CN100393863C

CN100393863C - Improved detergent composition

Info

Publication number: CN100393863C
Application number: CNB2003801031327A
Authority: CN
Inventors: S·阿查尔; A·M·舍特蒂
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 2002-11-15
Filing date: 2003-10-21
Publication date: 2008-06-11
Anticipated expiration: 2023-10-21
Also published as: ES2287532T3; MXPA05004942A; BR0315253A; PL376782A1; DE60313899T2; CN1711346A; RU2323963C2; EP1625195A1; AR042040A1; ZA200502826B; RU2005118430A; MY136648A; EP1625195B1; DE60313899D1; AU2003278170A1; ATE362509T1; PL202080B1; WO2004046292A1

Abstract

The invention relates to synergistic concentrated cleaning composition comprising one or more surfactants and one or more water swellable polymers that can absorb more than their weight of water. The composition can be converted into a voluminous paste or thick liquid by the simple addition of water prior to use, to ensure the spreadability of the composition on a large number of surfaces to be cleaned.

Description

Improved detergent composition

Technical field

The present invention relates to be fit to the synergy cleaning composition that contains tensio-active agent and polymers capable of swelling of washing rigid surface.

Background technology

The commercial hard surface cleaning composition contains one or more tensio-active agents and many abrasion resistant particles that is dispersed in wherein usually.Well known in the art is often to form abrasive material suspension system with tensio-active agent with electrolytical the combination.Can obtain liquid, paste, gel, powder and excellent various forms of cleaning composition.The typical abrasives that is used for these compositions comprises calcite and rhombspar.

Rigid surface in the family is cooker, kitchen wall and floor, operating table surface and washtub, shower wall, floor and support, other floors etc., and the article that speckle with dissimilar dirty trowel used for plasterings on these surfaces.The dirt of being infected with on cooker and the cooker end face has two types usually, promptly removable or clammy dirt and by dirt firm or that be difficult to remove drying shrinkage or that food cooked is formed.When firm accumulation of mud after for some time, the problem of removing these dirts becomes more outstanding, just needs suitable effort to wash.

The content of tensio-active agent is usually at most about 20% in the cleaning composition, and remainder is grouped into by other one-tenth.Abrasive material, washing assistant and filler constitute in the prescription very part and parcel.Must add these one-tenth and assign to improve the dispersibility of situation lower surface promoting agent on washing surface of particularly hand-washing.

In cleaning composition, used polymkeric substance to realize such as the structure and the various uses of dirt release function.EP 883670 (Unilever, 1998) discloses full-bodied the washing the dishes that have that is used to machine-wash and has used gelatinous composition.They have the two-pack tectonic system that comprises crosslinked polycarboxylate of 0.2-2% and pyrroles.

Big water gaging is added with abrasive material, washing assistant and filler, not only increased small product size, and improved cost thus, also increased from the manufactured place to the transportation difficulty that makes land used.

Therefore, need a kind of thickening and washing composition that can change into off-the-shelf behind the water that adds through the user.This concentrate composition has been saved transportation and packing cost than diluted composition.

The invention summary

The invention provides a kind of one or more tensio-active agents and one or more of comprising and to absorb synergy thickening and washing composition greater than the water-swelling polymer of the water of its deadweight.Said composition can change into a large amount of slurries or thick liquid by simply adding water before use, waits to wash lip-deep dispersiveness to guarantee said composition in big area.

Describe in detail

Here all that mention part and percentage ratio are the weight of composition except that other regulation.

Therefore the present invention provides a kind of synergy cleaning composition, and it contains:

A) one or more tensio-active agents of 5-95%;

B) 5-95% one or more can absorb water-swelling polymer greater than the water of its deadweight.

In specification sheets of the present invention, statement " cleaning composition " refers to the composition of pressed powder, tablet, pill or strip or slurry or gel form, and it can change into the product that volume increases after adding entry.The easier coating of the product of Huo Deing or be dispersed in and wait to wash on the surface like this.

Tensio-active agent

To contain the tensio-active agent that one or more are selected from negatively charged ion, nonionic, positively charged ion or amphoterics usually according to composition of the present invention.Preferably in the composition at least 10% of the tensio-active agent total amount, more preferably at least 40% of the tensio-active agent total amount is made up of nonionogenic tenside.Preferably the tensio-active agent in the composition is the 5-50% of composition, more preferably 5-25% (weight).

The anion surfactant of adequate types is the water-soluble salt of organosulfur acid monoester and sulfonic acid, and they have branching or straight chained alkyl that contains 8-22 carbon atom or the alkaryl that contains 6-20 carbon atom in the molecular structure of moieties.

The example of this anion surfactant is following water-soluble salt:

-long-chain (being 8-22 carbon atom) alcohol sulfate (hereinafter referred to as PAS) is particularly by by the Fatty Alcohol(C12-C14 and C12-C18) of fat or Oleum Cocois preparation or the alcohol sulfate that obtains derived from the sulfation of the synthol of oil;

-contain the alkylbenzene sulfonate of 6-20 carbon atom such as alkyl wherein;

-secondary sulfonated alkane.

Same suitable is following salt:

-alkyl glycerol ether sulfate is particularly derived from the ether sulfate of the Fatty Alcohol(C12-C14 and C12-C18) of fat and Oleum Cocois;

-glycerine monofatty ester vitriol;

-contain the vitriol of the ethoxylated aliphatic alcohols of 1-12 vinyloxy group;

-each molecule has 1-8 vinyloxy group unit, and alkyl wherein contain 4-14 carbon former in alkylphenol vinyloxy group ether sulfate;

-use the isethionic acid esterification also to use the reaction product of alkali neutral lipid acid.

The nonionogenic tenside of adequate types can be broadly described as by the simple alkylene oxide of water-wet behavior and the compound of the condensation reaction preparation of aliphatic series that has active hydrogen atom or alkyl aromatic hydrophobic compound.The hydrophilic chain that is connected with any specific hydrophobic group or the length of polyoxy alkylidene chain are easy to regulate, to obtain having the compound in equilibrium of expectation between hydrophilic element and hydrophobic element.So just can select to have the nonionogenic tenside of suitable HLB.Specific examples comprises:

-in the straight or branched configuration, have the fatty alcohol of 8-22 carbon atom and a condensation product of oxyethane, for example contain the coconut alcohol/ethylene oxide condensate of 2-15mol oxyethane in every mole of coconut alcohol;

-have a C ₆-C ₁₅The alkylphenol of alkyl and the condenses of oxyethane, wherein every mol alkylphenol 5-25mol oxyethane;

The reaction product of-quadrol and propylene oxide and the condenses of oxyethane, this condenses contain 40-80% (weight) vinyloxy group and have the molecular weight of 5000-11000.

The nonionogenic tenside of other types is:

-alkylpolyglycosides, it is the condensation product of long chain aliphatic and carbohydrate;

-having the tertiary amine oxide of structure RRRNO, one of them R is the 8-20 carbon atom alkyl,

Other R respectively are 1-3 carbon atom alkyl or hydroxyalkyl, for example dimethyl dodecyl amine oxide;

-having the oxidation tertiary phosphine of structure RRRPO, one of them R is the 8-20 carbon atom alkyl,

Other R respectively are 1-3 carbon atom alkyl or hydroxyalkyl, for example dimethyl dodecyl phosphine oxide;

-having the dialkyl sulphoxide of structure RRSO, one of them R is the 10-18 carbon atom alkyl,

Another R is methyl or ethyl, for example methyl tetradecyl sulfoxide;

-lipid acid hydroxyalkyl amide, for example glycollic amide;

The alkylene oxide condensate of-lipid acid hydroxyalkyl amide;

-alkyl sulfhydryl.

The special groups of tensio-active agent is the tertiary amine by the condensation acquisition of oxyethane and/or propylene oxide and long chain aliphatic amine.The performance of this compound in alkaline medium is similar to nonionogenic tenside, and the performance in acidic medium is similar to cats product.

According to can not necessarily containing both sexes, positively charged ion or zwitterionics in the composition of the present invention.

The suitable amphoteric surfactants compound that can not necessarily adopt is to contain the 8-18 carbon atom alkyl and aliphatic secondary amine and the derivative of tertiary amine, for example 3-dodecane alanine sodium, 3-dodecane aminopropanesulfonic acid sodium and the N-2-hydroxyl dodecyl-N methyl taurine sodium of the aliphatic group that replaced by the anionic water-soluble base.

The example of suitable cationic surfactants can find in the quaternary ammonium salt of the alkyl with one or two 8-20 carbon atom or aralkyl and two or three little aliphatic groups (for example methyl), for example cetyl trimethylammonium bromide.

The example of suitable zwitterionics can find in the derivative of aliphatic quaternary ammonium, sulfonium compound He the phosphonium compounds of the aliphatic group that has 8-18 carbon atom aliphatic group and replaced by the anionic water-soluble base, for example: 3-(N, N-dimethyl-N-cetyltrimethyl ammonium)-propane-1-sulfonate trimethyl-glycine, 3-(dodecyl methyl sulfonium)-propane-1-sulfonate trimethyl-glycine and 3-(n-Hexadecane ylmethyl Phosphonium)-ethane sulfonic acid betaine salt.Other known trimethyl-glycines are alkyl amido CAB, for example wherein alkyl amido derived from those of coco-nut oil fatty acid.

Other examples of suitable tensio-active agent are the compounds that are commonly used for tensio-active agent that provide in the known textbook: " Surface Active Agents ", the 1st volume, Schwartz and Perry, Interscience 1949; " Surface Active Agents ", the 2nd volume, Schwartz, Perry and Berch, Interscience 1958; The general version that ManufacturingConfectioners Company publishes " McCutcheon ' sEmulsifiers and Detergents "; " Tenside-Taschenbuch ", H.Stache, the 2nd edition, Carl Hauser Verlag, 1981.

Special preferred surfactant is with 1: 0.1-1: 10, more preferably 1: 0.1-1: the negatively charged ion of 1 mixed and the mixture of nonionogenic tenside.

Polymers capable of swelling:

Preferred water-swelling polymer is polyacrylic acid and polyacrylic ester, crosslinked acrylate polymers, guar gum and derivative thereof, starch-acrylate graft copolymer, the hydrolysate of starch-acrylonitrile graft copolymer, crosslinked polyoxyethylene, cross-linked carboxymethyl cellulose, such as the partial cross-linked water-swelling polymer of polyoxyethylene and polyacrylamide, iso-butylene/maleic acid etc.Particularly preferred water-swelling polymer is a polyacrylic acid, and most preferably part is neutralized into the cross linked polyacrylate of sodium salt.Being used for water-swelling polymer of the present invention can solid and liquid, preferably provides with solid form, for example particle, saccharoid, pill, thin slice, billet shape etc.

Preferably the water-swelling polymer in the composition accounts for the 5-75% of composition, more preferably 5-50% (weight).

The ratio of tensio-active agent and polymkeric substance is preferably 1: 0.1-0.1: 1, more preferably 1: 0.4-0.4: 1 scope.

Nonessential composition

Inorganic particle:

Insoluble solid phase particle is the nonessential composition according to composition of the present invention.

This particle preferably comprises water-fast abrasive material mutually.As selection, when abrasive material mixes before use with water, abrasive material can be partly dissolved and the excessive water that is present in the composition in, make the solubleness surplus of abrasive material, thereby abrasive material be present in the swollen mixture mutually with solid at aqueous phase.

The gel of polymers capable of swelling or slurry form ability and can reduce when having some ionogen.For example, calcium ion has reduced the swelling property as the cross linked polyacrylate of water-swelling polymer.Therefore when selecting abrasive material and inorganic particle, must carefully select to avoid this material.If must adopt this material, just have to it is reduced to minimum amount.

Suitable abrasive material can be selected from particulate zeolites, calcite, rhombspar, feldspar, silica, silicate, other carbonate, alumina, supercarbonate, borate, vitriol and such as poly polymeric material.

The Preferred abrasives that is used for the general applications cleaning composition has the Mohs' hardness of 2-6, but can adopt the more abrasive material of high rigidity for special applications.

Preferred abrasive material median size is the 0.5-400 micron, preferred 5-200 micron.

Other nonessential compositions

Can contain helpful other compositions of its scourability according to composition of the present invention.For example, said composition can contain the detergent builders such as nitrilotriacetate, polycarboxylate, citrate, dicarboxylic acid, water-soluble phosphate (for example mixture of poly-phosphate, orthophosphoric acid salt and pyrophosphate salt), zeolite and their mixture.Except that the composition of having mentioned, also can contain various other nonessential compositions according to composition of the present invention, for example solvent, tinting material, whitening agent, white dyes, soil-suspending agent, detersive enzyme, compatible SYNTHETIC OPTICAL WHITNER (particularly hypohalite) and sanitas.

The content of inorganic particle and other nonessential compositions can account for 90% of composition at most.

Therefore, according to a preferred aspect of the present invention, provide a kind of synergic cleaning composition, it contains:

A) one or more tensio-active agents of 5-50%, wherein at least 10% of the tensio-active agent gross weight is nonionogenic tenside,

B) 5-75% one or more can absorb greater than the water-swelling polymer of the water of its deadweight and

C) inorganic particle of nonessential maximum 90% (weight) and other conventional ingredients.

Therefore, the preferred aspect according to the present invention provides a kind of synergy cleaning composition, and it contains:

A) one or more tensio-active agents of 5-25% (weight), wherein at least 40% of the tensio-active agent gross weight is nonionogenic tenside,

B) 5-50% (weight) one or more can absorb greater than the water-swelling polymer of the water of its deadweight and

C) inorganic particle of 10-90% (weight) and other compositions commonly used.

The present invention will be described according to following indefiniteness embodiment.

Embodiment:

I. the influence of polymkeric substance-tensio-active agent interaction partners gel formation:

The composition of general introduction is by mixed surfactant and polymer manufacture in the table 1.Products therefrom is a meal.In every kind of these product, add 50g water, and placed 1-2 minute.Adding the visual appearance of water after product and the volume of gained gel is expressed in the table 1 equally.

The measurement of gel volume (ml) behind the adding excessive water:

Slurry/the thick liquid that forms among the foregoing description 1-6 is transferred to 250ml classification separately measure in the tube, and make volume reach 250ml by adding water.Content in the stirring graduated cylinder 1 minute is placed and is observed after sedimentation is spent the night.Content in the graduated cylinder is divided into two-phase (in embodiment 1,2,3 and 6).The gel deposition that is formed by polymers capable of swelling is in the bottom, and the upper strata is a water.Measure the volume of gel coat.The volume of gel (in the presence of excessive water) is illustrated in the gel formation ability of polymers capable of swelling in the presence of the tensio-active agent.What can infer is, gel volume is big more, and tensio-active agent is more little to the negative impact of polymers capable of swelling.

Table 1

Composition weight (g)	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
Composition weight (g)	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Linear alkylbenzene sulfonate	0.5	-	0.25	0.5	-	-
Fatty Alcohol(C12-C14 and C12-C18) 7EO (carbon chain lengths C ₁₂-C ₁₈)	-	0.5	0.25	-	0.5	-	Linear alkylbenzene sulfonate	0.5	-	0.25	0.5	-	-
	-	0.5	0.25	-	0.5	-	Cross linked polyacrylate (GE 500F Kolon Chemicals)	0.5	0.5	0.5	-	-	0.5
The water that adds	50	50	50	50	50	50	Cross linked polyacrylate (GE 500F Kolon Chemicals)	0.5	0.5	0.5	-	-	0.5
The water that adds	50	50	50	50	50	50	The product feature
Physical appearance behind the adding 50ml water	Soft gel	Good solid state gel	Gel	Liquid	Liquid	Soft gel	The product feature
Physical appearance behind the adding 50ml water	Soft gel	Good solid state gel	Gel	Liquid	Liquid	Soft gel	Gel volume (ml) behind the adding excessive water	58	68	60	0	0	75

Data show in the table 1, and polymkeric substance is absolutely necessary to forming gel, in the presence of nonionogenic tenside, this polymer formation good solid state gel.This point shows that gel length and volume are determined in being chosen in of tensio-active agent, and determines that thus the consistence of the slurry that forms is very important.

Ii. the characteristic of tensio-active agent is to the influence of gel formation:

The anion surfactant and the nonionogenic tenside of different ratios are studied in the composition of describing in the his-and-hers watches 2, to determine its influence to gel formation.The characteristic of product being mixed and studies gel with water.Measurement with gel volume (ml) behind the definite adding of the aforesaid method excessive water.Also estimated performance by the consideration detersive efficiency.

The measurement that washing is renderd a service:

Get 1g has dirt as brush and washing by the gel that adds the formation of 100g water in the 7.5g powder plate with apparatus.Different washing parameters and use properties during the mensuration washing operation.To wash to render a service based on general effect and be classified as the 1-5 level, wherein " 1 " refers to " poor " and " 5 " refer to the performance of " good ".

Table 2

Composition weight (g)	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13
Composition weight (g)	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13	Linear alkylbenzene sulfonate	1.5	-	-	1.5	-	1.35	0.9
The Fatty Alcohol(C12-C14 and C12-C18) C12-18 3EO of ethoxylation	-	1.5	-	-	1.5	0.15	0.6	Linear alkylbenzene sulfonate	1.5	-	-	1.5	-	1.35	0.9
	-	1.5	-	-	1.5	0.15	0.6	Cross linked polyacrylate GE 500F	1.5	1.5	1.5	-	-	1.5	1.5
Tripoly phosphate sodium STPP	0.2	0.2	0.2	0.2	0.2	0.2	0.2	Cross linked polyacrylate GE 500F	1.5	1.5	1.5	-	-	1.5	1.5
Tripoly phosphate sodium STPP	0.2	0.2	0.2	0.2	0.2	0.2	0.2	Alkaline silicate	0.3	0.3	0.3	0.3	0.3	0.3	0.3
Inorganic particle	4.4	4.4	4.4	4.4	4.4	4.4	4.4	Alkaline silicate	0.3	0.3	0.3	0.3	0.3	0.3	0.3
Inorganic particle	4.4	4.4	4.4	4.4	4.4	4.4	4.4	The water that adds	100	100	100	100	100	100	100
Add the product feature behind the water								The water that adds	100	100	100	100	100	100	100
Add the product feature behind the water								Physical appearance	Gel	Best solid gel	Gel	Liquid	Liquid	Gel	Good solid gel
Gel volume (ml)	98	142	152	0	0	126	100	Physical appearance	Gel	Best solid gel	Gel	Liquid	Liquid	Gel	Good solid gel
Gel volume (ml)	98	142	152	0	0	126	100	Washing	5	3	0	1	1	4	4

Data in the table 2 show that polymkeric substance is absolutely necessary for obtaining consistent gel, but for the effect very poor (embodiment 9) of washing.When not having polymkeric substance, just can not obtain gel when only having tensio-active agent, and detersive efficiency reduction (embodiment 10 and 11), because polymkeric substance helps the dispersion of active substance.With regard to gel formation and detersive efficiency, the performance of the composition among the embodiment 7,8,12 and 13 shows, the correct combination of tensio-active agent and polymkeric substance had both had best washing effect for obtaining, and the composition that has good gel-strength again is very important.

Claims

1. synergy cleaning composition that comprises tensio-active agent and polymkeric substance, wherein:

A) content of one or more tensio-active agents is 5-95%, and wherein nonionogenic tenside accounts at least 40 weight % of total surfactant;

B) content that can absorb greater than one or more water-swelling polymers of the water of polymkeric substance deadweight is 5-95%;

Wherein the weight ratio of tensio-active agent and water-swelling polymer is 1: 0.4-0.4: in 1 scope, and wherein water-swelling polymer is selected from the hydrolysate of polyacrylic acid, polyacrylic ester, crosslinked acrylate polymers, guar gum and derivative thereof, starch-acrylate graft copolymer, starch-acrylonitrile graft copolymer, crosslinked polyoxyethylene, cross-linked carboxymethyl cellulose, is selected from the partial cross-linked water-swelling polymer and the iso-butylene/maleic acid of polyoxyethylene and polyacrylamide.

2. according to the composition of claim 1, wherein water-swelling polymer is selected from the part neutral sodium salt of polyacrylic acid or cross linked polyacrylate.

3. according to any one composition of claim 1 to 2, wherein water-swelling polymer accounts for the 5-75% of composition.

4. according to the composition of claim 3, wherein water-swelling polymer accounts for the 5-50% of composition.

5. according to the composition of claim 1, wherein tensio-active agent is selected from negatively charged ion and nonionogenic tenside.

6. according to the composition of claim 5, wherein the weight ratio of anion surfactant and nonionogenic tenside is 0.1: 1-6: in 4 scopes.

7. according to the composition of claim 6, wherein the weight ratio of anion surfactant and nonionogenic tenside is 1: 1.

8. according to the composition of claim 1, wherein composition comprises the total surfactant that accounts for composition 5-50%.

9. composition according to Claim 8, wherein composition comprises the tensio-active agent that accounts for composition 5-25%.

10. according to the composition of claim 1, wherein composition is pressed powder, tablet, pill, strip, slurry or gel form.

11. according to the composition of claim 1, wherein water-swelling polymer is a solid form.

12. according to the composition of claim 11, wherein water-swelling polymer is particle, granular, pill, thin slice or hour hand shape.

13. according to the composition of claim 1, wherein composition contains inorganic particle and other conventional ingredients of maximum 90% in addition.

14. according to the composition of claim 1, wherein composition comprises the inorganic particle phase of 10-90%.

15. according to the composition of claim 13 or 14, wherein particle is water-fast or partly soluble abrasive material mutually.