• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A detergent packet includes a liquid detergent contained within a water soluble pouch. The water soluble pouch is formed from a film including at least one of a polymer of hydrolyzed vinyl acetate and a copolymer of hydrolyzed vinyl acetate and a second monomer. The liquid detergent includes between 5 wt% and 60 wt% water and between 0.5 wt% and 15 wt% inorganic sulfate.
    公开号:AU2013217544A1
    申请号:U2013217544
    申请日:2013-02-05
    公开日:2014-07-17
    发明作者:Carlton Wong；Yuki YASUI
    申请人:Aicello Chemical Co Ltd；
    IPC主号:B65D77-00
    专利说明:
    WO 2013/119537 PCT/US2013/024722 :1 TITLE OF THE INVENTION DETERGENT PACKET CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. §119(e) (i) and the benefit of co-pending U.S. Provisional Application No. 61/633,357 entitled "Pouch for liquid laundry detergent packaging" filed on February 9, 2012, which is incorporated in its entirety by reference herein. This application further claims priority under 35 U.S.C. § 120 and the benefit of co-pending U.S. Application No. 13/752,609 entitled "Detergent Packet" filed on January 29, 2013, which is incorporated in its entirety by reference herein. BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to detergent packets, in particular detergent packets including liquid detergent contained- within a water soluble pouch. Liquid detergent is used in the field of laundry, glass, floor and carpet cleaning. Consumers widely accept the packaging of liquid detergent in pre-measured amounts known as unit doses because of its convenience. Consumers WO 2013/119537 PCT/US2013/024722 2 have a tendency to use more detergent than sufficient or necessary, thus the unit dose detergent packaging prevents over-consumption and is more environmentally-friendly. When liquid detergent is packed in a pouch, the pouch must be dissolved in water for the liquid detergent to be used for cleaning objects. Consumers have demanded higher cleaning performance from liquid detergent. As a result, different active ingredients have been combined in liquids detergents to achieve higher performance. Some kinds of active ingredients may chemically react with one another when mixed. In order to prevent this chemical reaction, a separation packaging in a pouch may be employed. Liquid detergents may contain glycols as a diluent. In order to reduce costs, liquid detergent manufacturers have begun using water as a diluent. Water soluble pouches, however, do not have resistance against high water contents. In particular, water soluble pouches by their nature dissolve in cold water. The dissolution of a water soluble 5 pouch packed with a liquid detergent having a high water content descends with time. Moreover, the surface of a water soluble pouch packed with a liquid detergent having a high water content will become sticky. Accordingly, it has previously been difficult or impossible to provide a water soluble pouch containing a high water content liquid WO 2013/119537 PCT/US2013/024722 3 detergent having acceptable performance properties. 2. The Prior Art United States Patent No. 5,341,932 to Chen et al. relates to hazardous materials containing water with various ions but does not disclose a liquid detergent packaging or specific limitation for each salt concentration in the formulation. Chen et al. also fails to disclose the advantageous effect of adding sulfate on the deterioration of a water soluble pouch when it is dissolved in water. United States Patent No. 7,271,141 to Kaiser et al. relates to water soluble packages containing polyphosphate builder and special ratios of potassium to sodium ions. A detergent packet according to an embodiment of the invention does not require potassium ions or a special ratio of potassium to sodium ions. United States Patent No. 7,557,075 to Fregonese et al. relates to water soluble package with a liquid detergent containing a high volume water content, a polyphosphate builder material and Sorbitol. Fregonese et al. does not mention sulfate salts or the advantageous effect of adding sulfate on the deterioration of a water soluble pouch when it is dissolved in water. United States Patent No. 5,253,759 to Gouge et al. relates to a water soluble bag in bag arrangement for agrochemicals packaging wherein the bag WO 2013/119537 PCT/US2013/024722 4 in bag arrangement prevents the interaction of chemicals by separating. Gouge et al. does not disclose a detergent packaging or high water content packed chemicals. United States Patent No. 6,632,785 to Pfeiffer et al. relates to water soluble sachet packed gel form detergents and high volume of water. Pfeiffer et al. does not disclose a liquid detergent packaging, specific limitations for each salt concentration in the formulation or the advantageous effects of adding sulfate on the deterioration of a water soluble pouch when it is dissolved in water. United States Patent No. 7,642,226 to Verrall et al. relates to a water soluble co-polymer film packed a liquid detergent and film thickness range. United States Patent No. 6,787,512 to Verrall et al. relates to a water soluble co-polymer film containing a unit dose of liquid detergent. The Verrall et al. patents do not mention a liquid detergent containing water. SUMMARY OF THE INVENTION 5 ~The invention relates to detergent packets, in particular detergent packets including liquid detergent contained within a water soluble pouch. A detergent packet according to an aspect of the invention includes a water soluble pouch and a liquid WO 2013/119537 PCT/US2013/024722 5 detergent contained within the water soluble pouch. The water soluble pouch may be formed from a film including at least one of a polymer of hydrolyzed vinyl acetate and a copolymer of hydrolyzed vinyl acetate and a second monomer. The liquid detergent may include between 5 wt% and 60 wt% water and between 0.5 wt% and 15 wt% inorganic sulfate. In a further aspect of the invention a cation of the inorganic sulfate may include sodium, potassium, magnesium or aluminum. In a further aspect of the invention the 5 second monomer may include maleic acid, itaconic acid, methyl acrylate and/or 2-acrylamid-2-methylpropanesulfonic acid. In a further aspect of the invention a degree of hydrolysis of the film expressed as a mol percentage of vinyl acetate units converted to vinyl alcohol units may be 70 mol% to 100 mol%. In a further aspect of the invention the film may be between 50 microns and 100 microns thick. In another aspect of the invention, the detergent 5 packet further has an outer water soluble pouch packed with both the water soluble packet and an outer liquid detergent contained within the outer water soluble pouch. The outer liquid detergent may include less than 15 wt% of water and less than 10 wt% of inorganic sulfate.
    WO 2013/119537 PCT/US2013/024722 6 In a further aspect of the invention, a cation of the inorganic sulfate of the outer liquid detergent may include sodium, potassium, magnesium or aluminum. In a further aspect of the invention, the outer water soluble pouch may be formed from a film including a polymer of hydrolyzed vinyl acetate and/or a copolymer of hydrolyzed vinyl acetate and a second monomer. In a further aspect of the invention, the second monomer of the outer water soluble pouch may include maleic acid, itaconic acid, methyl acrylate and/or 2-acrylamid-2 methylpropanesulfonic acid. In a further aspect of the invention, a degree of 0 hydrolysis of the outer water soluble pouch expressed as a mol percentage of vinyl acetate units converted to vinyl alcohol units may be 70 mol% to 100 mol%. In a further aspect of the invention, the film of the outer water soluble pouch may be between 50 microns and 100 microns thick. 5 A water soluble pouch according to aspects of the invention can withstand high water content in a liquid or gel detergent by adding inorganic sulfate salts into the liquid laundry detergent. The amount of added inorganic sulfate salts may be from 0.5 wt% to 15 wt%. One inorganic WO 2013/119537 PCT/US2013/024722 7 sulfate which may be added to the liquid detergent is sodium sulfate salt, which may be preferable due to its efficiency, safety and economy. The solubility of a water soluble pouch decreases by adding water into liquid detergents. Adding the salts can solve a deterioration problem of the water soluble pouch. The added inorganic sulfate function to terminating the dissolution from inside of the water soluble pouch and to retard the saponification reaction of the water soluble film. The thickness of film making up a water soluble pouch according to an aspect of the invention may be more than 50 microns to prevent leakage of the liquid laundry detergent. 3 At a thickness below 50 microns, leakage occurs. At a thickness of above 100 microns, however, the dissolution rate of the pouch in water becomes slow and the film cost is not economical. Thus, a preferable film thickness is, for example, between 50 and 100 microns, in particular between 60 microns and 90 microns. A water soluble pouch according to aspect of the invention may be made by- a hydrolyzed polymer of vinyl acetate and/or a hydrolyzed copolymer of vinyl acetate and a second monomer. A degree of hydrolysis of the film, WO 2013/119537 PCT/US2013/024722 8 expressed as a mol percentage of vinyl acetate units converted to vinyl alcohol units, may be 70 mol% to 100 mol%. The second monomer in the copolymer film may be maleic acid, itaconic acid, methyl acrylate and/or 2-acrylamid-2 methylpropanesulfonic acid When the concentration of inorganic salts in the liquid detergent is less than 0.5% wt%, pinholes may be generated in the water soluble pouch during storage. When the concentration of inorganic salts in the liquid detergent is 5 greater than 20 wt%, however,, the liquid detergent loses its stability and phase separation may occur. A maximum water content of the liquid detergent in an aspect of the invention is 60 wt%. The addition of ) inorganic salts cannot prevent generation of leakage when the liquid detergent water content exceeds 60 wt%. Likewise, the addition of inorganic salts cannot prevent the deterioration for water solubility of the pouch when the liquid detergent water content exceeds 60 wt%. 5 The surface of the water soluble pouch gradually becomes sticky after being packed with a high water content liquid detergent. This stickiness problem can be solved by packing the pouch (an inner water soluble pouch) in an outer water soluble pouch also packed with a liquid detergent.
    WO 2013/119537 PCT/US2013/024722 9 The liquid detergent in the outer water soluble pouch may contain a smaller amount of water than that in the inner water soluble pouch. The liquid detergent in the outer water soluble pouch may contain water and inorganic sulfates. Moreover, the type of liquid detergent in the outer water soluble pouch may be the same as or different from type of liquid detergent in the inner water soluble pouch. This pouch in a pouch arrangement according to an aspect of the invention can solve the induced stickiness problems occurring in water soluble pouches containing high water content liquid detergents. Other problems occurring in water soluble pouches containing high water content liquid detergents which are overcome in a detergent packet according to aspects of the invention include machinability, blocking between pouches, pin holes and breakage of a pouch. The shape of a water soluble pouch according to aspects of the invention may be a capsule, a pillow , a pyramid or any other suitable shape. 5 DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION A liquid detergent used in a detergent packet according to embodiments of the invention is generally used in house and may be any liquid detergent having the specified water WO 2013/119537 PCT/US2013/024722 10 content and inorganic sulfate. The ingredients of a liquid or gel detergent may include alkyl-ether sulphate, linear-alcohol ethoxylate, monoethanolamine, triethanolamine, ethyleneglycol, propyleneglycol, enzymes, dyestuff and/or flagrance. The viscosity of the liquid detergent depends on the selected ingredients. It is also possible to add a thickener to the liquid detergent as an ingredient to prevent a leakage of a liquid detergent. The ethyleneglycol or propyleneglycol in the liquid detergent composition may be replaced with water to reduce costs. 5 A water soluble pouch used in a detergent pack according to embodiments of the invention may be made by a thermoforming method or a vertical form-fill-seal(FFS) method. The thermoforming method for making a water soluble pouch may be as follows. First, a bottom film is thermoformed by heating and vacuuming to make a pocket and then the pocket is filled with a liquid detergent. Next, a cover film is put on the pocket and the pocket is sealed 5 with water or heat, and cut. The form-fill-seal method for making a water soluble pouch may be as follows. First, a film is folded vertically and sealed with overwrapped edges both vertically and WO 2013/119537 PCT/US2013/024722 11 horizontally by heating. A liquid detergent is filled into the folded film and the top part is sealed and cut horizontally. 3 A hydrolyzed polymer of vinyl acetate or a hydrolyzed copolymer of vinyl acetate and a second monomer film used in a detergent packet according to embodiments of the invention may contain a plasticizer. The plasticizer may include glycerol, ethylene glycol, propylene glycol and/or trimethylolpropane. The amount of plasticizer may be 5 wt% to 30 wt%. At a plasticizer content below 5 wt%, the cold resistance of the film may be lost. At a plasticizer content above 30 wt%, the ability to process film into a pouch becomes poor. A preferred plasticizer content, is for example, 10 wt% to 20 wt%. A hydrolyzed polymer of vinyl ) acetate or a hydrolyzed copolymer of vinyl acetate and a second monomer film used in a detergent packet according to embodiments of the invention may also contain one or more anti blocking agents and surfactants. The thickness of the film is very important to prevent 5 leakage of a liquid detergent from the pouch in a detergent packet according to an embodiment of the invention. In a thermoforming method, a bottom film thickness becomes thinner during stretching to form a pocket. The film thickness should be at least 50 microns. At film WO 2013/119537 PCT/US2013/024722 12 thicknesses of less than 50 microns, pinholes may be created in the thinner areas of a bottom film. A preferred film thickness for a detergent packet according to embodiments of the invention is for example, 60 microns to 100 microns. At ) film thicknesses above 100 microns, the cost becomes higher and the dissolution time in water becomes longer. The costs for such films may make them unsuitable for a commodity item such as a detergent packet which must have a reasonable price. 5 The functions of an inorganic sulfate in the liquid detergent composition in detergent packets according to embodiments of the invention include the creation of a thin layer inside of the water soluble pouch. This thin layer is water-insoluble and keeps the shape of a pouch. A pouch 0 having this thin layer can easily dissolve by contacting the pouch with a large volume of water from outside of the pouch. The inorganic sulfate also works as a water softener for the washing water after dissolving. 5 Liquid detergent components may decrease the solubility of a water soluble pouch during storage. Moreover, high water contents in a liquid detergent accelerate the decrease in solubility. An inorganic sulfate added to the liquid detergent inhibits the decreasing of water solubility.
    WO 2013/119537 PCT/US2013/024722 13 A water content of less than 15 wt% in a liquid detergent may not make the surface of pouch sticky even after long time storage. In commercial practice, the problem of the surface of the pouch becoming sticky may be solved by powdering. The powdering procedure, however, makes production of pouches more difficult. Examples: 5 Example 1: A pouch was made from a 88 mcl% hydrolyzed polyvinyl acetate (JP18, Japan Vam & Poval Co.,Ltd) film. 18 wt% of glycerol was formulated in the film. The film thickness was 90 microns. The size of the pouch was 10 cm x 15 cm. An outer package was 50 micron thick high density 0 polyethylene. Na 2
    SO
    4 was added in the liquid detergent. The results are shown in Table 1. 5 WO 2013/119537 PCT/US2013/024722 14 Table 1 Liquid detergent Liquid detergent Liquid detergent Liquid detergent (a) (b) (a) (d) gram gram gram gram Alcohol(O12) Ethoxylate 60 40 20 10 Sodium lauryl Ether Sulphate 20 5 10 5 propyleneglycol 20 0 10 0 water 11 90 80 70 Na 2
    SO
    4 0, 17 10 22 Total 111,6 162 80 107 Alcohol(012) Ethoxylate 54% 25% 25% 9% Sodium lauryl Ether Sulphate 18% 8% 15% 5% propyleneglycol 18% 0% 13% 0% water 10% 62% 38% 65% NaESO. 0,5% 10.5% 12.5% 20.6% Total 100% 100% 100% 100% Appearance of detergent Transparent Transparent Transparent Transparent Appearance of pouch No wrinkle Many wrinkles No wrinkle many wrinkles after packaging Leakage after three months storage test at ambient No leakage Leakage No leakage Leakage conditions . I I Example 2: The pouch was made from a 88 mol% hydrolyzed polyvinyl acetate (JP18, Japan Vam & Poval Co.,Ltd) film. 18 wt% of glycerol was formulated in the film. The film thickness was 90 microns. The size of the 5 pouch was 10 cm x 15 cm. An outer package was 50 micron thick high density polyethylene. K2SO4, A12(SO4)3 or MgS04 was added in the liquid detergent. The results are shown in Tables 2-1 and 2-2.
    WO 2013/119537 PCT/US2013/024722 15 Table 2-1 Liquid Liquid Liquid Liquid detergent detergent detergent detergent (e) (W (h) (i) gram gram gram gram Alcohol(012) Ethoxylate 20 20 20 20 Sodium lauryl Ether Sulphate 10 10 10 10 propyleneglycol 10 10 10 10 water 8 30 80 70 K2S04 4 0 0 19 Mg SO4 0 4 0 0 Al 2 (SO4)a 0 0 4 0 Total 52 74 74 129 Alcohol(012) Ethoxylate 88% 27% 27% 16% Sodium lauryl Ether Sulphate 19% 14% 14% 8% propyleneglycol 19% 14% 14% 8% water 15% 41% 41% 54% K2S04 7.7% 0,0% 0.0% 14.7% Mg SO 4 0.0% 5,4% 0.0% 0,0% Als(SO4) 0.0% 0,0% 5,4% 0.0% Ibtal 100% 100% 100% 100% Appearance of detergent Transparent Translucent Translucent Transparent Appearance of pouch No wrinkle No wrinkle No wrinkle No wrinkle after packaging Leakage after three months storage test at ambient No leakage No leakage No leakage No leakage conditions 5 WO 2013/119537 PCT/US2013/024722 16 Table 2-2 Liquid Liquid Liquid Liquid detergent detergent detergent detergent ( (k) (M) (n) gram gram gram gram Alcohol(C12) Ethoxylate 20 20 20 10 Sodium lauryl Ether Sulphate 10 10 10 5 propyleneglycol 10 10 10 0 water 80 30 100 70 K2S04 0.3 0 0 20 Mg SO4 0 0.8 0 0 A1 2 (S0a 0 0 12 0 Total 70.8 70.8 152 105 Alcohol(012) Ethoxylate 28% 28% 18% 10% Sodium lauryl Ether Sulphate 14% 14% 7% 5% propyleneglycol 14% 14% 7% 0% water 43% 48% 66% 67% K2SO4 0,4% 0.0% 0% 19.0% Mg S04 0.0% 0.4% 0% 0.0% Al(SOda 0.0% 0.0% 7.9% 0.0% Total 100% 100% 100% 100% Appearance of detergent Transparent Transparent Translucent Transparent ) Appearance of pouch Wrinkles Wrinkles Many wrinkles Many wrinkles after packaging Leakage after three months storage test at ambient Leakage Leakage Leakage Leakage conditions 5 Example 3: The pouch was made from a 94 mol% hydrolyzed polyvinyl acetate and maleic acid copolymer (T-350, Nippon Gohsei Co.,Ltd) film. 10 wt% of glycerol was formulated in the film. The film thickness was 60 microns. The size of the pouch was 10 cm x 15 cm. An outer package WO 2013/119537 PCT/US2013/024722 17 was 50 micron thick high density polyethylene. The results are shown in Table 3. Table 3 Liquid Liquid Liquid Liquid Liquid detergent detergent detergent detergent detergent (a) (b) (h) (j (k) No Many Appearance of pouch wrinkle wrinkles No wrinkle Wrinkles Wrinkles after packaging Leakage after three months leakage Leakage No leakage Leakage Leakage storage test at ambient conditions Example 4: The pouch was made from a 99 mol% hydrolyzed polyvinyl acetate and 2-acrylamid-2 methylpropanesulfonic acid copolymer (Ultiloc 2025, Sekisui Chemical Co.,Ltd) film. 30 wt% of trimethylolpropane was formulated in the film. The film thickness was 40 microns and 75 microns. The pouch was made by a vacuum molding method. The shape of the pouch was round and the diameter was 7 cm. The depth of the round pouch was 1.5 cm. An outer package was 50 micron thick high density polyethylene. The results are shown in Table 4.
    WO 2013/119537 PCT/US2013/024722 18 Table 4 Liquid Liquid Liquid Liquid Liquid detergent detergent detergent detergent detergent Film thickness:75 microns (a) ( b) (e) ( Many Appearance of pouch No wrinkle wrinkles No wrinkle No wrinkle No wrinkle after packaging Leakage after three months No leakage leakage No leakage No leakage No leakage storage test at ambient conditions Liquid Liquid Liquid Liquid Liquid detergent detergent detergent detergent detergent Film thickness:40 microns (a) (b) (c) (e) (0 Many Appearance of pouch No wrinkle' wrinkles No wrinkle No wrinkle No wrinkle after packaging Leakage after three months Leakage Leakage Leakage Leakage Leakage storage test at ambient conditions ) Example 5: Liquid detergent (a) and (e) were packed with the pouch used at Example 4 having a thickness of 75 microns with and without inorganic salt respectively. The pouches were stored under 40 degrees Celsius for 2 weeks. The appearances of the pouches packed without Na 2
    SO
    4 and
    K
    2
    SO
    4 were swollen and some leakage was observed. A film 5 was cut off from each pouch and mounted in a 35 mm photo flame. The film fixed to the flame was dipped into rotating water at 10 degrees Celsius in a 1 liter beaker. Dissolution time was the time from the dipping to the disappearance of dispersed films in the water. The results WO 2013/119537 PCT/US2013/024722 19 are shown in Table 5. Table 5 Liquid Detergent (a) After storage Before storage without Na2S0 4 with NazS04 Dissolution tine (see) of film 80 120 84 Liquid Detergent (e) After storage Before storage without KsSO4 with K2S04 DiBSOlutii 0Sec) offilm 80 150 90 Accordingly, while several embodiments of the present invention have been described, it is obvious that many changes and modifications may be made thereunto without departing from the spirit and scope of the invention. 5
    权利要求:
    Claims (13)
    [1] 1. A detergent packet comprising: a) a water soluble pouch formed from a film comprising at least one of: (i) a polymer of hydrolyzed vinyl acetate; and (ii) a copolymer of hydrolyzed vinyl acetate and a second monomer; and b) a liquid detergent contained within said water soluble pouch, said liquid detergent comprising: (i) between 5 wt% and 60 wt% water and (ii) between 0.5 wt% and 15 wt% inorganic sulfate.
    [2] 2. The detergent packet according to claim 1, wherein 5 a cation of said inorganic sulfate is selected from the group consisting of sodium, potassium, magnesium and aluminum.
    [3] 3. The detergent packet according to claim 1, wherein WO 2013/119537 PCT/US2013/024722 21 a cation of said inorganic sulfate comprises sodium.
    [4] 4. The detergent packet according to claim 1, wherein said second monomer is selected from the group consisting of maleic acid, itaconic acid, methyl acrylate and 2-acrylamid 2-methylpropanesulfonic acid.
    [5] 5. The detergent packet according to claim 1, wherein a degree of hydrolysis of said film expressed as a mol percentage of vinyl acetate units converted to vinyl alcohol units comprises 70 mol% to 100 mol%.
    [6] 6. The detergent packet according to claim 1, wherein a thickness of said film is between 50 microns and 100 microns.
    [7] 7. The detergent packet according to claim 1, further comprising an outer water soluble pouch packed with both said water soluble pouch and an outer liquid detergent contained within said outer water soluble pouch, said outer liquid detergent comprising: i) less than 15 wt% of water; and ii) less than 10 wt% of inorganic sulfate. WO 2013/119537 PCT/US2013/024722 22
    [8] 8. The detergent packet according to claim 7, wherein a cation of said inorganic sulfate of said outer liquid detergent is selected from the group consisting of sodium, potassium, magnesium and aluminum.
    [9] 9. The detergent packet according to claim 7, wherein a cation of said inorganic sulfate of said outer liquid detergent comprises sodium.
    [10] 10. The detergent packet according to claim 7, wherein 5 said outer water soluble pouch is formed from a film comprising at least one of: (i) a polymer of hydrolyzed vinyl acetate; and D (ii) a copolymer of hydrolyzed vinyl acetate and a second monomer.
    [11] 11. The detergent packet according to claim 10, wherein said second monomer of said outer water soluble pouch is selected from the group consisting of maleic acid, 5 itaconic acid, methyl acrylate and 2-acrylamid-2 methylpropanesulfonic acid.
    [12] 12. The detergent packet according to claim 10, wherein a degree of hydrolysis of said outer water soluble WO 2013/119537 PCT/US2013/024722 23 pouch expressed as a mol percentage of vinyl acetate units converted to vinyl alcohol units comprises 70 mol% to 100 mol%.
    [13] 13. The detergent packet according to claim 10, wherein a thickness of said film of said outer water soluble pouch is between 50 microns and 100 microns. 5 0 5
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    法律状态:
    2014-08-28| TH| Corrigenda|Free format text: IN VOL 28 , NO 28 , PAGE(S) 3773 UNDER THE HEADING PCT APPLICATIONS THAT HAVE ENTERED THE NATIONAL PHASE - NAME INDEX UNDER THE NAME AICELLO CHEMICAL CO., LTD., APPLICATION NO.2013217544, UNDER INID (71) CORRECT THE APPLICANT NAME TO AICELLO CORPORATION |
    2016-02-04| MK1| Application lapsed section 142(2)(a) - no request for examination in relevant period|
    优先权:
    申请号 | 申请日 | 专利标题
    US201261633357P| true| 2012-02-09|2012-02-09||
    US61/633,357||2012-02-09||
    US13/752,609|US8802612B2|2012-02-09|2013-01-29|Detergent packet|
    US13/752,609||2013-01-29||
    PCT/US2013/024722|WO2013119537A1|2012-02-09|2013-02-05|Detergent packet|
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