EP1434848A1 - Portionierte wasch-, spül- oder reinigungsmittel in flexiblen wasserlöslichen behältern - Google Patents
Portionierte wasch-, spül- oder reinigungsmittel in flexiblen wasserlöslichen behälternInfo
- Publication number
- EP1434848A1 EP1434848A1 EP02800557A EP02800557A EP1434848A1 EP 1434848 A1 EP1434848 A1 EP 1434848A1 EP 02800557 A EP02800557 A EP 02800557A EP 02800557 A EP02800557 A EP 02800557A EP 1434848 A1 EP1434848 A1 EP 1434848A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- rinsing
- cleaning agent
- force
- agent according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
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- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
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- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
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- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
Definitions
- the present invention relates to portioned agents, in particular a portioned washing, rinsing or cleaning agent in a coating made of water-soluble materials.
- Such water-soluble packaging includes, for example, foil bags made of water-soluble polymers (so-called pouches) or - in particular in the field of pharmacy - gelatin capsules.
- the pouches have the disadvantage that the foil bags are quite sensitive to mechanical influences. During transport or handling, this can lead to undesired product leakage if the film is damaged due to carelessness. Simply touching it with pointed or cracked fingernails can damage it and lead to consumer frustration, which is undesirable especially in the area of household funds.
- Stable containers are subject to the disadvantage that they are brittle, stress cracks or fractures when subjected to a shock-like load (impact or drop) or irreversibly deform when subjected to force.
- thermoformed water-soluble containers for agrochemicals such as crop protection agents are disclosed:
- a non-planar sheet of water-dispersible material is filled and with a "lid” made of water-dispersible material through a circumferential sealing seam made of water-soluble or water-dispersible material locked.
- WO01 / 36290 discloses injection molded hollow bodies made of water-soluble polymers for detergents or cleaning agents, pharmaceuticals or fertilizers and detergents, rinsing agents or cleaning agents which are contained in such hollow bodies.
- the "containers” disclosed here are not flexible, but rigid and have the disadvantages described above.
- the object of the present invention was to provide a form of supply for all kinds of preparations, in particular for detergents, dishwashing detergents or cleaning agents, which saves the consumer the troublesome dosing process, but is free from the disadvantages mentioned above.
- the present invention therefore relates to a portioned composition
- a portioned composition comprising a preparation which is surrounded by a covering; where the unfilled envelope can be deformed along a path S T by a force F> 0 N and ⁇ 500 N and returns to its original shape after the application of the force no longer applies and / or a return speed v> 0 mm / min and ⁇ after the application of the deformation force 1000 mm / min.
- the portions according to the invention are particularly suitable as washing, rinsing or cleaning agents, so that preferred in the Preparations contained in preparations are active in washing, rinsing or cleaning.
- the unfilled coating of the portioned agents according to the invention can at least partially be reversibly deformed by the action of force and has a certain restoring speed after the force has ceased to apply.
- High restoring speeds (for example> 2000 mm / min) are achieved by rigid bodies which "spring back" into the initial shape, provided they do not remain in the pressed-in state. This behavior of "jumping back” is undesirable, since this can result in stress cracks in the casing, which allow product to escape.
- it is necessary to ensure a low restoring speed of the casing on the other hand, the casing should be able to be deformed without breaking or cracking.
- the force F is dependent on the depth of indentation, since the covering opposes increasing resistance to the penetrating body.
- the sheath can be deformed at all with a force of 500 N or less.
- the details relating to forces relate to the penetration depths of a round rod with an 8 mm diameter of 10, preferably 15, particularly preferably 20 and in particular 22 mm.
- the distance s-t is defined, not only the force but also the deformation work can be exactly determined.
- the envelopes according to the invention should be able to be at least partially reversibly deformed (in the case of irreversible deformation, no restoring speed would be measurable).
- the deformation is completely reversible, ie it is according to the invention portioned agents are preferred, in which the unfilled casing returns to its original shape after the application of force.
- the unfilled envelope can preferably be reversibly deformed even by lower forces.
- Portioned agents according to the invention are preferred here, in which the unfilled casing by a force F 100 100 N, preferably by a force F 3 60 60 N, particularly preferably by a force F 4 40 40 N and in particular by a force F 5 20 20 N is deformable.
- the restoring speed with which the unfilled casing approaches its original shape again after the application of the force is preferably also lower.
- Particularly preferred portioned agents are characterized in that the unfilled casing has a restoring speed v 500 500 mm / min, preferably v 100 100 mm / min, particularly preferably v 50 50 mm / min, further preferably v ⁇ 10 mm / min, after the application of the force and in particular has v ⁇ 1 mm / min.
- the distance S T is defined, not only the force but also the work of deformation can be exactly determined.
- the deformation work in the case of unfilled envelopes of portioned agents according to the invention is below certain values.
- rigid bodies require deformation work of at least 5 to 6 Nm
- portioned washing, rinsing or cleaning agents according to the invention are preferred, in which a deformation work w 5 5 Nm, preferably w 1 1 Nm, particularly preferably w 0 0, for the deformation of the unfilled casing , 5 Nm, more preferably w ⁇ 0.3 Nm and in particular w ⁇ 0.25 Nm is required.
- the unfilled casing can preferably be "turned inside out", ie it can be pushed through in such a way that the original inside becomes the outside and vide versa.
- This flexibility leads to the particularly increased resistance to leaks under pressure in comparison to rigid molded bodies (avoidance of stress cracks or breakage).
- a force F r > 0 N and 500 500 N preferably by a force F 2 ⁇ 100 N, particularly preferably by a force F 3 ⁇ 60 N and in particular by a force F 4 ⁇ 20 N after the loss of force returns to its original shape and / or
- Another parameter for characterizing particularly preferred portioned agents according to the invention is the crush resistance. This can be determined in the form of a force-displacement diagram using commercially available tablet testing devices. A Zwick Type 1425 universal testing machine was used for the purposes of the present invention.
- the compression resistance is determined in accordance with DIN 55526 Part 1 by the plastic container standing upright between the plates of a pressure test device is set and compressed, the compressive force and the plate path being recorded until the required compression resistance and plate path are reached or failure occurs due to critical deformation or leakage of the container.
- the printing press was set to an upsetting speed of 10 mm / min. The test process was then started.
- the force [N] exerted on the portion at a penetration depth of 22 mm was printed out on the connected printer.
- the crush resistance is given in N.
- the agents according to the invention are notable for increased flexibility compared to rigid, rigid hollow bodies.
- the flexibility and elasticity are expressed in particular in the possibility of reproducible multiple determination in the mechanical tests described, in particular in the determination of the resetting speed.
- the filled and / or unfilled casing at n times with n> 2, for example 3 or 4, preferably 8, 10, 15 or 20, repetition of the respective measurement of the restoring speed, the deformation work or of the crush resistance on an individual to be tested, a percentage standard deviation, based on the mean measured value, of less than 100%, preferably less than 50%, more preferably less than 40%, particularly preferably less than 30%, in particular less than 20%, in particular preferably less than 10%, extremely preferably less than 8%, for example less than 5%, advantageously less than 3%, for example less than 2% and extremely preferably less than 1%.
- the agents according to the invention can be made up universally for all compositions which can be packaged in water-soluble envelopes. Areas of application are, for example, the production of portions from agrochemicals (fertilizers and pesticides, etc.), foods ("degradable” beverage packaging, packaged food and nutritional additives, etc.), Animal feed, pharmaceuticals, dyes and fragrances, adhesives, cosmetics, or other industrial areas.
- agrochemicals fertilizers and pesticides, etc.
- foods degradable beverage packaging, packaged food and nutritional additives, etc.
- Animal feed pharmaceuticals, dyes and fragrances, adhesives, cosmetics, or other industrial areas.
- the agents according to the invention particularly preferably have the composition of a washing, rinsing or cleaning agent.
- the information below relates to this particularly preferred form of the present invention, but also applies in a completely analogous manner to other industrial fields of application.
- the wrapping of the portioned washing, rinsing or cleaning agents according to the invention is flexible, but nevertheless dimensionally stable.
- the term “dimensionally stable wrapping” is understood to mean that the shaped articles containing the detergent, cleaning agent or dishwashing agent portions have an inherent dimensional stability which enables them to be carried out under the usual conditions of manufacture, storage, transport and handling the consumer has a structure which is stable against breakage and / or pressure and does not collapse and which does not change over a long period of time even under the conditions mentioned.
- the pressure resistance of the dimensionally stable casing according to the invention is measured in such a way that empty casings, optionally provided with compartmentalizing devices, are sealed with foils or lids and an internally applied, constantly increasing vacuum is applied to these hollow articles at room temperature until the hollow article closes begins to collapse.
- the intrinsic dimensional stability of the hollow bodies should particularly preferably be such that, in the case of such vacuum collapse tests of hollow bodies which are not filled and optionally provided with compartmentalization devices, collapse does not begin before a vacuum of 900 mbar, preferably 750 mbar and in particular 500 mbar is reached ,
- the hollow bodies used according to the invention differ fundamentally from foils or so-called "pouches", as are also used to provide detergents, cleaning agents or dishwashing detergents.
- the dimensionally stable hollow bodies according to the invention also differ from coatings (subsequently applied to moldings):
- the hollow bodies according to the invention represent an independent, self-supporting covering which, as a rule, is filled with one or more washing-active, rinsing-active or cleaning-active component (s) exists and is then filled.
- coatings are applied to existing moldings (e.g. compacts, granules, extrudates, etc.) and then dried or cured; only then do they form an envelope surrounding the molded body.
- the coatings have a stability in which collapse does not begin until a vacuum of 250 mbar, preferably 100 mbar and in particular 20 mbar, is reached.
- Preferred detergent, dishwashing or cleaning agents according to the invention are further characterized in that the wall thickness of the casing is 100 to 5000 ⁇ m, preferably 200 to 3000 ⁇ m, particularly preferably 300 to 2000 ⁇ m and in particular 500 to 1500 ⁇ m.
- MFI flow index
- Polyvinyl alcohol types which are particularly suitable for injection molding in the context of the present invention are low-viscosity and have, for example, MFI values of 26-30 (at 190 ° C., 2.16 kg load, PVA Texas Polymers, Vinex 2019).
- Polyvinyl alcohol types particularly suitable for blow molding in the context of the present invention are medium to highly viscous and have, for example, MFI values of 6-8 (at 230 ° C., 2.16 kg load, PVA Texas Polymers, Vinex 2034/2144) or 9-11 (at 190 ° C, 10 kg load, PVA Texas Polymers, Vinex 5030).
- polymers are suitable as materials for the covering, portioned washing, rinsing or cleaning agents according to the invention being preferred, in which the covering comprises one or more materials from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, Includes polyester and polyether and mixtures thereof.
- the use of water-soluble polymers as the material for the covering is particularly preferred.
- portioned washing, rinsing or cleaning agents according to the invention have proven themselves, which are characterized in that the coating comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone (PVP), in particular polyvinylpyrrolidone with a molecular weight of 2,500 to 750,000 g / mol, polyethylene oxide, gelatin, cellulose, polyacrylamide, in particular polyacrylamide with a molecular weight of 5,000 to 5,000,000 g / mol, polyethyloxazoline and polymethyloxazoline with a molecular weight of 5,000 to 100,000 g / mol and their derivatives and their mixtures, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
- PVAL polyvinyl alcohol
- PVP polyvinylpyrrolidone
- PVP polyvinylpyrrolidone
- PVP polyvinylpyr
- polyvinyl alcohols are particularly preferred as materials for the covering.
- Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
- polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
- the manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
- polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
- Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable.
- the water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
- the polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- Portioned washing, rinsing or cleaning agents preferred in the context of the present invention are characterized in that the covering comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%.
- Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the covering, with portioned washing, rinsing or cleaning agents according to the invention being preferred, in which the covering comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmor 1 , preferably from 11,000 to 90,000 gmor 1 , particularly preferably from 12,000 to 80,000 gmol '1 and in particular from 13,000 to 70,000 gmol ' 1 .
- the water-soluble thermoplastic preferably the polyvinyl alcohol
- the degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.
- the polyvinyl alcohols described above are commercially available (absorbed into the Kuraray Specialties Europe KSE), for example under the trade name Mowiol ® ex Clariant.
- polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5- 88, Mowiol ® 8-88, and in particular blends respectively compounds such as L648, L734, Mowiflex LPTC 221 ex Clariant / KSE and the compounds from Texas Polymers, such as Vinex 2034.
- ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
- ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
- Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK ).
- acrylic acid-containing polymers such as. B. copolymers, terpolymers or tetrapolymers which contain at least 20% acrylic acid and have a molecular weight of 5,000 to 500,000 g / mol; as comonomers, particularly preferred are acrylate such as ethyl acrylate, methyl acrylate, hydroxy ethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and salts and esters thereof such as methyl methacrylate, ethyl methacrylate, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), methacrylate amidopropyl trimethyl ammonium chloride (MAPTAC ).
- TMAEMC Trimethylammoniummethylmethacrylatchlorid
- MATAC methacrylate amidopropyl trimethyl ammonium chloride
- Other monomers such as acrylamide, St
- Polyalkylene oxides preferably polyethylene oxides with molecular weights of 600 to 100,000 g / mol and their derivatives modified by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and their salts and their esters, acrylamide, styrene, styrene sulfonate and vinyl pyrrolidone (example: Poly (ethylene glycol - graft - vinyl acetate) are also particularly suitable for the production of the casings according to the invention .
- the proportion of polyglycol should be 5 to 100% by weight, the graft fraction should be 0 to 95% by weight; the latter can consist of one or consist of several monomers, a graft fraction of 5 to 70% by weight being particularly preferred, the water solubility decreasing with the graft fraction.
- polystyrene sulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts (meth) acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone; the comonomer content should be 0 to 80 mol% and the molecular weight should be in the range of 5,000 to 500,000 g / mol.
- comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate
- Polyurethanes in particular the reaction products of diisocyanates (e.g. TMXDI) with polyalkylene glycols, in particular polyethylene glycols with a molecular weight of 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol are also suitable for producing the coatings according to the invention.
- diisocyanates e.g. TMXDI
- polyalkylene glycols in particular polyethylene glycols with a molecular weight of 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol are also suitable for producing the coatings according to the invention.
- Polyesters with molecular weights of 4,000 to 100,000 g / mol based on dicarboxylic acids (e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid, etc.) and diols (e.g. polyethylene glycols, for example with molecular weights of 200 to 35,000 g / mol) are also advantageously used for the production of casings according to the invention, such as cellulose ether / ester, for. B.
- dicarboxylic acids e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid, etc
- graft polymers which are obtainable by radical polymerization of vinyl esters of aliphatic C1-C24 carboxylic acids in the presence of polyethers with an average molecular weight of at least 300 (number average), for example by the radical polymerization of vinyl acetate in the presence of polyethylene glycols with a molecular weight of 500 to 100,000, preferably a molecular weight of 1,000 to 50,000, and hydrolysis of 20 to 100 mol% of the vinyl acetate units of the graft polymers.
- the envelopes of the portioned washing, rinsing or cleaning agents according to the invention can be produced by conventional methods of thermoforming polymers, deep-drawing, so-called rotary die processes, blow molding (blow extrusion) and injection molding being of particular importance.
- thermoforming polymers deep-drawing, so-called rotary die processes, blow molding (blow extrusion) and injection molding being of particular importance.
- blow molding blow extrusion
- injection molding injection molding
- the hollow bodies can contain plasticizing agents. This can be particularly advantageous if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate have been selected as the material for the hollow bodies.
- the proportion of plasticizers is usually up to 15% by weight, values between 5 and 10% by weight being preferred.
- Glycerin, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proven particularly useful as plasticizers.
- demolding additives are important auxiliary substances that can be used in the injection molding compounds. From the groups of fatty substances and the fine particle substances have this as part of the present invention, in particular stearic acid and / or stearates and pyrogenic silica (Aerosil ®) as well as talc proven.
- the proportion of the demolding additives (based on the polymer) is usually up to 5% by weight, values between 0.5 and 2.5% by weight being preferred.
- fatty substances are understood to mean liquid to solid substances from the group of fatty alcohols, fatty acids and fatty acid derivatives, in particular the fatty acid esters, at normal temperature (20 ° C.).
- reaction products of fatty alcohols with alkylene oxides are among the surfactants (see above) and are not fatty substances in the sense of the invention.
- fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines etc. can preferably be used as fatty substances.
- the fatty alcohols which can be obtained from native fatty and oil alcohols are, for example, 1-hexanol (capro alcohol), 1-heptanol (oenant alcohol), 1-octanol
- Guerbet alcohols and oxo alcohols, for example C 13, are also according to the invention.
- 15 oxo alcohols or mixtures of alcohols with C 12 C 12 - ⁇ - - ⁇ alcohols easily be used as fatty substances.
- alcohol mixtures for example those such as the C 16 produced by Ziegler ethylene polymerization.
- 18 alcohols for example those such as the C 16 produced by Ziegler ethylene polymerization.
- Specific examples of alcohols which can be used as component b) are the alcohols already mentioned, and lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.
- C 10 Entformungszu accounts -3o-fatty alcohols preferably C12 - 24 - fatty alcohols, with particular preference from 1-hexadecanol, 1-octadecanol, cis-9-octadecene-1-ol, all-cis-9,12-Octadecadien- 1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.
- Fatty acids can also be used as mold release agents. Technically, most of these are obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage.
- Carboxylic acids which can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
- Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (tricarboxylic acid) and melotic acid (cerotic acid) 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoi
- Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C 8, wt .-% C 1 6 0 48 wt .-% C 12 18 wt .-% C14, 10 wt .-% Cie, 2 wt .-% C 8 , 8 wt .-% d 8 -, 1 wt .-% C 18 -), palm kernel oil fatty acid (approx.
- esters of fatty acids with alkanols, diols or polyols can be used as fatty acid esters, fatty acid polyol esters being preferred.
- Suitable fatty acid polyol esters are monoesters and diesters of fatty acids with certain polyols.
- the fatty acids which are esterified with the polyols are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, preference being given to using the technically obtained mixtures of the fatty acids, for example those of coconut, Acid mixtures derived from palm kernel or taig fat.
- acids or mixtures of acids with 16 to 18 carbon atoms are suitable for esterification with the polyhydric alcohols.
- sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols are suitable as polyols which are esterified with the abovementioned fatty acids.
- glycerol is used as the polyol which is esterified with fatty acid (s).
- fatty substances from the group of fatty alcohols and fatty acid glycerides are preferred as mold release additives.
- Particularly preferred mold release agents are fatty substances from the group of fatty alcohols and fatty acid monoglycerides. Examples of such preferred fatty substances are glycerol monostearic acid esters or glycerol monopalmitic acid esters.
- antioxidants In order to prevent undesirable changes in the injection molding compounds caused by the action of oxygen and other oxidative processes, these can contain antioxidants.
- This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
- Another object of the present application is a blow extrusion process for the production of casings according to the invention.
- blow molding residues may occur in the processes according to the invention, which, depending on the shape and configuration of the blow molded articles formed in one or more pieces, may turn out to be different in height.
- the blow mold residues are generally residues of the preform, which were not used for blow molding the hollow body and were separated from the preform by closing the blow molded hollow body and / or punching out and / or cutting out the blow molded body. It has been found that the blow mold residues can be recycled and can be returned to the process for producing the blow molded articles. Such blow mold residues are preferably recycled and thus returned to the original process.
- blow molding residues consisting of water-soluble polymer thermoplastics are collected, if necessary collected, and added to the original blow molding process.
- the blow molding residues can be charged with additional components, for example those which have been lost to the original blow molding composition due to the thermal treatment and are now missing the polymer composition of the blow molding residues, before they are returned to the manufacturing process of the blow molding bodies.
- Additional impact components are, for example, water or plasticizer components.
- the blow mold residues, which may be additionally acted upon, are preferably mixed with the blow molding compound originally used, preferably with the fresh polymer (compound) granulate even before melting, and then fed to the process.
- blow mold residues to the comminution station and / or to the mixer, in which any crushed blow mold residues are mixed with the original blow molding compound, which is present, for example, in the form of polymer granules or compounds, and / or to the extruder, by means of which the blow mold residue and the original blow molding compound are used again
- Preforms can be formed using devices familiar to those skilled in the art, preferably using conveyor belts, screw conveyors or pneumatically operated pipe systems.
- an additional detection step for leaks follows after the liquid-tight sealing of the hollow body.
- a purely visual assessment of the hollow bodies produced is possible in principle, but offers little advantages from an economic point of view, especially in industrial production with high product throughput, since it is very labor-intensive.
- Electronic detection systems for leaks have proven to be particularly advantageous.
- a particularly suitable detection system for determining leaks in, in particular filled with liquids, particularly preferably blow-molded, hollow bodies is the high-voltage leak detector (HVLD detector) sold by Rommelag.
- the detection method is based on the electrical conductivity of the filling material, which is encased by a non-conductive or only weakly conductive polymer. If there is a leak, the discharge current flows through the leak opening into the Hollow body and the detection of this current leads to the ejection of the damaged, filled hollow body.
- Suitable detectors are, for example, the HVLD 923 and HVLD 924 ex Rommelag.
- a critical point in connection with thermoplastic production processes is in the processing of water-soluble polymers, in particular polyvinyl alcohol, polyvinyl acetate or partially hydrolyzed polyvinyl acetate, the melting and the associated introduction of mechanical and thermal energy into the polymer material to be processed.
- the melting process of the polymer materials does not take place at a defined melting point, but over a longer melting range.
- the upper limit of the melting range can be so high that the crystals are difficult to melt in an extruder since unmelted crystallites presumably form a particle stream.
- the appearance of crystals in the polymer melts can lead to defects or specks in the container walls when processing such polymers.
- Increased input of thermal energy during the extrusion process to completely melt the crystals remaining in the melt can easily result in the formation of a decomposing or crosslinking material, the material then having specks that are similar to the structure of the specks that are crystalline in origin , however the only difference is the presence of a chemical bond instead of a physical bond.
- Increased crosslinking of the polymer material leads to a considerable change in the physical properties, in particular this can lead to a change in the elasticity of the polymer material in the end product or to poorer water solubility.
- the use of external plasticizers can help to solve the problem described, but the amount of such plasticizing agents is also limited. An increased use of plasticizer components can lead, for example, to the stickiness of the articles produced, which in turn then have less or no commercial value.
- the polymer is melted in an advantageous method in such a way that an excessive input of energy is avoided, which would lead to the decomposition of the material.
- the entry of both thermal and mechanical energy is particularly advantageous.
- the additional entry mechanical Energy causes the areas of crystallinity to be sheared, at the same time this seer energy can be dissipated or the input of thermal energy reduced to prevent the melting temperature from exceeding the decomposition temperature.
- the additional energy which is supplied for the implementation of the shear passes through the melt, the crystallinity being eliminated, and is dissipated in a further advantageous embodiment by cooling the melt, for example by a cooling jacket of the extruder.
- the requirements for the extruder in a preferred embodiment are in particular that it has intensive mixing elements so that the necessary shear energy can be provided.
- the extruder can, if necessary, remove the excess of the energy supplied, which is required when the polymer is heated, melted or sheared. This excess energy can be dissipated, for example, through the extruder housing, the extruder screw or by evaporating the plasticizer in the step of removing the volatile constituents.
- the extruder mixing the melt with high rotational speed of the screw preferably above 10 revolutions per minute, particularly preferably above 20 revolutions per minute, is particularly preferred operated above 70 revolutions per minute, extremely preferably above 150 revolutions per minute, in particular above 300 revolutions per minute, for example 400, 500 or 600 revolutions per minute.
- the extruder can be operated with a number of intensely kneading elements in line with the design of the screw, so that the required mechanical energy supply is created.
- the screw housing can also be operated at a temperature below the melting temperature of the polymer so that there is no net transfer of heat from the extruder.
- the result is a high level of mechanical energy delivery into the polymer sufficient to eliminate specks or crystalline portions of the polymer melt by displacing all of the crystalline regions from one another.
- a high input of kinetic energy into the polymer mass has proven to be advantageous.
- a high apparent wall shear rate is therefore particularly preferred within the scope of the invention.
- the shear rate is usually given as the angular rate ⁇ (t) (derivative of the angle of rotation ⁇ (t) after the time t) and expresses the ratio of the speed difference ⁇ v (delta v) of two layers flowing past each other to their distance ⁇ h (delta h) perpendicular to Flow direction.
- the shear rate in the extruder and optionally on the die head is above 1 s “1 , preferably above 2 s “ 1 , more preferably above 3 s “ ⁇ in particular above 5 s “ 1 , particularly preferably above 8 s “1 , more preferably above 10 s “ 1 , still more preferably above 20 s “ ⁇ further still above 40 s " ⁇ extremely preferably above 60 s "1 , advantageously above 100 s ' 1 and particularly advantageously above from 200 s "1 .
- the shear rates on nozzle devices are higher than on other components of the extruder.
- the shear rate at nozzle devices is above above 1 s “ ⁇ preferably above 2 s “ 1 , more preferably above 3 s “1 , in particular above 5 s “ ⁇ particularly preferably above 8 s “ ⁇ more preferably above 10 s “1 , even more preferably above 20 s “ 1 , further still above 40 s " ⁇ extremely preferably above 60 s " ⁇ advantageously above 100 s "1 and particularly advantageously above 200 s " ⁇ for example above 500 s " ⁇ 1000 s " 1 , 2000 s ' 1 or 4000 s "1 .
- a short residence time of the polymer material in the extruder is particularly advantageous in order to reduce the heat profile.
- Suitable residence times are less than one hour, preferably less than 30 minutes, particularly preferably less than 20 minutes, extremely preferably less than 10 minutes and in particular less than 5 minutes.
- thermoplastic melt in the extruder When designing the flow of the thermoplastic melt in the extruder and possibly on the blow head, it is particularly advantageous to ensure that any dead zones of the flow are avoided and ideally a narrow residence time distribution range, particularly preferably as a plug flow, is aimed for.
- This measure is intended to prevent even partial volumes in individual areas of the total thermoplastic in the form of a pent-up or back-flowing mass are exposed to an excessive thermal load with the known disadvantages.
- Suitable measures can consist in a suitable extruder design and / or in continuous and / or rounded and / or widened or tapered flow channel inner walls and transitions. It is therefore preferred that the extruder screw and possibly hose head devices have essentially no dead zones and / or essentially no backflow occurs.
- a preferred commercially available device is the twin-screw extruder from Werner and Pfleiderer, which is a rotating, fully intermeshing extruder.
- the screw is designed in a segment-like manner, so that a number of different screw elements can be arranged on wedged shafts, thereby achieving the degree of mixing desired for the particular application.
- the screw elements can vary along the screw, but two screws must fit together in order to achieve completely interlocking surfaces.
- screw conveying elements and kneading or mixing disks.
- the screw elements can have either a forward or negative slope, whereas the kneading disks can have a neutral slope in addition to the forward or negative slope.
- the kneading disks consist of staggered elliptical disks which are offset so that an overall conveying gradient is achieved.
- the width of the panes can vary from one element to another, but for one element the panes are equally wide.
- different screw elements can have different conveying slopes. The person skilled in the art can put together suitable screws in order to achieve the optimal shearing process and the optimal conveying effect, which lead to the desired end product.
- the degree of thermal crosslinking is desirable. Since the residues may have to go through the extrusion melting process several times, it has proven advantageous in the context of the present invention that the degree of post-crosslinking of the polymer used is so low that it can be recycled up to ten times.
- the degree of post-crosslinking can be determined from the average molecular weight of the polymer. The higher the degree of post-crosslinking due to extrusion and melt, the higher the increase in the average molecular weight of the polymer.
- the increase in the average molecular weight of the water-soluble polymer thermoplastic is below 15%, preferably below 10%, particularly preferably below 8%, extremely preferably below 5%, in particular below 2%, with a single pass through the extrusion process .
- the material for the covering, the wall thickness and the size of the covering are chosen such that the covering is immobile in still water of 20 ° C. in less than 300 seconds, preferably in less than 60 Dissolves seconds or releases the contents of the filling. It is not necessary for the entire molded body to dissolve spontaneously. Rather, it is sufficient if all of the components dissolve within the application period under the application conditions. For conventional washing or rinsing processes, this means temperatures of 20 ° C. and above, mechanical action and times of less than 200 minutes, preferably less than 60 minutes, in particular less than 20 minutes.
- the release of the ingredients of at least one compartment should, however, preferably take place in less than 300 seconds, in particular in less than 60 seconds. This can be done by using disintegration aids, by sealing a compartment with a thin, water-soluble film, by dissolving a "stopper" closing an opening, or in another conventional manner.
- the portioned washing, rinsing or cleaning agents according to the invention can be realized with particular advantage if the proportion of water-soluble polymers in the coating is high.
- the entire casing preferably consists only of the water-soluble polymers and, if appropriate, auxiliaries (see above).
- Portioned detergents, dishwashing detergents or cleaning agents according to the invention are preferred here, in which the coating contains the abovementioned polymers in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight of the casing.
- the portioned detergents, dishwashing detergents or cleaning agents according to the invention can be made up as detergents, cleaning agents or dishwashing agents, depending on which ingredients are enclosed in the casing.
- detergents for machine or manual dishwashing can be made up as detergents, cleaning agents or dishwashing agents, depending on which ingredients are enclosed in the casing.
- detergents for machine or manual dishwashing can be made up as detergents, cleaning agents or dishwashing agents, depending on which ingredients are enclosed in the casing.
- universal household cleaners for example, , Toilet cleaner, glass cleaner, etc.
- the selection of the ingredients in the detergent, dishwashing or cleaning agent compositions which are present within the casing can be different. Important ingredients of these compositions are described below.
- the detergent, dishwashing or cleaning agent compositions preferably contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants for textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants.
- the total surfactant content of the washing, rinsing or cleaning agent composition is preferably below 30% by weight, based on the total agent.
- Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical may be methyl-branched linearly or preferably in the 2-position or may contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- Preferred ethoxylated alcohols include, for example C 12 . ⁇ 4 - alcohols containing 3 EO, 7 EO or 4 EO, C 9 n-alcohol with 7 EO, C. 13 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 1 -i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . ⁇ 4 alcohol with 3 EO and C 12 . ⁇ 8 alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula I,
- RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
- R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
- [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula II
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 Carbon atoms
- C 1-4 alkyl or phenyl radicals are preferred
- [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.
- [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- non-ionic surfactants in portioned washing, rinsing or cleaning agent compositions according to the invention which are suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, based in each case on the total funds.
- Machine dishwashing detergents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.
- Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
- Preferred nonionic surfactants to be used as solid at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
- a particularly preferred non-ionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C ⁇ 6 - 2 o-alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won.
- a straight-chain fatty alcohol having 16 to 20 carbon atoms C ⁇ 6 - 2 o-alcohol
- C 18 alcohol preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won.
- the so-called “narrow rank ethoxylates" are particularly preferred.
- particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C 6 . 2 o-monohydroxyalkanols or C ⁇ o-alkylphenols or C 16 . 2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
- ethoxylated nonionic surfactant consist of C 6 . 2 o-monohydroxyalkanols or C ⁇ o-alkylphenols or C 16 . 2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
- the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
- Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
- Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
- the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
- Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight. and in particular make up up to 15% by weight of the total molecular weight of the nonionic surfactant.
- nonionic surfactants with melting points above room temperature contain 40 to 70% of one
- Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
- a further preferred portioned washing, rinsing or cleaning agent according to the invention contains nonionic surfactants of the formula
- R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
- R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
- R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
- R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl-, 2-butyl- or 2-methyl-2- Butyl radical
- x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can be different.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
- H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula can be different if x ⁇ 2.
- the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
- R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
- R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
- x stands for values between 1 and 30
- k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
- x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
- anionic, cationic and / or amphoteric surfactants can also be used, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent.
- the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
- the agents according to the invention can contain, for example, cationic compounds of the formulas III, IV or V as cationic active substances:
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9 . 13 - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12 -i 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , in Consideration.
- alkanesulfonates which are for example derived from C 12 . ⁇ 8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
- the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 2 o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 15 alkyl sulfates are preferred from a washing-technical point of view.
- 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- 21 alcohols such as 2-methyl-branched C 9 n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 2 - ⁇ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the content of anionic surfactants in preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.
- preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, run-in preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.
- builders bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, run-in preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants
- the builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
- the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
- Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO in addition to higher molecular weight representatives.
- the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
- Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91, preferably “3 , melting point 60 °) and as a monohydrate (density 2.04, preferably " 3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 ⁇ 7 ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
- NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
- Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
- KH 2 PO 4 is a white salt with a density of 2.33 like "3 , has one Melting point 253 ° [decomposes to form potassium polyphosphate (KPO 3 ) x ] and is easily soluble in water.
- Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1.68 gladly '3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1, 52 like "3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO, is an amorphous, white salt that is easily soluble in water.
- Trisodium phosphate, tertiary sodium phosphate, Na 3 PO are colorless crystals which like dodecahydrate have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% PO 5) like to have a density of 2.536 '.
- trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mol of NaOH, tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO, is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
- Tetrasodium diphosphate (sodium pyrophosphate), Na P 2 O 7 , exists in anhydrous form (density 2.534 like "3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like '3 , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution. The decahydrate complexes heavy metal salts and hardness and therefore reduces the hardness of the water.
- Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 '3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
- Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
- pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
- sodium tripolyphosphate sodium tripolyphosphate
- n 3
- Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
- pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
- these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
- Suitable crystalline, layered sodium silicates have the general formula NaMSi x ⁇ 2 ⁇ + ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and ⁇ -
- the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
- This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- Commercially available and preferably used in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta SpA is sold under the brand name VEGOBOND AX ® and through the formula
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
- the zeolite can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 18 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups, C ⁇ 2 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.
- Alkali carriers can be present as further constituents.
- Alkali metal sesquicarbonates alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.
- a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
- a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
- other ingredients may be present, washing, rinsing or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.
- Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients.
- the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
- the anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
- Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
- Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated connections are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.
- Common chelate complexing agents preferred within the scope of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
- Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
- the polymer-bound ones of the The resulting metal complexes can originate from just one macromolecule or they can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
- Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals.
- the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
- Hydroxyl groups is at least 5,
- Dishwashing detergent in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included.
- All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups.
- the following are preferably used individually or in a mixture: a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediamine triacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, isopropynedioic acid, nitrosedioic diacetic acid, nitrosedioic diacetic acid, and nitro-dio-diacetic acid, and nitro-dio-diacetic acid, nitro-3-dio-diacetic acid, nitro-3-dio-diacetic acid, and 3-nitro-dio-diacetic acid
- polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
- Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
- Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
- Deposit-inhibiting polymers can also have cobuilder properties.
- Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
- Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
- Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
- Polymeric polycarboxylates are also suitable as builders or scale inhibitors, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), where a UV detector was used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.
- Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
- the copolymers containing sulfonic acid groups are described in detail below.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
- the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
- biodegradable polymers made up of more than two different monomer units, for example those which, as monomers, are salts of acrylic acid and maleic acid, and also vinyl alcohol or vinyl alcohol derivatives, or the contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
- Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
- polymeric aminodicarboxylic acids their salts or their precursor substances.
- Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
- polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
- DE dextrose equivalent
- oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
- Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders.
- ethylenediamine-N, N'-disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
- Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
- hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
- Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
- HEDP is preferably used as the builder from the class of the phosphonates.
- the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
- the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below. Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and supply H 2 O in water.
- bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- bleach activators can be incorporated into the detergent tablets.
- Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- bleach catalysts can also be incorporated into the moldings.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
- Enzymes in particular include those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color.
- hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the soft
- Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
- Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
- Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
- Known cutinases are examples of such lipolytically active enzymes.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
- the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
- the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 2% by weight.
- the cleaning agents according to the invention for machine dishwashing may contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being of particular importance in the area of machine dishwashing.
- the known substances from the stand can be used of the technique.
- silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
- Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
- active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
- oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds.
- Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
- transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
- Zinc compounds can also be used to prevent corrosion on the wash ware.
- a wide number of different salts can be used as electrolytes from the group of inorganic salts.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
- the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
- Non-aqueous solvents which can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
- the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl - 3-methoxybutanol, propylene glycol t-butyl ether and mixtures of
- pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.
- the agents according to the invention can be colored with suitable dyes.
- Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
- Foam inhibitors which can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
- Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether as well as the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
- the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
- Optical brighteners can be added to the agents according to the invention in order to prevent graying and yellowing of the treated textiles remove. These substances absorb on the fiber and bring about a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results.
- Suitable compounds originate for example from the substance classes of 4,4'-diamino-2,2 '- stilbenedisulfonic (flavonic), 4,4'-biphenylene -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1,3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.
- the optical brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished composition.
- Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
- water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose.
- Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
- Polyvinylpyrrolidone can also be used.
- cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition
- the agents according to the invention are packaged as agents for automatic dishwashing, further ingredients can be used.
- machine-washed dishes are often subject to higher requirements than hand-washed dishes.
- dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still have whitish stains based on water hardness or other mineral salts, which, due to the lack of wetting agents, originate from dried water drops.
- Rinse aid In order to obtain crystal-clear and spotless dishes, it is therefore used successfully today Rinse aid.
- the addition of rinse aid at the end of the wash program ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and immaculately shiny at the end of the wash program.
- the automatic cleaning of dishes in domestic dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles.
- the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out.
- the temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection.
- rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the dishes.
- the agents according to the invention can be formulated as "normal" cleaners, which are used together with commercially available supplements (rinse aid, regeneration salt). It is particularly advantageous to dispense with the additional dosage of rinse aid with the products according to the invention. These so-called “2-in-1" products simplify handling and relieve the consumer of the additional dosage of two different products (detergent and rinse aid).
- products according to the invention which, as so-called “3in1” products, contain the conventional cleaners, rinse aids and a salt replacement function unite, provide.
- automatic dishwashing agents according to the invention are preferred which additionally contain 0.1 to 70% by weight of copolymers of i) unsaturated carboxylic acids ii) sulfonic acid group-containing monomers iii) optionally further ionic or nonionic monomers.
- copolymers have the effect that the items of crockery treated with such agents become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents.
- the invention is characterized by an improved “cleanability” of the treated substrates in later cleaning processes and by a considerable reduction in the drying time compared to comparable agents without the use of polymers containing sulfonic acid groups.
- drying time is generally understood to mean the meaning, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface.
- R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 Carbon atoms, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
- Preferred among these monomers are those of the formulas VIIa, VIIb and / or VIIc,
- H 2 C CH-X-SO 3 H (Vlla),
- H 2 C C (CH 3 ) -X-SO 3 H (VIIIb),
- ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds.
- the content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer.
- Polymers to be used with particular preference consist only of monomers of groups i) and ii).
- copolymers are made of
- R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated one or is unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
- Particularly preferred copolymers consist of
- H 2 C CH-X-SO 3 H (Vlla),
- H 2 C C (CH 3 ) -X-SO 3 H (VIIIb),
- copolymers contained in the compositions according to the invention can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii ) can be combined.
- Particularly preferred polymers have certain structural units, which are described below.
- agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -O- (CH 2 ) n - with n 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH- CH (CH 2 CH 3 ) -, are preferred.
- These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IX - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p- (IX),
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -O- (CH 2 ) n - with n 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH- CH (CH 2 CH 3 ) -, are preferred.
- acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, which changes the structural units in the molecule.
- Agents according to the invention which contain one or more copolymers are structural units of the formula X
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- maleic acid can also be used as a particularly preferred monomer from group i).
- preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XI
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -O- (CH 2 ) n - with n 0 to 4, for -O- (C e H 4 ) -, for -NH-C (CH 3 ) - or -NH- CH (CH 2 CH 3 ) - are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XII
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -O- (CH 2 ) n - with n 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH- CH (CH 2 CH 3 ) -, are preferred.
- automatic dishwashing agents which contain, as ingredient b), one or more copolymers which have structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII
- n and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic
- Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -O- (CH 2 ) n - with n 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH- CH (CH 2 CH 3 ) -, are preferred.
- the sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
- metal ions preferably alkali metal ions and in particular by sodium ions.
- Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
- the monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
- terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,
- the molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
- Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmor 1 , preferably from 4000 to 25,000 gmol '1 and in particular from 5000 to 15,000 gmor 1 .
- the content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.
- polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
- the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
- Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or Sokalan ® PA25 (BASF).
- the agents according to the invention can also be packaged as fabric softeners or washing additives. Depending on the intended use, additional ingredients can be used. Fabric softener compositions for rinse bath finishing are widely described in the prior art. Typically, these compositions contain as the active ingredient a cationic quaternary ammonium compound which is dispersed in water. Depending on the content of active substance in the finished plasticizer composition, one speaks of dilute, ready-to-use products (active substance contents below 7% by weight) or so-called concentrates (active substance contents above 7% by weight). Because of the lower volume and the associated lower packaging and transport costs, the textile softener concentrates have advantages from an ecological point of view and have become more and more established on the market.
- portioned fabric softeners according to the invention preferably contain cationic surfactants which have already been described in detail above (formulas XII, XIII and XIV).
- "Softener portions” according to the invention particularly preferably contain so-called ester quats. While there are a large number of possible compounds from this class of substances, esterquats are used according to the invention with particular preference, which can be prepared in a manner known per se by reacting trialkanolamines with a mixture of fatty acids and dicarboxylic acids, optionally subsequent alkoxylation of the reaction product and quaternization is described in DE 195 39 846.
- esterquats produced in this way are outstandingly suitable for the production of portions according to the invention which can be used as fabric softeners. Since, depending on the choice of the trialkanolamine, the fatty acids and the dicarboxylic acids and the quaternizing agent, a large number of suitable products can be prepared and used in the agents according to the invention, a description of the esterquats to be used according to the invention via their route of production is more precise than the specification of a general formula.
- portioned fabric softeners are preferred in which a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which optionally alkoxylates and then in was quaternized in a known manner, is present in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight.
- triethanolamine is particularly preferred, so that further preferred portioned fabric softeners of the present invention are a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, that optionally alkoxylated and then in a manner known per se was quaternized, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-%.
- All acids obtained from vegetable or animal oils and fats can be used as fatty acids in the reaction mixture to produce the esterquats.
- a fatty acid that is not solid at room temperature, i.e. pasty to liquid, fatty acid can be used.
- the fatty acids can be saturated or mono- to polyunsaturated regardless of their physical state.
- pure fatty acids can be used, but also the technical fatty acid mixtures obtained from the cleavage of fats and oils, these mixtures again being clearly preferred from an economic point of view.
- individual species or mixtures of the following acids can be used in the reaction mixtures for producing the ester quats for the clear aqueous fabric softener according to the invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid, behenic acid , Lignoceric acid, cerotinic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, ⁇ - and ß-elaestainic acid, gadoleic acid, erucic acid, brassidic acid.
- fatty acids with an odd number of carbon atoms can also be used, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid,
- Pentacosanoic acid Pentacosanoic acid, heptacosanoic acid.
- fatty acids of the formula XIII in the reaction mixture for the preparation of the esterquats is preferred, so that preferred portioned fabric softener is a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII,
- R 1 -CO-OH (XIII) in which R1-CO- represents an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5 : 1, which was optionally alkoxylated and then quaternized in a manner known per se, contained in the compositions in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight.
- Suitable dicarboxylic acids which are suitable for the preparation of the esterquats to be used in the agents according to the invention are, in particular, saturated or mono- or polyunsaturated ⁇ - ⁇ -dicarboxylic acids.
- saturated species oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic and dodecanoic acid, brassylic acid, tetra- and pentadecanoic acid, thapic acid as well as hepta-, octa- and nonadecanoic acid, eicosanoic acid, eicosanoic acid and eicosanoic acid and also called phellogenic acid.
- Dicarboxylic acids which follow the general formula XXIII are preferably used in the reaction mixture, so that portioned agents according to the invention are preferred which are a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids of the formula XIV,
- X represents an optionally hydroxyl-substituted alkylene group with 1 to 10 carbon atoms, in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, in quantities from 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.
- agents are particularly preferred which are a reaction product of triethanolamine with a mixture of fatty acids and adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which is then known per se Was quaternized in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% in the compositions
- the agents according to the invention can also be provided with further additional benefits.
- color transfer inhibiting compositions agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt release or prevention of re-soiling, antibacterial agents, UV protection agents, color-refreshing agents, etc. can be formulated.
- the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
- the agents according to the invention can contain antimicrobial agents.
- antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the inventive agents.
- the agents can contain antioxidants.
- This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
- Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
- External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
- Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect.
- silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
- the viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.
- the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
- Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
- Substituted benzotriazoles are furthermore phenyl-substituted acrylates in the 3-position (Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.
- Envelopes according to the invention in the form of hemispheres, cups, with an inner radius of 24 mm were produced by injection molding on a hydraulic screw-type injection molding machine type 221 M from Arburg. These cups were then optionally filled with agent and (both in filled and in unfilled versions) sealed with a welded-on, also water-soluble, cover film in a liquid-tight manner.
- the water-soluble casing material for taking up the cleaning-active composition was a thermoplastically processable PVA blend from Texas Polymers, U.S.A., type "Vinex 2019" (Melt Flow Index 26-30; 2.16 kg; 190 ° C).
- the polymer pellets, metered in via a metering screw, were drawn into the injection molding extruder and melted from the feed to the die head as the temperature profile increased (zone 1: 140 ° C; zones 2 to 5: 160 ° C to 195 ° C; die: 210 ° C), then fed to the cyclically closed injection mold via the injection point for spraying out the articles.
- Half of the half-shells were each filled with 25 ml of the low-water detergent composition described below.
- Silicone oil 1, 0 The filled / unfilled half-shells were then welded along a circumferential brim (web width 2 mm) with a water-soluble PVA film in a multi-cavity sealing tool from lllig Maschinenbau
- the casings were subjected to mechanical stress tests using a universal testing machine from Zwick, type 1425, these mechanical measurements being carried out both immediately after the casings were produced and after conditioning in a standard climate of 23 ° C. and 50% relative humidity (12 hours).
- Bubble-extruded, water-soluble casings were produced in-line using the blow-fill-seal process and then checked for their repeated mechanical strength.
- blow-extrudable PVA compounds eg "Vinex 2034" ex Texas Polymers
- Vinex 2034 ex Texas Polymers
- type "bottelpack system 2012” with quadruple blow head, sequential flow
- L 734" "KSE Mowiflex LPTC 221” ex Clariant / Kuraray
- the parisons extruded from the PVA blend were pushed into the opened blow mold and the tubular preforms were cut off below the mold by means of a cutting iron (warm cutter).
- the mold was closed, which at the same time was thermally sealed on the bottom of the respective preform by means of the clamping effect.
- an integrated blowing and filling sleeve unit inserted into the neck area of the respective preform in the tool, the respective preform was molded onto the spherical die walls of the respective tool cavities by means of compressed air and by means of a vacuum applied to the mold.
- the total shell weight was 1.5 g, with products formed very regularly in all four cavities with regard to their wall thicknesses (wall thickness s in the area of the base jaw approx. 300 ⁇ m; in the equatorial area, at the predetermined breaking point, approx. 70 to 100 microns).
- Each casing was filled with 50 ml of a low-water liquid detergent formulation of the following composition via the integrated blowing and filling quill unit.
- the integrated, four-part blowing and filling quill unit was withdrawn from the tool and then the upper jaws of the Tool closed so that the necessary sealing of the casing to a liquid-tight PVA container was carried out via thermal sealing.
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)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10149718 | 2001-10-09 | ||
DE10149718A DE10149718A1 (de) | 2001-10-09 | 2001-10-09 | Portionierte Wasch-, Spül-oder Reinigungsmittel in flexiblen wasserlöslichen Behältern |
PCT/EP2002/009970 WO2003031556A1 (de) | 2001-10-09 | 2002-09-06 | Portionierte wasch-, spül- oder reinigungsmittel in flexiblen wasserlöslichen behältern |
Publications (1)
Publication Number | Publication Date |
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EP1434848A1 true EP1434848A1 (de) | 2004-07-07 |
Family
ID=7701872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02800557A Ceased EP1434848A1 (de) | 2001-10-09 | 2002-09-06 | Portionierte wasch-, spül- oder reinigungsmittel in flexiblen wasserlöslichen behältern |
Country Status (4)
Country | Link |
---|---|
US (1) | US20040219297A1 (de) |
EP (1) | EP1434848A1 (de) |
DE (1) | DE10149718A1 (de) |
WO (1) | WO2003031556A1 (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070253926A1 (en) * | 2006-04-28 | 2007-11-01 | Tadrowski Tami J | Packaged cleaning composition concentrate and method and system for forming a cleaning composition |
US7614202B2 (en) * | 2007-11-27 | 2009-11-10 | Atlas Vac Machine Co., Llc | Sealer and interchangeable tooling therefor |
DE102009027158A1 (de) * | 2009-06-24 | 2010-12-30 | Henkel Ag & Co. Kgaa | Maschinelles Geschirrspülmittel |
EP2302026A1 (de) * | 2009-09-15 | 2011-03-30 | The Procter & Gamble Company | Waschmittelzusammensetzung mit Tensidladungspolymeren |
GB201010374D0 (en) * | 2010-06-21 | 2010-08-04 | Mtp Innovations Ltd | Disinfectant composition |
DE102014206093A1 (de) * | 2014-03-31 | 2015-10-01 | Henkel Ag & Co. Kgaa | Verpackung mit einem wenigstens eine Dünnstelle aufweisenden Behälter und mit mehreren Portionspackungen sowie Verfahren zur Detektion ausgelaufener Portionspackungen |
US10703895B2 (en) | 2015-12-24 | 2020-07-07 | Nippon Shokubai Co., Ltd. | Water-soluble film and method for manufacturing same |
US10975340B2 (en) * | 2017-05-16 | 2021-04-13 | The Procter & Gamble Company | Active agent-containing fibrous structure articles |
US10975339B2 (en) | 2017-05-16 | 2021-04-13 | The Procter & Gamble Company | Active agent-containing articles |
Citations (1)
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WO2002006431A2 (de) * | 2000-07-14 | 2002-01-24 | Henkel Kommanditgesellschaft Auf Aktien | Kompartiment-hohlkörper enthaltend wasch-, reinigungs- oder spülmittelportion |
Family Cites Families (24)
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US3300546A (en) * | 1965-10-05 | 1967-01-24 | American Cyanamid Co | Water soluble envelope prepared from a graft polymer of alkyl acrylate on a polyvinyl alcohol/polyvinyl acetate co-polymer |
IL37405A0 (en) * | 1970-08-12 | 1971-10-20 | Du Pont | Cold water soluble plastic films |
DE2501464A1 (de) * | 1974-01-29 | 1975-07-31 | Procter & Gamble | Bleichverfahren |
US3945936A (en) * | 1974-01-29 | 1976-03-23 | The Procter & Gamble Company | Bleaching article |
US4155971A (en) * | 1976-08-18 | 1979-05-22 | E. I. Du Pont De Nemours And Company | Method of making water-soluble films from polyvinyl alcohol compositions |
US4176079A (en) * | 1977-04-20 | 1979-11-27 | The Procter & Gamble Company | Water-soluble enzyme-containing article |
US4115292A (en) * | 1977-04-20 | 1978-09-19 | The Procter & Gamble Company | Enzyme-containing detergent articles |
US4286016A (en) * | 1979-04-12 | 1981-08-25 | The Drackett Company | Pouch bleach |
US4886615A (en) * | 1985-08-05 | 1989-12-12 | Colgate-Palmolive Company | Hydroxy polycarboxylic acid built non-aqueous liquid cleaning composition and method for use, and package therefor |
EP0221651A1 (de) * | 1985-09-27 | 1987-05-13 | Kao Corporation | Wasserlösliches Polyvinylalkoholderivat |
EP0245759A3 (de) * | 1986-05-14 | 1990-05-02 | Henkel Kommanditgesellschaft auf Aktien | Vorratspackung eines festen Reinigerblocks und Verfahren zu deren Herstellung |
DE3808695A1 (de) * | 1988-03-16 | 1989-10-05 | Henkel Kgaa | Fluessiges waschmittel |
US4806261A (en) * | 1988-04-11 | 1989-02-21 | Colgate-Palmolive Co. | Detersive article |
US5110640A (en) * | 1990-05-18 | 1992-05-05 | Colgate-Palmolive Company | Detergent pouch construction |
EP0737245B1 (de) * | 1993-12-30 | 2000-02-23 | Ecolab Inc. | Stabiler hygroskopischer reinigungsartikel |
DE19539846C1 (de) * | 1995-10-26 | 1996-11-21 | Henkel Kgaa | Esterquats |
US6040286A (en) * | 1995-12-26 | 2000-03-21 | Huff; Karen L. | Through-the-washer-dryer pouch-type detergent bag and method of use |
ATE229548T1 (de) * | 1998-03-03 | 2002-12-15 | Aquasol Ltd | Wasserlösliche folien |
GB2352725A (en) * | 1999-07-30 | 2001-02-07 | Mcbride Robert Ltd | Detergent packaging |
ATE273868T1 (de) * | 1999-11-17 | 2004-09-15 | Reckitt Benckiser Uk Ltd | Spritzgegossener wasserlöslicher behälter |
WO2001044433A1 (de) * | 1999-12-13 | 2001-06-21 | Henkel Kommanditgesellschaft Auf Aktien | Waschmittel-, spülmittel- oder reinigungsmittel-portionen mit kontrollierter wirkstoff-freisetzung |
DE10048448A1 (de) * | 2000-07-14 | 2002-04-11 | Henkel Kgaa | Kompartiment-Hohlkörper II |
DE10040724A1 (de) * | 2000-08-17 | 2002-03-07 | Henkel Kgaa | Mechanisch stabile, flüssig formulierte Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen |
CA2426023C (en) * | 2000-11-27 | 2007-05-22 | The Procter & Gamble Company | Dishwashing method |
-
2001
- 2001-10-09 DE DE10149718A patent/DE10149718A1/de not_active Ceased
-
2002
- 2002-09-06 WO PCT/EP2002/009970 patent/WO2003031556A1/de not_active Application Discontinuation
- 2002-09-06 EP EP02800557A patent/EP1434848A1/de not_active Ceased
-
2004
- 2004-04-08 US US10/821,165 patent/US20040219297A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002006431A2 (de) * | 2000-07-14 | 2002-01-24 | Henkel Kommanditgesellschaft Auf Aktien | Kompartiment-hohlkörper enthaltend wasch-, reinigungs- oder spülmittelportion |
Non-Patent Citations (1)
Title |
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See also references of WO03031556A1 * |
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US20040219297A1 (en) | 2004-11-04 |
WO2003031556A1 (de) | 2003-04-17 |
DE10149718A1 (de) | 2003-04-17 |
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