JPH06501729A - liquid detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] liquid detergent composition Technical field FIELD OF THE INVENTION This invention relates generally to aqueous liquid detergent compositions, and more particularly to hard surfaces, e.g. , highly greasy properties from dishware and other articles used in food preparation and consumption The present invention relates to a liquid detergent composition intended to remove soils.

Background technique Liquid detergent compositions intended for use as dishwashing products typically contain a "core" surfactant. one or more sulfate and sulfonate anionic detergents as agents and foam boosters It takes the form of an aqueous solution containing an agent or a mixture with a foam stabilizer. Foam stabilizers are can take the form of amide derivatives, amine oxides, and ethoxylated fats. aliphatic alcohols, zwitterionic surfactants, such as betaine, or some of these It is a mixture of things. The amount of these types of substances used usually ranges from 2 to 8 parts by weight of the composition. % by weight, usually within the range of 3 to 5% by weight.

One group of amide derivatives that have been suggested for foam enhancement and stabilization purposes are N-alkanoyl -N-alkylglucamine. These substances are derived from glucose and two lower alkylamines are reacted with glucose to produce glucamine, and then This is treated with a methyl ester of a fatty acid of the desired chain length to produce N-alkanoyl-N- It can be produced by providing an alkyl glucamine.

Compounds of this type are described, for example, in US Pat. No. 2,703,798, WO 831 No. 04412 and British Patent No. 809060.

The last patent mentioned is an organic sulfuric acid that has a sulfate or sulfonic acid group in its molecular structure. At least one water-soluble salt of the reaction product and 5 to 6 of the water-soluble organic sulfuric acid reaction product A detergent composition is disclosed containing an amide derivative of the above type in an amount of 0% by weight. Ami Derivatives are used in Latin American countries, where cleaning is done at low temperatures of around 100 liters. It is said to provide improved foaming properties of the composition at temperatures below 'F.

Although the patent contemplates that the surfactant combination can be used alone, A newly exemplified embodiment combines a phosphate builder and a sodium sulfate filler. It is a granular product.

Applicant has disclosed that N-alkanoyl-N-alkyl glucamide as a core surfactant. builder-free fluids containing combinations of surfactants and sulfonated or sulfonated surfactants. Detergent compositions in body or gel form exhibit superior foaming mileage (mi) compared to known products. leage) from hard surfaces with benefits in performance and considerable skin mildness. has now been discovered to provide significant improvement in the removal of grease stains. anion monkey Phate or sulfonate surfactants and N-alkanoyl-N-alkyl groups Mixtures with Cumin are a means of obtaining improved foaming of built products at lower wash temperatures. However, it has now been found that grease removal and The performance aspects of skin and skin mildness properties were previously unrecognized.

Demonstration of invention Therefore, according to the invention, by weight of the mixture a) at least one water-soluble anion 5% to 95% of surfactant salts, b) 9 of the mixture 5-5% by weight general formula (where Z is a linear chain having at least three hydroxy groups directly connected to the chain) A polyhydroxyhydrocarboxyl moiety having a dolocarpyl chain; minutes are derived from glucose and its mixture with maltose; maltose is a mixture of R is a saturated or unsaturated aliphatic group having 8 to 16 carbon atoms or or a mixture of such groups, where R is C-C alkyl or C2-C4 hydroxy is an alkyl group) one or more compounds having a core surfactant mixture (15-65% by weight of the composition) comprising; It has a 2" crack mineral hardness (Ca:Mg ratio 3:1) and a temperature of 48℃. A 0.12% by weight aqueous solution of the surfactant mixture of said composition in water is: i) spinny less than 0.2 Pacm using 99.7% purity triolein stain; Drop interfacial tension (IFT) ID: One or more anionic surfactant components alone Grease stains obtained under the same conditions in the same test using a 0.12% solution of polypropylene cup (PPC) test with at least 1.4 times the removal value. Grease dirt removal value A builder-free liquid or gel in the form of a physically stable aqueous solution characterized by having A detergent composition is provided.

For the purposes of this invention, "physically stable" means no precipitation after storage for 3 months at a temperature of 21°C. This is interpreted to mean maintenance of a single phase state. If the product contains an emulsifying agent, No or minimal settling of the emulsifier should occur. Furthermore, the IFT and water-soluble anionic sulfate or sulfonate worlds for PPC test measurements. The one or more cations of the surfactant correspond to the one or more cations in the detergent composition. If a mixture of cations is present, each cation It will be the weight percentage present in the mixture.

A preferred composition according to the present invention comprises a component (b) compound (polyhydroxyhydrocarbon The building part is derived from glucose or its mixture with maltose, (accounting for up to 25% by weight of the mixture). Commercially available technical grade glucose contains maltose as an impurity in an amount of up to 5% by weight. For the purposes of the present invention, What is referred to below as glucamine is a corresponding substance derived from maltose up to 5% by weight. It should be interpreted as a substance that includes.

Suitable anionic sulfate or sulfonate surfactants include alkyl Containing on average up to 6 moles of ethylene oxide per mole of ethoxysulfate. C-C alkyl ethoxy sulfate, C1 to C18 baraffin sulfone N-09~C17 acyl N-01~C4 alkyl glucamine sulfate Examples are:

Compositions useful according to the invention include N-coconut acyl in an amount of 9 to 15% by weight of the composition. -C12-C14 alkyl ethoxy sulfate together with N-methylglucamine Average of 0.4 to 4.0, preferably 0.3 to 3.0 ethylene per mole of Primary C1°-C14 alkyl ethoxy sulfate containing oxide group (9-18% by weight of the composition).

Preferred compositions have a weight ratio of anionic surfactant to glucamine of 2:1 to 1:1. use. A particularly preferred composition is C12-C14 alkyl ethquin sulfate. Weight 10-18? 6 and glucamine surfactant 7-15% by weight. . The alkyl ethquin sulfate itself is preferably in a weight ratio of 2.1 to 5:1. A substance having an average of about 0.8 mole 1 mole of ethylene oxide and ethylene oxide in a ratio of about 4:1. It consists of a mixture of substances having an average of 3.0 moles of oxide per mole.

Preferably, the composition according to the invention comprises C1o-C16 alkyl mono- or di- C-C3 alkanolamide, C12-C16 alkyl or alkylamidoben tine, 012-C14 alkyl sulfobetaine, C1o-C16 alkyl di-C Alkyl or diC2-4 hydroxyal 1-4 Kylamine oxide, an average of 7 to 12 moles of ethylene oxide per mole of alcohol C-012 primary alcohol ethoxylates containing side groups and mixtures thereof It also contains 1 to 8% by weight, most preferably 2 to 7% by weight of a foam enhancer selected from compounds. .

Preferred foam enhancers are in amounts of 1 to 5%, preferably 1.5 to 3% by weight of the composition. C12-C14 alkyl betaine and C-C, □th in an amount of 6-8% by weight of the composition. From a mixture with a primary alcohol ethquinate (preferably C alkyl EO8) It had become.

Another preferred component of such compositions is more preferably up to 1.5 weight 96 of the composition. is 0,5. Mg++ in an amount of ~1.0% by weight. Particularly preferred compositions include In addition to magnesium ions, it also contains calcium in an amount of 0.3-0.5% by weight .

BEST MODE FOR CARRYING OUT THE INVENTION The detergent composition according to the invention comprises 15 to 65% by weight of the composition, preferably 20 to 50% by weight of the composition. %, more preferably a mixture of core surfactants in an amount of 22-40% by weight. . The mixture contains 95-5% by weight of the mixture N-C8-C16 acyl N-C-C4 Along with the alkyl glucomine non-ionic surfactant detergent, as little as 5-95% by weight of the mixture. at least one water-soluble anionic sulfate or sulfonate surfactant salt; It will be. Preferably, the mixture contains 20% to 80% anionic surfactant and alkaline surfactant. Quilglucamine 80% to 20%, most preferably anionic surfactant 40% to 7 0% and 60% to 30% alkylglucamine.

Anionic surfactants are essentially any organic sulfate or sulfonate. It is usually a C11-C15 alkylbenzene, although it can also be a surfactant salt. "C10' = C16 alkyl sulfate and alkyl ethoxysaccharide Those containing up to 6 moles of ethylene oxide per mole of sulphate xy analogue, 013-018 paraffin sulfonate, C10””C16 oleph Insulfone "C10" 20 alkyl glyceryl ether sulfonate, c -c17 acyl-N-C1-C4 alkyl or 02-C4 hydroxyalkyl selected from luglucamine sulfate and mixtures of any of the foregoing.

Preferably, the anionic surfactant is an alkyl ethoxy sulfate, an alkyl selected from glyceryl ether sulfonates and paraffin sulfonates.

The alkylbenzene sulfonates useful in the compositions of the present invention include substantially linear alkylbenzene sulfonates. the alkyl group has 10 to 16 carbon atoms, preferably 11 to 13 carbon atoms A substance having an average carbon chain length of 11.8 is most preferred. phenyl Although the sex distribution, i.e. the point of attachment of the alkyl chain to the benzene nucleus, is not critical, Preferred are alkylbenzenes with a high 2-phenyl isomer content.

Preferred alkyl sulfates include those in which the alkyl group has 10 to 16 carbon atoms, more preferably preferably with an average of 12 to 14 carbon atoms (preferably in the linear chain) It is an alkyl sulfate. Natural fat or Ziegler oleaf, in-growth, or or C1o-016 alcohol derived from oxo synthesis, with suitable alkyl groups. constitute the source. Examples of synthetically derived materials include Shell Chemicals Dobanol 23 (marketed by Country) Limited ( Ethyl (registered trademark), sold by Ethyl Corporation yl) 24, manufactured by BASF GmbH under the trade name Lutensol (Lutenso CI3~C15 Alco with a ratio of C 67% and C1533% sold in l) Synperonic blends and sold by ICI Limited (Synperonic) (registered trademark) and Liquitimica Italiana. An example of this is the Lial 125 sold by the company. alcoholic Examples of naturally occurring substances that are raw materials are coconut oil and palm kernel oil and the corresponding fatty acids. .

Alkyl ethoxy sulfate surfactants contain C1o to C16 alcohols and average Primary alkyl ethoxylates derived from condensates with up to 6 ethylene oxide groups Consists of cisulfate. C10""C1B alcohol itself is an alkyl sal It can be obtained from any of the sources mentioned above in the case of the phase component. 012～0 13 alkyl ether sulfates are preferred.

A conventional base-catalyzed ethoxylation process to yield an average degree of ethoxylation of 6 Distribution of individual ethoxylates with 1 to 15 ethoxy groups per mole of alcohol , and the desired average can therefore be obtained in various ways. specific to use Different degrees of ethoxylation resulting from ethoxylation techniques and subsequent processing steps such as distillation and/or blends of materials with different ethoxylate distributions can be prepared. Ru. For example, alkyl sulfates and alkyl triethoxy ether sulfates Foaming and degreasing performance equivalent to that provided by blending with and degreasing performance by reducing the amount of alkyl sulfate and alcohol 1 Using an alkyl ether sulfate having an average of about 2 ethoxy groups per mole, It has been found that it can be obtained by using

In preferred compositions according to the invention, the average degree of ethoxylation is between 0.4 and 1.0. The material has an average degree of ethoxylation of 2.0 to 4.0, more preferably about 0.8. Preferably, the alkyl ethoxy sulfate in combination with a substance having a A mixture is used.

The secondary alkanesulfonates useful in this invention have 13 to 18 carbon atoms per molecule. It has elementary atoms, more preferably 13 to 15 atoms per molecule. These spaces The sulfonate is preferably cut in paraffin corresponding to said chain length using a well-known standard. Manufactured by subjecting to the action of sulfur dioxide and oxygen according to the oxidation method . The product of this reaction is a secondary sulfonic acid, which in turn is a secondary sulfonic acid. The acid is neutralized with a suitable base to provide the water soluble secondary alkyl sulfonate. similar Secondary alkyl sulfonates can be prepared by other methods, e.g. by sulfochlorination methods. In this sulfochlorination method, chlorine and sulfur dioxide are The resulting sulfonyl chloride is hydrolyzed and neutralized. Produces secondary alkyl sulfonate. No matter which technique is used, sulfonates has no or only a limited proportion of unreacted starting hydrocarbons and is free of inorganic salts. Manufacture as a monosulfonate with little or no by-products is usually desirable. Similarly, the proportion of disulfonates or higher sulfonates is Although it may be limited, some amount may exist. Monosulfonate is terminally sulfonated or the sulfonate group may be attached on the 2-carbon or other carbon of the linear chain. You may. Similarly, the accompanying dihydrogen usually produced when excess sulfonating agent is present. Sulfonates are sulfonates distributed on different carbon atoms in a paraffin base. may have a monosulfonate group, and a mixture of a monosulfonate and a disulfonate is , may exist.

of monoalkanesulfonates in which the alkane has 14 and 15 carbon atoms Particularly preferred are mixtures (sulfonates are C14-C15 paraffins in a weight ratio of 1: 3 to 3=1).

Olefin sulfonates useful in the present invention include alkene-1-sulfonates and alkene-1-sulfonates. Alkene hydroxysulfonate and alkene disulfonate and hydroxydisulfone P.F. on July 25, 1967.

Commonly Assigned U.S. Patent No. 3332 issued to Fraumer and A. Kerasler. Preferred alkyl glyceryl ether sulfonates described in US Pat. is derived from coconut oil and tallow ether.

Other sulfate surfactants include N-C9-C acyl-N-C1-C4 acyl. Lucil Glucamine Sulfa ate, preferably the C9-C17 acyl group is derived from coconut oil or palm kernel oil. It is something that can be done. These materials are disclosed in U.S. Pat. No. 2,717,894. It can be manufactured by

Counterions for anionic surfactant components include sodium, potassium, magnesium, Any one of ammonium or alkanol-ammonium or their It can be a mixture. In the case of the liquid composition of the invention, sodium is preferred. Although potassium is a suitable counterion, the composition of the present invention is completely transparent and precipitated. If it is important to have a high resistance to gluteal formation, sodium or Also preferred.

In the gel-form composition of the present invention, sodium is added to potassium for the purpose of forming a gel. or ammonium. A preferred liquid detergent composition according to the invention is , has a chill point of less than 8°C, preferably less than 5°C, and is oxidized by ammonium ions. at least partially neutralize.

If calcium and/or magnesium ions are present, oxidation The surfactant acid can be introduced as a compound or hydroxide to neutralize the surfactant acid, or water can be added to the composition. Can be added as a soluble salt. However, a significant amount of such salts can be used according to the present invention. Additions to dishwashing compositions may reduce the temperature at which inorganic salt crystals form in the composition upon cooling. therefore, the amount added in this way should be minimized.

In a preferred composition according to the present invention, calcium ions and magnesium ions The mixture with Ca contains up to 1% by weight of the composition, more preferably 0.3-0. 5% by weight of Ca and up to 1.50% by weight of Mg 1, preferably from 0.5 to 1 May be added to provide 1.0% by weight Mg++. The preferred mixture is mug rich in nesium, more preferably providing a Ca”:Mg weight ratio of 1:1 to 1:4. Ru. Compositions containing Mg and/or Ca have extremely low water hardness. 6 Clark) conditions, and also product concentrations higher than 0.5% by weight are of particular value. be.

The second core surfactant component of the builder-free liquid compositions of the present invention has the general formula (wherein Z is a linear hydrogen chain having a small number of A polyhydroxyhydrocarbyl moiety having a dolocarpylic chain, said moiety is Derived from glucose and its mixture with maltose, maltose is /Ifl It accounts for 33% by weight or less of a substance, and R is a saturated or unsaturated aliphatic group having 8 to 16 carbon atoms. group or a mixture of groups, and R1 is C1-C4 alkyl or C2-C4 hydroxylalkyl group) It is a compound of

R can be derived from any of the hydrocarpyl radicals described above for anionic surfactants. It is preferably natural in origin. Preferably, R has 12 carbon atoms. It has an average chain length of ~14 and is derived from coconut oil or palm kernel oil. R1 is good Preferably, it is a methyl group.

The synthesis of the present glucamine compounds is known in the art and does not form part of the present invention. . As mentioned above, U.S. Pat. No. 2,703,798 discloses that N-alkanoyl-N - Typical manufacturing method for alkyl glucamines (the process has two main steps) ) is disclosed. The first step is to combine glucose and primary alkylamine with hydrogen. and reacted at high temperature and pressure in the presence of a hydrogenation catalyst to produce glucamine. includes doing. This is then reacted with an ester at high temperature to form an N-alkaline Noyl-N-alkylglucamine is produced. Add a small amount of sodium methoxide. It has been found that it is advantageous to add it as a catalyst in the second step of the process.

N-alkanoyl-N-alkylglucami in liquid and gel form compositions of the invention The preferred amount of FFI is 8-25% by weight, more preferably 9-18% by weight, Most preferably it is 10-15% by weight.

Physically stable compositions according to the present invention provide calcium ions in the absence of magnesium ions. can be formulated using mu-ions, unreacted starting materials, impurities and by-products, especially High purity N-alkanoyl-N-alkylglucami with minimal fatty acid content Requires the use of

In the broadest aspect of the invention, the remainder of the liquid detergent composition is made up of water. or, in the case of gel-form compositions, by a gelling agent and water. Ru.

However, in preferred compositions, other functional ingredients are also included and one type of The total weight of the above surfactant and glucamine component is preferably 20 to 40% by weight. Preferably, it is within the range of 22 to 30% by weight.

A highly desirable optional ingredient is one or more foam control agents or foam boosters, which typically Present in individual amounts of 1-8% by weight of the composition. These substances consist of additional It also has functional value, for example as a soil suspending agent. one such increase The foaming agent is C1o-016 alkyl mono or di-C2-C3 alkanolamide. Examples include coconut alkyl monoethanolamide, coconut Alkyl jetanolamide and palm kernel and coconut alkyl mono-olamide and di-isopropaturamide. palm kernel or coconut tree The kill residues may be "all cut" including C1o and cl-min, and may be a so-called "narrow cut" c12-C fraction. c - c Alki Combination of group 14 10 1B Origin can also be used.

Another useful foam enhancer has the general formula (In the formula, R is CLO=c1B alkyl, and R2 is C1-C3 alkyl. the law of nature, R3 is -(CH2)3 group or H ■ -(CH2-CH-CH2) group, and Y is i n and m are O or 1, X- is CH2C00- or SO3; however, if X- is CH2C00- If m is 0 and X- is S03, then n is O and m is 1 ) It is a zwitterionic surfactant.

More preferably, R1 has an average carbon chain length of 12 to 16 carbon atoms and is a synthetic source. (in this case, the chain may contain some branching), or natural fats (in this case, the chain may have some branching); In some cases, the chain is linear and contains trace amounts of C8-C1o and C14-C18 moieties. may be derived from).

The synthesis source of the R1 group is the same as described above for the alkyl group in the anionic surfactant component. It may be the same as

Still other types of foam enhancers useful in the present invention include the general formula R1R2R3N→0, where R , is an alkyl group having 10 to 16 carbon atoms, and R2 and R3 are each independently 01 to 16. amine group (selected from C3 alkyl and C2-C3 hydroxyalkyl groups) It is oxido. Preferred members of this class include dimethyldodecylamine oxide, dimethyltetradecylamine oxide, bis-(2-hydroxyethyl ) dodecylamine oxide and their analogues (dodecyl or tetradecyl portions derived from natural sources such as coconut oil and palm kernel oil).

Preferred foam control agents are ethoxylated alcohols or ethoxylated alcohols of the above composition. It is a mixture of

The ethoxylated alcohol has an average of 1.5 to 25 ethoxylated alcohols per mole of alcohol, more preferably or containing from 2 to 15, most preferably from 6 to 10 moles of ethylene oxide. Consisting of 6-013 aliphatic alcohol ethoxylates. fatty alcohol ethoxylate Sylates are ethoxylated alcohols containing on average less than 8 moles of ethylene oxide 1% by weight or less of non-ethoxylated alcohol, and ethoxylated alcohol When containing an average of 8 to 25 moles of ethylene oxide per mole of alcohol, Contains less than 2% by weight of non-ethoxylated alcohol.

The starting alcohol may be a primary or secondary alcohol, but is preferably is a primary alcohol which may be derived from natural or synthetic sources. Thus, natural oil The products of fat or Ziegler olefin augmentation reactions or oxo synthesis are all carbon They may be used as sources of hydrogen chains, and their structures may be linear or branched in type. Good too.

A preferred alcohol chain length range is 09-c11.

The reason for this is that when ethoxylates produced from such alcohols are blended, the It was found that the foaming volume and mileage performance of the composition according to the invention are optimal. It is empty. Also, for performance reasons, hydrophilic and lipophilic ballasts of ethoxylated alcohols (HLB)i;1. ．． 8.0 to 17.0°, preferably 11.0 to 17.0 ．． Most preferably, it is within the range of 11,0 to 15.0. preferable Alcohol ethoxylates contain an average of 8 ethylene oxides per mole of alcohol. primary alkyl containing on average 10 carbon atoms in the alkyl chain fused with the side group; Cole ethoxylate.

Alkyl ethoxy sulfates as anionic surfactant components were discussed. As shown in FIG. Shiv The conversion method uses 1 to 15 moles of ethylene oxide per mole of alcohol. resulting in a distribution of sylate species.

An increase in E is due to a slight change in this distribution, mainly due to non-Et v Although an increase in E3-5 results in a decrease in the amount of oxides, v There will still be 5-10% of this material remaining in the ethoxylated product.

In the liquid dishwashing detergent composition of the present invention, this amount of non-ethoxylated would give rise to temperature/chill point problems and/or would be unacceptable to consumers and Producing products with fatty alcohol odors that cannot be masked by detergent fragrances It would be cheating. Acceptable non-ethoxylated alcohols in ethoxylated alcohol components The maximum amount of 1% by weight was found to be 1% by weight. More preferably non-ethoxy The amount of ethoxylated alcohol is 0.7% or less, most preferably ethoxylated alcohol. less than 0.5% by weight of the component.

Distillation under vacuum is used to remove undesirable substances and this Also remove a portion of the ethoxylate fraction, thereby increasing the E of the remaining material. Ru.

V In a preferred embodiment of the invention, the amount of monoethoxylate is It is less than 5% by weight of coal.

In preferred compositions according to the invention, the combination of foam regulators or foam enhancers is , each present in an amount of 1 to 10% by weight, more preferably 2 to 8% by weight. Ru.

One such preferred combination is 012-c14 alkyl dimethyl betaine and condensed with an average of 7 to 9 moles of ethylene oxide per mole of alcohol. 09-c11 alcohols (each substance present in an amount of 2-8 1% by weight of the composition).

In preferred compositions, the remainder of the formulation is a hydrotrope-water system (hydrotrope-water system). The rope is made of urea, Ct　””’　Cs aliphatic alcohol, lower alkyl or dia alkylbenzene sulfonates, e.g. toluene sulfonate, xylene sulfonate nate, or cumene sulfonate, or a mixture of any of these. It consists of

Usually a single hydrotrope will be adequate to provide the required phase stability, but The composition according to the invention preferably achieves the desired viscosity and remains stable and Urea-alcohol-water, alcohol-lower alcohol alkylbenzene sulfonate - water, urea - lower alkylbenzene sulfonate - Use a mixture such as water. Compositions having an organic active concentration of less than about 40% by weight In some cases, the preferred alcohol hydrotrope comprises 3 to 10% by weight of the composition, preferably Preferably ethanol (usually in a mixture with urea) used at 4-8% by weight. . For compositions with organic active concentrations greater than about 40% by weight, ethanol Mixtures of urea and/or lower alkylbenzene sulfonates are preferred. Yes. Mixtures of hydrotropes are, of course, cost-effective, independent of stability/viscosity considerations. Can be used for efficacy reasons.

Other components of the liquid detergent composition of the present invention include ethylene glycol distearate. Emulsifying agents such as guar gum, thickening agents such as guar gum, glutaraldehyde, pronopol Bactericides such as (Bronopol) (registered trademark), benzoxytriazole anti-fogging agents such as, heavy metal chelating agents such as EDTA, ETDMP, fragrances and and dyes. The PH of the composition may be anywhere within the range of 6.0 to 8.5. However, as manufactured, the composition usually has a pH of 6.5 to 7.3 and a desired degree of completion. A final pH adjustment operation is carried out to obtain the product pH. In the case of colored products, the pH is Preferably, it is within the range of 6.5 to 7.2 in order to maintain color stability.

Although the compositions of the present invention can be prepared in a number of ways, the zwitterionic surfactants incorporated therein The agent is added at the end of the process if it does not actually constitute the last ingredient to be added. That's preferable. This indicates that the zwitterionic surfactant under the acidic conditions present at the beginning of the process It minimizes the risk of deterioration of the sexing agent and also facilitates control of the viscosity of the finished product. Gurkha Min surfactants contain less than 4 or more than 10 to prevent hydrolysis of the surfactant. It should not be exposed to too high a pH.

Thus, the one or more anionic surfactants have a pll adjusted from 4 to 10. can be prepared as an aqueous solution of an alkali metal salt or an ammonium salt; After mixing the aqueous solution with N-alkanoyl-N-alkylglucan, the ethoxylated mixed with an ionic surfactant and one or more other foam enhancers and hydrotropes; Calcium or magnesium ions are then converted into water such as chloride, sulfate, etc. Can be introduced as a soluble salt. The zwitterionic surfactant and minor components are then adjusted to Add at the same time as adjusting the viscosity. This method utilizes conventional techniques and equipment It has the advantage of lowering the chill point temperature (where inorganic salts precipitate as crystals in a liquid). resulting in the introduction of additional chloride or sulfate ions, which may increase Ru.

Preferred groups containing alkyl ethoxy sulfates as anionic surfactants In the composition, the desired alcohol and alcohol ethoxylate are - Mixable and single sulfation and neutralization then for these two substances It can be carried out. For this purpose, alcohols and alcohol ethoxylates are , should be mixed in a weight ratio of 4:3 to 1:6. However, the most preferred technique In the technique, the amount of alcohol and ethoxylated alcohol species is Single alcohol ethoxylate controlled to give desired ratio of quality Prepare the stock.

Sulfation (sulfonation) of alcohols and alcohol ethoxylates is a trioxidation Do not use any of the usual sulfonating agents such as sulfur or chlorosulfonic acid. Can be used. Neutralization of the alkyl ether sulfates and alkyl sulfates is then carried out using appropriate with alkali or with magnesium, calcium, or magnesium/calcium The process is carried out with a slurry of oxide or hydroxide. The amount of anionic surfactant is the desired C a and all of the Mg++ ions to be added in this way. If not sufficient, the remainder can be added in the form of a water-soluble salt.

The gel composition of the present invention can be prepared using the general method described in U.S. Pat. No. 4,615,819. It can be prepared using

The composition according to the invention has a low threshold, which is an indication of its ability to emulsify grease and oil stains. Removes surface tension (IFT) and grease stains from surfaces and suspends them in solution. High polypropylene cup (PPC) wear and excellent skin It is characterized by its mild skin.

This combination is not normally found in liquid detergent compositions.

Furthermore, the composition according to the invention has a high resistance to both hard and soft water compared to prior art compositions. Shows excellent foam mileage performance.

The tests used to measure these parameters are described below.

1) Interfacial tension (IFT) IFT measurements measure the ability of a surfactant sample to emulsify soil under a defined set of conditions. give instructions. IFT Spinning Drop Tensile Testing Machine and Univergity ・Eve Texas Model 500 (at the University of Texas in Austin, Texas, USA) Therefore, it was measured by the manufacturer. Two pieces of equipment: FRG D2000 handle Lug 61 Polsteller Chaussee 85-99a Pissenskaftlichier Model site (S ITE) 04 under conditions representative of those encountered in European manual dishwashing practices. It was used in Thus, a 2° Clark or The measurements were taken using a product concentration of 0.12% by weight in water with a hardness of 18'. The sample temperature was ±1°C. The final name is from Gillingham, Dorset, UK. Supplied by Aldrich Chemical Company Limited of New Road The purity of triolein was 99.7% (the remaining 0.3% was mixed free fat). fatty acids). Results are quoted in Pacm (I Pacm -10 dynes/cm).

, 2) Polypropylene cup loss (PPC) Polypropylene cup test The method includes testing all products under conditions that simulate those found in manual dishwashing practices. Measure grease handling ability. The test is performed at a temperature lower than that at which the fat melts. Includes measurement of the amount of solid fat removal from the base of a polypropylene cup.

The fat stain is made by preparing the following mixture of fats.

Solid 100% vegetable oil [Pain de Burgess Hill, West Sussex, UK] Spree Crisp rNJ Dry (5 pryCRISP rNJ DRY)) 70% liquid 100% corn Oil [CPC (UK) Limited of Claygate House, Etzier, Salih, UK MAZZOLA produced by MAZZOLA 130% miscible After heating the mixture, it is cooled and stored at a temperature of 0°C. For use, fat 150 ml of fat is melted in a glass beaker and kept at 70-75°C. 15 pieces 250 ml clean dry polypropylene rebore (TRIPOUR) cup. by weighing each cup and pouring it directly into the base of the cup without spilling onto the sides. Then, 6.00±0.03 g of fat was weighed and supplied to each. hold the cup flat , the fat is allowed to solidify in a thermostatic chamber at 21±1° C. for 2-3 hours.

A 0,12% solution of the test product was prepared at 50-55 °C, 100 ± 0,1 g was added to 5 Add to each of the glass jars and then seal the glass jars with lids. dense Place the sealed jars in a water bath placed in a constant temperature room and remove the solution in each jar from 43. Set at 45-46°C so that the temperature is 8±0.1°C. Similar method for each test subject Test products and standard products for comparison of test products are tested.

Then pour the contents of the jar along the side walls, being careful not to disturb the fat at the bottom. 1/2 cup at 21°C before transferring to a water bath and holding for 10 minutes. Let stand flat for 2 hours. Upon cooling, fat precipitation lines appear on the surface of the solution in the cup. It will be done. Repeat this dosing and cooling sequence for each kabboo jar combination. cormorant. After 10 minutes, quickly empty each cup, dry the inside of the cup, and remove the rim and fat lining. Remove all material that adheres to the cup wall between the in-levels. Then, After drying in an oven for 2 hours at 30°C, before drying for a further 1 hour at 50°C. Stand the cup top side down on an absorbent kitchen roll and drain for 5 minutes. . Then reweigh the cup. The average between the original weight of fat and what remains after the test The average weight difference is calculated for the 5 samples. This difference is obtained using standard products. divided by the weight difference to give a value expressing the performance ratio between the test product and the standard product. . Products according to the invention have a performance ratio greater than about 1.3, preferably at least It shows a performance ratio of about 1.4.

For testing purposes, the standard product is ground at the same concentration and in the same general area as the experimental product. It should have the ability to handle leases. This means that the standard (reference) product under conditions that give a fat removal rate of 20-35% while the test product has a fat removal rate of 20-80%. of liquid and solid fats that serve as stain compositions so that they can have a removal rate This can be achieved by adjusting the weight ratio. The same batch of fat was tested and shall be used for reference products.

3) Complete cure and foam mileage Total cure is the total volume of foam generated during a standard dishwashing test and the perceived It is a measure of foaming ability. Foam mileage is a standard for product concentration, temperature and water hardness. Measurement of the foam load required to reduce foam in a test solution to a specified minimum under conditions It is a value. It reflects the perceived useful life of a manual dishwashing solution. same test The foam mileage of the composition under test conditions was Grease stains were used in the mechanical foaming test method described.

Test condition Product concentration 0.12% Water temperature 48℃ Hydrosclerosis 2″ Clark and 18″ Clark mixed food stains Rice/minced meat/egg "Real Meal" Chin Thanh Brand φ Minst Beef and Onion' 1X392g Chin Amprosia Creamed Rice Pudding” 1×439g 1 egg 2% mixed free fatty acids (MFFA) in corn oil★25ml Corn oil 25ml 2% MFFA in corn oil ★ 60g 1 Kinges Linn, Norfolk, UK Marketed by Master Hu Noz of 2 Marketed by Ampusia Creamery, Lifton, Devon, UK 3 McDougall, Imperial Way, Walton Grange, Reading, UK Marketed by Zφ Catering Tooth Limited ★Oleic acid 4g, linoleic acid 4g, stearic acid 2g, valmitic acid 5g 1 pure 735g of pure corn oil.

Test method The method involves the use of long Four cylinders with a length of 30 cffl and a diameter of 10 c+n are used. each cylinder 500 ml of a product solution with a concentration of 0.12% and a temperature of 48° C. are charged into the container. outside Use two cylinders for one of the products to be compared, and use the inner two for the other product. Used for products.

Rotate the cylinder for 2 minutes, stop, measure the initial foam, then measure the typical dirt load. Add in 2 ml aliquots. After 1 minute, restart the cylinder and wait for 1 minute. Rotate.

Note the foam height and add 2 ml of soil to each cylinder. After 1 minute, remove the cylinder. Restart. This process ensures that the foam height in the cylinder is less than 0.6c+n. It continues until

The sum of all bubble height measurements for each test (i.e., if the bubble height is less than 0.6 cm) ) constitutes a total cure measurement.

One product is designated as a reference, and the foam index and foam mileage numbers are based on the following standards. Calculate for other products vs. r reference products.

Foam index of test product Complete cure of test product -X100 Complete cure of reference product Foam mileage of test product The invention is illustrated by the following non-limiting examples. All parts and percentages are unless otherwise specified. It is based on weight.

Example 1 Alkyl ethoxy sulfate surfactant and N-lauroyl-N-methylgluca A wide range of core surfactant systems were prepared containing mixtures with min. Alkyleto Oxysulfate with an average of 0.8 moles of ethylene oxide per mole of alcohol derived from 012-C14 primary alcohol condensed with ammonium ion and magnesium ions to neutralize 1 mole of alkyl ethoxy sulfate. It contained 0.22 moles of magnesium per liter. Core surfactant concentration 30% A mock product was first prepared in distilled water. Next, a 0.12% by weight solution of this product was added to Prepared in soft water (2" Clark) or hard water (18' Clark) and carried out the test method described above. Use a 2" cleaner for IFT and PPC grease stain removal. Tested in water. This method uses alkyl ethoxy sulfate vs. alkyl gluka Min ratio 100: 0.75: 25.65: 35.50: 50.2 5:75 and 0:100, and the results are shown below.

IFT (Pacm) AES:GA weight ratio Hydrosclerosis 100:0 75:25 85:35 50:50 25 Near 5 0: 1002° 0.35 0.12 0.12 0.14 0.16 0.10a Addition of lukyglucamine to anionic surfactant is indicated by IFT value as by significant improvement in grease emulsification, and increased PF6 soil removal value. As shown, it can be seen that this results in a significant improvement in grease soil handling.

Using the test method described above, the co-surfactant mixture was tested for overall cure height and foam mileage. The performance was also evaluated.

However, the results were not indexed against the standard product, but Reported directly as digits.

AES:GA weight ratio 100:0.95:5 90:10 75:25 65:35 50:50 0 :100 hardness 2′ Clark Real Meal 26015.0 344/6.5 416/7.5 567/ 10.0 657/10.0 604/10.5 4511^10.0 dirt Grease stain 250/4.5 277/4.11 33315.5 407/ 8.0 528/8.5 355/6.5 100/2.018'Clark Real Meal 30015.5 415/6.11 498/8.0 595 /9.5 600/9.7 621/10.0 40071O. 0 dirt Grease stains 302/4.8 31815.0 369/6.0 380/[ i, 0 34815.5 283/4.1 64/1.0 Grease dirt load conditions Considering both the grease stain removal data and the foaming data below, the grease Preferred ranges of mixtures for both removal and foaming performance include alkyl ethoxy sulfates. alkyl glucamine 75:25 to alkyl ethoxy sulfate: al Quilglucamine 50: It can be seen that it is up to 50. The optimum is about 65235 be. 100% alkylglucamine systems provide comparable grease removal performance, but , total foaming and foam mileage are seriously inadequate, especially under grease soiling conditions.

Example 2 The following compositions A-E were prepared.

Composition A represents a comparative commercial liquid detergent dishwashing product, while compositions B, C, D and and E are related to the present invention.

N-coconut"t fullh noyl-N 12.5 10.0 g, 0 12.8- Methylglucamine First class 7tl, +-/L4)-1-shiLz-)14.0 B, 0 4.0 g, 0 7. OMg Iono 0.35 0.20 0.25 0.5 - Coconut Tumonoethanolamide 3.8 - Sodium cumene sulfonate 1 ．． 0 1.0 2.0 2.0 2.0 Ethanol 4.5 5.0 5.0 5.0 5.0 Urea 0.5 - - - Water - 1111 ---------- Remainder (assumed to be 100) ------- 1a Contains an average of 10 ethylene oxide units per mole of alcohol and is non-ethylene 2% by weight of silica alcohol without IFTSPPC and foam marriage values for all five The results obtained for the product are shown below.

1, 1 FT (Pacm) B.C.D.E. 2° Clark 0.15 0.08 0.08 0.09 0.0818″ Lark 0.11 0.0B 0.06 0.07 0.0B3, complete cure/foam Illidge l Match dirt B.C.D.E. 2° Clark 100/100189/16718B/170135/1281 42/1291.8° Clark 100/100145/140177/153 121/119138/150 Grease stain 2° Clark 100/loo 132/129130/132123/122 150/15018° Clark 100/10095/113 98/115 10B/107102/99ff1l’T/IF 01/IIC (177Tlv w mm bll-pm m m rsls-g to m p-m m-tb ＋m　m　m　rwwtｽ-111鯵一一-is　em-! -Pva-Country-E 11P~axis t111--mO&, wmM-*mmmm-y++mMbrm-1 --Continuation of 12103/92 front page (81) Specified times EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD , TG), AT, AU, BB, BG, BR, CA, CH, C3, DE, DK.

ES, FI, GB, HU, JP, KP, KR, LK, LU, MC, MG, MN, MW, NL, No, PL, RO, SD, SE, 5U (72) Inventor: Foley, Beater Robert, Newcastle, UK N, Tyne, South, Gosforth, Bowsden, Terrace, 18

Claims (15)

[Claims] 1. by weight of mixture a) at least one water-soluble anionic sulfate or sulfonate surfactant; general formula of the agent salt 5% to 95%, b) 95 to 5% by weight of the mixture ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein Z is a linear carbon having at least three hydroxy groups directly connected to the chain) It is a polyhydroxyhydrocarbyl moiety having a hydrogen chain, and the moiety is maltose and its mixture with maltose, maltose is derived from R is a saturated or unsaturated alkyl group having 8 to 16 carbon atoms or and R1 is C1-C4 alkyl or C2-C4 hydroxyl. rukyl group) one or more compounds having a core surfactant mixture (15-65% by weight of the composition) comprising; Thereby a 2° Clark mineral hardness (Ca:Mg ratio 3:1) and a temperature of 48°C. A 0.12% by weight aqueous solution of the surfactant mixture of said composition in water is: i) spinny less than 0.2 Pacm using 99.7% purity triolein stain; Drop interfacial tension (IFT) ii) One or more anionic surfactant components alone Grease stains obtained under the same conditions in the same test using a 0.12% solution of Grids in polypropylene cup (PPC) tests greater than 1.3 times the friction removal value. soil removal value A builder-free liquid or gel in the form of a physically stable aqueous solution characterized by having detergent composition. 2. The polyhydroxyhydrocarbyl moiety of component (b) contains glucose and its and maltose (maltose accounts for less than 25% by weight of the mixture). A builder-free liquid or gel detergent composition according to claim 1, comprising: 3. 20% to 50% of the mixture of core surfactants, more preferably 22% to 40% A builder-free liquid or gel form according to any one of claims 1 and 2, comprising: Detergent composition. 4. The mixture of core surfactants comprises (a) 20% to 80% and (b) 80% to 2 0%, more preferably from (a) 40% to 70% and (b) 60% to 30%. A builder-free liquid or gel detergent according to any one of claims 1 to 3, Composition. 5. Component (a) is on average up to 6 moles per mole of alkyl ethoxy sulfate. C10-C16 alkyl ethoxy sulfate containing ethylene oxide, C10-C18 alkyl glyceryl ether sulfonate, C10-C16 para Finsulfonate, C9-C17 syl-N-C1-C4 alkyl glucamine salt Any one of claims 1 to 4 selected from ruphate and mixtures thereof. A builder-free liquid or gel detergent composition as described in Section. 6. Component (a) has an average of 1.5 or more per mole of alkyl ethoxy sulfate. On average 0 per mole of lower ethoxy groups, preferably alkyl ethoxy sulfate ．． Primary C12-C14 alkyl ethoxy sulfur containing 4 to 1.0 groups The builder-free composition according to any one of claims 1 to 5, comprising an ate surfactant. - Detergent compositions in liquid or gel form. 7. Mg+ in an amount up to 1.5%, preferably 0.5-1.0% by weight of the composition The builder-free liquid according to any one of claims 1 to 6, or Gel type detergent composition. 8. Ca++ in an amount up to 1%, preferably 0.3-0.5% by weight of the composition. 8. A builder-free liquid or gel form composition according to claim 7. 9. Incorporating one or more foam-boosting substances, each of which represents from 1 to 8% by weight of the composition. A builder-free liquid according to any one of claims 1 to 8, present in an amount of Gel type detergent composition. 10. The foam-boosting substance is a C10-C16 alkyl mono- or di-C2-C3 alkali. Nolamide, C12-C16 alkyl or alkylamidobetaine, C12 ~C16 alkyl sulfobetaine, C10-C16 alkyl, diC1-4 alkyl or diC2-4 hydroxyalkylamine oxide, per mole of alcohol C9 to C12 primary alcohol containing an average of 7 to 12 ethylene oxide groups 10. A non-billed compound according to claim 9, selected from polyethoxylates and mixtures thereof. Detergent compositions in liquid or gel form. 11. C12-C14 alkyl dimethyl betaine and average per mole of alcohol C9 to C11 primary alcohol condensed with 7 to 9 moles of ethylene oxide on average; wherein each substance is present in an amount of 2 to 8% by weight of the composition. The builder-free liquid detergent composition according to any one of items 9 and 10. 12. Urea, C1-C3 aliphatic alcohol, lower alkyl or dialkylben a hydrotrope selected from zenesulfonates or mixtures of any of them; A builder-free liquid detergent composition according to any one of the preceding claims, further comprising: . 13. Any one of the preceding claims having a chill point below 8°C, preferably below 5°C. A builder-free liquid dishwashing detergent composition as described in Section. 14. 1. The physical composition according to any one of the preceding claims, wherein the composition comprises an emulsifier. A stable builder-free liquid dishwashing detergent composition. 15. Bill-free according to any one of the preceding claims, having a pH of 6.0 to 8.5. Detergent compositions in liquid or gel form.