JPH06510550A - cleaning 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] cleaning composition FIELD OF THE INVENTION The present invention relates to cleaning compositions.

A cleaning composition consisting of a suspension of a builder in an organic liquid containing a surfactant is Are known. Non-aqueous compositions of this type with good stability are covered by European Patent No. 300. 96 and 120.659.

However, it is difficult to completely exclude water from cleaning agents, so we reduce their water sensitivity. It is desirable to lower it.

The decrease in water sensitivity is due to the dispensability of those substances. It is thought that this will help. That is, this introduces them into the wash 4M. becomes easier.

A cleaning composition is charged in the Uni-yh, and water passes through it and is removed together with the water. introducing the cleaning composition into the washing machine by conveying the cleaning agent into the washing zone; Can be done. Compositions with poor dispensing suitability will result in solid deposits that will build up inside the unit. There is a possibility that it will remain. Optionally, the cleaning composition is placed in a container, which is then introduced into the clean zone. Containers may become dry, especially if access to them is restricted. If not, solid deposits may be left inside when the cleaning agent is charged. It's possible. Particularly in the latter case, a composition with low or low water sensitivity may improve dispensing suitability. It is thought that

The inventors have surprisingly found that when amine oxides are present in their compositions, We found that small amounts of water were tolerated. In general, the amount of water is up to 5 mol per mol, preferably not more than 3 mol, more preferably not more than 2 mol, and For example, it should be 0.5-19 moles, preferably per mole of amine oxide. 1. 0-1. It is 7 moles. Water is solid water of crystallization--this is referred to in this specification. m, which is unrelated to , refers to water that is not included.

Anhydrous amine oxides are known or generally they are made of e.g. 65% water by weight. It is commercially available as an aqueous solution containing. Clearly this type of solution is not intended for the purpose of the present invention. therefore, according to one aspect of the invention, they are included in liquid laundry detergent compositions. A means is provided for converting the composition into a composition useful for inclusion in a composition.

The present invention 1) Organic liquid phase consisting of amine oxide: 11) Solid bilge.

1ii) up to 5 moles per mole of amine oxide, preferably not more than 2 moles, such as For example, 0.5 mol to 2 mol or less, preferably 1. 0-1. 7 moles of water ( other than solid water of crystallization present) A liquid cleaning composition comprising:

The builder is suitably water soluble and bleach may optionally be present. .

The present invention also provides l amine oxide suitable for inclusion in a liquid cleaning agent: 11 Polyalkylene glycol, preferably ethylene glycol residues and Optionally consisting of propylene glycol residues, more preferably polyethylene glycol, and lii up to 5 moles per mole of amine oxide, preferably not more than 2 moles, and For example, a composition containing from 0.5 mol to 2 mol or less, preferably from 1 to 1.7 mol of water. It becomes more.

The composition has good stability and ironability due to the addition of suitable builders. is a liquid laundry detergent with easy-iron properties. Allows for the preparation of cleaning agents. Weight ratio of polyalkylene glycol to amine oxide is 0. 5°1-2°1 is appropriate.

This Mi composition is prepared by converting an aqueous solution of amine oxide into polyalkylene gellicol, preferably or in the presence of polyethylene glycol, preferably at 40-80°C under reduced pressure. It may be prepared by distillation, preferably at a temperature of 65-75°C. present invention Surprisingly, researchers found that the presence of polyalkylene glycols Reduces the problem of gel formation that can interfere with distillation when distilled directly It was found that the effect of

We use builder, polyethylene glycol and preferably other non-ionic When used with surfactants, amine oxides can iron fabrics washed in them. We have found that this makes it easier to hang up.

Therefore, the present invention also provides 111 Polyalkylene glycol with a molecular weight of 100-1500, preferably poly Nonionic surfactants other than ethylene glycol and preferably amine oxides agent, and preferably bleaching agent For example, a laundry detergent composition.

Reducing phosphate concentrations in wastewater for environmental reasons in many parts of the world It is hoped that Phosphates in cleaning agents, especially condensed phosphates, e.g. Although the use of sodium tripolyphosphate has been common for many years, today it is It is regulated by law for environmental reasons. Therefore, it does not contain phosphates. It is desirable to prepare cleaning compositions that have good cleaning performance.

The present invention is also phosphate-free and suitable as a laundry detergent composition; ) Amine oxide.

2) Hydroxycal containing 2-6 -COOH groups and 1-5 10H groups Bonic acid.

3) at least 10, preferably at least 100, for example 150-2 000, preferably 200-1000 -COOH groups up to 5 moles, preferably not more than 2 moles of water per mole of amine oxide ( (excluding that present as water of crystallization).

The polycarboxylic acid is polyacrylic acid, such as maleated polyacrylic acid. and more preferably carboxymethylcellulose, suitably with a molecular weight of 1oo-toooo, e.g. 100-500, linked glucose units and suitably the degree of substitution (proportion of OH groups converted to carboxymethyl form) 35-85%, preferably 45-80%.

The hydroxycarboxylic acid is for example tartrate or preferably citrate .

this! The fl composition contains 2-10% by weight of the above component (3), preferably 3-9% by weight. % by weight, more preferably 5-8% by weight. This is 2 〇-50% by weight, preferably 25-40% by weight of the above component (2) is suitably contained. It's urgent.

The composition preferably exhibits a substantially neutral or alkaline reaction, with acidic substances is neutralized with ammonium, substituted ammonium, or preferably alkali metal ions. It is preferable to be harmonized. At least 1 part by weight of component 3 for every 8 parts by weight of component 2 It is preferable that there be

The liquid composition may contain 25-70% by weight, preferably 30-60% by weight, e.g. Preferably it contains 60% by weight total solids. The solid preferably consists of a builder , which may be present in an amount of 25-60% by weight of the total composition. Bleach, such as alcohol Perborates or percarbonates of potassium metals, such as sodium, account for 0 of the total composition. - present in an amount of 25% by weight, such as 1-20% by weight, preferably 5-20% by weight; I can do it. optionally at least 10, preferably at least 100, even Polymers containing 150-2000, preferably 200-1000 COOH groups. A carboxylic acid, suitably carboxydimethylcellulose, may also be present.

The liquid phase may represent, for example, 5-55% by weight of the total composition, preferably 10% of the total composition. -40% by weight of polyalkylene glycol, preferably polyethylene glyco; and suitably 5-25%, preferably 7-20% by weight of the total composition. Suitably, non-ionic surfactants are included. The amine oxide is preferably a liquid 5-100%, more preferably 5-50% by weight of the organic material of the phase.

Builders are, for example, condensed phosphates, silicates or zeolites, or 2- Hydroxycarboxylic acids containing 6 -COOH groups and 1-5 10H groups, such as Toe is citric acid or tartaric acid. But it is a condensed phosphate, e.g. alkali metals, especially sodium salts, such as sodium tripolyphosphate. It is preferable that there be.

The molecular weight of polyethylene glycol is 100-1500, suitably 150-50 It is 0.

Compositions according to the invention may be formulated as pourable liquids. is preferable. For this purpose, the liquid detergent composition is prepared from the solid content Wi liquid in the liquid medium. It is preferable that The solids may be of average particle size up to 10 μm. composition Suitably, the material has a pour point of 10°C or less. style The dynamic point was measured according to ASTM test method designation D97-66 approved in 1971. sell. It is desirable that at least 90% of the particles have a particle size of 10 μm or less in diameter. .

Average particle size can be determined by number average method or weight average method. 1.2-8μm is preferred Yes.

The surfactant component of the composition may consist of a nonionic surfactant. it is alkylene Oxide derivatives are suitable, and the alkylene oxide is preferably an ethyl oxide derivative. lene and/or propylene oxide. It is an amine, an alkylphenol reaction of alcohols or alkanols with ethylene and/or propylene oxide It is very suitable that the product is a product. The alkyl group of alkylphenol is a straight chain or branched, containing 6-20 carbon atoms, e.g. 6-12 carbon atoms. May contain. Alkanols have 6-20 carbon atoms, preferably 10-16 carbon atoms. May contain carbon atoms. The alkanol is preferably a straight chain or monobranched alkanol. It is a primary or secondary alkanol with a kill chain. Nonionic surfactants are 1- Suitably it contains 10, preferably 3-8 alkylene glycol residues. This should be understood as an average value.

Surfactants consist essentially of amine oxides, which contain 10-18 carbon atoms. , preferably one alkyl group having 12-46 carbon atoms, and ClC s Contains two other groups independently selected from alkyl or hydroxyalkyl groups It is preferable. The composition may optionally contain two or more nonionic surfactants. good. The pour point can be improved by changing the liquid phase composition, e.g. using a low pour point surfactant. It can be adjusted by containing and/or polyethylene glycol.

10-50% by weight, preferably 15-30% by weight of surfactant may be present. Appropriate. Alternatively, the surfactant may be anionic or cationic. Good too.

These anionic or cationic surfactants may be of known types; Anionic surfactants include, for example, soaps, alkylbenzenes or olefin surfactants. Honate, alcohol sulfate or alcohol alkoxylate sulfate and the cationic surfactant is C-C10-22, preferably C-C16. -18 alkyl, lower alkyl ammonium salt or hydroxide, etc. For example, chloride or sulfate, or the fabric softener CIG-16 alkyl, cy-lower alkyl (e.g. methyl), substituted ethyl-ammonium- It is appropriate to have something. The substituent of the ethyl group may be an OCR group, in the formula R is a Cl3-2□alkyl group, and the anion of this salt is an R3O,- group. where R is lower alkyl, such as methyl. The lower alkyl group is It is appropriate that it is a methyl group.

Polyalkylene glycols, e.g. polyethylene/polypropylene glycol , or preferably polyethylene glycol. this is It contributes to the effectiveness of the composition in cleaning fabrics and has favorable biodegradability.

Polyalkylene glyco with average molecular weight 100-400, preferably 150-300 preferred. These tend to lower the pour point of liquid compositions and therefore This is because it makes them easier to use in cold environments. 10-50% by weight, preferred Preferably, 25-45% by weight of polyalkylene glycol is present. be.

It is very suitable that the composition contains a bleaching agent, which is an alkali metal perborate. Salts or percarbonates are suitable. If desired, a bleach activator (bl (aah activator) may be included. 1-20% by weight, preferred Suitably, 2-15% by weight of bleach is present.

Mi compositions contain additives commonly found in cleaning compositions, such as optical brighteners, It may also contain renaminetetraacetic acid, dyes, fragrances and/or enzymes.

In the composition according to the invention, the solid dispersion in the nonionic surfactant is preferably a solid dispersion. It is extremely stable if the particle size is up to 10 μm. Even if the solid is separated However, the resulting phase is usually loosely aggregated and can be easily redispersed. Ru. Proper relative amounts of solids, polyethylene glycol and surfactant in the composition is selected, the liquid fills the spaces between the loosely packed solid particles. Therefore, there is almost no separation.

The composition according to the invention can be prepared by a method consisting of kneading the ingredients together. Appropriate.

The weight percentages given herein refer to the total weight of the composition, unless circumstances require otherwise. It is relative to weight.

Example 1 Dehydration of alkyldimethylamine oxide The nitrogen was removed by the following method. Substituted at atoms, chain distribution 70%-C12, 27%-C14 and 3%- Amine oxide containing an alkyl group that is C16 and two methyl groups (DMA O) in polyethylene glycol (molecular weight 200) (PEG 200) A 50% w/w solution is prepared.

1 equivalent of PEG200 was added to DMA0 in aqueous solution (approximately 33% by weight DMA0)4 Add to equivalent amount.

N2 bleed to bottom and 2 foot degassing column or scrub head, then water 2OL quick fix that goes through the condenser to the sputum collection container and vacuum control device. Water is removed by vacuum distillation in a Quickfit flask.

1. to the boiler. Load with a filling amount not exceeding 3-1/2 (to provide foam spacing) Meni). The contents were stirred to 1100 r with a stirrer paddle and a nitrogen bleed introduced. Stir at p. Apply vacuum and adjust nitrogen bleat to keep flow to a minimum do. Once vacuum is established, gradually increase the temperature to 6C)-75C. Fine tune the vacuum Foaming can be controlled by adjusting the temperature of the foam, or if desired, adding a silicone antifoaming agent to 0.0 5-0, 1 equivalent level can be added to the reaction mixture.

Once the theoretical amount of water has been removed, measure the boiler moisture.

Distillation conditions/ 20L scale, 12 hours, 50mmHg, 60℃ 500m1 scale, 3 hours, 45 mmHg, 75°C Under these conditions except for 60% DMA (adding a smaller amount of PEG200) the product is solid at room temperature. and liquid in the case of 50% amine oxide material.

60% w/w 50% w/w Amine oxide 61. O amine oxide 50.0 Free amine 0. 7. Play Released amine 0. 6H203, 5N20 5.0 ,, PEG200 about 35. OPEC200 approx. 44.5 Example 2 Formulation A was prepared as follows. Mix the liquid ingredients, mix 7 parts by weight with enzyme and bentonite, and homogenize the rest. The product is mixed with other solid components using a sizer to give an average particle size of 3 μm (weight average). Kneaded until smooth. These two mixtures are then mixed together using a homogenizer. Ta.

Formulation B was prepared as follows: Mix ingredients other than the enzyme using a homogenizer until the weight average particle size is 3 μm. Kneaded. The enzyme was then added and mixed using a homogenizer.

Compound Compound A B Sodium citrate 27% Sodium tripolyphosphate 37% Sodium carbonate 5% 5% Calhoki dimethyl cellulose ° 1% 5% Sodium disilicate 2% 1 circle "Leukophor" 0 Fluorescent brightener 0.3% 0. 3% Enzyme (Protease + Amylase) 0.3% 0.3%" Synberonic ( Synperonic) "λ32.5% 13" Zinobelonic" 87K 7 % 3.8% polyethylene glycol Molecular weight 200 (PEG 200) 32% 36% DMA0 (100%) ) 10% 7.5% sodium perborate monohydrate 10 circles tetraacetyl Ethyleneamine 3%°''Courrose A610 Commercial product sold as 0, degree of substitution 5-0. 7. Estimated molecular weight 60.000- 100.000 “Zinoperonic” A3 and Sibeloni/Ri87, respectively. on average 3 moles of ethylene oxide, and 7 moles of ethylene oxide 92% or and propylene oxide, 2 parts of C13 primary alkanol and C A mixture of 1 part I5 primary alkanols (both containing some 2-methyl branching) It is a product condensed with

Above: All percentages are based on weight.

These formulations were tested as laundry detergents by: Formulations A and B. Performance was compared to that of commercially available cleaners as follows. The washing test was carried out using Zanu s　s　1) It was carried out using a FL1030 washing machine and was washed at 40℃ and 60℃. It was tested in water with a hardness of 90 ppm Ca. EMPA or Tarefelt ( The performance of each product was evaluated using standard fabrics from Krefeld. washing machine For each wash, four test pieces (10 x 10 cm) of different types of test cloth were placed on the It was loaded with 2 kg of clean cloth as ballast. Each test fabric is reflective of each city Measurements were taken at 10 different locations to assess the increase in rate.

The amount of cleaning agent used is 60g per use for formulations A and B, and 60g for commercially available products. It was 180g.

The results were as follows: compound A　B　Commercially available product Cloth 40@C60"C40@C60"C40"C60°CDGIAIOI 37 ．． a 50.4 40.0 51.0 29.5 45.9 Crefeld IO C46,752,22B, 8 43.9 here, 7 49.7 ENPA 104 Ko B, 6 5 Ko, 1 1 Ko, Ko 52.4 2 F, 9 46.8 Cre 7 Eld 20C55,359,637,454,231,049,1rxpx uz (blood fi) 77.1 7B, 9 31.5 49. a f7.7 ao, 9E KPA o2 (cocoa) 25.1 4f, B 34.9 47.6 28.3 51.4EIGA 114 (red wine) Ko 1.7 35.6 4S, L 6 7.2 41.0 43.9 Crefuel F l0K (coffee) 56.2 5 9.9 66.9 F2. 56.6 61.4 The values shown are the reflectance after washing. % increase.

The above results show better performance compared to using 3 times the weight of the commercial product.

Easy to iron After using the formulation for two weeks, the fabric was easier to handle when ironed. 27 out of 29 people answered 11.

Substantially equivalent to formulations, but improved to make them more appealing to consumers. The weight of the formulation can be prepared by - to - Synperonic A3 23. S2B 2.4 Shinberonitsuta 871 71.56 Fufu, 2P E G 200 320+452 32+lDMA0 (100% Toshite) 97.447 9.7 Sodium Carbonate 41.9SB 4.81 Ku Lerose'A61Q 9.967 1.0 Sodium disilicate la, 954 19 Sodium tripolyphosphate 36G, 261 36.6 Ethylenediamine tetra Acetic acid 2.002 0.2 Fluorescent brightener 2.998 0.3 Blue colorant 0.029 0.0 Silicone antifoaming agent Q, S8B 0.1 bentonite clay 28.956 2.97 I□, 2.492 0.2 Fragrance 3.000 0. Ko Amylase enzyme in brothiase 3.000 0.3!99.500 100. ．． 0 Example 3 A suspension containing approximately 50% solids was prepared consisting of the ingredients in the following table. Formula C is Shigenobu It was kneaded to an average particle size of 3 μm on average. Pond formulations are pre-milled solid particles The particle size was not measured.

Compound Compound Compound “Dequest’20160 Phosphate Bilgoo 5% Sodium citrate 32% 32% 32% Sodium carbonate 10% 10% Carboxymethyl cellulose′″ 6% 6% 2% Sodium disilicate 1% 1% 1% “Tinopal” CBS-X Fluorescent Whitening Agent 0.2% 0.2% 0.2% Enzyme (protease + amylase) 0.3% 0.3% 0. Seagull “Symbelonic” A3 3.75% 3.75 volumes 3,7 5 demons “Jino to o=futa’87K 11.25% 11.25% 11.25% po Liethylene glycol Molecular weight 200 25.5 Tsuta 25.5% 34.5% Tetraacetyl ethylene Amine 3% “Synprolam 35DIIQ 10% 10 Sodium Perborate Monohydrate 7% Cour Rose commercial product sold as A161, degree of substitution 0, 5-0. 7. Estimation Molecular weight 60.000-100.000 “Synperonic’ A3 and” Synpero Nick “87 contains an average of 3 moles of ethylene oxide, and 7 moles of ethylene oxide, respectively. A mixture of 92% ethylene oxide and 8% propylene oxide was mixed with Cl31! - 2 parts alkanol and 1 part C15 primary alkanol (both with some 2-mer The product is condensed with a mixture of (containing tyl-branched chains). ``Sinproram'35 DMQ is the above C13 and CIS alkano substituted at its nitrogen atom. is an amine oxide containing an alkyl group corresponding to a methyl group, and two methyl groups. .

'', -3% is the weight.

These formulations were tested as laundry detergents according to formulations A, B and C. The performance of the was compared with that of commercially available cleaning agents as follows. The washing test was carried out using Mie le) carried out using a W451 washing machine with hard water at 40°C and 60°C. (French standard hardness at 36° C.). From EMPA or Crefeld The performance of each product was evaluated using standard fabrics. Each of the three washing machines has different Four test pieces (10XLOcm) of the same type of test fabric were used as ballast for each wash. and 2 kg of clean cloth. Each test fabric is evaluated for increased reflectance in each city In order to do this, measurements were taken at 12 different locations. The amount of cleaning agent used is 60g for formulations A, B and C and 180g for commercial products. .

The results were as follows.

1 1 Compound 1 1 1AIBIcI Commercial product 1 1 cloth 140・c 16oac 140・C160・C140・c 16oac 14011C1aollclIKMPAIOl 134.7 13(1,51 32-a lx2. ) 124.5 122.1 119.15 1 xa, s lWhat are the numbers shown? % increase in 0 reflectance after Ic rinsing.

The above results show better performance compared to using 3 times the weight of the commercial product.

Commercial products contain approximately 1/3 weight water, so the comparison in terms of total chemical content is approximately 1/3 by weight. It is done in a ratio of 2.

Example 4 Two types of liquid cleaning compositions consisting of solids dispersed in liquids having the following compositions were prepared as follows. The tested Sodium tripolyphosphate 36,7 40.15 Bentonite clay 2.9 − Sodium carbonate 4.8 5.00 Sodium silicate 1.9 2.00 Carboxymethyl cellulose 1.0 1.00 Sodium ethylenecyaminetetraacetate Um 0.2 0.2 Fluorescent brightener 0.3 0.3 Enzyme neck 0.3 0.3 Titanium dioxide 0.25 0.25 Simperonik A3 2.4 2.4 87K 7.2 7.5 polyethylene glycol, molecular weight 200 32. 0 40. 0 Dimethyl Cocoamine Oxide 9.8 NIL Fragrance 0.25 0.8 Both compositions were then supplemented with 1%, 1.5%, 2%, 25% and 3% (by weight) of water. Added in quantity.

Viscosity is shown at 20° C. after 45 minutes and (where indicated) after 1 day.

A B Amount of water added Viscosity If (Poise) Viscosity (Poise) 45 minutes 1 day 45 minutes 1 day 0.0% 48.0 46.0 1.0% 50.8 70.8 2.0% 60.2 x 39.0 3.5% 90.4 70.9 304.0 3403.0% 800,000 ．． 0 706. QOo, 0 These data indicate that the composition containing the amine oxide Showing that it was more resistant to decomposition by water.

Compositions A and B are used in draw dispensers. It was also tested for dispensing suitability in a commercially available ZANUSHI LLI machine with a wash -4 At the beginning of the process, 2.5 times more for Iil composition B than for composition A. Residue was left on the tray.

International Investigation Report OrT/l! 11027I’lnO&? 0rrtao o’il nnc1ai Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, 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, MG, MN, MW, NL, No, PL, R○, RU, SD, SE, US

Claims (11)

[Claims] 1. It contains an organic liquid phase consisting of an amine oxide and a solid phase consisting of a builder. up to 5 moles per mole of carbon oxide, such as from 0.5 mole to less than 2 moles, preferably Preferably, 1.0-1.7 mol of water (existing as water of crystallization in the existing solid) (excluding liquid cleaning compositions). 2. Contains amine oxide and polyalkylene glycol; Up to 5 mol per mole, preferably up to 2 mol, such as 0.5-2 mol, preferably or 1-1.7 moles of water, suitable for inclusion in a liquid cleaning agent. A product. 3. Amine oxide, builder, and polyalkylene with a molecular weight of 100-1500 A cleaning composition containing glycol. 4. A liquid cleaning composition substantially free of phosphates, the composition comprising: , hydroxycarboxylic acids containing 2-6 COOH groups and 1-5 OH groups, and polycarboxylic acids containing at least 10 COOH groups, Up to 5 moles of water per mole of oxide, preferably not more than 2 moles (based on solid matter present) (excluding that present as water of crystallization). 5. the amine oxide is an alkyl group having 10-18 carbon atoms, and C1 -2 other groups independently selected from C3 alkyl groups or hydroxyalkyl groups The composition according to any one of claims 1 to 4, comprising: 6. The builder is a condensed phosphate, zeolite, silicate, or 2-6 COO Claimed hydroxycarboxylic acid containing H group and 1-5 OH groups The composition according to any one of items 1 to 5. 7. The set according to claim 6, wherein the builder is a condensed alkali metal phosphate. A product. 8. Claims 1 to 7, wherein the builder is citric acid or tartaric acid. The composition according to any one of the above. 9. Claim 1, comprising polyethylene glycol with a molecular weight of 150-500. The composition according to any one of items 1 to 8. 10. The weight ratio of polyalkylene glycol and amine oxide is suitably 0.5: 1-2:1. A composition according to any one of claims 1 to 9, wherein the ratio is 1-2:1. 11. The composition according to any one of claims 1 to 10, comprising a bleaching agent. thing.