EP2109663A1 - Agent de nettoyage pour surfaces en verre - Google Patents

Agent de nettoyage pour surfaces en verre

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Publication number
EP2109663A1
EP2109663A1 EP07802796A EP07802796A EP2109663A1 EP 2109663 A1 EP2109663 A1 EP 2109663A1 EP 07802796 A EP07802796 A EP 07802796A EP 07802796 A EP07802796 A EP 07802796A EP 2109663 A1 EP2109663 A1 EP 2109663A1
Authority
EP
European Patent Office
Prior art keywords
acid
formula
radical
acids
carbon atoms
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.)
Granted
Application number
EP07802796A
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German (de)
English (en)
Other versions
EP2109663B1 (fr
Inventor
Arnd Kessler
Haitao Rong
Wolfgang Wick
Matthias Schweinsberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Sustech GmbH and Co KG
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Publication date
Application filed by Henkel AG and Co KGaA, Sustech GmbH and Co KG filed Critical Henkel AG and Co KGaA
Priority to PL07802796T priority Critical patent/PL2109663T3/pl
Publication of EP2109663A1 publication Critical patent/EP2109663A1/fr
Application granted granted Critical
Publication of EP2109663B1 publication Critical patent/EP2109663B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to the technical field of glass surface cleaners, and more particularly to agents which reduce glass corrosion in machine cleaning of glass surfaces.
  • Damage to the surface of glassware during cleaning and / or rinsing operations has been a well-known problem due to the leakage of minerals from the glass composition, accompanied by hydrolysis of the silicate network, and deposition of silicate material on the glass Glassware takes place.
  • a special case of this problem is the field of automatic dishwashing, as it is known, for example, to a consumer when rinsing glassware in a domestic dishwasher.
  • the above-described phenomena can lead to damage to the glass surfaces, which manifest themselves in opacities, scratches, streaks or the like.
  • Such impairments to the appearance of machine-washed glassware are still one of the most common problems that occur when using mechanical cleaning agents.
  • document EP 0383482 describes automatic dishwashing detergents containing insoluble zinc salts, which are distinguished by improved glass corrosion protection.
  • the insoluble zinc salts must have a certain particle size to achieve such an effect.
  • WO 00/39259 discloses water-soluble glasses according to DIN ISO 719 which contain at least one glass corrosion-inhibiting active substance whose proportion by weight of the glass is not more than 85% by weight and which is released from this glass under the conditions of the cleaning and / or rinsing process ,
  • US 2003/0153712 A1 discloses a polyurethane prepolymer having terminal alkoxysilane and hydroxyl groups.
  • a polyether-diol is first reacted with stoichiometric diisocyanate, and the resulting isocyanate-hydroxy compound is then further treated with an aminosilane to introduce the silyl groups.
  • the described, two-armed polyalkoxylates representing prepolymers are used for the production of sealants and adhesives.
  • US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as the central unit.
  • the polyethylene glycol derivatives described in the document are said to be suitable for the preparation of biodegradable polymeric hydrogels and for medical-pharmaceutical use, for example for implants.
  • the object of the present invention is to provide means for reducing the glass corrosion when mechanically cleaning glass surfaces, which have advantages over conventional means, in particular a better efficacy and / or advantages in terms of freedom from formulation of the active substances contained in the agent.
  • silyl polyalkoxylates in the automated cleaning of glass surfaces causes an improvement in the drying performance of the cleaned surfaces. This is understood in particular to mean a shortening of the drying time and / or a reduction in the formation of limescale and deposits on the cleaned surfaces.
  • the present invention therefore provides the use of a multi-branched silicone polyalkoxylate of the formula (I) for reducing glass corrosion and / or for improving the drying performance in the mechanical cleaning of a glass surface, where in the formula (I)
  • A is a divalent polyoxyalkylene radical, where the m + n attached to Z
  • Polyoxyalkylenreste may be different from each other, and wherein a radical A is in each case connected via an oxygen atom belonging to Z with Z and an oxygen atom belonging to A with B or hydrogen,
  • OR 1 is a hydrolyzable group
  • R 1 and R 2 independently of one another represent a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer from 1 to
  • silyl polyalkoxylates of the formula (I) in the mechanical cleaning of glass surfaces causes an improvement in the drying performance of the cleaned surfaces. It is particularly advantageous if the silyl polyalkoxylates are used in a rinse cycle downstream of the cleaning cycle.
  • An improvement in the drying performance has the advantage, for example, in the usual household dishwashing, that the consumer can take the cleaned dishes earlier from the machine and reuse after the program has expired.
  • this improvement means that the consumer can use dishwashing cycles with lower temperatures (eg 4O 0 C), where previously the drying result was not satisfactory.
  • multi-armed silyl polyalkoxylates contain polymer arms which are essentially star-shaped or radially bonded to a central unit.
  • a silyl polyalkoxylate of the formula (I) or a mixture of several of these compounds is used, wherein the weight average molecular weight is from 500 to 50,000, preferably from 1,000 to 20,000, and most preferably from 2,000 to 10,000.
  • the silyl polyalkoxylate preferably contains 0.3 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% silicon, based on the total weight of the silyl polyalkoxylate.
  • Z preferably represents an at least trihydric, in particular tri-to octahedral, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms, where the radical may be saturated or unsaturated and in particular also aromatic.
  • Z is particularly preferably the trivalent radical of glycerol or the trihydric to hexahydric radical of a sugar, for example, the hexavalent residue of sorbitol or the octahedral residue of sucrose.
  • the x-valent radical of one of the abovementioned polyols is to be understood as meaning that molecule fragment which remains from the polyol after removal of the hydrogen atoms from x alcoholic or phenolic hydroxyl groups.
  • Z can stand for any central unit which is known from the literature for the preparation of star-shaped (pre) polymers.
  • n 0, 1 or 2 and m is a number from 3 to 8.
  • A is preferably selected from poly-C 2 -C 4 -alkylene oxides, more preferably a (co) polymer of ethylene oxide and / or propylene oxide, in particular a copolymer having a propylene oxide content of up to 60% by weight, preferably up to to 30 wt .-% and particularly preferably of up to 20 wt .-%, which may be random and / or block copolymers.
  • another preferred embodiment of the invention is the use of multi-arm silyl polyalkoxylates of the formula (I) in which A is - (CHR 3 -CHR 4 -O) p -, where R 3 and R 4 independently of one another are hydrogen, Methyl or ethyl and p is an integer from 2 to 10,000.
  • B is in particular a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20 carbon atoms.
  • divalent low molecular weight organic radicals are short-chain aliphatic and heteroaliphatic radicals such as - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (O) -NH- (CH 2 ) 3 - and -C (O) -NH-X-NH-C (O) -NH- (CH 2 ) 3 -, wherein X is a bivalent aromatic radical such as the phenylene radical or an alkylidene radical.
  • B is a bond or the radical -C (O) -NH- (CH 2 ) 3 -.
  • R 1 and R 2 independently of one another are methyl or ethyl, and r is 2 or 3.
  • Examples of radicals -Si (OR 1 ) r (R 2 ) 3 . r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl, trimethoxysilyl, triethoxysilyl or tri-t-butoxysilyl radicals, but very particular preference is given to trimethoxysilyl and triethoxysilyl radicals.
  • R 1 and R 2 are the same and are methyl or ethyl.
  • r stands for the number 3.
  • the sum m + n is preferably 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, and coincides with the number of arms which is bound in the compound (I) to the central unit Z.
  • the central unit therefore preferably has 3 to 50, in particular 3 to 10 and more preferably 3 to 8 oxygen atoms, which serve as attachment points for the arms.
  • n is 0.
  • the ratio n / m is between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1 /.
  • a mixture of at least two, in particular two to four, different multi-armed silyl polyalkoxylates of the formula (I) is used.
  • the at least two different multi-armed silyl polyalkoxylates differ in the number of their arms.
  • a first silyl polyalkoxylate having 3 to 6 arms is combined with a second silyl polyalkoxylate having 6 to 10 arms.
  • two different multi-arm silyl polyalkoxylates are usually present in a quantitative ratio of from 99: 1 to 1:99, preferably from 49: 1 to 1:49, and especially from 9: 1 to 1: 9.
  • the use of the multi-armed silyl polyalkoxylates of the formula (I) is carried out in the presence of at least one hydrolyzable silicic acid derivative.
  • Hydrolyzable silicic acid derivatives are to be understood as meaning in particular the esters of orthosilicic acid, in particular the tetraalkoxysilanes and very particularly preferably tetraethoxysilane.
  • the quantitative ratio of silyl polyalkoxylate or silyl polyalkoxylate mixture to the at least one hydrolyzable silicic acid derivative 90:10 to 10:90, preferably 50:50 to 10:90, and especially 40:60 to 20:80.
  • multi-arm silyl polyalkoxylates of the general formula (I) used according to the invention are not known from the literature, their preparation can be carried out by functionalization of suitable polyhydric polyalkoxylate precursors in analogy to known functionalization processes of the prior art.
  • the two-armed polyurethane prepolymer with terminal alkoxysilane and hydroxyl groups described in US 2003/0153712 A1 is prepared by first reacting a polyether-diol with stoichiometric diisocyanate, and then further reacting the obtained isocyanate-hydroxy compound with an aminosilane for the introduction of silyl groups.
  • the synthesis principles used there can be basically transferred to the preparation of multi-armed polyalkoxylates according to the teachings of the present invention.
  • US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as a central unit and which falls under the general formula (I) of the present invention.
  • Suitable polyalkoxylate precursors for the preparation of the SiIyI-polyalkoxylates used according to the invention are themselves multi-arm polyalkoxylates which already have the above-described multi-arm structure and which each have a hydroxyl group at the ends of the polymer arms which is partially or completely group (n) -B -Si (OR 1 ) r (R 2 ) 3 - r can be converted.
  • the polyalkoxylate precursors of the silyl polyalkoxylates used according to the invention can be represented by the general formula (II)
  • suitable polyalkoxylate precursors are known from the literature under the name star-shaped or multi-arm polyether polyols. These polyalkoxylate precursors are prepared by polymerization of the appropriate monomers, especially ethylene oxide and / or propylene oxide, using polyfunctional small molecules such as glycerol or sorbitol as initiator. Examples of polyhydric polyether polyols are ethoxylates or propoxylates of glycerol, sucrose and sorbitol, as described in US Pat. No. 6,423,661. Due to the statistical nature of the polymerization reaction, the above information on the polymer arms of the invention understand used silyl polyalkoxylates, especially in terms of arm length and arm number (m + n) each as a statistical average.
  • Suitable polyalkoxylate precursors are also commercially available in part.
  • An example of this is Voranol 4053, a polyether polyol (poly (ethylene oxide-co-propylene oxide)) from DOW Chemicals. It is a mixture of two different polyether polyols, consisting of a 3-armed polyether polyol with glycerol as the central unit and an 8-arm polyether polyol with cane sugar as the central unit.
  • the arms represent random copolymers of about 75% EO and about 25% PO, the OH functionality (hydroxy end groups) is an average of 6.9 at a weight average molecular weight of about 12000. This results in a Ratio of about 78% 8-arm polyether polyol and about 22% 3-arm polyether polyol.
  • Wanol R420 from WANHUA, China, which is a mixture of a linear poly (propylene / ethylene) diethylene glycol and an 8-arm polyether polyol (poly (propyleneoxy / ethyleneoxi) sucrose) in a ratio of about 15 -25: 85-75 represents.
  • polyether polyol Voranol CP 1421 from DOW Chemicals, which is a 3-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of about 75/25 and a weight average (Weight average molecular weight) of about 5000 is.
  • Triethoxysilyl butyraldehydes epoxy silanes such as (3-glycidoxypropyl) trimethoxysilane, anhydride silanes such as 3- (triethoxysilyl) propyl succinic anhydride, halogen silanes such as
  • the group B is in such a case, for example, exclusively in a bond, or it comprises, when an isocyanatosilane was used as a functional silane, together with the terminal oxygen atom of group A, for example, a urethane group and the atomic group, in the starting isocyanatosilane between the isocyanato group and the silyl group stands.
  • a polyalkoxylate precursor of the general formula (II) is reacted with a relation to the total of the terminal hydroxy groups substoichiometric amount of a functional silane, ie there are as described above first -B-Si (OR 1 ) r (R 2 ) 3 - r groups, but not all terminal hydroxy groups in the polyhydric polyalkoxylate precursor.
  • polyaromatic polyalkoxylates which carry both hydroxy and -Si (OR 1 ) r (R 2 ) 3 - r groups.
  • R 1 OH
  • the remaining or a part of the remaining hydroxy groups can be - as described - to radicals -B- Si (OR 1 ) r (R 2 ) 3 . r be modified.
  • Another object of the present invention is a method for machine cleaning a glass surface in which the glass surface is brought into contact with a multi-arm silyl polyalkoxylate of the formula (I).
  • this is done in such a way that the silyl polyalkoxylate is metered in the form of a solution in water and / or a non-aqueous solvent in the course of the cleaning process and brought into contact with the glass surface.
  • the solution of the silyl polyalkoxylate has an acidic pH, in particular a pH of from 1 to 6, preferably from 2 to 4.
  • the solution preferably contains an acidifying agent.
  • this comprises a purification step and an adjoining final rinse step in which the silyl polyalkoxylate is metered in during the rinse step and brought into contact with the glass surface.
  • the silyl polyalkoxylate in the course of the cleaning step of a cleaning process according to the invention.
  • the silyl polyalkoxylate for example, in addition to a cleaning agent usually used in such a method can be dosed simultaneously or sequentially, or it can also be dosed as part of a cleaning agent.
  • the silyl polyalkoxylate forms a part of the cleaning agent.
  • the silyl polyalkoxylate can be incorporated in a conventional manner in a cleaning agent.
  • the cleaning agent is preferably a water-soluble portion pack, in particular in the form of a tablet or a deep-drawn or injection-molded portion pack made of a water-soluble film.
  • the silyl polyalkoxylate is integrated in such a cleaning agent in basically the same way as is usually the case with the cleaning agents responsible for rinsing.
  • agents which, in addition to the silyl polyalkoxylates, also contain at least one nonionic surfactant.
  • the present invention accordingly also provides an agent, in particular cleaning agent, preferably for cleaning a glass surface, comprising a) from 0.05 to 10, preferably from 0.1 to 7, particularly preferably from 0.2 to 5 and in particular from 0.3 to 3,% by weight % of at least one multi-arm silyl polyalkoxylate of the formula (I)
  • Z is an (m + n) -valent radical having at least three carbon atoms
  • A is a divalent polyoxyalkylene radical, where the m + n attached to Z
  • Polyoxyalkylenreste may be different from each other, and wherein a radical A in each case via an oxygen atom belonging to Z with Z and one belonging to A.
  • Oxygen atom is connected to B or hydrogen
  • OR 1 is a hydrolyzable group
  • R 1 and R 2 are independently a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer of 1 to 3, and m is an integer> 1 and n is 0 or an integer> 1, and m + n has a value of 3 to 100, b) 0.1 to 40% by weight of nonionic surfactant (s), and c) if desired, water and / or one or more substances selected from anti-corrosive agents, acidifiers, non-aqueous solvents and solubilizers.
  • s nonionic surfactant
  • agents according to the invention contain at least one multi-armed silyl polyalkoxylate in those preferred embodiments which have already been described in the preceding text as preferred embodiments of the silyl polyalkoxylates of the formula (I).
  • the agent may optionally contain further components, which are described in more detail below.
  • the optional components according to their nature and the amount used are to be selected so that there are no undesirable reactions with the silyl polyalkoxylates, which could affect the stability of the composition.
  • the agent in addition to the at least one multi-arm silyl polyalkoxylate of the formula (I) and a nonionic surfactant, the agent also contains water and / or a nonaqueous solvent and optionally also an acidifier. It may be particularly preferred if the agent also contains no other ingredients.
  • the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
  • the temperature of the main rinse varies depending on the machine type and program level choice between 30 and 75 0 C.
  • rinse cycle rinse aid are added from a dosing tank in the machine, which are usually present in liquid form.
  • a further embodiment of the invention is therefore an agent as described above which constitutes a means for mechanically cleaning a glass surface, in particular a rinse aid for automatic dishwashing, and in particular contains components as further optional constituents, such as are customary constituents of a rinse aid from the state known in the art.
  • the agents according to the invention contain at least one nonionic surfactant.
  • nonionic surfactants are preferably polyalkylene oxides, in particular alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may linear or preferably methyl branched in the 2-position or linear and methyl-branched radicals in a mixture may contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -i 4 -alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, C 13.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside satisfy the general formula R0 (G) z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.
  • nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the following formula
  • RCO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R ⁇ is hydrogen
  • [Z] is a linear or branched polyhydroxyalkyl radical having 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 following formula
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci_ 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives thereof residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced 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.
  • particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • rinse aids according to the invention are preferred which contain surfactants of the general formula (III) as nichionic surfactant (s)
  • R 1 is -O- (CH 2 -CH 2 -O) w - (CH 2 -CHR 2 -O) x - (CH 2 -CH 2 -O) y - (CH 2 -CHR 3 -O) z -H (III)
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 .
  • the preferred nonionic surfactants of the formula (III) can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula (III) may vary depending on the origin of the alcohol. When native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • R 1 in formula (IM) is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • Preferred agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which have a C. 9-i 5 alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • Low-foaming nonionic surfactants are used as preferred surfactants.
  • the agents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
  • compositions are characterized in that they contain nonionic surfactant (s) (e) with a melting point above 2O 0 C, preferably above 25 0 C, more preferably between 25 and 6O 0 C and particular between 26.6 and 43, 3 0 C, included.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity 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 which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as
  • Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C- ⁇ 6 - 2 o-alcohol), preferably a cis-alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 mole Gained ethylene oxide.
  • C- ⁇ 6 - 2 o-alcohol a straight chain fatty alcohol having 16 to 20 carbon atoms
  • a cis-alcohol preferably a cis-alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 mole Gained ethylene oxide.
  • the so-called “narrow rank ethoxylates" are particularly preferred.
  • particularly preferred agents include ethoxylated (s) nonionic surfactant (s), which / from C 6 - 2 o-monohydroxy alkanols or C 6 - 2 o-alkyl phenols or C 16-2 o-fatty alcohols and more than 12 mol, preferably more was recovered as 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol (s).
  • s ethoxylated nonionic surfactant
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight 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 part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.
  • nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 Wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Non-ionic surfactants that can be used with particular preference are available, for example, under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred agent according to the invention contains nonionic surfactants of the formula
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R 3 in the above formula may 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, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • 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 may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, 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 is 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 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl
  • x is n-butyl, 2-butyl or 2-methyl-2-butyl
  • x are values between 1 and 30
  • k and j are values between 1 and 12, preferably between 1 and 5
  • R 1 O [CH 2 CH (R 3 ) O] X CH 2 CH (OH) CH 2 OR 2 in which x is 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 may also be used in conjunction with the surfactants mentioned, these having only minor importance owing to their foaming behavior in automatic dishwashing, and in most cases only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent used, provided that the agent is a machine dishwashing detergent.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
  • surfactant-capped surfactants and nonionic surfactants with butoxy groups are preferably also usable as nonionic surfactants.
  • the first group includes in particular representatives of the formula
  • R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms
  • R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, which is optionally substituted with 1, 2, 3, 4 or 5 hydroxy groups and optionally with further ether groups
  • R 3 is -H or methyl, ethyl, n-propyl, / so-propyl, n-butyl, / so-butyl or terf Butyl and x can take values between 1 and 40.
  • R 2 may optionally be alkoxylated, wherein the alkoxy group is preferably selected from ethoxy, propoxy, butoxy groups and mixtures thereof.
  • surfactants of the above formula in which R 1 n represents a C 9 or CII is 15 alkyl group in this case, R 3 H and x assumes a value of 8 to 15, while R 2 is preferably a straight-chain or Branched saturated Alkrest stands.
  • Particularly preferred surfactants can be defined by the formulas C 9 -ii (EO) 8 -C (CH 3 ) 2 CH 2 CH 3 , Cn.i 5 (EO) i 5 (PO) 6 -Ci 2 -i 4 , C 9 , ii (EO) 8 (CH 2 ) 4 CH 3 .
  • surfactants are also suitable.
  • Such surfactants can be defined by the formula
  • R 1 (EO) a (PO) b (BO) c in which R 1 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c is between 1 and 30, preferably between 1 and 20.
  • R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also usable with preference.
  • Particularly preferred representatives of this group of surfactants can be represented by the formulas C 9 H (PO) 3 (EO) 13 (BO) 15 , C 9 H 1 (PO) 3 (EO) 13 (BO) 6 , C 11 ( PO) 3 (EO) 13 (BO) 3 , C 11 (EO) 13 (BO) 6 , C 9 H (EO) 13 (BO) 3 , C 11 (PO) (EO) 13 (BO) 3 , C ⁇ 11 (EO) 8 (BO) 3 , C ⁇ 11 (EO) 8 (BO) 2 , C 12 _ 15 (EO) 7 (BO) 2 , C 9 _ - I 1 (EO) 8 ( BO) 2 , C 9 ⁇ 1 (EO) 8 (BO).
  • a particularly preferred surfactant of the formula C 13 . 15 (EO) 9 . 10 (BO) 1 . 2 is commercially available under the name Plurafac ® LF 221st It is also possible to use a surfactant of the formula C 12 with preference. 13 (EO) 10 (BO) 2 .
  • agents in particular rinse aids, are preferred which contain the at least one nonionic surfactant in amounts of from 1 to 30% by weight, preferably from 2.5 to 25% by weight, particularly preferably from 3.5 to 20 Wt .-%, and in particular from 5 to 15 wt .-%, each based on the agent included.
  • the glass corrosion-inhibiting multi-armed silicone polyalkoxylates can also be used in combination with other glass corrosion protection agents known from the prior art.
  • compositions according to the invention additionally contain, in addition to the glass corrosion-inhibiting multi-arm silyl polyalkoxylate, at least one corrosion-protecting agent which is suitable for reducing glass corrosion when mechanically cleaning a glass surface.
  • This at least one optionally additionally present corrosion-protective agent is in particular selected from the group of the magnesium and / or zinc salts of at least one monomeric and / or polymeric organic acid, wherein the at least one acid is selected is from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms, the resin acids, the aromatic mono , Di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids.
  • Suitable additional agents which are capable of providing corrosion protection for glassware in cleaning and / or rinsing operations, particularly in a dishwashing machine are compounds containing zinc in oxidized form, i. Zinc compounds in which zinc is cationic.
  • magnesium salts are also preferred. Both soluble and poorly soluble or insoluble zinc or magnesium compounds can be present in the compositions according to the invention, with poorly soluble or non-soluble compounds having to be stabilized against settling in a suitable manner (for example via the parameters particle size of the particles and viscosity of the composition).
  • agents according to the invention contain at least one magnesium and / or zinc salt of at least one monomeric and / or polymeric organic acid.
  • the acids concerned preferably originate from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be included in the compositions according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
  • methanoic acid formic acid
  • ethanoic acid acetic acid
  • propionic acid propionic acid
  • pentanoic acid valeric acid
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • Octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid dodecanoic acid (lauric acid)
  • tridecanoic acid tridecanoic acid
  • tetradecanoic acid myristic acid
  • heptadecanoic acid margaric acid
  • octadecanoic acid stearic acid
  • eicosanoic acid arachic acid
  • Docosanoic acid behenic acid
  • tetracosanoic acid behenic acid
  • Methylpentanoic acid 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-
  • Pentylnonanoic acid 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-
  • Nonyltridecanoic acid 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid) and 3,5-dicarboxybenzoic acid (Trimesionklare).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid and alginic acid.
  • hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-
  • Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid) and 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid) and 4-oxopentanoic acid (levulinic acid).
  • amino acids alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine and histidine.
  • polyacrylic acid polymethacrylic acid
  • alkylacrylamide / acrylic acid copolymers alkylacrylamide / methacrylic acid copolymers
  • Alkylacrylamide / methylmethacrylic acid copolymers copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers and vinylpyrrolidone / vinyl acrylate copolymers.
  • the spectrum of the preferred zinc salts of organic acids ranges from salts which are sparingly soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, to those salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 2O 0 C water temperature).
  • zinc zincate, zinc acetate, zinc lactate, zinc tosylate (p-toluenesulfonic acid Zn salt) and zinc gluconate are included in the group of soluble zinc salts.
  • the agents according to the invention comprise at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate, Zinc lactate and / or Zinkeitrat acts.
  • zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.
  • the at least one anticorrosive agent optionally additionally present in the composition according to the invention, in addition to the glass corrosion-inhibiting multi-arm silyl polyalkoxylate, is particularly preferred in the composition in amounts of from 0.2 to 15% by weight, preferably from 0.5 to 10% by weight preferably from 1, 0 to 7.5 wt .-% and in particular from 2 to 5 wt .-%, in each case based on the agent.
  • the agents according to the invention may contain water and / or other active ingredients and / or auxiliaries ad 100%.
  • the most important ingredients which may be present in the agents according to the invention in addition to multi-arm silicone polyalkoxylates and nonionic surfactants are described below.
  • Acidifying agents can be added to the compositions according to the invention, in particular to set a desired pH. Both inorganic acids such as, for example, hydrochloric or sulfuric acid and organic acids such as, for example, acetic acid, lactic acid or citric acid are suitable here, provided they are compatible with the other ingredients.
  • the agent according to the invention is a rinse aid
  • solid mono-, oligo- and polycarboxylic acids is particularly advantageous.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • the acidifying agents in particular mono-, oligo- and polycarboxylic acids, particularly preferably tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid and especially citric acid, can be used in the agents according to the invention, for example in amounts of from 0.5 to 15% by weight. %, preferably from 1 to 7.5 wt .-%, particularly preferably from 2 to 5 wt .-% and in particular from 2.5 to 4 wt .-%, each based on the agent, be contained.
  • the agents according to the invention may also contain, as buffer substances, salts of the abovementioned acids, i. the acidifying agents described above may be partially neutralized in the composition of the invention.
  • Preferred here are the alkali metal salts, and among these, the sodium salts are particularly preferred.
  • Especially preferred according to the invention is the use of trisodium citrate.
  • the agents according to the invention have an acidic to slightly alkaline pH, in particular a pH of up to 9. Preference is given to pH values from 1 to 6, with pH values from 2 to 4 being very particular are preferred.
  • Non-aqueous solvents which can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-
  • Diethylene glycol methyl ether diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether or mixtures of these solvents.
  • Ethanol is very particularly preferred as the non-aqueous solvent.
  • compositions according to the present invention may further contain hydrotropes, also called solubilizers.
  • hydrotropes also called solubilizers.
  • the addition of such substances causes a poorly soluble substance in the presence of the hydrotrope, which is itself no solvent, becomes water-soluble.
  • Substances which cause such solubility improvement are termed hydrotropes or hydrotropes.
  • Typical hydrotropes e.g. in the preparation of liquid detergents or cleaning agents, are XyIoI and Cumolsulfonat.
  • Other substances e.g. Urea or N-methylacetamide increase the solubility by a structure-breaking effect, in which the water structure in the vicinity of the hydrophobic group of a poorly soluble substance is degraded.
  • Agents preferred in the context of the present invention comprise solubilizers, preferably aromatic sulfonates of the formula
  • each of R 1 , R 2 , R 3 , R 4 , R 5 is independently selected from H or a C 1 - S - alkyl or alkenyl radical and X is a cation.
  • Preferred substituents R 1 , R 2 , R 3 , R 4 , R 5 are independently selected from H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl or neo-pentyl.
  • at least three of said radicals R 1 to R 5 are hydrogen atoms, with aromatic sulfonates being preferred in which three or four substituents on the aromatic ring are hydrogen atoms.
  • the remaining or the remaining two radicals can take any position to the sulfonate group and each other.
  • the radical R 3 is an alkyl radical
  • R 1 , R 2 , R 4 , and R 5 are H (para-substitution).
  • aromatic sulfonates in the context of the present invention are toluene, cumene or xylene sulfonate.
  • paraisomer is preferred in the context of the present invention.
  • Para-isopropylbenzenesulfonate is also the preferred compound in the case of the cumene sulfonates.
  • XyIoI is used industrially mostly as a mixture of isomers
  • the technically available xylene sulfonate also represents a mixture of several compounds resulting from the sulfonation of ortho, meta and para xylene result.
  • X in the general formula given above represents a cation, for example an alkali metal cation such as sodium or potassium.
  • X may also represent the equivalent charge portion of a more cost cation, such as Mg 2+ / 2 or Al 3+ / 3, wherein the said cations, sodium is preferred.
  • Further preferred embodiments of the present invention are means for mechanically cleaning a glass surface, in particular rinse aid for automatic dishwashing, comprising a) 0.05 to 10, preferably 0.1 to 7, particularly preferably 0.2 to 5 and in particular 0.3 to 3 wt .-% of at least one multi-armed silyl polyalkoxylate of the formula (I) b) 0.1 to 40, preferably 1 to 20, particularly preferably 5 to 20 wt .-% of at least one nonionic surfactant, in particular a mixture of at least one Polyalkoxylate and at least one end-capped poly (oxyalkylated) nonionic surfactant c) 0 to 15, preferably 1 to 10, particularly preferably 2 to 7 wt .-% of at least one Acidaimssstoffs d) 1 to 20, preferably 2 to 15, particularly preferably 3 to 10 wt % of at least one nonaqueous solvent and / or solubilizer e) water.
  • composition is a concentrate which is to be diluted before use, then the content of nonionic surfactants is in the upper range of the stated range, while for a ready-to-use agent it is in the lower range of the indicated range, and preferably up to about 15% by weight. -% is.
  • the agents according to the invention may additionally comprise one or more substances from the groups of soil release polymers, dyes and fragrances.
  • soil release compounds which prevent the re-soiling of surfaces and / or facilitate the removal of soil after a single use are so-called "soil release compounds".
  • the soil release compounds which can be used according to the invention include all known compounds known in the prior art.
  • Particularly suitable are cationic polymers, in particular polymers with imino groups, cationic cellulose derivatives or cationic homo- and / or copolymers with quaternized ammonium alkyl methacrylate groups as monomer units.
  • the cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups as soil release compounds.
  • monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; qua
  • Natural polyuronic acids and related substances as well as polyampholytes and hydrophobized polyampholytes, or mixtures of these substances, are particularly preferred within the scope of the invention.
  • the agents according to the invention can be dyed with suitable dyes.
  • Dyes which are preferred in the context of the present invention and whose selection is not difficult for the skilled person, possess a high storage stability and insensitivity to the other ingredients of the compositions and to light, and in particular no pronounced substantivity towards dishes in order not to stain them.
  • Preferred for use in the compositions according to the invention are all colorants which can be oxidatively destroyed and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, is, as well as mixtures thereof with suitable. blue dyes.
  • CI Color Index
  • Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.
  • the colorants When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the surfaces to be treated and, in particular, for plastics possibly present at the same time. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the compositions according to the invention varies. For highly soluble colorants, such as the Basacid Green ® above or also above Sandolan Blue ®, are typically dye concentrations in the range of a few 10 -2 to 10 3 selected wt .-%.
  • the appropriate concentration of the colorant is typically a few 10 3 to 10 wt .- ⁇ 4%.
  • compositions according to the invention may furthermore comprise at least one perfume, in particular a perfume.
  • the agent of the invention is a dishwasher detergent or a rinse aid, can be eliminated by late release of the perfume in the rinse cycle often occurring in dishwashers "alkali odor" when opening the machine.
  • Fragrances may also be added to the compositions within the scope of the present invention to enhance the aesthetics of the products and to provide the user with a visually and sensory "typical and distinctive" product in addition to the performance of the product.
  • all substances and mixtures of substances which are customary for the perfuming of cleaning agents and which are compatible with the other constituents of the agents according to the invention may in principle be used as perfume oils or fragrances.
  • Another object of the present invention is the use of an agent as described above to reduce glass corrosion and / or to improve the drying performance of cleaning a glass surface mechanically, especially in automatic dishwashing.
  • the starting material used was a polyether polyol which is a 6-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of 80/20 and a molecular weight of 12,000 g / mol, obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator.
  • the polyether polyol was heated under vacuum for 1 h at 80 0 C with stirring.
  • Voranol CP 1421 from DOW Chemicals was dried under vacuum with stirring for 1 h at 80 0 C.
  • To 2.04 g (0.41 mmol) of the dried polyether polyol was slowly added 317 mg (1.0 equivalents) of 3-isocyanato-propyltriethoxysilane.
  • the reaction mixture was further stirred under inert gas at 100 ° C. for 2 days until the vibration band of the NCO group disappeared upon IR measurement.
  • Voranol 4053 from DOW Chemicals was vacuum with stirring for 1 h at 80 0 C dried.
  • To 209 g (16.9 mmol) of the dried polyether polyol was added 20.9 mg (0.01%).
  • Dibutyltin dilaureate and 30.3 g (1, 0 equivalents) of 3-isocyanato-propyl-triethoxysilane slowly added.
  • the reaction mixture was further stirred under inert gas at room temperature for 2 days until the NCO band disappeared on IR measurement.
  • the product was obtained, which in each case has a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol and represents a mixture of a 3-armed and an 8-armed polyalkoxylate in a ratio of about 20/80, as a colorless viscous liquid.
  • a formulation F with the following composition was prepared: 1.0% by weight of the triethoxysilyl-terminated polyalkoxylate from Example 1 20.0% by weight of ethanol 79.0% by weight of water.
  • a continuous domestic dishwashing machine type Miele G 6xx various commercially available drinking glasses and plates were rinsed at a water hardness of 0-1 ° dH with a commercial, available as Tab machine dishwashing detergent.
  • 1 ml of Formulation F was automatically metered directly into the machine.
  • the following table shows the results for glass corrosion (haze and line corrosion) after 50 rinse cycles:
  • silyl polyalkoxylate As the silyl polyalkoxylate, the six-armed triethoxysilyl-terminated polyalkoxylate of Synthesis Example 1 was used.
  • the formulation G consisted of: x g silyl polyalkoxylate (values of x see table) y g tetraethoxysilane (values of y see table)
  • silyl polyalkoxylate the mixture containing a three-armed and an eight-armed
  • Triethoxysilyl-terminated polyalkoxylate from Synthesis Example 3 is used.
  • the formulation G consisted of: x g of silyl polyalkoxylate (values of x see table) ad 100 g of water.

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Abstract

L'invention concerne l'utilisation d'un silyle-polyalcoxylate à plusieurs branches de formule (I), (H-A)n-Z-[A-B-Si(OR1)r(R2)3-r]m (I), dans laquelle Z représente un radical (m+n) valent comprenant au moins trois atomes de carbone, A représente un radical polyoxyalkylène bivalent, les m+n radicaux polyoxyalkylène reliés à Z pouvant être différents les uns des autres et un radical A étant relié avec B ou l'hydrogène par un atome d'oxygène appartenant à Z et un atome d'oxygène appartenant à A, B représente une liaison chimique ou un radical organique bivalent ayant de 1 à 50 atomes de carbone, OR1 représente un groupement hydrolysable, R1 et R2 représentent indépendamment l'un de l'autre un groupement alkyle linéaire ou ramifié ayant de 1 à 6 atomes de carbone et r représente un nombre entier de 1 à 3, m présente un nombre entier ≥ 1, n représente 0 ou un nombre entier ≥ 1 et m+n représente une valeur de 3 à 100, pour la réduction de la corrosion du verre et/ou pour l'amélioration des performances de séchage lors du nettoyage automatique d'une surface de verre. L'invention concerne également un agent, notamment pour le nettoyage de surfaces en verre, contenant les composés de formule (I).
EP07802796A 2006-12-05 2007-08-22 Agent de nettoyage pour surfaces en verre Not-in-force EP2109663B1 (fr)

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US (1) US7897554B2 (fr)
EP (1) EP2109663B1 (fr)
AT (1) ATE483014T1 (fr)
DE (1) DE502007005234D1 (fr)
PL (1) PL2109663T3 (fr)
WO (1) WO2008068061A1 (fr)

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
DE102008008593A1 (de) * 2008-02-12 2009-08-13 Schott Ag Anti-Kratz-Beschichtung, Verfahren zu deren Herstellung und deren Verwendung
DE102009029060A1 (de) * 2009-09-01 2011-03-03 Henkel Ag & Co. Kgaa Mittel zur Behandlung harter Oberflächen
GB201019988D0 (en) * 2010-11-25 2011-01-05 Reckitt Benckiser Nv Composition
CN105829517B (zh) 2013-12-16 2020-01-17 3M创新有限公司 洗涤剂和漂洗助剂组合物以及方法
CN113748192B (zh) 2019-04-12 2023-08-29 埃科莱布美国股份有限公司 抗微生物多用途清洁剂及其制备和使用方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3825678A1 (de) 1988-07-28 1990-02-01 Wacker Chemie Gmbh Reinigungs- und/oder konditioniermittel fuer glaskeramikoberflaechen, enthaltend organopolysiloxane
US4917812A (en) 1989-02-13 1990-04-17 The Procter & Gamble Company Granular automatic dishwasher detergent composition providing glassware protection containing insoluble zinc compound
US5073286A (en) * 1989-11-20 1991-12-17 Basf Corporation Stable alkyl and/or aryl silyl ether capped polyether surfactants for liquid cleaning agents containing hypohalite bleaches
AR019107A1 (es) 1998-04-27 2001-12-26 Dow Global Technologies Inc Polioles de alto peso molecular, proceso para su preparacion y uso de los mismos.
DE19860670A1 (de) 1998-12-29 2000-08-10 Benckiser Nv Wasserlösliches Glas als Korrosionsschutz in einer Geschirrspülmaschine
EP1245667B1 (fr) * 2001-03-26 2005-10-26 The Procter & Gamble Company Procédé de nettoyage de surfaces dures avec un produit liquide comprenant un agent de blanchiment
DE10204523A1 (de) 2002-02-05 2003-08-07 Bayer Ag Alkoxysilan- und OH-Endgruppen aufweisende Polyurethanprepolymere mit erniedrigter Funktionalität, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung
KR20040040782A (ko) 2002-11-08 2004-05-13 선바이오(주) 신규한 헥사-암 폴리에틸렌글리콜과 유도체 및 그의합성방법
EP1553160B1 (fr) * 2003-12-29 2007-10-17 The Procter & Gamble Company Compositions de rinçage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008068061A1 *

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ATE483014T1 (de) 2010-10-15
PL2109663T3 (pl) 2011-04-29
US20090298736A1 (en) 2009-12-03
EP2109663B1 (fr) 2010-09-29
DE502007005234D1 (de) 2010-11-11
WO2008068061A1 (fr) 2008-06-12
US7897554B2 (en) 2011-03-01

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