CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority of US patent applications 15/732,556 and 15/732,557 having filing dates of November 27, 2017. The entire content of these prior US patent application 15/732,556 and 15/732,557 is herewith incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to toy, bubble forming solutions which are luminescent and it provides a system a n d co m pos iti o n enhancing the luminescence and/or reflection as seen by the observer.

BACKGROUND OF THE INVENTION

Surfactant solutions have been used for many years in children's toys to create bubbles. The simplest toy comprises a ring that is first dipped into the surfactant solution, then held near the mouth so that exhaled air forced through the ring causes the surfactant film therein to release as one or more bubbles. A plurality of rings may be enjoined to form a dipping device that can be waved manually in the air to create a large number of bubbles from a single loading of surfactant solution. Manual pumps may also be used to generate a stream of bubbles by forcing air through a nozzle that is supplied by a reservoir of surfactant solution. A continuous stream of bubbles may be shot from a toy gun wherein a motorized pump forces air and surfactant solution into a nozzle when an electrical trigger is depressed. Still other toys use a motor driven fan to direct a stream of air through revolving windows having a film of surfactant solution within them. These more elaborate systems are designed for the purpose of greatly increasing the rate at which a great number of bubbles may be created.

Other ways to stimulate excitement from bubble producing toys is to add visual effects to the surfactant solution. Dyes used for this purpose can make bubbles that are brightly colored. Similarly, U.S. patent 5,961 ,894 teaches the use of fluorescent dyes. Rainbow patterns in bubbles can be created by adding polyethylene glycol to the surfactant composition. Attempts have been made to add light-reflecting glitter to impart sparkle to the bubbles, but to date, these attempts have failed to produce an invention that actually forms bubbles having any significant amount of glitter within them, or one that forms bubbles that last for more than just two to three seconds before they burst. The present invention solves the problem of short-lived bubbles having virtually no visible glitter.

Many attempts have been made to increase one’s enjoyment from blowing bubbles by making the bubbles luminous in some way. United States patents 5,961 ,894 and 6,737,393 describe ways to make fluorescent bubbles that respond to invisible ultra-violet light or to invisible infra-red light. U n ited States patents 5,246,631 and 9,109,156 provide the means to create chemiluminescent bubbles. The invention of United States patent 5,308,546 utilizes phosphorescence. In practice, these inventions produce bubbles that appear feebly luminous at best, or they may produce bubbles that exhibit no perceptible luminescence at all even though the bubble forming solutions as packaged in a bottle may appear brightly luminous when activated. The difficulty in seeing any significant luminescence can be worsened by interference from ambient light, or from the excitation light used to generate the luminescence. Inventions involving ultra-violet light introduce the risk of eye injury arising from improper use, and the chemicals associated with chemiluminescent inventions can present themselves as possible hazards by means of ingestion, skin absorption, or eye contact. The present invention solves the problems of poor

performance and potential danger.

SUMMARY OF THE INVENTION

Luminescence is the release of energy in the form of light and some of the ways it can be manifested are phosphorescence, fluorescence, chemiluminescence, triboluminescence, cryoluminescence, and

thermoluminescence. The most practical of these modes of light emission for the purpose of making luminous, toy bubbles, in the opinion of the inventor, is that of fluorescence because it can be readily generated and fine-tuned for performance as a component of a system, wherein such a system comprises a light source, a fluorescer that responds optimally to that light source, and a viewing filter that substantially transmits the color of the fluorescence but substantially blocks all other colors of light. The present invention described herein is able to create for the observer bubbles that appear brilliantly fluorescent and contrasted by a dark or black background.

Bubble forming compositions for children's toys are typically aqueous solutions of at least one surface active agent and film producing substance. Endless variations are possible and they can be modified as desired to exhibit preferred properties, or to suspend water insoluble materials such as a glitter. The glitter found in the prior art is of the thermoplastic kind, specifically, polyester film which has been finely cut. This kind of glitter tends to be deleterious to the structural integrity of bubbles, perhaps due to its hydrophobic nature or to its sharp angularity. Furthermore, polyester glitter tends to adhere to the wetted, contact surface of the bubble generating mechanism rather than release into the bubbles as they form, perhaps because of its attraction to the other thermoplastics involved. Another problem is that polyester glitter is relatively large in flake size due to limitations associated with cutting it from sheets, which may explain why it can impair bubble formation or fail to transfer into the bubbles. Aluminum flake glitter can be obtained in a suitable flake size, however, it interacts with water to release hydrogen, making the aqueous composition acidic and therefore unstable over time with respect to viscosity. Quite surprisingly and unexpectedly, it has been discovered that a glitter made from mica enables one to readily blow bubbles having both a high degree of durability and a highly visible concentration of glitter within them. DETAILED DESCRIPTION OF THE INVENTION

For the luminescence embodiment of the invention, the preferred kind of light for the present invention is visible light because it can be economically produced and because it is less hazardous with respect to eye injury as compared to invisible, ultra-violet light. Moreover, a broader range of fluorescent colors are readily obtainable by using visible light excitation. Light emitting diodes (LED's) are available in a wide range of colors across the visible spectrum from 400 nanometers (nm) to 700 nm, and they can be easily incorporated into battery operated, childrens toys, making them ideal as the source of excitation light for the present invention. Colored LED's emit a relatively narrow bandwidth of light which is characterized by a peak frequency of light. One can choose as an active ingredient in a bubble forming solution a fluorescer, typically a fluorescent dye, that has an absorption maximum, i.e. an excitation maximum that corresponds to the peak emission frequency from the LED to achieve the highest efficiency with respect to fluorescence intensity. A color filter is included in the system to remove unwanted interference from the excitation light and from ambient light by being placed between the fluorescent bubbles and the observer's eyes as a viewing filter. The appropriate, color filter is one that transmits most or all of the fluorescence, being matched to the emission maximum of the fluorescer, but blocks most or all of any other sources of light. This kind of color filter is defined in the art as "selective" in that it excludes all frequencies of light except for the one(s) or the bandwidth desired. A selective viewing filter can be used to enhance the visibility of other kinds of luminous bubbles such as those mentioned herein as the cited references.

The following list of visible excitation light, fluorescer, and color filter are some of the sets that can be used as a system in accordance with the present invention.

1- Purple LED (410 nm), fluorescer is 7-(diethylamino)coumarin-3- carboxylic acid having excitation maximum at 409 nm and emission maximum at 473 nm, and a blue color filter. 2- Blue LED (465 nm), fluorescer is 2-(4-dimethylaminostyryl)-1 -methyl quinolinium iodide having excitation maximum at 463 nm and emission maximum at 512 nm, and a green color filter.

3- Green LED (530 nm), fluorescer is Rhodamine 6G having excitation maximum at 528 nm and emission maximum at 551 nm, and a yellow color filter.

4- Yellow LED (545 nm), fluorescer is Rhodamine B isothiocyanate having excitation maximum at 543 nm and emission maximum at 580 nm, and an orange color filter.

5- Orange LED (580 nm), fluorescer is 3-3'-diethyloxadicarbocyanine iodide having excitation maximum at 579 nm and emission maximum at 603 nm, and a red color filter.

6- Red LED (605 nm), fluorescer is 5(6)-carboxynaphthofluorescein-N- succinimidylester having excitation maximum at 602 nm and emission maximum at 672 nm, and a far-red color filter.

It is most desirable to use combinations such that the excitation color and the emission color of the fluorescer are two or more filter colors apart so that a high degree of enhancement can be obtained through even those filters of relatively low selectivity, like those manufactured as plastic films or sheets.

Suitable color filters are commercially available, for instance as manufactured by Rosco Laboratories, Inc., providing a full range of color filters under the name Roscolux™, as thin sheets of plastic film, which can conveniently matched with LED's and fluorescers. D&C Red 28, a water- soluble dye that is particularly effective in an aqueous, surfactant based, bubble forming solution as a fluorescer, is excited by green light to emit red light, which is a shift of three filter colors (i.e. yellow-orange-red). This color shift, that is, its Stokes Shift in nanometers (nm), is wide enough for the Roscolux films to produce visually striking, color enhancement. This same level of color enhancement can be obtained from dyed, transparent thermoplastics that can be extruded into sheets or molded into shapes.

Films, sheets, and shapes can be made into windows, lenses, shields, or other paraphernalia best designed for the particular bubble making toy, through which to observe the fluorescent bubbles.

Because the embodiment of the viewing filter must be positioned at some location between the luminous bubbles and the eyes of the observer, it further functions as personal protection from misuse or accidents involving intense light from the toy or irritating chemicals from the bubble forming solution.

The brightness of the luminescence from bubbles can be further accentuated by adding to the bubble forming composition a light-reflecting substance. The light reflecting substance may be contained in the bubble forming composition with or without fluorescence or other luminescent composition constituents. Metal oxide coated micas (see the inventor's co-pending patent application entitled, "Toy Bubble Forming Composition Containing Glitter") and hollow, glass microspheres are well-suited for aqueous formulations because of their relative density to water and because they are naturally hydrophilic, making them easy to disperse. Hollow glass microspheres having an average diameter of about 10 microns are the preferred reflective substance because they more uniformly distribute themselves within the formed bubbles. Potters Industries (PQ Corporation) manufactures several retro-reflective silicates in the form of glass microbeads having an extremely high index of reflection. White compounds such as calcium carbonate, magnesium oxide, and magnesium or zinc stearates are also effective. The following composition, parts by weight, is one that is excellent for suspending a reflective

substance:

95 parts distilled water

30 parts of cocamidopropyl betaine, 36% solution

1.2 parts sodium coco sulfate needles, 100% active 1 part Botanistat PF-64 preservative (Botanigenics, Inc., Chatsworth, CA)

0.4 parts xanthan gum

0.4 parts propylene glycol alginate

Example 1 : To the above composition was added 0.2 parts by weight Acid Red 92 and 2 parts by weight Iriodin 153 Flash pearl, a metal oxide coated mica from EMD Millipore Corp, Billerica, MA. Bubbles were illuminated using an aqua (505 run, 3-watt) LED and viewed through a face mask fabricated from a filmic sheet of Roscolux #25 Orange Red having 14% transmittance. The result was that even in ambient lighting conditions the fluorescent bubbles could be easily seen from over 4 feet away.

Example 2: To the above composition was added 0.2 parts by weight Acid Red 52 and one part by weight hollow glass microspheres having a diameter ranging between 9 and 13 microns. I n a darkened room, bubbles were illuminated using a green (525 nm, 3-watt) LED and viewed through glasses fabricated from a filmic sheet of Roscolux #26 Light Red having 12% transmittance. The result was that the bubbles appeared brightly red up to a distance of about 6 feet.

Example 3: To the above composition was added 0.05 parts by weight Rhodamine 6G and 4 parts by weight glass microspheres having a reflective index of 0.93. Bubbles were illuminated by a green (525 nm, 3- watt) LED and viewed through a window made of 1/8 inch thick, red, acrylic plastic. The result was that in night-time conditions the bubbles could be seen from across the room as red globes contrasted by black space.

When acid dyes are chosen, the fluorescer care must be taken to avoid inadvertent staining of the skin and clothing, which can occur when the hand-held toys are prone to dribbling the bubble forming composition. It was discovered that the addition of sodium carbonate completely prevents any staining by these dyes. A suitable range for sodium carbonate in the composition is about 0.1 percent to about 1 percent by weight. According to an embodiment of the invention, an aqueous, bubble forming composition is provided that contains glitter, wherein the glitter is strongly both lipophilic and hydrophilic and therefore able to preferentially release from the contact surface of the bubble forming toy while maintaining the structural integrity of the bubbles. The glitter may be provided together with or without luminous substances depending on whether light effects only coming from reflection or in addition luminous light effects triggered by excitation light such as fluorescence or phosphorescence are desired.

Glitters produced from mica, particularly from mica that has been surface treated with a metal or an oxide thereof, are what is believed to be novel in relation to the present invention. While not fully understood by the inventor, it is thought that the hydrophilic nature of mica, combined with the lipophilic nature of its metallic coating, are perhaps why it is able to preferentially release from the bubble generating aperture and improve the longevity of bubble life. To reiterate, a typical composition for making bubbles comprises water and some surfactant, and so cohesion within the composition can be created by the attraction of mica to water and by the attraction of the metal coating thereon to the lipophile on the surfactant's molecule. These attractions are believed to be vital during the developmental stage when the bubble begins to expand and exit the toy's ring or nozzle. Cohesion within the bubble's structure must be strong enough to contain the higher, internal air pressure relative to the lower, external air pressure. Otherwise, the bubble will disintegrate and burst.

Metallized micas are available in a range of colors, depending of the metal itself. For example, titanium dioxide is used to make a silvery luster. Iron oxides create a range of golden colors. Copper oxides yield reddish tones. Chromium oxides are associated with green shades. Other metal oxides can produce iridescent colors.

Mica based glitters are available in flake sizes as small as 10 microns. Micas having a flake size up to 200 microns may be used when the bubble walls are sufficiently thick, but in general a range of 40 to 150 microns is suitable, and the preferred range is 70 to 100 microns. Larger flake sizes produce more sparkle than do smaller flakes sizes. A suitable range of concentration of this glitter is about 0.1 percent by weight to about 5 percent by weight, although higher concentrations may be used to create densely glittered bubbles. Trials demonstrate that bubble life is about 8 seconds at a minimum, but is typically 12 to 20 seconds, and often more than 30 seconds, when the concentration of glitter is less than about 4 percent by weight. One glitter type, a family of metallic micas, which produces exemplary results, is Iriodin™ , manufactured by EMD Performance Materials Corporation. Iriodin™ Flash Pearl 153 and Iriodin™ Solar Gold 325 are two choices for silver and gold glitters respectively.

A bubble forming composition that may be used in accordance with the present invention is, percent by weight:

2 % cocamidopropykle betaine, 36% solution

1 % BotanistatTM PF-64 (by Botanigenics, Inc. Chatsworth, CA)

1.2 % sodium coco sulfate, 94-100% active

0.4 % xanthan gum

0.4% propylene glycol alginate

95% distilled water

These examples are not intended to be limiting as many variations are possible without departing from the scope of the present invention a defined in terms of the claims.