WO1992021744A2 - Dry bleach composition with improved dispersibility - Google Patents
Dry bleach composition with improved dispersibility Download PDFInfo
- Publication number
- WO1992021744A2 WO1992021744A2 PCT/US1992/004500 US9204500W WO9221744A2 WO 1992021744 A2 WO1992021744 A2 WO 1992021744A2 US 9204500 W US9204500 W US 9204500W WO 9221744 A2 WO9221744 A2 WO 9221744A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- surfactant
- calcium stearate
- dry
- oxidant
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
Definitions
- This invention relates to dry fabric bleaching products for household use, and more particularly to such dry bleach products based upon peroxygen bleaches, which are formulated to exhibit improved dispersibility/solubility in cold water.
- Bleaching compositions have long been used in households for the bleaching and cleaning of fabrics.
- Liquid bleaches based upon hypochlorite chemical species have been used extensively, as they are inexpensive, highly effective, easy to produce, and stable.
- the advent of modern synthetic dyes and the use of modern automatic laundering machines have introduced new requirements in bleaching
- a particularly preferred peroxygen bleach is sodium perborate which is suitable for a dry granular formulation.
- sodium perborate is combined with an alkalinity booster/builder such as sodium carbonate and is used as a laundry additive.
- an alkalinity booster/builder such as sodium carbonate
- JP 60-96698 (Hara et al), describes a method for manufacturing a granular detergent composition wherein 0.5 to 5 weight percent of calcium stearate or other water insoluble powder is added to a granulated detergent product specifically to improve solubility in cold water.
- JP 62-228000 Saito et al describes and claims a high density granular detergent
- composition also employing a hydrophobic powder such as calcium stearate, as a means of improving cold water
- JP 64-20298 to Nakamura et al also describes and claims a high density granular detergent composition having as its object the attainment of a better cold water dissolution rate.
- This application points out one of the disadvantages in the use of hydrophobic fine powders to attain satisfactory dissolution rates, that is, while the hydrophobicity of the powder may aid dispersion, it can also impede dissolution.
- the present invention is a dry, fabric bleaching composition
- a dry, fabric bleaching composition comprising
- the laundry additive composition of the present invention exhibits a dramatic reduction in cold water residue compared with similar compositions of the art having no calcium
- a method of making the composition of the present invention comprises dry blending the peroxygen bleach and alkaline builder, as well as any other dry
- the initial dry blending step may be replaced by an agglomeration step wherein the oxidant and builder are coagglomerated with an agglomerating agent.
- the builder be preloaded with a low level (less than about 5%) surfactant prior to agglomerating with the oxidant.
- Figures 1 and 2 are graphs showing the effect on bulk solution dissolution of various levels of calcium stearate powder (as calcium stearate). The data were obtained using a sodium perborate/sodium carbonate laundry additive matrix, and wash conditions were a water temperature of 4.5°C, 100 ppm hardness and five pounds of ballast. Results were obtained as
- Fig. 1 is a graph showing the effect of 0.25 weight percent of calcium stearate on bulk solution dissolution compared to a control having no calcium stearate;
- Fig. 2 is a graph showing the effect of 0.5 weight percent of calcium stearate on bulk solution dissolution compared to the same control.
- the present invention is a dry, fabric bleaching composition
- a dry, fabric bleaching composition comprising
- a first method of making the composition of the present invention comprises dry blending the peroxygen bleach and alkaline builder, as well as any other dry ingredients. To this is added the calcium stearate powder which is further blended until completely dispersed, uniformly coating the other dry ingredients. Generally about 5-10 minutes in a tumble style mixer is required. Last, any liquids, particularly nonaqueous liquids such as surfactant, are applied using a coarse spray, which continuing to mix, to result in a uniformly coated dry mixture.
- a second method of making the composition of the present invention is an agglomeration process wherein the oxidant material and alkaline builder are agglomerated prior to addition of the calcium stearate powder.
- the alkaline builder is first preloaded with surfactant, and any additional liquid additives.
- surfactant is applied to the builder in a mixer, preferably, a tumble-style or falling curtain rotary mixer, and mixed sufficiently for the builder to substantially absorb the surfactant.
- Sufficient surfactant is applied to the builder to result in a final product (after agglomeration) surfactant content of 0 to about 5 wt. %, preferably about 0.1 - 3 wt.%.
- surfactant to builder weight basis about 0-20 wt. % surfactant is applied to the builder, more preferably about 1- 15 wt. %.
- the preloaded builder and oxidant are then charged to the agglomerator.
- Any agglomerating apparatus known to the art may be employed and preferred are rotary or vertical turbo agglomerators.
- any agglomerating agent may be used, with sodium silicate and polyacrylates preferred.
- the agglomerate is then mixed with the calcium stearate powder and any additional dry ingredients in a mixing means, especially a rotary or tumble mixer.
- bleaches are peroxygen or peracid bleaches in solid form.
- Preferred peroxygen bleaches include sodium percarbonate, sodium perborate, sodium phosphate
- peroxyhydrate potassium permonosulfates and metal peroxides.
- Sodium perborate is most preferred and may be in the form of tetrahydrate or monohydrate.
- Bleach activators also known as peracid precursors, can be included with the peroxygen
- activators include tetraacetyl
- NOGPS nonanoyloxy benzene-sulfonate
- NOGPS nonanoylglycoylphenol sulfonate
- the peracid percursor is added in an amount effective to provide oxidizing power, and generally in a mole ratio to oxidant bleach of about 0.1:1 to 10:1.
- Peracid bleaches may be advantageous in terms of bleaching performance. Examples include perazelaic and diperazelaic acids, diperoxydodecanedioic acid (DPBDA) and alkyl monoperoxysuccinic acid.
- DPBDA diperoxydodecanedioic acid
- alkyl monoperoxysuccinic acid alkyl monoperoxysuccinic acid.
- the bleach is present in an amount sufficient to provide effective bleaching, e.g., from about 5 to 50% by weight active, preferably from about 8-25% by weight active, most preferably from about 10 to 13% by weight active depending on the bleaching species chosen.
- Alkaline Builder An alkaline builder material is added to provide to a pH of between about 8-12. The builder also has the capacity to sequester or precipitate hardness ions (e.g. Ca 2+ and
- bicarbonates are suitable builders, and preferred are sodium and/or potassium carbonates.
- the carbonate acts as the
- weight percent of the composition at least about 25%, Preferably 50%, most preferably 80% carbonate is employed. Higher levels can be employed, however, at levels greater than about 90% there is insufficient room for the other ingredients which contribute to the overall
- Very low levels of a calcium stearate powder are important to significantly reduce the levels of CWR in the dry peroxygen bleaching matrix.
- Preferred are calcium stearates, available, for example, from The Synthetic Products Company (Synpro), of Cleveland, Ohio.
- Examples of particularly preferred calcium stearate are Synpro's finely-sized grades, especially grades 1 5, 12B, 24-46, 114-36, NF and Food Grade.
- the calcium stearate powder has a particle size distribution such that at least 95 percent is smaller than a US 200 mesh screen, and has a bulk density of about 0.1-0.4 g/cm . More
- the calcium stearate powder has a particle size distribution such that at least 99% i s smaller than a US 200 resh screen, and 95* is smaller than a 400 mesh screen
- a fine particle size is important to ensure effective coating of the other dry ingredients to result in a hydrophobic
- Granulometer measurements reveal that the most preferred calcium stearate fine powder has a median grain size of less than about 25 microns, preferably less than about 10 microns.
- a surfactant may be provided to prevent "dusting" of the dry ingredients, particularly sodium carbonate, sodium perborate, and fluorescent whitening agents. It is most preferred to use at least one nonionic surfactant, especially C 1-4
- alkoxylated aliphatic alcohols and C 1-4 alkoxylated alkyl phenols. Particularly preferred are ethoxylated/propoxylated c 8-14 alcohols. There should be at least about three alkoxy groups per alcohol, preferably at least about nine. Examples of preferred ethoxylated/propoxylated aliphatic alcohols are BASF Corporation's traderoarked INDUSTROL, and PLURAFAC.
- NEODOL polyethoxylated alcohols manufactured and marketed by the Shell Chemical Company under the trademark "NEODOL”.
- NEODOLS are NEODOL 25-7 which is a mixture of 12 to 15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule, NEODOL 23-65, a C 12 _ 13 mixture with about 6.5 moles of ethylene oxide, and NEODOL 25-9, a C l2-15 mixture with about 9 moles of ethylene oxide.
- Total surfactant content may range from 0 to about 5%, preferably from about 0.1 to 3%, more preferably from 0.2 to 1% and most preferably from about 0.2 to 0.3%. It is to be noted that higher levels of surfactant, and/or its application as an overly fine spray, tends to cause agglomeration of the calcium stearate powder, thus severely reducing its effectiveness. It is also preferred to a ratio of surfactant to calcium stearate powder be from about 3:1 to 1:5.
- Adjuncts may be added in an amount of from 0 to about 5% and are useful to improve or enhance efficacy, aesthetics and/or consumer acceptance of the overall formulation.
- Enzymes are a particularly preferred adjunct, and may be selected from amylases, proteases, cellulases, and lipases.
- the hydrolytic enzyme should be present in an amount of about 0.01-2%, more preferably about 0.5-1%, by weight of the detergent. Mixtures of any of the foregoing hydrolases are desirable, especially protease/amylase blends.
- Dyes such as Monastral blue and anthraquinone dyes (such as those described in Zielske, U.S. 4,661,293, and
- pigments e.g. titanium dioxide and ultramarine blue which are also suitable colorants, can be selected.
- Anti-redeposition agents such as
- carboxymethylcellulose are potentially desirable.
- Seguestrants such as EDTA, citric acid, polyphosphonates, aminopolyphosphonates, and the like, may also be desirable to complex transition metal ions which can destabilize bleaches.
- Fluorescent whitening agents are desirable
- FWAs are absorbed on fabrics during the washing and/or bleaching process. FWAs function by absorbing ultraviolet light, which is then emitted as visible light, generally in the blue wavelength ranges. The resultant light emission yields a brightening and whitening effect, which counteracts yellowing or dulling of the bleached fabric.
- Such FWAs are available commercially from sources such as Ciba Geigy Corp. of Basel, Switzerland, under the trade name "Tinopal”. Incorporation of the FWAs may be afforded by mixing a binding agent and bulking agents e.g., Na 2 SO 4 , and colorants. The mixture is then compacted to form particles, which are admixed into the bleach product. If added, the FWA particles may comprise from about 0.1% to 1% by weight of the composition.
- a fragrance which imparts a pleasant odor to the bleaching composition is generally included.
- fragrances are subject to oxidation by bleaches, they may be protected by
- polymeric materials such as polyvinyl
- fragrance beads are soluble in water, so that fragrance is released when the bleach composition is dissolved in water, but the fragrance is protected from oxidation by the bleach during storage.
- Buffering, building, and/or bulking agents may also be present. Boric acid and/or sodium borate are preferred agents to buffer the pH of the composition. Other buffering agents and cobuilders such as sodium and potassium silicate, sodium phosphate, sodium tripolyphosphate, sodium tetraphosphate, aluminosilicates (zeolites), and organic builders such as sodium sulfosuccinate may be added. Optionally, fillers such as sodium sulfate are added. Buffer, builder, and bulking agents are included in the product in particulate form such that the entire composition forms a free-flowing dry product. Buffers and cobuilders and/or bulking agents may range from 0 to about 80%, preferably 10-50% by the weight of composition.
- liquid ingredients are preferably sprayed onto the dry
- liquids particularly nonaqueous liquids such as nonionic surfactants
- the liquid application apparatus should be selected to deliver a relatively coarse spray, and mixing should be gentle to moderate.
- a desired coarse spray may be obtained by a pump-fed non-atomizing nozzle, having a fan-shaped spray pattern.
- An example is a nozzle sold under the name T-Jet 11002. It is within the scope of the dry-blending-process of the present invention, however, to preload surfactant or other liquids onto sodium carbonate prior to blending in the remaining dry ingredients, and prior to adding any remaining liquid
- the spray density of surfactant is less important as long as the carbonate is sufficiently mixed during and after spraying to assure maximum absorption of surfactant. It is preferred to employ a
- preloading and the surfactant may be applied using an air-fed atomizing spray apparatus.
- Dry adjuncts may be added at any time during the process, for example with the sodium perborate and carbonate or after the addition of all liquid ingredients.
- CWR calcium stearate powder
- the measurement of CWR is accomplished by placing a measured quantity of laundry composition, as a single pile, in the bottom of a washing machine. Ballast (10 lbs. of polycotton pillow cases) is piled on top of the composition. The washing machine is set to run a gentle eight minute cycle with 4.5°C incoming wash water. At the end of a complete wash cycle the ballast is removed and undissolved composition collected and weighed.
- Table I The data of Table I was obtained by placing 110 g of a sodium perborate/sodium carbonate - based additive formulation, containing 0.25 weight percent calcium stearate as the calcium stearate powder, in a pile in a washing machine. Ten pounds of ballast, in the form of polycotton pillowcases were added, and the wash was conducted at a water temperature of 4.5°c, with the results shown in the table. All mesh sizes are US mesh. Table I
- C-F Grades C-F, however, yielded an acceptable level of CWR.
- the results of Table I are accurate to within 5.0 g, thus C-F should be considered equal to each other.
- C-F should be considered equal to each other.
- CWR is expressed as a percentage by comparing final weight of laundry product with the initial weight. Expressed as a percentage of additive remaining after a wash cycle, less than about 30% more preferably, less than about 10% and most preferably less than about 5% CWR is acceptable.
- Table II shows the minimum amount of calcium stearate powder (as calcium stearate) necessary to achieve acceptable CWR levels.
- the calcium stearate was added to a sodium
- composition at least about 0.05 wt. %, preferably at least about 0.15 wt. % calcium stearate is important to reduce CWR to acceptable levels.
- the tilt plate is a twelve inch long smooth surfaced-plate, upon which is placed about 100 g of sample, in a single pile. The plate is tilted to various angles and the angle at which the sample begins to flow is noted.
- FIGS 1 and 2 illustrate bulk solution conductivity
- Conductance is expressed in millisiemens/cm, and increases with dissolution of the sample.
- the 0.5% level thus is a maximal level (for a sodium perborate/sodium carbonate additive formulation) above which the beneficial effects of the stearate on additive dissolution is reduced.
- Table V lists the laundry performance improvements achieved when the additive containing 0.5 wt. % calcium stearate is placed at the bottom of a washer for a cold water wash.
- Tables VI and VII illustrates the importance of the method of the present invention. Mixing time of dry ingredients and order of addition of surfactant and/or any liquids (e.g., fragrance) can impact stearate dispersion, thereby affecting CWR.
- the product of Table VI was made as a 10 lb.
- A perborate plus 0.25 wt. % calcium stearate
- Table VI shows that a minimum of ten minutes of mixing (in a small tumble mixer with gentle-moderate mixing) the dry ingredients is necessary to attain an acceptable CWR value.
- Table VI also illustrates the disadvantages of using a fine surfactant spray, as this tends to cause agglomeration of the calcium stearate particles and increase CWR unless mixing is continued for a long time.
- the spray apparatus used to obtain the mixture of Table VI was an atomizing sprayer embodying a pressure of about 25 psi at 2 g/min delivery. These spray conditions are accordingly not preferred where surfactant is added last.
- a scale up was run in a 100 lb. batch Pelligrini mixer (a baffled, tumble mixer) set to provide vigorous mixing.
- a surfactant/fragrance mixture was applied as a coarse spray using a T-Jet 11002 Nozzle at 40 psi and 300 g/min delivery.
- a substantial decrease in CWR was evidenced by these process parameters, as shown in Table VII.
- A perborate plus 0.25 wt. % calcium stearate
- the coarser spray also improved CWR of the B samples, apparently by sharply reducing the tendency of the fine powder to agglomerate. Generally, only five minutes of mixing the dry ingredients, followed by another five minutes after
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SK1363-93A SK136393A3 (en) | 1991-06-05 | 1992-05-28 | Dry bleach composition with improved dispersibility |
PL92301427A PL170052B1 (en) | 1991-06-05 | 1992-05-28 | Perborate bleaching composition in solid form and method of obtaining same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71047391A | 1991-06-05 | 1991-06-05 | |
US710,473 | 1991-06-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1992021744A2 true WO1992021744A2 (en) | 1992-12-10 |
WO1992021744A3 WO1992021744A3 (en) | 1993-01-07 |
Family
ID=24854181
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/004500 WO1992021744A2 (en) | 1991-06-05 | 1992-05-28 | Dry bleach composition with improved dispersibility |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0587747A1 (en) |
CA (1) | CA2108038A1 (en) |
MX (1) | MX9202703A (en) |
PL (1) | PL170052B1 (en) |
SK (1) | SK136393A3 (en) |
WO (1) | WO1992021744A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6773625B2 (en) | 2002-08-26 | 2004-08-10 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Dry bleach compositions |
WO2004085588A1 (en) * | 2003-03-24 | 2004-10-07 | Unilever Plc | Detergent composition or component therefor |
AU2004279319B2 (en) * | 2003-09-23 | 2010-11-04 | Abyrx, Inc | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
US7955616B2 (en) | 2003-09-23 | 2011-06-07 | Orthocon, Inc. | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2432523A1 (en) * | 1973-07-04 | 1975-01-30 | Lion Fat Oil Co Ltd | PROCESS FOR IMPROVING THE PROPERTIES OF GRILLY DETERGENTS AND CLEANING AGENTS |
EP0079105A1 (en) * | 1981-11-09 | 1983-05-18 | Unilever N.V. | Foam-controlled washing agents |
DE3438654A1 (en) * | 1983-10-31 | 1985-05-09 | Lion Corp., Tokio/Tokyo | Process for the preparation of a granular detergent and cleaning agent |
US4618445A (en) * | 1983-05-19 | 1986-10-21 | Lever Brothers Company | Peroxide bleach and compositions comprising said bleach |
-
1992
- 1992-05-28 PL PL92301427A patent/PL170052B1/en unknown
- 1992-05-28 SK SK1363-93A patent/SK136393A3/en unknown
- 1992-05-28 EP EP19920913284 patent/EP0587747A1/en not_active Withdrawn
- 1992-05-28 WO PCT/US1992/004500 patent/WO1992021744A2/en not_active Application Discontinuation
- 1992-05-28 CA CA 2108038 patent/CA2108038A1/en not_active Abandoned
- 1992-06-05 MX MX9202703A patent/MX9202703A/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2432523A1 (en) * | 1973-07-04 | 1975-01-30 | Lion Fat Oil Co Ltd | PROCESS FOR IMPROVING THE PROPERTIES OF GRILLY DETERGENTS AND CLEANING AGENTS |
EP0079105A1 (en) * | 1981-11-09 | 1983-05-18 | Unilever N.V. | Foam-controlled washing agents |
US4618445A (en) * | 1983-05-19 | 1986-10-21 | Lever Brothers Company | Peroxide bleach and compositions comprising said bleach |
DE3438654A1 (en) * | 1983-10-31 | 1985-05-09 | Lion Corp., Tokio/Tokyo | Process for the preparation of a granular detergent and cleaning agent |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6773625B2 (en) | 2002-08-26 | 2004-08-10 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Dry bleach compositions |
WO2004085588A1 (en) * | 2003-03-24 | 2004-10-07 | Unilever Plc | Detergent composition or component therefor |
US7674762B2 (en) | 2003-03-24 | 2010-03-09 | The Sun Products Corporation | Detergent composition or component therefor |
AU2004279319B2 (en) * | 2003-09-23 | 2010-11-04 | Abyrx, Inc | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
US7955616B2 (en) | 2003-09-23 | 2011-06-07 | Orthocon, Inc. | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
US8105628B2 (en) | 2003-09-23 | 2012-01-31 | Orthocon, Inc. | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
US8337879B2 (en) | 2003-09-23 | 2012-12-25 | Orthocon, Inc. | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
Also Published As
Publication number | Publication date |
---|---|
PL170052B1 (en) | 1996-10-31 |
CA2108038A1 (en) | 1992-12-06 |
SK136393A3 (en) | 1994-07-06 |
WO1992021744A3 (en) | 1993-01-07 |
MX9202703A (en) | 1993-08-01 |
EP0587747A1 (en) | 1994-03-23 |
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