This invention relates to a clear shampoo comprising a polysiloxane component and methods for making the same. In one embodiment, the polysiloxane component comprises a side chain component having a hindered amine group.

The concept of cleansing and conditioning detersive products has drawn great attention since its launch in the early 1980""s. From a technical point, cleansing and conditioning are contradictions, since conditioning has to deposit some ingredients on an object and cleansing has to remove the deposited ingredients from the object. To combine cleansing and conditioning in detersive products means when the product removes the dirt from the object, the product also simultaneously deposits some conditioning ingredients on the object. The conditioning effects depend on the equilibrium between the removed dirt, conditioning ingredient and deposit conditioning ingredients. For hair products, conditioning involves depositing certain agents onto the hair to give it the protection, softness, shine and detangling effects. Less deposition means less conditioning and more deposition means more conditioning or over conditioning.
To achieve proper conditioning formulations, chemists are faced with the challenge of choosing the appropriate conditioning ingredients, the proper ratio of conditioning ingredients to surfactants and methods of incorporating conditioning ingredients into the detersive system to form stable products.
A conditioning ingredient should have the basic characteristic of being water-insoluble, easy to be spread and have some affinities with the application objects. Polysiloxane, such as dimethicone, and derivatives are water-insoluble and are widely used conditioning ingredients. Furthermore, polysiloxanes usually give good hair protection, softening, shine and detangling effects.
The various technical methods for incorporating polysiloxanes, such as dimethicone, into the detersive products have been patented. The focus is on the particle size distribution of dimethicone surfactant emulsion and stability of the shampoo. Smaller particle size means more stability and more deposition to the targeted object.
Although some success has been achieved in being able to incorporate polysiloxanes, such as dimethicones, into detersive compositions, other challenges still remain. It remains a challenge to be able to formulate a stable conditioning/detersive composition, especially when a polysiloxane (e.g. dimethicone) is employed. Considering the regular viscosity of the detersive composition and the relatively lightweight of the conditioning ingredients, it is very difficult to achieve a long-term stability of the products. For example, the products tend to separate with the conditioning ingredients settling on top of the water-detergent solution. Furthermore, it remains a challenge to be able to formulate a clear stable conditioning/detersive composition, especially when the conditioning ingredient is a polysiloxane.
There continues to be a need to have a more stable formulation having a conditioner and a detersive composition. In particular, there is a need to have a clear detersive formulation which comprises a polysiloxane.
The present invention meets this need and provides for a stable, clear detersive composition having a polysiloxane component. In one embodiment, the present invention provides for a clear detersive composition comprising a conditioner. A clear conditioning/detersive composition includes, for example, a conditioning shampoo which is substantially clear.
The term xe2x80x9cclearxe2x80x9d as used herein means a substantial amount of light may pass through. Alternatively, the term xe2x80x9cclearxe2x80x9d means transparent or translucent, as opposed to opaque.
In accordance with the invention, a composition comprising an emulsifier component and a polysiloxane component is provided. The polysiloxane component comprises at least one side chain component A having the general formula:
R1 is an H, OH or a C1-C5 hydrocarbon; X is a C1-C10 hydrocarbon, a heteroatom or
Z is a heteroatom and d is 0 to about 6.
Further in accordance with the present invention, the composition further comprises a detersive component. For example, the composition comprises about 5% to about 60% of the detersive component, about 0.01% to about 10% of the emulsifier component, and about 0.01% to about 10% of the polysiloxane component.
Still further in accordance with the present invention, a method of making a clear shampoo is provided. The method comprises the steps of forming a micro-emulsion of a polysiloxane component, and combining the micro-emulsion with a detersive component. The micro-emulsion is formed by combining a non-ionic emulsifier with a polysiloxane component.
Any feature or combination of features described herein are included within the scope of the present invention provided that the features included in any such combination are not mutually inconsistent as will be apparent from the context, this specification, and the knowledge of one of ordinary skill in the art.
Additional advantages and aspects of the present invention are apparent in the following detailed description and claims.
The present invention is, in part, based upon the surprising discovery that a polysiloxane component may be combined with a detersive component to form a clear composition, preferably a clear shampoo. In a broad embodiment, the composition comprises an emulsifier component and a polysiloxane component.
Without wishing to limit the invention to any theory or mechanism of operation, it is believed that a clear composition, for example a clear shampoo composition, may be produced by combining a detersive component with preformed micro emulsion comprising a polysiloxane component. The micro emulsions may or may not remain intact after it is combined with a detersive component.
In one embodiment, a composition of the present invention remains stable (for example remain clear) for about 360 days after manufacturing.
In one embodiment, the micro emulsions are formed by mixing the emulsifier components with the polysiloxane components, preferably in the presence of water. For example, micro emulsions are formed by homogenizing emulsifier components with polysiloxane components in a tank at about 40 to about 70 degrees C. In one embodiment, a homogenizer employed is model number ME 100 LC by Charles Ross and Son, Hauppauga, N.Y. In one embodiment, the ratio (by weight) of the emulsifier component to the polysiloxane component in a micro emulsion is about 1:1, 1:2, 1:3, or 1:4.
In one embodiment, emulsifier components include a non-ionic emulsifier. In another embodiment, the emulsifier components include a non-ionic emulsifier and at least one of an anionic emulsifier and an amphoteric emulsifier. The anionic amphoteric emulsifiers are selected from the anionic and amphoteric surfactants, respectively.
Non-limiting examples of non-ionic surfactants include: Capryleth-n, where n=4, 5; Deceth-n, where n=3, 4, 5, 6, 8, 9, 10; Undeceth-n, where n=3, 5, 7, 8, 9, 11; Coceth-n, where n=3, 5, 7, 8, 10; C9-11 Pareth-n, where n=5, 6, 8; C9-15 Pareth-8; C11-15 Pareth-n, where n=3, 5, 9, 12, 15, 20, 30, 40; C11-21-Pareth-n, where n=3, 10; C12xe2x88x921xe2x88x92n, where n=3, 5, 7, 9, 12; C12-14 Pareth-n, where n=5, 7, 9, 12; C12-15 Pareth-n, where n=2, 3, 4, 5, 7, 9, 10, 11, 12; C12-16 Pareth-n, where n=5, 7, 9; C14-15 Pareth-n, where n=4, 7, 8, 11, 12, 13; C20-22 Pareth-30; C20-40 Pareth-n, where n=3, 10, 24, 40; C22-24 Pareth-33; C30-50 Pareth-n, where n=3, 10, 40; C40-60 Pareth-n, where n=3, 10; C12-14 Sec-Pareth-5; C12-14 Sec-Pareth-n, where n=8, 9, 15, 20, 30, 40, 50; C11-15 Sec-Pareth-12; Dihydrocholeth-n, n=15, 20, 30; Glycereth-n, where n=7, 12, 20, 26, 31; Hydrogenated Talloweth-n, where n=12, 25; Isoceteth-n, where n=10, 15, 20, 30; Isodeceth-n, where n=4, 5, 6; Isolaureth-n, where n=3, 6, 10; Isosteareth-n, where n=2, 3, 10, 12, 20, 22, 25, 50; Laneth-n, where n=5, 10, 15, 16, 20, 25, 40, 50, 60, 75; Laureth-n, where n=1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 20, 21, 23, 25, 30, 40, 50; Myreth-n, where n=2, 3, 4, 5, 10; Octyldodeceth-n, where n=5, 10, 16, 20, 25, 30; Oleth-n, where n=2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 16, 20, 23, 24, 25, 30, 35, 40, 44, 50, 106; PPG-2-Ceteareth-9; PPG-4-Ceteareth-12; PPG-10-Ceteareth-20; PPG-1-Ceteth-n, where n=1, 5, 10, 20; PPG-2-Ceteth-n, where n=1, 5, 10, 20; PPG-2-Ceteth-n, where n=5, 10, 20; PPG-4-Ceteth-n, where n=1, 5, 10, 20; PPG-5-Ceteth-20; PPG-8-Ceteth-n, where n=1, 2, 5, 10; PPG-n Cetyl Ether, where n=10, 20, 28, 30, 50; PPG-2 C12-15 Pareth-6; PPG-4 C13-15 Pareth-15; PPG-5 C9-15 Pareth-6; PPG-6 C9-11 Pareth-n, where n=5, 12, 11; PPG-3 C12-14 Sec-Pareth-7; PPG-4 C12-14 Sec-Pareth-5; PPG-5 C12-14 Sec-Pareth-7; PPG-5 C12-14 Sec-Pareth-9; PPG-1-Deceth-6; PPG-2-Deceth-10; PPG-4-Deceth-n, where n=4, 6; PPG-6-Deceth-n, where n=4, 9; PPG-8 Deceth-6; PPG-14 Deceth-6; PPG-6-Decyltetradeceth-n, where n=12, 20, 30; PPG-13 Decyltetradeceth-24; PPG-20-Decyltetradeceth-10; PPG-9-Ethylhexeth-5; PPG-20-Glycereth-30; PPG-24-Glycereth-24; PPG-66-Glycereth-12; PPG-2-Isodeceth-n, where n=4, 6, 9, 12; PPG-3-Isodeceth-n, where n=1, 9; PPG-3-Isosteareth-9; PPG-12-Laneth-50; PPG-3-Laureth-9; PPG-4 Laureth-n, where n=2, 5, 7; PPG-6-Laureth-3; PPG-25-Laureth-25; PPG-9-Steareth-3; PPG-23-Steareth-34; PPG-30 Steareth-4; PPG-34-Steareth-3; PPG-1 Trideceth-6; PPG-4 Trideceth-6; PPG-6 Trideceth-8; Sorbeth-n, where n=6, 20, 30, 40; Tocophereth-n, where n=5, 10, 12, 18, 50; Trideceth-n, where n=2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 20, 21, 50; Ceteth-n, where n=1, 2, 3, 4, 5, 6, 7, 10, 12, 14, 15, 16, 17, 18, 20, 23, 24, 25, 30, 40, 45; Ceteareth-n, where n=3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 22, 23, 24, 25, 27, 28, 29, 30, 33, 34, 40, 50, 55, 60, 80, 100; Cetoleth-n, where n=6, 10, 11, 15, 20, 22, 24, 25, 30; Choleth-n, where n=5, 10, 15, 20, 24, 30; Steareth-n, where n=2, 3, 4, 5, 6, 7, 8, 10, 11, 13, 14, 15, 16, 20, 21, 25, 27, 30, 40, 50, 80, 100; and Beheneth-n, where n=5, 10, 20, 25, 30.
Non-limiting examples of anionic surfactants which may be employed as emulsifiers include: Alkyl ether sulfates, Alkyl sulfates, xcex1-Olefin sulfonates, sulfocuccinates, Alkyl isethionates, Acyl amides, Acyl peptides, Alkyl ether carboxylates, Alkyl phosphates, Acylamphoglycinates, Acylamphopropionates and Amine oxides, Ammonium C12-15 Alkyl Sulfate, Ammonium Capryleth Sulfate, Ammonium Coco-Sulfate, Ammonium C12-15 Pareth Sulfate, Ammonium Laureth-n Sulfate, where n=3, 5, 7, 9, 12; Ammonium Lauryl Sulfate, Ammonium Myreth Sulfate, Ammonium Myristyl Sulfate, Ammonium Nonoxynol-4 Sulfate, Ammonium Nonoxynol-30 Sulfate, DEA-C12-13 Alkyl Sulfate, DEA-C12-15 Alkyl Sulfate, DEA-Cetyl Sulfate, DEA-C12-13 Pareth-3 Sulfate, DEA-Laureth Sulfate, DEA-Lauryl Sulfate, DEA-Myreth Sulfate, DEA-Myristyl Sulfate, Magnesium Coco-Sulfate, Magnesium Laureth-n Sulfate, where n=2, 5, 8, 16; Magnesium Lauryl Sulfate, Magnesium Myreth Sulfate, Magnesium Oleth Sulfate, Magnesium PEG-3 Cocamide Sulfate, Magnesium Sulfate, Magnesium/TEA-Coco-Sulfate, MEA-Laureth Sulfate, MEA-Lauryl Sulfate, MIPA C12-15 Pareth Sulfate, MIPA-Laureth Sulfate, MIPA-Lauryl Sulfate, Mixed Isopropanolamines Lauryl Sulfate, Potassium Glycol Sulfate, Potassium Lauryl Sulfate, Potassium Persulfate, Potassium Sulfate, Protamine Sulfate, Sodium C8-10 Alkyl Sulfate, Sodium C12-13 Alkyl Sulfate, Sodium C12-15 Alkyl Sulfate, Sodium C12-18 Alkyl Sulfate, Sodium C16-20 Alkyl Sulfate, Sodium Cellulose Sulfate, Sodium Cetearyl Sulfate, Sodium Cetyl Sulfate, Sodium Cholesteryl Sulfate, Sodium Chondroitin Sulfate, Sodium Coceth Sulfate, Sodium Coceth-30 Sulfate, Sodium Coco/Babassu Sulfate, Sodium Coco/Hydrogenated Tallow Sulfate, Sodium Cocomonoglyceride Sulfate, Sodium Coco-Sulfate, Sodium C9-15 Pareth-3 Sulfate, Sodium C10-15 Pareth Sulfate, Sodium C12-13 Pareth Sulfate, Sodium C12-15 Pareth Sulfate, Sodium C13-15 Pareth-3 Sulfate, Sodium C12-14 Sec-Pareth Sulfate, Sodium Cyclodextrin Sulfate, Sodium Deceth Sulfate, Sodium Decyl Sulfate, Sodium Dermatan Sulfate, Sodium Dextran Sulfate, Sodium Dicocoylethylenediamine PEG-15 Sulfate, Sodium Ethylhexyl Sulfate, Sodium Laneth Sulfate, Sodium Laureth Sulfate, where n=2, 2, 5, 7, 8, 12, 40; Sodium Lauryl Sulfate, Sodium/MEA-PEG-3 Cocamide Sulfate, Sodium Myreth Sulfate, Sodium Myristyl Sulfate, Sodium Nonoxynol-1 Sulfate, Sodium Nonoxynol-3 Sulfate, Sodium Nonoxynol-4 Sulfate, Sodium Nonoxynol-6 Sulfate, Sodium Nonoxynol-8 Sulfate, Sodium Nonoxynol-10 Sulfate, Sodium Nonoxynol-25 Sulfate, Sodium Octoxynol-2 Sulfate, Sodium Octoxynol-6 Sulfate, Sodium Octoxynol-9 Sulfate, Sodium Oleth Sulfate, Sodium Oleyl Sulfate, Sodium Stearoyl Chondroitin Sulfate, Sodium Stearyl Sulfate, Sodium Sucrose Octasulfate, Sodium Tallow Sulfate, Sodium Trideceth Sulfate, Sodium Tridecyl Sulfate, TEA-C10-15 Alkyl Sulfate, TEA-C12-13 Alkyl Sulfate, TEA-C12-14 Alkyl Sulfate, TEA-C12-15 Alkyl Sulfate, TEA-Coco-Sulfate, TEA-C12-13 Pareth-3 Sulfate, TEA-Laneth-5 Sulfate, TEA-Laureth Sulfate, TEA-Lauryl Sulfate, TEA-Oleyl Sulfate, TEA-PEG-3 Cocamide Sulfate, TIPA-Laureth Sulfate, TIPA-Lauryl Sulfate, Ammonium C9-10 Perfluoroalkylsulfonate, Ammonium Cumenesulfonate, Ammonium Dodecylbenzenesulfonate, Ammonium Xylenesulfonate, Calcium Dodecylbenzenesulfonate, Calcium Lignosulfonate, Calcium Pantetheine Sulfonate, Cocamidopropyl Dimethylammonium C8-16 Isoalkylsuccinyl Lactoglobulin Sulfonate, DEA-Dodecylbenzenesulfonate, DEA-Methyl Myristate Sulfonate, Disodium Bisethylphenyl Triaminotriazine Stilbenedisulfonate, Disodium Cetyl Phenyl Ether Disulfonate, Disodium Cocoamphocarboxyethyl-hydroxypropylsulfonate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Distyrylbiphenyl Disulfonate, Disodium Lauriminobishydroxypropylsulfonate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Methylene Dinaphthalenesulfonate, Isopropylamine Dodecylbenzenesulfonate, Magnesium Lauryl Hydroxypropyl Sulfonate, MIPA-Dodecylbenzenesulfonate, Potassium Cumenesulfonate, Potassium Dodecylbenzenesulfonate, Potassium Lauryl Hydroxypropyl Sulfonate, Potassium Phenylbenzimidazole Sulfonate, Potassium Toluenesulfonate, Potassium Xylene Sulfonate, Sodium Benzotriazolyl Butylphenol Sulfonate, Sodium C13-17 Alkane Sulfonate, Sodium C14-18 Alkane Sulfonate, Sodium C9-22 Alkyl Sec Sulfonate, Sodium C14-17 Alkyl Sec Sulfonate, Sodium Caproamphohydroxypropylsulfonate, Sodium Capryloamphohydroxy-propylsulfonate, Sodium Caprylyl Sulfonate, Sodium C8-16 Isoalkylsuccinyl Lactoglobulin Sulfonate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoglyceryl Ether Sulfonate, Sodium Cocomonoglyceride Sulfonate, Sodium C12-14 Olefin Sulfonate, Sodium C14-16 Olefin Sulfonate, Sodium C14-18 Olefin Sulfonate, Sodium C16-18 Olefin Sulfonate, Sodium C14-15 Pareth-PG Sulfonate, Sodium C12-15 Pareth-3 Sulfonate, Sodium C12-15 Pareth-7 Sulfonate, Sodium C12-15 Pareth-15 Sulfonate, Sodium Cumenesulfonate, Sodium Decylbenzenesulfonate, Sodium Dodecylbenzenesulfonate, Sodium Guaiazulene Sulfonate, Sodium Hexyldiphenyl Ether Sulfonate, Sodium Hydroxymethane Sulfonate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lignosulfonate, Sodium Methylnaphthalenesulfonate, Sodium Naphthalenesulfonate, Sodium Naphthol Sulfonate, Sodium m-Nitrobenzenesulfonate, Sodium Octoxynol-2 Ethane Sulfonate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Palm Glyceride Sulfonate, Sodium Pantetheine Sulfonate, Sodium Phenolsulfonate, Sodium Phenylbenzimidazole Sulfonate, Sodium Polydimethylglycinophenolsulfonate, Sodium Polynaphthalenesulfonate, Sodium Polystyrene Sulfonate, Sodium Shale Oil Sulfonate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoxy PG-Hydroxyethylcellulose Sulfonate, Sodium Toluenesulfonate, Sodium Tridecylbenzenesulfonate, Sodium Xylenesulfonate, TEA-Dodecylbenzenesulfonate, TEA-Phenylbenzimidazole Sulfonate, TEA-Tridecylbenzenesulfonate, Ammonium Lauryl Sulfosuccinate, Cholesteryl C16-18 Alkenyl Succinate, Decyl Succinate, Diammonium Lauramido-MEA Sulfosuccinate, Diammonium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diethoxyethyl Succinate, Diethylhexyl Sodium Sulfosuccinate, Diethylhexyl Succinate, Diethyl Succinate, Diglycol Guanidine Succinate, Diheptyl Sodium Sulfosuccinate, Disodium Cetearyl Sulfosuccinate, Disodium Cocamido MEA-Sulfosuccinate, Disodium Cocamido MIPA-Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coco-Glucoside Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium C12-15 Pareth Sulfosuccinate, Disodium C12-14 Sec-Pareth Sulfosuccinate, Disodium C12-14 Sec-Pareth-5 Sulfosuccinate, Disodium C12-14 Sec-Pareth-7 Sulfosuccinate, Disodium C12-14 Sec-Pareth-9 Sulfosuccinate, Disodium C12-14 Sec-Pareth-12 Sulfosuccinate, Disodium Cystinyl Disuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth-6 Sulfosuccinate, Disodium Dimethicone Copolyol Sulfosuccinate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Isodecyl Sulfosuccinate, Disodium Isostearamido MEA-Sulfosuccinate, Disodium Isostearamido MIPA-Sulfosuccinate, Disodium Isostearyl Sulfosuccinate, Disodium Laneth-5 Sulfosuccinate, Disodium Lauramido MEA-Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate, Disodium Lauramido PEG-5 Sulfosuccinate, Disodium Laureth Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauryl Sulfosuccinate, Disodium Myristamido MEA-Sulfosuccinate, Disodium Nonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA-Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG-2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate, Disodium PEG-4 Cocamido MIPA-Sulfosuccinate, Disodium PEG-5 Laurylcitrate Sulfosuccinate, Disodium PEG-8 Palm Glycerides Sulfosuccinate, Disodium PEG-8 Ricinosuccinate, Disodium Ricinoleamido MEA-Sulfosuccinate, Disodium Sitostereth-14 Sulfosuccinate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Stearyl Sulfosuccinate, Disodium Succinate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA-Sulfosuccinate, Disodium Tetrapropenyl Succinate, Disodium Tridecylsulfosuccinate, Disodium Undecylenamido MEA-Sulfosuccinate, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Wheat Germamido MEA-Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Glyceryl Stearate Succinate, Hydroxypropyl Methylcellulose Acetate/Succinate, Isostearyl Diglyceryl Succinate, Methoxy-PEG-7 Rutinyl Succinate, PEG-20 Hexadecenylsuccinate, PEG-50 Hydrogenated Castor Oil Succinate, PEG-3 PPG-20 Succinate, Potassium Dextrin Octenylsuccinate, Potassium PEG-50 Hydrogenated Castor Oil Succinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium Dextrin Octenylsuccinate, Sodium/MEA Laureth-2 Sulfosuccinate, Sodium PEG-50 Hydrogenated Castor Oil Succinate, Sodium Starch Octenylsuccinate, TEA-Dextrin Octenylsuccinate, TEA-PEG-50 Hydrogenated Castor Oil Succinate.
Ammonium Laureth-6 Carboxylate, Ammonium Laureth-8 Carboxylate, Cetyl C12-15-Pareth-9 Carboxylate, Cetyl PPG-2 Isodeceth-7 Carboxylate, Isopropyl C12-15-Pareth-9 Carboxylate, Isopropyl PPG-2-Isodeceth-7 Carboxylate, Magnesium Laureth-11 Carboxylate, MEA-Laureth-6 Carboxylate, MEA PPG-6 Laureth-7 Carboxylate, MEA-PPG-8-Steareth-7 Carboxylate, Potassium Laureth-3 Carboxylate, Potassium Laureth-4 Carboxylate, Potassium Laureth-5 Carboxylate, Potassium Laureth-6 Carboxylate, Potassium Laureth-10 Carboxylate, Potassium Trideceth-n, where n=3, 3, 7, 15, 19, Sodium Capryleth-2 Carboxylate, Sodium Capryleth-9 Carboxylate, Sodium Ceteth-13 Carboxylate, Sodium C9-11 Pareth-6 Carboxylate, Sodium C11-15 Pareth-7 Carboxylate, Sodium C12-13 Pareth-n Carboxylate, where n=6, 8, 12, Sodium C12-15 Pareth-n Carboxylate, where n=6, 7, 8, Sodium C14-15 Pareth-8 Carboxylate, Sodium C12-14 Sec-Pareth-8 Carboxylate, Sodium Isosteareth-6 Carboxylate, Sodium Isosteareth-11 Carboxylate, Sodium Laureth-3 Carboxylate, Sodium Laureth-n Carboxylate, where n=4, 5, 6, 8, 11, 12, 13, 14, 17, Sodium Lauryl Glycol Carboxylate, Sodium PEG-6 Cocamide Carboxylate, Sodium PEG-8 Cocamide Carboxylate, Sodium PEG-3 Lauramide Carboxylate, Sodium PEG-4 Lauramide Carboxylate, Sodium PEG-7 Olive Oil Carboxylate, Sodium PEG-8 Palm Glycerides Carboxylate, Sodium Trideceth-3 Carboxylate, where n=3, 4, 6, 7, 8, 12, 15, 19, Sodium Undeceth-5 Carboxylate.
Ammonium Cocoyl Sarcosinate, Ammonium Lauroyl Sarcosinate, Isopropyl Lauroyl Sarcosinate, Potassium Cocoyl Sarcosinate, Potassium Lauroyl Sarcosinate, Sodium Cocoyl Sarcosinate, Sodium Lauroyl Sarcosinate, Sodium Myristoyl Sarcosinate, Sodium Palmitoyl Sarcosinate, TEA-Cocoyl Sarcosinate, TEA-Lauroyl Sarcosinate, TEA-Oleoyl Sarcosinate, TEA-Palm Kernel Sarcosinate, Palmitoyl Oligopeptide, Pantothenic Acid Polypeptide, Ammonium Cocoyl Isethionate, Dibromopropamidine Diisethionate, Hexamidine Diisethionate, Sodium Cocoyl Isethionate, Sodium Isethionate, Sodium Lauroyl Isethionate, Sodium Myristoyl Isethionate, Sodium Oleoyl Isethionate.
Aluminum Dicetyl Phosphate, Benzalkonium Cetyl Phosphate, C8-10 Alkyl Ethyl Phosphate, C9-15 Alkyl Phosphate, Ceteareth-2 Phosphate, Ceteareth-4 Phosphate, Ceteareth-5 Phosphate, Ceteareth-10 Phosphate, Ceteth-8 Phosphate, Ceteth-10 Phosphate, Cetyl Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate, Cocoyl Hydroxyethylimidazolinium PG-Chloride Phosphate, C6-10 Pareth-4 Phosphate, C12-13 Pareth-10 Phosphate, C12-15 Pareth-n Phosphate, where n=2, 3, 6, 8, 9, 10; C12-16 Pareth-6 Phosphate, DEA-Ceteareth-2 Phosphate, DEA-Cetyl Phosphate, DEA-C8-18 Perfluoroalkylethyl Phosphate, DEA-Oleth-3 Phosphate, DEA-Oleth-n Phosphate, where n=5, 10, 20; DEA-Polyperfluoroethoxymethoxy PEG-2 Phosphate, Deceth-9 Phosphate, Deceth-4 Phosphate, Deceth-6 Phosphate, Diceteareth-10 Phosphate, Dicetyl Phosphate, Di-C12-15 Pareth-n Phosphate, where n=2, 4, 6, 8, 10; Dilaureth-4 Phosphate, Dilaureth-10 Phosphate, Dimyristyl Phosphate, Dioleth-8 Phosphate, Disodium Lauryl Phosphate, Disodium Oleyl Phosphate, Glycereth-26 Phosphate, Hydrogenated Vegetable Glycerides Phosphate, Hydroxyethyl Cetyldimonium Phosphate, Isosteareth-2 Phosphate, Laneth-4 Phosphate, Laureth-n Phosphate, where n=1, 2, 3, 4, 7, 8; Lauryl Phosphate, Linoleamidopropyl PG-Dimonium Chloride Phosphate, Manganese Glycerophosphate, MEA-Dicetearyl Phosphate, Myristamidopropyl Dimethylamine Dimethicone Copolyol Phosphate, Myristamidopropyl Dimethylamine Phosphate, Nonoxynol-3 Phosphate, Nonoxynol-4 Phosphate, Nonoxynol-6 Phosphate, Nonoxynol-9 Phosphate, Nonoxynol-10 Phosphate, Nonyl Nonoxynol-n Phosphate, where n=7, 8, 9, 10, 11, 15, 24, Oleth-n Phosphate, where n=2, 3, 4, 5, 10, 20, Oleyl Ethyl Phosphate, Oleyl Phosphate, Palmeth-2 Phosphate, PEG-15 Cocamine Oleate/Phosphate, PEG-26-PPG-30 Phosphate, PEG-45 Stearate Phosphate, Potassium C9-15 Alkyl Phosphate, Potassium C12-13 Alkyl Phosphate, Potassium Cetyl Phosphate, Potassium Deceth-4 Phosphate, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Dimethicone Copolyol Panthenyl Phosphate, Potassium Dimethicone Copolyol Phosphate, Potassium Glycerophosphate, Potassium Isosteareth-2 Phosphate, Potassium Lauryl Phosphate, Potassium Monofluorophosphate, Potassium Trideceth-6 Phosphate, PPG-21 Butyl Ether Phosphate, PPG-25 Butyl Ether Phosphate, PPG-35 Butyl Ether Phosphate, PPG-5-Ceteth-10 Phosphate, PPG-10 Cetyl Ether Phosphate, Sodium Coco PG-Dimonium Chloride Phosphate, Sodium C13-15 Pareth-8 Butyl Phosphate, Sodium C13-15 Pareth-8 Phosphate, Sodium Diceteareth-10 Phosphate, Sodium Dihydroxycetyl Phosphate, Sodium Dilaureth-10 Phosphate, Sodium Dioleth-8 Phosphate, Sodium Emuamidopropyl PG-Dimonium Chloride Phosphate, Sodium Glyceryl Oleate Phosphate, Sodium Laureth-4 Phosphate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauryl Phosphate, Sodium Milkamidopropyl PG-Dimonium Chloride Phosphate, Sodium Monofluorophosphate, Sodium Oleamidopropyl PG-Dimonium Chloride Phosphate, Sodium Oleth-7 Phosphate, Sodium Oleth-8 Phosphate, Sodium Olivamidopropyl PG-Dimonium Chloride Phosphate, Sodium Steareth-4 Phosphate, Sodium Sunfloweramidopropyl PG-Dimonium Chloride Phosphate, Sodium Zinc Cetyl Phosphate, Stearamidoethyl Diethylamine Phosphate, Stearamidoethyl Ethanolamine Phosphate, Stearamidopropyl PG-Dimonium Chloride Phosphate, Steardimonium Hydroxypropyl PEG-7 Dimethicone Phosphate, Steareth-2 Phosphate, Steareth-3 Phosphate, Stearyl PG-Dimonium Chloride Phosphate, Stearyl Phosphate, TEA-C12-13 Alkyl Phosphate, TEA-Dimethicone Copolyol Phosphate, TEA-Polyphosphatel Triceteareth-4 Phosphate, Triceteth-5 Phosphate, Tricetyl Phosphate, Tri-C12-15 Pareth-n Phosphate, where n=2, 6, 8, 10, Tricresyl Phosphate, Trideceth-n Phosphate, where n=3, 6, 10, Trilaureth-4 Phosphate, Trilauryl Phosphate, Trioleth-8 Phosphate, Trioleyl Phosphate, Trisodium Lauroampho PG-Acetate Chloride Phosphate, Tristearyl Phosphate.
Non-limiting examples of amphoteric surfactants which may be employed as emulsifiers include: Almondamido-propyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Canolamidopropyl Betaine, Capryl/Capramidopropyl Betaine, Cetyl Betaine,. Cocamidoethyl Betaine, Cocamidopropyl Betaine, Coco-Betaine,Coco/Oleamidopropyl Betaine, Decyl Betaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betainem Lauramidopropyl Betaine, Lauryl Betaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betainem Oleamidopropyl Betaine, Oleyl Betaine, Olivamidopropyl Betaine, Palmamidopropyl Betaine, Palmitamidopropyl Betaine, Palm Kernelamidopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl Betaine, Wheat Germamidopropyl Betaine, Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Laurtrimonium Trichlorophenoxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl/Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, PPalmitamine Oxide, PEG-3 Lauramine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Wheat Germamidopropylamine Oxide.
In one embodiment, the composition comprises about 0.01% to about 10% of an emulsifier component, preferably about 0.01% to about 8%, more preferably 0.1% to about 5%, even more preferably 0.1% to about 5%. Preferably, the emulsifier components form micro emulsions with the polysiloxane components.
In one embodiment, the composition comprises about 0.01% to about 10% of a non-ionic emulsifier, preferably about 0.01% to about 8%, more preferably 0.1% to about 5%, even more preferably 0.1% to about 5%. Preferably, the emulsifier components form micro emulsions with the polysiloxane components.
In one embodiment, the composition comprises about 0.01% to about 5% of a non-ionic emulsifier and at least one of about 0.1% to about 5% of an anionic emulsifier/surfactant and an amphoteric emulsifier/surfactant.
In one embodiment, the composition comprises about 0.01% to about 10% of a polysiloxane component. Preferably, the composition comprises about 0.05% to about 6%, more preferably about 0.10% to about 5% of the polysiloxane component.
The popularity of polysiloxane, or dimethicone and dimethicone derivatives, in shampoo compositions originate from their chemical and physical properties. There is a weak inter-molecular interaction between polysiloxane molecules and continuing rotation around Sixe2x80x94C and Sixe2x80x94O bonds of the polysiloxane molecules because of the longer Sixe2x80x94C and Sixe2x80x94O than Cxe2x80x94C and Cxe2x80x94O in regular organic compound. Thus, there is much more space around the silicon atoms and therefore render the polysiloxane excellent spreadbility. Polysiloxane and derivatives also have high refractive index. Furthermore, polysiloxane and derivatives can deliver a smooth feel, detangling and sheen effect to hair.
In one embodiment, the polysiloxane component has the general formula:
wherein a, b and c are independently 0 to about 1000, preferably 0 to about 500, more preferably 0 to about 100. xe2x80x9cs.c.c.xe2x80x9d as used herein means side chain component. A side chain component is any atom, molecule, polymer or chemical entity which may be covalently attached to the Si of the polysiloxane component. For example, one side chain component may be a hydrocarbon, for example a C1-C10 hydrocarbon or a hydroxide, and another side chain component on the same polysiloxane component may be a hydroxide.
In a preferred embodiment, the polysiloxane component has the general formula:
wherein a, b and c are independently 0 to about 50.
In a preferred embodiment, the polysiloxane component comprises about 2 to about 1000 Si, preferably about 4 to about 500 Si, more preferably about 10 to about 300 Si.
In one embodiment, the polysiloxane component comprises at least one side chain component A having the general formula:
R1 is an H or a C1-C5 hydrocarbon, and X is a C1-C10 hydrocarbon, a heteroatom or
wherein Z is a heteroatom and d is 0 to about 6. Non-limiting examples of heteroatoms useful in this invention includes N, O, S and P. In a preferred embodiment, Z is O (oxygen) and d is about 3.
In one embodiment, the cyclic moiety of the side chain component is saturated. In another embodiment, the cyclic moiety is substituted. For example, the a side chain component A of the polysiloxane component may include the general formula:
wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently an H, a C1-C10 hydrocarbon, an ester, carboxyl or a halogen, and X is a C1-C10 hydrocarbon, a heteroatom or
wherein Z is a heteroatom and d is 0 to about 6. Preferably, X is a C1-C5 hydrocarbon or a heteroatom. In one embodiment, X is a heteroatom selected from the group consisting of N, O, Si, P, and S. In a preferred embodiment, R1, R4, R5, R6 and R7 are H""s and R2, R3, R8 and R9 are C1 alkyls. Also, in a preferred embodiment, the cyclic moiety is a 5 or 6 member ring.
For example, a side chain component A of a preferred polysiloxane component of this invention has the general formula:
Side chain component A employed in accordance with this invention preferably has a xe2x80x9chindered aminexe2x80x9d, or a secondary restricted monoamine function group. Preferably, the molecules can be partially protonated at normal shampoo pH range (pH 4-7). The hindered amine functional group is believed to render several beneficial effects. For example, it is believed that the hindered amine polysiloxane (or dimethicone) has more hair or skin affinity and give more conditioning effects. Furthermore, a shampoo comprising a polysiloxane component with a hindered amine functional group is more stable gives more hair softness, smoothness and shine than a shampoo which does not have a hindered amine group.
In one embodiment, the ratio of the Si to the side chain component A in a polysiloxane component is 1:1, preferably 1:0.1, more preferably 1:0.01, even more preferably 1:0.001.
In one embodiment, every other Si of the polysiloxane component has a side chain component A. In another embodiment, every third Si has the side chain component A. In yet another embodiment, every forth, fifth or sixth Si has a side chain component A.
In one embodiment, a polysiloxane component comprises a set of adjacent Si""s of the polysiloxane component having side chain component A followed by a set of adjacent Si""s having side chain components which are not side chain component A. See, for example, the molecule M below:
wherein m and n are independently 0 to about 200. See also the molecules identified at www.nicnas.gov.au/publications/CAR/new/NA/NAFULLR/NA08 00FR/NA819FR.pdf as of Nov. 30, 2001, the disclosure of which is incorporated in its entirety herein by reference. In a preferred embodiment, the polysiloxane component comprises propoxytetramethyl piperidinyl dimethicone. Preferably, the propoxytetramethyl piperidinyl dimethicone has a molecular weight of about 10,000 to about 100,000.
In one embodiment, the polysiloxane component has a viscosity in the range of about 1 cps (centistoke) to about 1,000,000 cps (centistoke). Preferably, the polysiloxane component has a viscosity in the range of about 100 cps to about 500,000 cps. More preferably, the polysiloxane component has a viscosity in the range of about 1,000 cps to about 100,000 cps. For example, the polysiloxane component may have a viscosity of about 3,000 cps to about 4,000 cps, preferably about 3,500 cps.
In one embodiment, the polysiloxane component has a viscosity in the range of less than about 1,000,000 cps (centistoke). Preferably, the polysiloxane component has a viscosity of less than about 500,000 cps. More preferably, the polysiloxane component has a viscosity of less than about 100,000 cps. Even more preferably, the polysiloxane component has a viscosity of less than about 10,000 cps.
In one embodiment, the polysiloxane component has a viscosity in the range of more than about 1 cps (centistoke). Preferably, the polysiloxane component has a viscosity of more than about 1,000 cps. More preferably, the polysiloxane component has a viscosity of more than about 3,000 cps. Even more preferably, the poly siloxane component has a viscosity of more than about 10,000 cps.
The amine contents of the polysiloxane components vary with viscosity. The particular value of amine content corresponding to a certain range of viscosity may be determined readily by one of ordinary skill in the art. The amine content of the polysiloxane component may be about 200 to about 40,000 (ppm, N) at about room temperature.
In one embodiment, the polysiloxane component comprises the molecule M and has a viscosity of about 500 to about 6,000 cps at room temperature. In a preferred embodiment, the polysiloxane component comprises the molecule M and has a viscosity of about 1,000 to about 5,000 cps at room temperature. In a more preferred embodiment, the polysiloxane component comprises the molecule M and has a viscosity of about 2,000 to about 4,000 cps at room temperature. In an even more preferred embodiment, the polysiloxane component comprises the molecule M and has a viscosity of about 3,000 to about 4,000 cps, for example about 3,500 cps at room temperature.
In one embodiment, the polysiloxane component is water insoluble. In one embodiment, the polysiloxane component is a colorless, viscous liquid. In one embodiment, the shelf life of the polysiloxane is up to 12 months from date of manufacture.
In one embodiment, the composition comprises about 0.01% to about 10% of an emulsifier component and about 0.01% to about 10% of a polysiloxane component. In one embodiment, the emulsifier component is a mixture of non-ionic emulsifier and an anionic emulsifier (and/or amphoteric emulsifier). For example, the emulsifier component may comprise more than about 90%, more than about 80%, more than about 50%, more than about 30% or more than about 10% of non-ionic emulsifier.
Preferably, the emulsifier component and the polysiloxane component form a micro-emulsion. For example, an emulsifier component comprising an anionic emulsifier (e.g. Capryeth-3) and a non-ionic emulsifier (e.g. Undeceth-5) is added to propoxytetramethyl piperidinyl dimethicone and water to form a micro-emulsion of propoxytetramethyl piperidinyl dimethicone.
The mixture containing the micro-emulsion may be designated as xe2x80x9cphase Axe2x80x9d. Phase A may be added to a detersive component, designated as xe2x80x9cphase Bxe2x80x9d, to form a clear composition. A detersive component comprises a chemical or formulation which is effective for cleaning, preferably cleaning hair. For example, the detersive component may comprise one or more of the anionic surfactants or amphoteric surfactants identified herein. In one embodiment, a detersive component may also include emulsifier components, for example the non-ionic emulsifiers above.
In one embodiment, the composition comprises about 5% to about 60% of the detersive component, preferably about 10% to about 50%, more preferably about 20% to about 40%, even more preferably about 20% to about 30%.
A detersive component may further comprise a shampoo additive component. Shampoo additive components include any chemical or formulation that adds to the beneficial qualities of a shampoo. Shampoo additive components include, without limitation, ingredients for boosting foam, protecting the integrity of composition, increasing viscosity, covering the odor of raw material and increasing the attraction of the shampoo. Non-limiting examples of shampoo additive components include alkylamide MEA or alkylamide DEA, Sodium Chloride, preservatives, fragrance and colors.
In one embodiment, the composition comprises about 5% to about 60% (by weight) of the detersive component, 0.01% to about 10% (by weight) of the emulsifier component and about 0.01% to about 10% (by weight) of the polysiloxane component. Preferably, the polysiloxane component comprises a propoxytetramethyl piperidinyl dimethicone.
In one embodiment, the ratio (by weight) of phase A:phase B is about 0.1:99.9, 1:99, 2:98.
We hereby incorporate the disclosures of U.S. Pat. Nos. 5,540,952, 5,277,968 and 6,040,288 in their entirety by reference.

Clear conditioning detersive compositions containing polysiloxanes with at least one cyclic side chain


A method and apparatus for accelerating a laser stripping process carried out in a reactive gas mixture, comprising carrying out the stripping process in the presence of an accelerating effective amount of NxOy gas.

The present invention relates to U.V. laser surface treatment methods, particularly to the removal of foreign materials from substrate surfaces. More particularly, the invention relates to an improved chemistry for dry stripping process employing UV-laser radiation and reactive chemistry for the removal of photoresist from semiconductor wafers.
In the manufacturing of various products it is necessary to apply a layer of protective material on a surface, which must be removed after a specified manufacturing step has been concluded. An example of such process is the so-called xe2x80x9cphotolithographyxe2x80x9d process, which is widely used in the manufacturing of integrated circuits. In this process, a pattern is created on a surface using a layer of protective material illuminated through a mask, and the surface is then treated with a developer which removes material from the unmasked portions of the surface, therefore leaving a predetermined pattern. The surface is then treated by ion implantation or by etching agents, which introduce the implanted species into the unmasked portions of the surface, or removes material from unmasked portions. Once these processes are completed, the role of the protecting mask ends and it must be removed. The process is conventional and well known in the art, and is described, e.g., in R. K. Watts, xe2x80x9cLithographyxe2x80x9d, VLSI Technology, S. M. Sze, ed., McGraw-Hill, N.Y., 1988, Chpt. 4.
Two main photoresist stripping methods exist in the modern VLSI/ULSI (Very/Ultra Large Scale Integration) circuits industry (D. L. Flamm, xe2x80x9cDry PlasmaResist Strippingxe2x80x9d, Parts 1, 2 and 3; Solid State Technology, August, September and October 1992):
1) Wet stripping which uses acids or organic solvents;
2) Dry stripping, which uses plasma, O3, O3/N2O or U.V./O3-based stripping.
Both methods are problematic and far from being complete, especially when taking into consideration the future miniaturization in the VLSI/ULSI industry. The current technology is capable of dealing with devices having feature sizes of about 0.5 xcexcm, but before the end of the century the expectation is that the workable size of the devices is expected to be reduced to 0.25 xcexcm. The expected size changes require considerable changes in the manufacturing technology, particularly in the stripping stage. The prior art photoresist stripping techniques described above will be unsuitable for future devices, as explained hereinafter.
Utilizing only the wet stripping method is not a perfect solution, as it cannot completely strip photoresist after tough processes that change the chemical and physical properties of the photoresist in a way that it makes its removal very difficult. Such processes include, e.g., High Dose Implantation (HDI), reactive Ion Etching (RIE), deep U.V. curing and high temperatures post-bake. After HDI or RIE the side walls of the implanted patterns or of the etched walls are the most difficult to remove.
In addition, the wet method has some other problems: the strength of stripping solution changes with time, the accumulated contamination in solution can be a source of particles which adversely affect the performance of the wafer, the corrosive and toxic content of stripping chemicals imposes high handling and disposal costs, and liquid phase surface tension and mass transport tend to make photoresist removal uneven and difficult.
The dry method also suffers from some major drawbacks, especially from metallic and particulate contamination, damage due to plasma: charges, currents, electric fields and plasma-induced U.V. radiation, as well as temperature-induced damage, and, last but not least, from incomplete removal. During various fabrication stages, as discussed above, the photoresist undergoes chemical and physical changes which harden it, and this makes the stripping processes of the prior art extremely difficult to carry out. Usually a plurality of sequential steps, involving wet and dry processes are needed to remove completely the photoresist.
The art has addressed this problem in many ways, and commercial photoresist dry removal apparatus is available, which uses different technologies. For instance, UV ozone ashers are sold, e.g. by Hitachi, Japan (UA-3150A), dry chemical ashers are also available, e.g., by Fusion Semiconductor Systems, U.S.A., which utilize nitrous oxide and ozone to remove the photoresist by chemical ashing at elevated temperatures, microwave plasma ashing is also effected, e.g., as in the UNA-200 Asher (ULVAC Japan Ltd.). Also plasma photoresist removal is employed and is commercially available, e.g., as in the Aspen apparatus (Mattson Technology, U.S.A.), and in the AURA 200 (GASONICS IPC, U.S.A.).
More recently, photoresist removal has been achieved by ablation, using laser UV radiation, in an oxydizing environment, as described in U.S. Pat. No. 5,114,834. The ablation process is caused due to strong absorption of the laser pulse energy by the photoresist. The process is a localized ejection of the photoresist layer to the ambient gas, associated with a blast wave due to chemical bonds breaking in the photoresist and instant heating. The partly gasified and partly fragmented photoresist is blown upwards away from the surface, and instantly heats the ambient gas. Fast combustion of the ablation products occurs, due to the blast wave and may also be due to the photochemical reaction of the UV laser radiation and the process gases. The main essence of the process is laser ablation with combustion of the ablated photoresist which occurs in a reactive gas flowing through an irradiation zone. The combination of laser radiation and fast combustion provides simultaneous lowering of the ablation threshold of hard parts of the photoresist (side walls). The combusted ablation products are then removed by vacuum suction, or by gas sweeping leaving a completely clean surface.
While U.S. Pat. No. 5,114,834 provides an important novel process, it still does not provide a high throughput, which is industrially convenient, viz., an industrially acceptable number of wafers that can be stripped during a given time. The laser stripping throughput is determined by the stripping rate or by the number of laser pulses needed for providing complete stripping of a unit area of the photoresist per unit of time.
While reference will be made throughout this specification to the ablation of photoresist from semiconductor wafers, this will be done for the sake of simplicity, and because it represents a well known and widely approached problem. It should be understood, however, that the invention described hereinafter is by no means limited to the stripping of photoresist from wafers, but it applies, mutatis mutandis, to many other applications, such as stripping and cleaning of photoresist from Flat Panel Displays (FPD) or removal of residues from different objects, such as lenses, semiconductor wafers, or photomasks.
It has now surprisingly been found, and this is an object of the invention, that it is possible to accelerate a given laser removal process by reducing the number of pulses while carrying out the stripping process in the presence of a specific gas composition consisting of O2/O3 and NxOy, wherein NxOy indicates one or more nitrogen oxides, x and y having the appropriate values for the given oxide or mixtures of oxides.
Four different gas compositions are preferred according to the present invention:
1) O2:O3 (Comparative)
2) O2/O3:NxOy
3) O2:NxOy
4) NxOy
This surprising result is obtained by providing additive amounts of NxOy gases in the reactive gas stream which oxidizes the ablated photoresist and enhances laser etching of hard side-walls. The effect of NxOy is significant, since contents of less than 5% of the total gas flow are capable of doubling the stripping throughput. Gas percentages given herein are given by volume, unless otherwise specified.
The method of improving the throughput of stripped substrates in an laser stripping process, according to the invention, comprises adding to the reactive gas mixture an accelerating effective amount of one or more gases of the formula NxOy, wherein x and y have the appropriate values for the given oxide or mixture of oxides, to reduce the number of pulses needed for a complete removal. Typically, NxOy comprises a gas selected from the group consisting of NO, N2, N2O3, N2O4, NO3 and NO4.
As will be appreciated by the skilled person, NxOy can be generated by a number of methods. According to a preferred embodiment of the invention, NxOy is generated by exciting N2O gas. A simple and effective method of exciting N2O gas is by silent or corona discharge.
The process is schematically illustrated in FIG. 1. Oxygen is excited in a first corona discharge ozone generator indicated by numeral 1, to produce a mixture of O2 and O3, in proportions depending on the discharged energy in the generator. N2O is excited in a second corona discharge device indicated by numeral 2, to produce a mixture of NO, NO2 and N2O gases (NxOy). The NxOy, O2 and O3 are fed to the process chamber (numeral 3). In the process chamber the wafer which is swept by the aforementioned reactive gases is irradiated by U.V. Laser radiation 4, and stripping takes place. The gases passing through the chamber are exhausted through the vent 5.
As stated, even very low amounts of NxOy are useful in effectively reducing the number of pulses needed to completely remove the film. According to a preferred embodiment of the invention the content of NxOy in the total reactive gas stream varies according to the pressure in the process chamber. Typical pressures are in the range of 0.1-2 bar, preferably 0.3-0.99 bar. For example, at xcx9c0.4 bar the optimum content of excited N2O is xcx9c5% (v/v) (See FIG. 2). As will be appreciated by the skilled person, the optimal content of NxOy will vary as a function of many operating conditions, such as the laser pulse energy fluence, the pulse repetition rate, the laser wavelength, the laser beam incidence angle, the height of the optical window above the wafer surface, the total pressure in the process chamber, the substrate temperature, the scanning velocity of the laser beam footprint, the flow velocity of the reactive gas mixture, as well as the partial pressures of reactive gas mixture components. These parameters will have to be determined specifically for specific stripping tasks. Determination of the optimal O2/O3:NxOy ratio, however, can be easily carried out by the skilled person for a given system, and does not impose an excessive burden on the planning of operating conditions. The optimal operating conditions may be determined, for example, by using statistical optimization software.
Without wishing to be bound by any particular theory, the inventors believe that the surprising results achieved by the invention are due to the processes illustrated in the xe2x80x9cReaction Schemexe2x80x9d in FIG. 3.
Other gases may be added to the O2/O3:NxOy gas composition to improve the removal, especially of inorganic residues. Such gases must include chlorine and/or fluorine atoms, e.g., Cl2, F2, NF3, NOCl, NOF, Cl2O, ClO2, CF4, CClF3, HCl, HF, SF4 and SF6.
The invention also encompasses the apparatus for carrying out the laser stripping of a coated or contaminated surface according to the invention. Such apparatus comprises:
a laser U.V. radiation source;
a process chamber suitable to contain the surface to be stripped, said chamber being provided with gas inlet(s) and gas outlet(s);
at least one source of oxygen or of ozone; and
at least one source of NxOy.
The above and other characteristics and advantages of the invention will be better understood through the following illustrative and non-limitative examples.

Laser stripping improvement by modified gas composition


A water structure formed from a pair of flexible tubes or sleeves that each receive a volume of water and are maintained within a containment sleeve, and including a vertical tube fitted through the containing sleeve to pass between and is separated from the water filled flexible tubes or sleeves.

1. Field of the Invention
This invention relates to structures for damming water courses, controlling water flow, working and support structures, and the like, and, in particular, is to provide a low cost and easily constructed tubular sleeve or envelope arrangement with divider or baffle walls, and/or multiple sleeves or envelopes with arrangements for maintaining the filled sleeves or envelopes together to form a variety of structures.
2. Prior Art
A need for easily installable dam structures, and the like, particularly structures that are relatively inexpensive, non-permanent, reusable and are durable has been early recognized by the inventor who has been awarded U.S. Pat. No.""s 5,059,065 and 5,125,767 for joining water structures together to form hydraulic damming structures, and the like. Such structures have been found to be very useful for safely and reliably containing or controlling water and are also particularly useful for controlling oil or chemical spills, for flood control, and the like. Such control structures are also useful, for example, for temporary damming operations such as may be involved in agricultural, construction, or like operations for de-watering work sites, fields, or the like, for use as temporary breakwaters, coffer dams, and the like.
Heretofore it has been recognized that fluid filled flexible control structures and barriers can be used for retention of water, control of water flow and wave action, and a number of configurations of dams and barriers formed as temporary structures have been developed. Additional to the U.S. patents of the inventor, some other such arrangements are shown, for example, in U.S. Patents to: Mesnager, U.S. Pat. No. 2,609,666; Mesnheger, U.S. Pat. No. 3,246,474; Imbertson, et al, U.S. Pat. No. 3,355,851; Renfro, U.S. Pat. No. 3,465,530; Tabor, U.S. Pat. No. 3,834,167; Hornbostel, Jr., U.S. Pat. No. 3,373,568; Hepworth, et al, U.S. Pat. No. 3,957,098, Suga, et al, U.S. Pat. No. 4,279,540; Muramatsu, et al, U.S. Pat. No. 4,299,514; Tsuiji, et al, U.S. Pat. No. 4,314,774; Clem, U.S. Pat. No. 4,501,788; Paoluccio, U.S. Pat. No. 4,555,201; Holmberg, U.S. Pat. No. 4,690,585; Stevens, U.S. Pat. No. 4,784,520; and Brodersen, U.S. Pat. No. 4,799,821. The above show various containment, dam and barrier configurations ranging from permanent to portable structures, and include, as shown in Stevens and Brodersen, structures for encircling a chemical or oil spill. Additionally, a Swiss patent No. CH657,884 to Fure shows a dam type containment structure. Further, a breakwater arrangement is shown in a U.S. patent to Sample, No. 4,729,691, that includes a plurality of sand filled bags that are contained within an outer sleeve to serve as a barrier in an erosion control system. The above cited patents generally involve inflatable envelope arrangements that include some anchor structures therewith, and are generally restricted in that they don""t rely on water to form the structure and include anchors that must be permanently installed. Further, most such earlier arrangements require extensive site preparation and a number actually include a concrete bottom and sidewalls to provide for structure stability and barrier support thereby precluding their use as temporary water structures as provided by the present invention.
Summarizing, none of the above set out arrangements, provide, a simple barrier arrangement or arrangements of barriers that include filled or partially filled sleeves or envelopes with arrangements for anchoring the sleeves or envelopes, and which filled sleeves or envelopes can themselves support other structural elements to perform a number of functions as do the embodiments of the present invention. Where the above set out earlier patents of the inventor teach water containing sleeves or envelopes formed into a structure for arrangement as a dam, or the like, and a connecting sleeve arrangement for use with such water structures, neither of these patents involve the various arrangements for maintaining the water filled sleeves or envelopes together or for anchoring them along their lengths, or for their uses with other structures as does the present invention.
It is therefore a principal object of the present invention to provide a hydraulic structure that is formed from a section or sections of water filled sleeves, envelopes, or the like, that may be fitted together in end-to-end, or in intersecting relationship, for forming dams, breakwaters, piers, bridging structures, docks, platforms for drilling, and the like, where such formed structure will be stable even when subjected to a transverse hydraulic force or forces as would tend to move the structure.
Another object of the present invention is to provide a single or plurality of water filled sleeves, envelopes or the like, that are formed or connected to resist movement when a transverse or side hydraulic force, or the like is directed thereagainst.
Another object of the present invention is to provide, with a single sleeve as a water filled structure, a longitudinal center divider, longitudinal baffle, or spaces longitudinal baffles for discouraging or dampening a side load within the water filled sleeve as could be created by application of a transverse or side hydraulic load into the sleeve as could roll the sleeve.
Another object of the present invention is to provide a water filled structure formed from a pair of sleeves as water bodies, water columns, envelopes, or the like, that are filled with water and are to be connected together along longitudinal shared surfaces so as to preclude their separation when a transverse or side hydraulic load force is applied to either or both of the water filled structures.
Still another object of the present invention is to include, with a pair of water filled sleeves, envelopes, or the like, that are maintained together along longitudinal shared surfaces, or with a single sleeve that includes a center dividing wall, a further component, components, or devices therewith to allow, for example, the water filled structure to be used as a drilling platform, dock, bridge, or the like.
Still another object of the present invention is to provide a water filled structure that can include a floating arrangement such as a styrafoam core, separate air or lighter than water filled sleeves, tubes, containers, or the like fitted therein, to produce a buoyancy in the water filled structure so as to facilitate its being used as a floating platform, boom, dock, break water or the like.
Still another object of the present invention is to provide a sleeve, envelope, or the like that includes an arrangement for fitting a replacement sleeve or envelope into a damaged sleeve or envelope that contains water without a necessity to completely drain the damaged sleeve or envelope.
Still another object of the present invention is to provide a water filled structure formed from a single or number of sleeves, envelopes, or the like, with the single sleeve to include a dividing wall, baffle, or the like, and with the plurality of sleeves maintained together, and may include a separate buoyancy arrangement, with the structure arranged to be easily filled with water and includes drain and fill ports that are all conveniently and safely operated even in a desolate and/or unimproved area, which sleeves, envelopes, or the like, are easy to maintain, and can be installed with minimum to no site preparation.
The present invention is in at least one flexible sleeve or envelope arrangement or arrangements that can be closed at its ends to receive and retain a volume of water. Such single sleeve preferably includes a dividing wall or walls or other baffle arrangement to prohibit an applied transverse hydraulic force from rolling the water containing sleeve. The dividing wall can be formed to extend the length of the sleeve and is connected at longitudinal axis along the sleeve or envelope inner surface, dividing the sleeve into two or more compartments. Or individual wall sections can be secured along their opposite edges to the sleeve inner surface, with gaps or spaces left between the individual sections that then functions as baffles, or, alternatively a single longitudinal dividing wall having a plurality of holes or openings formed therethrough and can be secured to the sleeve inner surface, dividing the sleeve into two or more sections, to function as a baffle. Such single sleeve or envelope with dividing wall, walls or baffle arrangement can include inlet and exhaust valves, as needed, and can further include an air inlet or bleed valve arrangement, within the scope of this disclosure.
Additional to a single sleeve that is divided by a longitudinal wall, multiple walls, baffle, or baffles, the invention can include a pair or more of tubes sleeves or envelopes that are connected together as by an adhesive, hot weld, or the like, along shared surfaces to form a pair of connected containers that, when water filled, will resist rolling apart when a side or transverse or side hydraulic load or force is applied thereto. Such single sleeve pair of sleeves, or multiple sleeves can be connected end to end with like sleeve arrangements utilizing a coupling sleeve arrangement like that shown in my earlier U.S. Pat. No. 5,059,065, or the like. So arranged, a control structure is provided as for damming or dewatering operations, that can include inlet and vent valve arrangements for passing water or air into and draining water and air from the individual sleeves. Also, an additional sleeve or envelope, sleeves or envelopes, can be provided to contain the multiple sleeves for maintaining the pair of bodies water filled sleeves or envelopes together, and such arrangement or arrangements can include additional structure such as, a vertical tube for use in drilling operations, or a horizontal tube to function as a calvert, buoyancy tube or tubes, to be filled with a buoyant material such as to provide buoyancy in water to the structure.
Additionally, a sleeve having a number or compartments formed therein to individually receive a buoyance material to provide a desired buoyancy in water for use as a dock, platform, roadway bridge arrangement, or like type structure, can be so arranged within the scope of this disclosure.
A preferred sleeve arrangement is an open sleeve or envelope that can be closed at its ends and is formed from an appropriate flexible material. The sleeve, envelope or sleeves or envelopes may be reinforced internally, or externally may be contained in an additional sleeve, and may include a mat or web material secured thereto, or the like. Further, the invention may include an arrangement for fitting as by pulling, or the like, a second sleeve or envelope through a damaged first sleeve or envelope without a necessity for first fully draining the damaged sleeve or envelope. In practice a flexible polyethylene plastic tube manufactured by Layfield Plastics, having a range of wall thickness of from four (4) to ten (10) millimeters has been used successfully for the invention, though, it should be understood, the invention is not limited to any particular sleeve or tube manufacture or thickness, and can utilize sleeves of greater or lesser wall thickness, can include a further enclosing sleeve, and have a mat, of metal, fiber, glass or like secured thereto to provide reinforcement to the structure, within the scope of this disclosure.

Flexible hydraulic structure with right angle tube fitted therethrough