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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
• • 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
  • C11D10/00—Compositions of detergents, not provided for by one single preceding group
  • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
• • 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
  • C11D3/046—Salts
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents

Definitions

• a detergent portion unit is naturally determined not only by process-related aspects but also by the ability to provide a product that meets consumer needs.
• a key means of communicating product quality and promise is its appearance, including the shape and color of the portion unit. This is particularly true for water-soluble film pouches, whose soluble films are generally transparent and reveal the solid or liquid detergent they contain. While colored, i.e., non-white, liquid detergents can be easily obtained by adding appropriate dyes, the provision of white liquid detergents is more challenging because the opacifiers previously used in their production are increasingly being viewed critically from an ecological perspective. against this background, the provision of an ecologically acceptable opacifier is a relevant development goal in the field of liquid detergents and laundry detergents.
• the production of liquid detergents is usually carried out using a sequential process, during which the detergent ingredients are mixed together in a chronological sequence.
• the respective intermediate products and the final product are mixed with energy input.
• the final product is characterized not only by the most homogeneous distribution of active ingredients, but also by rheological properties suitable for handling by the consumer.
• the type and timing of the adjustment of these rheological properties during the production process influences the efficiency of the process as well as the final product quality, since the rheological properties of the intermediate and final products are closely related to the Homogenization during production requires energy input and mechanical stress on the intermediate and final products and their components.
• the application was based on the objective of providing an efficient process for producing visually appealing, concentrated liquid detergents.
• the resulting detergents should be particularly suitable for packaging in water-soluble foil pouches.
• a salt of a divalent cation is introduced into the liquid composition. This is preferably done via a secondary line through which the salt is continuously introduced into the main line.
• the inorganic salt of a divalent cation is introduced into the liquid composition in step b) in the form of an aqueous solution, preferably an alkaline aqueous solution.
• the addition of the salt of a divalent cation results in the development of a cloudy white appearance and a sufficiently high and stable viscosity, which is advantageous for further processing and subsequent use.
• the development of both physical properties of the liquid composition is promoted by thorough mixing of all ingredients. It is therefore further preferred to provide the outlet opening of the secondary line, through which the solution of the inorganic salt of a divalent cation is introduced into the main line, within the effective range of a mixing device installed within the main line.
• the mixing device can be a static or dynamic mixer.
• the inorganic salt of a divalent cation in step b) is selected from the group of salts of divalent metallic cations, in particular magnesium and calcium salts, preferably from the group consisting of magnesium chloride, magnesium sulfate, calcium chloride, and calcium sulfate, in particular from the group consisting of magnesium chloride and calcium chloride, most preferably calcium chloride.
• the organic salt of a divalent cation is preferably introduced into the liquid composition in step b) in the form of a dispersion, particularly preferably in the form of an alkaline aqueous dispersion.
• the dispersion of the organic salt of a divalent cation is preferably introduced into the liquid composition continuously via a branch line into the main line.
• the outlet opening of the branch line is preferably located within the effective range of a mixing device installed within the main line.
• the inorganic salt of a divalent cation and the organic salt of a divalent cation may be introduced into the liquid composition in step b) together or separately.
• the molar ratio of the divalent cation introduced in step b) in the form of an aqueous solution of an inorganic salt of a divalent cation to the divalent cation introduced in step b) in the form of a dispersion of an organic salt of a divalent cation is 1:10 to 10:1, preferably 1:6 to 6:1 and in particular 1:3 to 3:1.
• a first essential component of the liquid, surfactant-containing detergent and the first liquid composition is the surfactant, which is contained in the liquid, surfactant-containing detergent at 20 to 80 wt.%, preferably at 30 to 75 wt.% and in particular at 40 to 70 wt.%.
• the group of surfactants includes nonionic, anionic, cationic, and amphoteric surfactants.
• the compositions according to the invention can comprise one or more of the aforementioned surfactants.
• Particularly preferred compositions contain at least one anionic surfactant as the surfactant.
• alkene and hydroxyalkanesulfonates, and disulfonates such as those obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• Preferred alk(en)yl sulfates are the salts of the sulfuric acid semiesters of fatty alcohols with 12 to 18 carbon atoms, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or of oxo alcohols with 10 to 20 carbon atoms, and those semiesters of secondary alcohols with these chain lengths.
• alkyl sulfates with 12 to 16 carbon atoms and alkyl sulfates with 12 to 15 carbon atoms, as well as alkyl sulfates with 14 and 15 carbon atoms are preferred.
• 2,3-Alkyl sulfates are also suitable anionic surfactants.
• AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
• the index n in formula (A-1) is an integer from 1 to 50, preferably from 1 to 20, and in particular from 2 to 10. n is most preferably 2, 3, 4, 5, 6, 7, or 8.
• X is a monovalent cation or the nth part of an n-valent cation, preferred being the alkali metal ions, including Na + or K + , where Na + is highly preferred. Further cations X+ can be selected from NH 4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
• the stated degree of ethoxylation represents a statistical mean, which can be a whole or fractional number for a specific product.
• the stated degrees of alkoxylation represent statistical mean, which can be a whole or fractional number for a specific product.
• Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• the composition contains at least one anionic surfactant of the formula (A-3), in the R' and R" are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y + represents a monovalent cation or the nth part of an n-valent cation (in particular Na + ).
• liquid surfactant-containing detergents preferably produced by the process according to the invention contain as surfactant at least one anionic surfactant, preferably at least one anionic surfactant from the group consisting of C 8-18 alkylbenzenesulfonates, C 8-18 olefinsulfonates, C 12-18 alkanesulfonates, C 8-18 estersulfonates, C 8-18 alkyl sulfates, C 8-18 alkenyl sulfates, fatty alcohol ether sulfates, in particular at least one anionic surfactant from the group of C 8-18 alkylbenzenesulfonates.
• anionic surfactant preferably at least one anionic surfactant from the group consisting of C 8-18 alkylbenzenesulfonates, C 8-18 olefinsulfonates, C 12-18 alkanesulfonates, C 8-18 estersulfonates, C 8-18 alkyl sulfates, C 8-18 alkenyl
• the liquid, surfactant-containing detergent and the first liquid composition contain fatty acid.
• the liquid, surfactant-containing detergent contains 4 to 12 wt. %, preferably 6 to 10 wt. %, of fatty acid, based on its total weight.
• This weight fraction refers to the weight fraction of the liquid, surfactant-containing detergent produced by the process and includes both the fatty acids provided in step a), i.e., the fatty acid-containing organic salts of a divalent cation optionally introduced in step a), and any fatty acids added at a different time.
• the fatty acids can be in acid form or in the form of their salts.
• Preferred fatty acids are selected from the group caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and mixtures thereof.
• the detergent produced according to the invention contains a solvent as a fourth essential component.
• the proportion of the solvent in the total weight of the detergent preparation is preferably 12 to 32 wt.% and in particular 15 to 30 wt.%.
• the liquid, surfactant-containing detergent contains, based on its total weight, 7 to 20 wt.%, preferably 10 to 18 wt.%, of organic solvent.
• composition of some of the preferred liquid detergents containing surfactants can be found in the following tables (data in wt.% based on the total weight of the detergent unless otherwise stated).
• formula 1 Formula 2
• Formula 3 Formula 4
• Surfactant 20 to 80 30 to 75 30 to 75 40 to 70 fatty acid 2 to 15 4 to 12 4 to 12 6 to 10 inorganic and organic salt of a divalent cation 0.3 to 8 0.3 to 8 0.4 to 6 0.5 to 4 solvent 8 to 35 12 to 32 12 to 32 15 to 30 Misc to 100 to 100 to 100 to 100 Formula 6
• Formula 7 Formula 8 Formula 9
• Formula 12 Formula 13 Formula 14
• Preferred monovalent cations are selected from the group of monovalent metallic cations.
• Preferred salts of monovalent cations due to their availability and low cost, are selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, most preferably from the group consisting of sodium chloride.
• the liquid, surfactant-containing detergent contains, based on its total weight, preferably 12 to 30 wt.%, preferably 15 to 25 wt.% non-ionic surfactant.
• composition of some other particularly preferred liquid detergents can be found in the following tables (data in wt.% based on the total weight of the detergent unless otherwise stated).
• Formula 1b Formula 2b Formula 3b Formula 4b Total surfactant 20 to 80 30 to 75 30 to 75 40 to 70
• Formula 7b Formula 8b Formula 9b
• the liquid, surfactant-containing detergent preferably has a viscosity (21°C, Brookfield viscometer type DV-II. Pro, spindle no. 2, 20 rpm) above 400 mPas, preferably above 1000 mPas.
• the liquid, surfactant-containing detergent is preferably in the form of a structured system.
• the main types of structured systems used in practice are based on dispersed lamellar, spherulitic, and weakly lamellar phases.
• the liquid, surfactant-containing detergent preferably contains a spherulitic phase.
• Spherulitic phases comprise spherical bodies, commonly referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells.
• the spherulites are dispersed in an aqueous phase in the manner of a classic emulsion and interact to form a structured system.
• Preferred liquid detergents comprise lamellar spherulites, preferably with a maximum diameter of 10 to 100 ⁇ m, more preferably with a maximum diameter of 25 to 50 ⁇ m.
• the liquid, surfactant-containing detergent preferably has a yield point (TA Instruments rotational rheometer AR 2000, 20°C, cone plate with 40 mm diameter, 2° cone angle) above 0.1 Pa, preferably above 0.3 Pa.
• NTU Nephelometric Turbidity Unit
• the turbidimeter type HACH Turbidimeter 2100Q from Hach Company, Loveland, Colorado (USA) is used in conjunction with the calibration substances StablCal Solution HACH (20 NTU), StablCal Solution HACH (100 NTU) and StablCal Solution HACH (800 NTU), all of which can also be ordered from the Hach Company.
• StablCal Solution HACH (20 NTU), StablCal Solution HACH (100 NTU) and StablCal Solution HACH (800 NTU) all of which can also be ordered from the Hach Company.
• the measurement is carried out in a 10 ml measuring cuvette with a cap filled with the composition to be analyzed, and the measurement is carried out at 20 °C.
• molded bodies exhibit a perceptible turbidity within the meaning of the invention, visible to the naked eye.
• the turbidity (HACH Turbidimeter 2100Q, 20°C, 10 ml cuvette) of the liquid, surfactant-containing detergent is preferably above 60 NTU, more preferably above 100 NTU, and especially above 400 NTU.
• the liquid, surfactant-containing detergent produced according to the invention may be free of enzymes and/or fragrances. These ingredients are not included, in particular, because they can adversely affect the turbidity and thus the appearance of the formulation.
• liquid detergents which, based on their total weight, contain less than 2% by weight, less than 1% by weight, preferably less than 0.1% by weight and in particular no enzyme preparation are preferred.
• liquid detergents which, based on their total weight, contain less than 2% by weight, preferably less than 1% by weight, particularly preferably less than 0.1% by weight and in particular no fragrance.
• the liquid detergent contains at least one optical brightener, preferably a stilbene-type optical brightener. This is present in the liquid detergent, based on its total weight, in an amount above 0 wt. %, but preferably in an amount below 1 wt. %, particularly preferably in an amount below 0.6 wt. %.
• Stilbene-type brighteners for use in the liquid detergent are preferably selected from the group of triazinyl derivatives of 4,4'-diamino-2,2'-stilbenesulfonic acid.
• DAS1 diphenyl-4-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino]stilbene-2,2-disulfonate
• DSBP diphenyl-4-bis(2-sulfostyryl)biphenyl
• the liquid, surfactant-containing detergent may comprise at least one red, blue, or violet dye.
• This dye is present in the liquid detergent, based on its total weight, in an amount above 0 wt.%, but preferably in an amount below 0.1 wt.%, particularly preferably below 0.02 wt.%, for example, between 0.001 and 0.01 wt.%.
• Such a dye serves, for example, the purpose of masking a possible yellowish tint of the preparation.
• the dye is selected from the group of low-molecular-weight dyes.
• Suitable low-molecular-weight dyes include dyes that fall into the color index (CI) classifications Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Red, and Basic Violet.
• the dye is selected from the group of polymeric dyes.
• Suitable polymeric dyes include conjugated chromogens (dye-polymer conjugates) and polymers in whose backbone chromogens are polymerized.
• These polymeric dyes include, for example, dyes commercially available under the name Liquitint® , such as Liquitint® Violet CT, CMC-conjugated CI Reactive Blue 19 with the product name AZO-CM-Cellulose, alkoxylated polymeric triphenylmethane dyes, or alkoxylated polymeric thiphene dyes.
• a dye-clay conjugate is used as the dye.
• the group of these dyes includes, among others, conjugates of smectite clay or montmorillonite clay or hectorite clay or saponite clay with a cationic/basic dye from the group CI Basic Yellow 1 to 108, CI Basic Orange 1 to 69, CI Basic Red 1 to 118, CI Basic Violet 1 to 51, CI Basic Blue 1 to 164, CI Basic Green 1 to 14, CI Basic Brown 1 to 23, CI Basic Black 1 to 11.
• Suitable photobleaching agents include aluminum phthalocyaninesulfonate or zinc phthalocyaninesulfonate, or mixtures thereof, as commercially available under the name Tinolux® .
• liquid surfactant-containing detergent is enclosed in a water-soluble film following step c) to form a detergent portion unit.
• water-soluble film in a deep-drawing apparatus and to combine it with the liquid detergent to form a detergent portion unit.
• Water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
• polyvinyl alcohol and polyvinyl alcohol copolymers generally involves the hydrolysis of intermediate polyvinyl acetate.
• Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.
• Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester.
• such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, or mixtures thereof; among the esters, C 1-4 alkyl esters or hydroxyalkyl esters are preferred.
• AMPS 2-acrylamido-2-methyl-1-propanesulfonic acid
• Other suitable monomers include ethylenically unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.
• the water-soluble films may contain additional active ingredients or fillers as well as plasticizers and/or solvents, especially water.
• the group of other active ingredients includes, for example, materials that protect the ingredients of preparation (A) enclosed in the film material from decomposition or deactivation by light exposure.
• Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable for this purpose.
• the detergent portion unit has at least four receiving chambers which are surrounded by a water-soluble film, wherein one receiving chamber is filled with the liquid surfactant-containing detergent and the other three receiving chambers are filled separately from one another with a second, a third and a fourth colored detergent which is different from one another and from the first liquid surfactant-containing detergent.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)

Priority Applications (3)

Applications Claiming Priority (1)

Publications (2)

Family

ID=77910561

Family Applications (1)

Country Status (3)

Families Citing this family (1)

Family Cites Families (3)

• 2021
  • 2021-09-22 EP EP21198252.5A patent/EP4155374B1/de active Active
  • 2021-09-22 PL PL21198252.5T patent/PL4155374T3/pl unknown
• 2022
  • 2022-08-15 WO PCT/EP2022/072753 patent/WO2023046369A1/de not_active Ceased

Also Published As

Similar Documents

Legal Events