and packed in bags or containers made 30 of a water soluble material such as polyvinyl alcohol.
Bags made from a film of polyvinyl alcohol have been found to be particularly useful. The composition may be packe~ into the bag and the bag entrance heat sealed to store the composition for use.
Preferred embodiments of the invention will now be described by reference to the accompanying examples.
~; , ' - .
. ~
~: ~ ' : ' '~ ' WO90/10~ PCT/A~90/00005 ~ - 5 - ` 2~7~2~
Example 1 Fluorescein LT (ICI Brand) B.S.S. 100 92 parts Phenolic Microballoons (DEs include wte Brand) 1.8 parts Sodium Carboxy Methyl Cellulose 1.3 parts (DIACEL 1130) Glycerol 4.6 parts ThP Fluorescein LT is dried in an oven at 100C
for twenty-four hours. It is then sieved using a B.S.S.
10 100 sieve. The sodium carboxy methyl cellulose is dissolved in water to a concentration of 3 g per 100 ml.
The glycerol is added to the solution whilst continuing to stir for a further five minutes. The fluorescein is mixed with the microballoons and the solution of sodium -15 carboxy methyl cellulose and glycerine in water is added to the mixture to form a composition having a paste having a thick consistency. The mixture is poured onto a plastic sheet to a thickness of approximately 3 mm and dried in an oven at 40C for 72 hours and finally 100C
20 for a further 2~ hours. The composition is then removed from the oven and the resultant dried biscuit is ~roken into flakes of approximately 10 mm by flexi~g the plastic sheet or snapping the flakes off the biscuit with an appropriate tool.
By experimentation it has been discovered that the composition is considerably more effective when formed into flakes in this way rather than extruded and cut into pellets.
Example _ Flake Mixture Fluorescein LT (ICI Brand~ sieved BSS 100 97.7 parts Phenolic Microballoons (DE Brand) 1.5 parts Sodium Carboxyl Methyl Cellulose 0.8 parts (DIACEL 1130) ' ~
:
wo 90/10~ 2 ~ 6 - PCT/AU90/00005 ' .
Procedure The SCMC sample is first pre-wetted with ethanol then dissolved in water, stirring whilst heating.
When fully dissolved the mixture takes on a viscous 5 "clag-like" appearance and is added while still warm to the dye and microballooon admix and thoroughly blended into a runny paste.
The mixture is then poured onto non-stick trays to a thickness of approximately 3-5 mm and dried at 40C
10 for 72 hours. The semi-dried cake is inverted to allow proper drying of the reverse side ~approximately 48 hours). The cake is then broken into smaller, more manageable sizes and dried at 105C + 5C to remove residual moisture (approximately 48 hours). Once dried 15 the cakes can be broken into the required size -(approximately 1 cm square) and stored in a desiccator until needed.
Example 3 Preliminary tests were conducted off-shore with 20 the aim of evaluating various dye packages for the size ~-and duration of the mark produced. The following fluorescein configurations were tested.
(i) 7 x 10 g pellets, density 1.68 g cm 3 (ii) 7 x 10 g pellets, density 1.57 9 cm 3 (iii) 7 x 10 g pellets, density 1.54 g cm 3 (iv) 32 g loose filled, paper sealed (v) buoyant flakes* 80 g net weight (vi? buoyant foam pellets* 50 g net weight (vii) sieved (BSS 100) 32 g loose packed *Con~iguration (v) used fluorescein in combination with phenolic microballoons with polyvinyl acetate (PVA) as a binder and ~vi) used an open-cell foam pellet into which the dye had been secreted.
- : :: ::
, ~ ~ .
WO90/100~ PCT/AU90/00005 2 0 ~ 7 2 2 ~ ~:
Observations were made of the size of the dye mark produced and its duration. The conditions were overcast with 12-15 knot gusting wlnds and intermittent showers. The sea was relatively calm at the trial site 5 with a sea-state between 1 and 2.
By far the most effective configuration was found to be the buoyant flakes (v). A large area was marked in a very short space of time and the maximum efficiency of the fluorescent properties of the dye 10 emerged because the spot was near the surface.
Variation of density in the pressed pellets had only a small effect on the signals produced. All gave a serviceable though "streaky" signal which after 15 minutes was approximately 0.5 m wide by 15 m long.
The buoyant pellet configuration (vi) performed rather poorly with the dye leaching out far too slowly and the wind and wave action carrying the pellet far away ~rom the original launch site.
The loose filled powder configuration (iv) gave 20 a good initial signal however much of the spot was lost with the larger grains sinking.
~ The sieved BSS 100 sample (vii) also gave a good initial signal but the grains could be seen to sink to the sea-bed.
The specification of U.S. Patent No. 3,263,012 discloses a composition which purports to overcome these problems. The composition dlsclosed comprises a fluorescein compound bound in a matrix of polyvinyl alcohol resin containing glycerine and borax. The 15 composition is pressed into a cake and made into a relatively thin plate like object. The principal object of the invention disclosed in this U.S. patent is to supply a composition that provides a controlled release of dye into water over an extended period of time, for 20 example up to 45 days. The purpose of the glycerine is said to be to swell the polyvinyl alcohol resin and to dissolve the dye thereby permitting the dye to diffuse -into the resin and to be encapsulated in the resin matrix. In ad~ition, the specification states that the 25 glycerine partially controls the rate of diffusion of the dye from the polyvinyl alcohol matrix into the water when the device is ejected into the sea. The more glycerine the greater the rate of emission of dye into the water.
The presence of borax appears to be for the purpose of 30 maintaining the cohesive strength of the resin matrix.
As distinct from the objects of earlier inventions the Royal Australian Navy identified the need for a marine dye composition which could be used to locate a submarine launched pyrotechnic signal (SLMPS).
35 The dye needed to be observable for approximately thirty minutes thereby aiding in the recovery of any message -- , ' ~ ~ ~ 3 ~ 2Q~72~5 carried by the signal or to locate the submarine that fired the signal. Previously, such signals were provided with a flare that had a duration of seventy-five seconds to two minutes. `
An object of the present invention is to provide a composition that is capable of releasing dye on the surface of water for a period up to thirty minutes.
Accordingly, the present invention provides a marine dye composition comprising a water soluble or 10 dispersible dye, a density controlling means that enables the relative density of the composition to be adjusted by variation of its content in the composition and a water soluble or dispersible binding agent for binding the composition together.
Suitable dyes include Fluorescein LT marketecl by ICI Australia. It is described in the colour index as CI acid yellow 73 Constitution No. 5350 and is essentially the sodium salt of hydroxy-ortho-carboxy-phenyl fluorene. Fluorescein is 20 visible at concentrations in water above 25 p.p.m..
Below this it appears to be colourless.
Another suitable dye composition is known as "Seamarker Dye Composition" and consists of a mixture of three dye CI acids; Red 51, Red 50 and Yellow 73. The 25 predominantly red colouration of this marker comes from the sodium salt of rhodamine disulphonic acid. The sodium salt of fluorescein may also be used.
Suitable density controlling means may comprise any means for introducing permanent air pockets into the 30 composition. This may be achieved with microballoons of a plastics material such as polyethylene or- phenol formaldehyde. Microballoons ha~ing a bulk density of approximately .01 g/cc are pr~ferred. Microballoons made from polyethylene are particularly preferred.
~
: .
4 7 2 ~ 5 Preferred binding agents include water soluble derivatives of cellulose such as sodium carboxy methyl cellulose. Grades of sodium carboxy methyl cellulose are available with varying degrees of solubility. This is 5 regulated by the degree of substitution oE the polar groups by carboxy methyl groups. The rate at which the dye dissolves in sea water can therefore be determined by selecting an appropriate grade of sodium carboxy methyl cellulose.
Polyvinyl alcohol may also be used as a binder.
However, polyvinyl alcoho] is not a preferred binder because it was found to be rather messy and time consuming to use.
The relative density of the compositions of the 15 present invention can be adjusted such that it is about l. Such compositions float at the surface and maximize the aerial visibility of dye dissolved from the composition. Compositions that rapidly provide a patch of dissolved dye on the water surface can also be 20 produced. This can be particularly useful when trying to attract the attention of aircraft especially from a life raft. Dye spots can be produced within lO minutes that are visible from a distance of up to 5 km.
The composition of the present invention may be 25 packaged and displayed in a variety of ways depending on the proposed use. Small granules or pellets may be inserted into a vial for attachment to a lift jacket.
For use as an aerial marker the composition may be formed into larger pellets and packed in bags or containers made 30 of a water soluble material such as polyvinyl alcohol.
Bags made from a film of polyvinyl alcohol have been found to be particularly useful. The composition may be packe~ into the bag and the bag entrance heat sealed to store the composition for use.
Preferred embodiments of the invention will now be described by reference to the accompanying examples.
~; , ' - .
. ~
~: ~ ' : ' '~ ' WO90/10~ PCT/A~90/00005 ~ - 5 - ` 2~7~2~
Example 1 Fluorescein LT (ICI Brand) B.S.S. 100 92 parts Phenolic Microballoons (DEs include wte Brand) 1.8 parts Sodium Carboxy Methyl Cellulose 1.3 parts (DIACEL 1130) Glycerol 4.6 parts ThP Fluorescein LT is dried in an oven at 100C
for twenty-four hours. It is then sieved using a B.S.S.
10 100 sieve. The sodium carboxy methyl cellulose is dissolved in water to a concentration of 3 g per 100 ml.
The glycerol is added to the solution whilst continuing to stir for a further five minutes. The fluorescein is mixed with the microballoons and the solution of sodium -15 carboxy methyl cellulose and glycerine in water is added to the mixture to form a composition having a paste having a thick consistency. The mixture is poured onto a plastic sheet to a thickness of approximately 3 mm and dried in an oven at 40C for 72 hours and finally 100C
20 for a further 2~ hours. The composition is then removed from the oven and the resultant dried biscuit is ~roken into flakes of approximately 10 mm by flexi~g the plastic sheet or snapping the flakes off the biscuit with an appropriate tool.
By experimentation it has been discovered that the composition is considerably more effective when formed into flakes in this way rather than extruded and cut into pellets.
Example _ Flake Mixture Fluorescein LT (ICI Brand~ sieved BSS 100 97.7 parts Phenolic Microballoons (DE Brand) 1.5 parts Sodium Carboxyl Methyl Cellulose 0.8 parts (DIACEL 1130) ' ~
:
wo 90/10~ 2 ~ 6 - PCT/AU90/00005 ' .
Procedure The SCMC sample is first pre-wetted with ethanol then dissolved in water, stirring whilst heating.
When fully dissolved the mixture takes on a viscous 5 "clag-like" appearance and is added while still warm to the dye and microballooon admix and thoroughly blended into a runny paste.
The mixture is then poured onto non-stick trays to a thickness of approximately 3-5 mm and dried at 40C
10 for 72 hours. The semi-dried cake is inverted to allow proper drying of the reverse side ~approximately 48 hours). The cake is then broken into smaller, more manageable sizes and dried at 105C + 5C to remove residual moisture (approximately 48 hours). Once dried 15 the cakes can be broken into the required size -(approximately 1 cm square) and stored in a desiccator until needed.
Example 3 Preliminary tests were conducted off-shore with 20 the aim of evaluating various dye packages for the size ~-and duration of the mark produced. The following fluorescein configurations were tested.
(i) 7 x 10 g pellets, density 1.68 g cm 3 (ii) 7 x 10 g pellets, density 1.57 9 cm 3 (iii) 7 x 10 g pellets, density 1.54 g cm 3 (iv) 32 g loose filled, paper sealed (v) buoyant flakes* 80 g net weight (vi? buoyant foam pellets* 50 g net weight (vii) sieved (BSS 100) 32 g loose packed *Con~iguration (v) used fluorescein in combination with phenolic microballoons with polyvinyl acetate (PVA) as a binder and ~vi) used an open-cell foam pellet into which the dye had been secreted.
- : :: ::
, ~ ~ .
WO90/100~ PCT/AU90/00005 2 0 ~ 7 2 2 ~ ~:
Observations were made of the size of the dye mark produced and its duration. The conditions were overcast with 12-15 knot gusting wlnds and intermittent showers. The sea was relatively calm at the trial site 5 with a sea-state between 1 and 2.
By far the most effective configuration was found to be the buoyant flakes (v). A large area was marked in a very short space of time and the maximum efficiency of the fluorescent properties of the dye 10 emerged because the spot was near the surface.
Variation of density in the pressed pellets had only a small effect on the signals produced. All gave a serviceable though "streaky" signal which after 15 minutes was approximately 0.5 m wide by 15 m long.
The buoyant pellet configuration (vi) performed rather poorly with the dye leaching out far too slowly and the wind and wave action carrying the pellet far away ~rom the original launch site.
The loose filled powder configuration (iv) gave 20 a good initial signal however much of the spot was lost with the larger grains sinking.
~ The sieved BSS 100 sample (vii) also gave a good initial signal but the grains could be seen to sink to the sea-bed.
Claims (21)
1. A marine dye composition comprising a water soluble or dispersible dye, a density controlling means for adjusting the relative density of the composition by variation of its content during manufacture of the composition and a water soluble or dispersible binding agent for binding the composition together.
2. A marine dye composition according to Claim 1 wherein the density controlling means comprises a means for introducing permanent air pockets into the composition.
3. A composition according to Claim 1 wherein the density controlling means comprises microballoons of a plastics material.
4. A marine dye composition according to Claim 3 wherein the plastics material is polyethylene.
5. A marine dye composition according to Claim 3 wherein the plastics material is phenol formaldehyde.
6. A marine dye composition according to Claim 3 wherein the plastics material has a bulk density of about .01 g/cc.
7. A marine dye composition according to any one of Claims 1 to 6 wherein the water soluble or dispersible dye is fluorescein.
8. A marine dye composition according to any one of Claims 1 to 6 wherein the water soluble or dispersible dye is a mixture of red 51, red 50 and yellow 73 CI
acids.
acids.
9. A marine dye composition according to any one of Claims 1 to 8 wherein the water soluble or dispersible binding agent is a water soluble derivative of cellulose.
10. A marine dye composition according to Claim 9 wherein the water soluble derivative of cellulose is a sodium carboxy methyl cellulose.
11. A marine dye composition according to any one of Claims 1 to 8 wherein the water soluble or dispersible binding agent is polyvinyl alcohol or polyvinyl acetate.
12. A marine dye composition according to any one of the preceding claims wherein the composition has a relative density that is about 1.
13. A marine dye composition according to Claim 6 wherein the microballoons comprise from 1.5 to 1.8 percent by weight of the composition.
14. A marine dye composition according to any one of Claims 1 to 13, wherein the water soluble or dispersible dye comprises from 90 to 98 percent by weight of the composition.
15. A marine dye composition according to Claim 14 wherein the water soluble or dispersible binding agent comprises from 0.8 to 1.3% by weight of the composition.
16. A marine dye composition according to any one of the preceding claims, wherein the composition includes up to 5% by weight of glycerol.
17. A method of making a marine dye composition according to Claim 1 comprising the steps of mixing the water soluble or dispersible dye with the density controlling means to form a premix;
mixing the water soluble or dispersible binding agent with water to form a solution or dispersion of the binding agent in water;
mixing the solution or dispersion with the premix to form a paste;
pouring the paste into moulds to a depth of about 3 mm;
drying the paste in an oven at a temperature of less then 50°C until most of the water has been evaporated;
drying the paste for about a further 24 hours at a temperature of about 100°C;
removing the composition from the moulds and breaking it into pellets or flakes suitable for use.
mixing the water soluble or dispersible binding agent with water to form a solution or dispersion of the binding agent in water;
mixing the solution or dispersion with the premix to form a paste;
pouring the paste into moulds to a depth of about 3 mm;
drying the paste in an oven at a temperature of less then 50°C until most of the water has been evaporated;
drying the paste for about a further 24 hours at a temperature of about 100°C;
removing the composition from the moulds and breaking it into pellets or flakes suitable for use.
18. Pellets formed from a marine dye composition according to any one of Claims 1 to 17.
19. Flakes formed from a marine dye composition according to any one of Claims 1 to 17.
20. Vials containing a marine dye composition according to any one of Claims 1 to 17.
21. Heat sealed polyvinyl alcohol bags containing a marine dye composition according to any one of Claims 1 to 17.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPJ290589 | 1989-02-23 | ||
| AUPJ2905 | 1989-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2047225A1 true CA2047225A1 (en) | 1990-08-24 |
Family
ID=3773739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2047225 Abandoned CA2047225A1 (en) | 1989-02-23 | 1990-01-05 | Marine dye composition |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0459986A4 (en) |
| CA (1) | CA2047225A1 (en) |
| NZ (1) | NZ231916A (en) |
| WO (1) | WO1990010044A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9822729D0 (en) * | 1998-10-20 | 1998-12-16 | Wrc Plc | Release system for a marker substance |
| US6916492B2 (en) | 2001-03-30 | 2005-07-12 | Council Of Scientific & Industrial Research | Natural nontoxic multicolor fluorescent protein dye from a marine invertebrate, compositions containing the said dye and its uses |
| DE10117303A1 (en) | 2001-03-30 | 2002-10-31 | Council Scient Ind Res | Bioactive extract, useful e.g. as natural fluorescent dye obtained from marine organisms, has specific characteristics e.g. yellowish-green color, amorphous nature, water solubility and insolubility in organic solvents |
| US6689391B2 (en) | 2001-03-30 | 2004-02-10 | Council Of Scientific & Industrial Research | Natural non-polar fluorescent dye from a non-bioluminescent marine invertebrate, compositions containing the said dye and its uses |
| US6956122B2 (en) | 2001-09-05 | 2005-10-18 | Council Of Scientific & Industrial Research | Multiple fluorescent natural dye compound from a marine organism |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2716961A (en) * | 1952-12-29 | 1955-09-06 | Theodore B Manheim | Water marking device |
| US3048464A (en) * | 1959-04-07 | 1962-08-07 | Carl E Fisher | Water soluble dye form and method of making |
| US3263012A (en) * | 1963-09-30 | 1966-07-26 | Nadler Coleman | Dye composition |
| US4219438A (en) * | 1970-12-18 | 1980-08-26 | American Cyanamid Company | Composition for marking and identification purposes |
| DE3019260C2 (en) * | 1980-05-20 | 1981-12-17 | Peter 7630 Lahr Kollmer | Afterglow paint containing binding agents |
-
1989
- 1989-12-21 NZ NZ23191689A patent/NZ231916A/en unknown
-
1990
- 1990-01-05 WO PCT/AU1990/000005 patent/WO1990010044A1/en not_active Ceased
- 1990-01-05 CA CA 2047225 patent/CA2047225A1/en not_active Abandoned
- 1990-01-05 EP EP19900901511 patent/EP0459986A4/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0459986A4 (en) | 1992-04-01 |
| EP0459986A1 (en) | 1991-12-11 |
| WO1990010044A1 (en) | 1990-09-07 |
| NZ231916A (en) | 1991-09-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |