CN103492544B

CN103492544B - Hard surface treatment composition

Info

Publication number: CN103492544B
Application number: CN201280020247.9A
Authority: CN
Inventors: S.达斯; K.杜特塔; A.弗拉马尼克
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 2011-04-25
Filing date: 2012-04-03
Publication date: 2015-05-27
Anticipated expiration: 2032-04-03
Also published as: EA201301192A1; ZA201307836B; WO2012146464A1; CN103492544A; EP2702129B1; AR086479A1; ES2535020T3; PL2702129T3; EP2702129A1; EA024738B1

Abstract

The present invention is in the field of hard surface treatment compositions. The invention particularly relates to hard surface treatment compositions that provide easier cleaning upon the subsequent cleaning. It is an object of the present invention to provide a composition that, upon use, renders a surface hydrophobic and to provide good cleaning. It has been found that poly aluminium chloride and a soap in combination with a poly vinyl alcohol and non-ionic or cationic surfactant provides both good cleaning and good stain/soil repellence.

Description

Hard surface treatment composition

Invention field

The invention belongs to Hard surface treatment composition field.The present invention be more particularly directed to follow-up clean time the Hard surface treatment composition of more easy cleaning is provided.

Background of invention

Hard surface in family or office usually uses and comprises one or more tensio-active agents and the liquid composition of also possible pH adjusting agent as citric acid or sodium citrate salt is clean.This cleaning compositions can with dilution (in water) or undiluted form, to spray or to use cloth or other mode wiping easily any to use.Optionally, this cleaning compositions can be fallen from surface washing after the cleaning.Contributing to more easily removing the material processing of dirt and/or spot in follow-up clean period if hard surface to be cleaned can adopt, is then favourable.This is called next cleaning benefit (next time cleaning benefit).

When not cleaning at once after deposit, the dirt on hard surface may become more difficult removing.When not clean immediately, dirt may be attached on the surface more, more tacky and usually more tough and tensile, needs more effort to clean.Although not bound by theory, the dirt of this more difficult removing may be due to the reaction etc. of chemical transformation, dirt and the environmental factors such as oxygen in dirt exsiccation effect, dirt.Some dirts are easier than other there is malleableize (toughening) reaction and process.The dirt comprised or contain chemical unsaturated oil & fat is passed in time and may be become very tough and tensile and be difficult to clean, especially when exposing at elevated temperatures.Even light also can cause such fatty soil pass in time and toughen.Except environmental factors, the character on the surface residing for dirt and composition also can affect the malleableize process of dirt.

WO 02/18531 discloses a kind of method for cleaning hard surfaces, wherein with this surface of antioxidant process, then makes this surface dirty, subsequently this surface clean.Before making dirty, use antioxidant treat surface, cause more easily removing dirt in follow-up cleaning.Antioxidant can be present in cleaning compositions or the rinse composition used after the cleaning.Furthermore disclosed the cleaning compositions preferably comprising antioxidant with the concentration of 0.1-10 % by weight.Tannic acid example is especially effective.

WO 2006/108475 A1 discloses the method removing fatty soil from hard surface, and described method comprises following consecutive steps: (a) is with liquid cleansing composition process hard surface; B () makes fatty soil deposit; And (c) this surface clean is to remove fatty soil.

WO 2010/069731 A1 discloses process fabric substrate and makes this base material repel various dirt and spot and make it be hydrophobic method and composition.It is disclosed that a kind of method by using the composition of soap and water-soluble trivalent or tetravalent metal to process base material, and wherein said composition keeps pH to be less than 6 by adding pH adjusting agent.

In WO04037944 A1, disclose self-cleaning surface, it is disclosed that for the preparation of the method and composition by the self-cleaning surface of water, particularly disclose the water-based system for the formation of transparent self-cleaning surface.In the method for WO04037944 A1, provide a kind of aqueous mixture, it comprises the nano particle with the particle diameter being less than 300 nanometers and is selected from and can forms the water-soluble hydrophobic surface-modifying agent of continuous film and the surface-modifying agent of water-dispersible hydrophobic surface-modifying agent from the aqueous solution.This aqueous mixture is administered on the surface, after water evaporation, forms automatically cleaning Clear coating on said surface.In one embodiment, this aqueous mixture is not substantially containing the organic solvent except agglomerated solvent.

Although there are these advantages, disclosed in prior art, antioxidant also may suffer shortcoming.The residue of the antioxidant on the hard surface such as in kitchen and bathroom and/or nano particle may be considered as harmful and undesired by human consumer.

Art discloses the sanitising agent based on microemulsion (such as US 5,759,983 and US 5,741,760) comprising metallic soap and silicon materials.But when using said composition, owing to lacking surface hydrophobicity, these compositions do not provide required stain resistance.

Therefore, still expect to make surfaces hydrophobic and good clean composition is provided.

Do not wish to be bound by theory, it is believed that tensio-active agent can provide good cleaning usually, but tensio-active agent makes surfaces hydrophilic, this makes surface that water-based grime more easily occur instead of water-based spot is repelled.

Therefore, an object of the present invention is to provide a kind of composition, it can make surfaces hydrophobic after using.

Another object of the present invention is to provide and a kind ofly provides good clean composition.

Surprisingly, the clean and good stain/soil repellency that the combination of polymerize aluminum chloride and soap and polyvinyl alcohol and nonionic or cats product provides good is simultaneously had been found that.

Invention summary

Therefore, the invention provides a kind of Hard surface treatment composition, it comprises the soap of the polymerize aluminum chloride (PAC) of 0.01-1%w, the C8-C18 lipid acid of 0.01-1%w, the season silicone oil (quaternary silicon oil) of the tensio-active agent being selected from nonionogenic tenside or quaternary ammonium cation tensio-active agent of 0.05-1%w, the polyvinyl alcohol (PVA) of 0.05-1%w and 0.1-1%w, the pH that wherein said composition has is 3 to 5, and PAC: the ratio of soap is 3:2 to 2:3.

In second aspect, the invention provides a kind of method processing base material, it comprises and composition according to the present invention is applied to hard surface and makes the step successively of this surface drying, does not wherein have this surface of rinsing between the steps.

In the 3rd, the invention provides a kind of bottled cleaning compositions comprised according to composition of the present invention.

For those of ordinary skill in the art, by reading following detailed description and claims, the aspects, features and advantages of these and other will become apparent.In order to avoid causing query, any feature any other side used in the present invention of one aspect of the present invention.Word " comprise " be intended to represent " comprising " but not necessarily " by ... composition " or " by ... form ".In other words, listed step or option need not to be exhaustive.Notice, the example provided in following specification sheets is intended to set forth the present invention and do not intend to limit the invention to these examples itself.Similarly, unless otherwise stated, all per-cent is weight/weight percent.Except in operation embodiment and comparative example or except explicitly pointing out in addition, quantity of material or reaction conditions, the physical properties of material and/or all numerical value of purposes in this specification sheets, are indicated to should be understood to be modified by word " about ".X and y is understood to include with the numerical range that " x to y " form represents.When for special characteristic, when describing multiple preferable range with " x to y " form, should be appreciated that all scopes also considering the different end points of combination.

Detailed Description Of The Invention

The present invention comprises polymerize aluminum chloride (PAC), the soap of C8-C18 lipid acid, the tensio-active agent being selected from nonionogenic tenside or quaternary ammonium cation tensio-active agent, PVA (polyvinyl alcohol) and polysiloxane.

Cleaning compositions according to the present invention is preferred for directly using.PH is 3 to 5.

polymerize aluminum chloride

Polymerize aluminum chloride is a kind of known polyelectrolyte.Polymerize aluminum chloride (PAC) can be defined as general formula [Al (OH) _acl _b] _nthe non-stoichiometric oligopolymer of aluminium chlorohydroxide, wherein a value is preferably in the scope of 1.5 to 1.9, b preferably in the scope of 1.1 to 1.5, wherein a+b=3.Aluminium content is generally 12-20%.

Commercially available PAC containing a small amount of impurity, may comprise the SO of trace ₄ ^2-, CO ₃ ^2-, NO ₃ ^-, Br ^-, HCO ₃ ^-and HSO ₄ ^-but such impurity exists with the concentration being less than 2 % by weight, being more preferably less than 1 % by weight, being also more preferably less than 0 weight .5% or being even less than 0.1 % by weight accounting for described PAC usually.

The PAC concentration that exists in the composition is 0.01-1 % by weight, preferably at least 0.1%, more preferably at least 0.25%, or even 0.5 % by weight.

In addition, consider to have hybrid metal system at context of the present invention, it comprises the second metal-salt of aluminium (from PAC) and 0.01 to 1 % by weight.Described second metal-salt is selected from divalence and trivalent metal salt, is preferably selected from calcium, zinc and iron (III).When there is described second metal-salt, the ratio of described PAC and described second metal-salt is preferably in the scope of 9:1 to 3:2.

soap

Soap according to the present invention is an alkali metal salt of C8-C18 lipid acid.The preferred embodiment of this lipid acid is saturated fatty acid, is selected from lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and combination thereof; And unsaturated fatty acids, such as myristoleic acid, Zoomeric acid, hexadecylenic acid (Sapienic acid), oleic acid, elaidic acid, isooleic acid, linolic acid, trans,trans-Linoleic acid (Linoelaidic acid) and alpha-linolenic acid and combination thereof.Basic metal is sodium, potassium, lithium or their mixture.Also the salt of the combination of saturated fatty acid and unsaturated fatty acids is considered.

The naturally occurring mixture mainly comprising one or more C8-C18 soaps, preferably one or more lipid acid as listed above is also included within scope of the present invention.The example of this mixture is the salt of coco-nut oil fatty acid and palm kernel fatty acid.

In order to avoid causing query, " mainly " refer to described soap weight at least 50%, more preferably at least 60%, also more preferably at least 70%, even more preferably at least 80% or even at least 90%.

The soap concentration that exists in the composition is 0.01-1 % by weight, preferably at least 0.1%, more preferably at least 0.25%, or even 0.5 % by weight.

The ratio of PAC and soap is 3:2 to 2:3, preferred 4:3 to 3:4, or even 5:4 to 4:5 to obtain optimum.

Under these ratios, it is found that surface cleaning (gloss) and hydrophobic result are best.

tensio-active agent

Glass or plastic containers suitable in the context of the present invention and quaternary ammonium cation tensio-active agent.Also quaternary ammonium cation tensio-active agent and the combination both nonionogenic tenside is considered.

The tensio-active agent that those skilled in the art this area fully aware of is usually known, the textbook known as being described in is as " Surface Active Agents ", 1st volume, Schwartz & Perry, Interscience 1949, 2nd volume, Schwartz, Perry & Berc, Interscience 1958, and/or by the current edition " McCutcheon's Emulsifiers and Detergents " of Manufacturing Confectioners Company publication or at " Tenside-Taschenbuch ", H. Stache, the second edition, Carl Hauser Verlag, in 1981.

nonionogenic tenside

Preferred glass or plastic containers.Nonionogenic tenside is also well known in the art.They are made up of water soluble polyalkylene oxygen base (polyalkoxylene) (preferably 3 to 10 oxyethyl groups and/or propoxy-) or single-or two-alkylolamide base and organic hydrophobic group chemical combination usually, wherein said organic hydrophobic group derived from, such as, have 9 to 15 carbon atoms fatty alcohol (optional side chain, such as methyl branch), wherein alkyl is containing the alkylphenol (preferably 12 to 20 carbon atoms) of 6 to about 12 carbon atoms of having an appointment, wherein each alkyl contains the dialkyl phenol of 6 to 12 carbon atoms, alkyl has primary of 10 to about 24 carbon atoms, the second month in a season or tertiary fatty alcohol (or its alkyl-blocked derivative) monocarboxylic acid, with polyoxypropylene (polyoxypropylene).

Wherein fatty acid-based alkyl contains 10 to about 20 carbon atoms and silane alcohol base (alkyloyl) has the lipid acid list of 1 to 3 carbon atom-and two-alkylolamide is also common.Single-and two-alkylolamide derivative any one in, optionally, polyoxyalkylene (polyoxyalkylene) part of the hydrophobic parts combining group and molecule below may be there is.

In all tensio-active agents containing poly-alkylene oxide group, poly-alkyleneoxy moiety is made up of average 2 to 20 ethylene oxides (ethylene oxide) group, propylene oxide (propylene oxide) group or its mixture usually.Mentioned kind is included in European patent specification EP-A-0,225, in 654 describe, particularly as whole liquid phase or its a part use those.

Particularly preferably be those ethoxylated non-ionic surface active agents, it is the condensation product with the fatty alcohol of 9 to 15 carbon atoms and oxyethane (the being generally understood as mean value) condensation of 3 to 12 moles.The example is condensation product or its mixture of the oxyethane of C9 to C15 alcohol and 3 or 7 moles.These can be used as unique nonionogenic tenside or with describe in EP-A-0 225 654 those combine.

cats product

Cats product according to the present invention is quaternary surfactant, is characterised in that described ammonium salt has general formula: R1R2R3R4N+ X-, and wherein R1 to R4 is alkyl or aryl, and X ^-for inorganic anion.

Preferably, at least one of alkyl or aryl R1-R4, but be usually no more than two for having the alkyl or aryl of C12-C18 alkyl chain length, and all the other alkyl are C1-C3 alkyl.

In quaternary ammonium salt according to the present invention, R1 is preferably C14-C16 straight chained alkyl, and R2-R4 is preferably methyl.

Particularly preferred quaternary ammonium cation tensio-active agent is benzalkonium chloride (alkyldimethyl benzylammonium chloride) and cetylpyridinium chloride (CPC).

Nonionogenic tenside or cats product or its mixture concentration that exists in the composition are 0.05-1 % by weight.In order to obtain best hydrophobicity result, this concentration is preferably 0.1 to 0.8%, more preferably no more than 0.5%, or even at the most 0.4 % by weight.

polyvinyl alcohol

Polyvinyl alcohol (PVOH, PVA or PVAl) is a kind of water miscible synthetic polymer.In the context of the present invention, consider homopolymer and the multipolymer of PVA, but homopolymer is most preferred.The homopolymer of vinyl alcohol or multipolymer preferably have molecular weight 10 ³to 10 ⁷u (u is atomic mass unit (SI), also referred to as " amu " or " dalton ", " D " or " Da "), more preferably 10 ⁴to 10 ⁶u, most preferably 30,000 to 500,000 u.

The PVA concentration that exists in the composition is 0.05-1 % by weight.

PVA: the ratio of tensio-active agent is preferably at least 1:1, more preferably 1:1 to 15:1, also more preferably 2:1 to 15:1.

Under these ratios, find that PVA polymkeric substance can improve the clean effect of tensio-active agent, and can not surface hydrophilicity be caused.

season silicone oil

In order to provide the repellency of oily dirt and spot further, described composition comprises season silicone oil further.Preferred season, silicone oil was polysiloxane.The typical example of this preferred polysiloxane is the siloxanes being selected from following A class, category-B and C class.

a. cyclomethicone

Cyclomethicone is defined by following general formula I, wherein m be more than or equal to 3 integer, and R is straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, alkenyl or alkynyl moiety.

more preferably as shown in formula IIa, IIb and IIc, wherein m is the cyclomethicone of 3,4 or 5.Particularly preferably be low viscosity cyclomethicone, comprise hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

b. Simethicone

simethicone is defined by following general formula III:

Wherein R or R1 is selected from straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, alkenyl or alkynyl moiety ,-H ,-OH usually.R and R1 can be identical or different.

Simethicone is commercially available obtainable, and the wide region of viscosity is 1X10 ^-6to 6X10 ^-2m ²/ sec, wherein n=1-100,000, preferred n=1-1500, most preferably n=1-200.Below provide its table of example.

Viscosity (m ²/sec)	Approximate molecular weight	Approximate " n " value
			0.000005	800	9
0.00005	3780	53
			0.0001	6000	85
0.0002	9430	127
			0.00035	13650	185
0.0005	17350	230
			0.001	28000	375
0.01	67700	910
			0.06	116500	1570
0.1	139050	1875

c. silicone elastomer

Silicone elastomer is defined by following general formula I V:

Described season, silicone oil can exist with the concentration being less than 1 % by weight in the composition.Described composition preferably comprises and is less than 0.5 % by weight, but is preferably greater than 0, and 1 % by weight.

abrasives

Optionally, also abrasives can be comprised according to composition of the present invention.

The consumption of abrasive grain is at least 0.1%, preferably 0.5%.In order to keep the transparent characteristic of whole composition, the maximum of particle is 20%, preferably 10%, more preferably 5%.

Described particle can be made up of abrasives known in the art.Therefore, their granulometric composition of inorganic abradant such as silicon-dioxide, silicate, calcite etc. that can be known by one or more.They can by polymer beads, the compositions such as such as polyethylene, polypropylene, polycarbonate.Specially suitable is the particle of biodegradable polymkeric substance (plastics than deriving from starch as known in the art).

Alternatively, described abrasive grain can be made up of softer material such as hard wax and fat, hard fatty acids, hard fatty acids soap etc.Such material also can mix with the fine particle of any known abrasive material or with other material (preferred solid material is applicable to improve cleaning course and the particle forming desired size thus).

In semi-transparent combination thing, in order to have visual attraction to human consumer, described particle is preferably macroscopic, namely obviously visible respectively with naked eyes.These are different from most of abrasive powders particle, the median size that most of abrasive powders particle has usually is far below 0.3mm and in most cases 0.1mm (100 μm) at the most, or being even less than 0.05mm, it also considered for opaque composition in context of the present invention.

Therefore, for semi-transparent combination thing, the median size that particle according to the present invention has is 0.3 to 2.5mm, be preferably greater than 0.5 and 1.5mm at the most, and for opaque composition, particle diameter is preferred lower than 0.3 mm.

And if described particle has quite uniform particle diameter, namely they all have the particle diameter in median size ± 70% scope, and preferably ± 50%, the particle diameter in the scope of more preferably ± 30%, then the visual attraction of said composition significantly strengthens.

If described particle has determine minimum spherical, then particle and therefore all the visual attraction of composition can strengthen further, make ratio between the longest and the shortest diameter of particle in either direction for 3:1, preferably 2:1 or even 1.5:1 at the most at the most.Particularly preferably be and there is circle, the particle of preferred smooth circle.This particle can pass through miniaturation method (prilling processes) preparation, and described method comprises makes particulate material melting, converts it into drop, after this (cools drop in empty stream at gas.Therefore, various method and suitable equipment are known in the art, and can be applied to Organic abrasive (prerequisite is that they have enough low fusing point).By various condensing method known in the art, use cohesion tackiness agent if necessary, dystectic powder such as inorganic abradant powder can be made the particle of suitable shape.

Although can be made up of colourless liquid and the solid particulate with its natural colour (being white in many cases) according to cleaning compositions of the present invention, if but described liquid and described particle have visibly different color, then said composition can remarkable more attractive to human consumer.They can have the different colourities of same color, deep blue particles such as in light blue liquid, or preferably, described liquid and described particle have contrasting colour, white particle such as in blueness, green or yellow liquid, or vice versa, or the coloured particle in different colored liquid.

Optional member

Described composition can comprise spices, SYNTHETIC OPTICAL WHITNER, antiseptic-germicide, fluoropolymer and repellent materials further.

Described spices can be any commercially available obtainable water-soluble or mixable flavor compositions.

Gloss other as known in the art and clean improve auxiliary agent such as 2-phenoxyethyl alcohol (obtaining from Dow is commercially available with Dowanol) and can add with the concentration of the 0.05-0.5 % by weight of composition.

pH

Be 3 to 5 according to the pH of composition of the present invention.

Not wishing to be bound by theory, it is believed that when preparing described composition, PAC and fatty acid separation and part combine, and obtain the mixture of acid PAC and basic soap, to give the overall pH of 3 to 5.

It is believed that aluminium salt forms different positively charged aquated species at acidic in water, such as: Al ₂(OH) ₂ ⁴⁺and Al ₃(OH) ₄ ⁵⁺.Polymerize aluminum chloride also can form Al in the solution ₁₃o ₄(OH) ₂₄ ⁷⁺, and the pKa that lipid acid has is 4.5, causes the pH scope in mixture to be 3-5.Think that this can cause hydrophobic compound deposition from the teeth outwards.

solvent

Described composition is preferably waterborne liquid, but also consider comprising the preparation prepared in the mixed solvent of alcohol (comprising methyl alcohol, ethanol and/or Virahol), wherein the ratio of water and solvent is 20:1 to 99:1.

surface treatment method

The invention provides a kind of method processing base material, it comprises and composition according to the present invention is applied to hard surface and makes the step successively of this surface drying, does not wherein have this surface of rinsing between the steps.

Usually, dirt deposition is stood after the treatment in described surface.

When by compositions-treated of the present invention, find that the repellency of this surface to water-based spot is stronger.

As further step, treatment in accordance with the present invention composition or another kind of composition can be used, preferably with treatment in accordance with the present invention composition this surface clean again.

product form

Described composition can with the form of any commercially available obtainable liquid composition, usually to comprise the packaged of the bottle of liquid.

Preferred use trigger spray applicator applying said compositions.Trigger spray applicator can make human consumer fast and easily use, and in addition, the air of appropriate amount is brought in composition by it, and this contributes to formation of foam.

Therefore, composition of the present invention can by any suitable tool storage and distribution, but spray applicator is particularly preferred.Pump-type distributor (no matter spraying or non-atomizing pump) is also fine.Therefore, the invention provides a kind of container for liquid hard surface cleaning agent, described container comprises the reservoir containing hard surface cleaning composition of the present invention and the spray dispenser for distributing said composition with Sprayable.Described spray dispenser is preferably trigger-type sprayer, but can be for spraying or any machine tool of aerosol form atomizing of liquids.

Now, the present invention will be set forth by following non-limiting example.

Embodiment

material:

PAC: polymerize aluminum chloride (from Grasim, India)

Soap: DCFA (the Na-salt of the cocoyl-lipid acid of distillation, from Godrej Industries Ltd, India)

Silicon: poly-methylhydrogen silicone (PMHS) (from Aldrich, USA); Polydimethylsiloxane (PDMS)

Water: distilled water (from Scientific Distillery, Bangalore)

The non-ionic ethoxylated alcohol of NI (EO3, EO7 and EO3:EO7=1:1, EO5); EO=oxyethane

Abrasive material: silicon-dioxide

PVA: polyvinyl alcohol (from Aldrich)

Zn ₂nO ₃zinc nitrate hexahydrate (from Merck)

CaCl ₂calcium chloride dihydrate (from Merck)

FeCl3 iron(ic) chloride (or iron(ic) chloride (III), from Merck)

Positively charged ion: cetylpyridinium chloride (CPC)

the method of application (oily repellency test) of oil:

The sweet oil (Bertolli) of 25 microlitres is coated with on a glass slide equably.The preparation of 0.5 mL is used on the glass surface.Liquid level is made to stop about 30 seconds on the glass surface.With paper handkerchief cleaning glass window surface until its complete drying.

water repellency (hydrophobicity) is tested:

Kruss protractor is used glass slide measures seat to drip (sessile droplet) contact angle by being placed in by the distillation water droplet of 10 microlitres.This angle is analyzed by image J software application Drop snake plug-in unit.

Contact angle is greater than 60 and is considered to good, and it is preferred for being greater than 75.

cleaner assay (being measured except oiliness by gloss):

Use glossmeter, under 60 degree of reflection angle, the gloss of glass slide after relative black background (RGB=0,0,0) measures and processes.Gloss number higher than 100 is considered to acceptable, is good higher than 110.

Embodiment 1: the impact that contact angle and the oily dirt of glass slide are cleaned

In this experiment, compare according to the effect of composition of the present invention (Ex1) with the various combination (Comparative Example A An is to G) of identical component (wherein at least one of PAC, soap, silicon or tensio-active agent).

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	eO wt %	contact angle	at the gloss of 60 °
								a	0	0	0	0.05	0	26	109
b	0.6	0	0	0.05	0	72	104
								c	0	0.6	0	0.05	0	53	115
d	0	0	0.1	0.05	0	62	103
								e	0	0	0	0.05	0.1	29	118
f	0.6	0.6	0.1	0.05	0	82	113
								g	0.6	0.6	0	0.05	0	74	112
ex1	0.6	0.6	0.1	0.05	0.1	82	128.

This table display composition ratio according to the present invention does not contain the better of any combination performance of one of described composition.

Embodiment 2: the type of nonionic EO is on stain resistance and clean impact:

In this embodiment, the PAC of comparing embodiment composition Ex2a-Ex4 and different amount and soap, also confirm that dissimilar nonionic obtains similar result simultaneously.

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3 wt%	eO7 wt%	contact angle	at the gloss of 60 °
										ex2a	0.04	0.04	0.1	0.05	0.1	0.1	0	74	130
ex2b	0.04	0.04	0.1	0.05	0.1	0	0.1	72	126
										ex2c	0.6	0.6	0.1	0.05	0.1	0.1	0	81	120
ex3	0.6	0.6	0.1	0.05	0.1	0	0.1	83	123
										ex4	0.6	0.6	0.1	0.05	0.1	0.05	0.05	82	128.

The type of EO is for showing without any impact, and upper table shows the PAC of different concns and the performance of soap change stain resistance (contact angle).

Embodiment 3: the amount of nonionic EO is on stain resistance and clean impact:

In this embodiment, confirm compared with comparing embodiment J, in embodiment E x5-Ex8, non-ionic amount should be greater than 0.05%.Display nonionic and PVA in described scope but do not show containing another comparing embodiment (K) of PAC and soap yet and obtain poor contact angle result (hydrophobicity).

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt%	contact angle	at the gloss of 60 °
									j	0	0.6	0	0	0	0	24	116
ex5	0.6	0.6	0.1	0.05	0.1	0.05	78	111
									ex6	0.6	0.6	0.1	0.05	0.1	0.25	80	126
ex7	0.6	0.6	0.1	0.05	0.1	0.5	64	128
									ex8	0.6	0.6	0.1	0.05	0.1	0.75	50	131
k	0	0	0	0.05	0.1	0.25	26	104.

The change of nonionogenic tenside obtains best clean under being presented at least 0.05% tensio-active agent, and the tensio-active agent of 0.05-0.5% obtains best stain resistance, although still obtain acceptable result under higher surfactant concentration.

It is unfavorable for hydrophobicity because of its relative orientation from the teeth outwards to find the tensio-active agent (amphipathic molecule) of more a large amount.

Embodiment 4: the type of tensio-active agent is on stain resistance and clean impact:

In this embodiment, nonionogenic tenside (ex 9) and cats product (Ex 10) and anion surfactant (comparative example M) is compared.

group	pAC wt%	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	tensio-active agent	tensio-active agent wt%	contact angle	at the gloss of 60 °
										ex9	0.6	0.6	0.1	0.05	0.1	eO3:EO7=1:1	0.25	80	126
ex10	0.6	0.6	0.1	0.05	0.1	cPC	0.25	78	117
										m	0.6	0.6	0.1	0.05	0.1	naLAS	0.25	68	67.

The above results display anion surfactant can not provide sufficiently high contact angle or clean (gloss).

Embodiment 5: the pH of described treatment agent is on stain resistance and clean impact:

Following table is presented to be compared with the comparing embodiment N outside described scope, O with P according to the composition (Ex 10 and 11) within the scope of pH of the present invention.

group	pAC wt%	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt %	pH	contact angle	at the gloss of 60 °
										n	0.6	0.6	0.1	0.05	0.1	0.1	2	76	101
ex10	0.6	0.6	0.1	0.05	0.1	0.1	4	80	122
										ex11	0.6	0.6	0.1	0.05	0.1	0.1	5	77	121
o	0.6	0.6	0.1	0.05	0.1	0.1	6	38	122
										p	0.6	0.6	0.1	0.05	0.1	0.1	8	29	131.

Stain resistance reduces at a high ph, thus preferred pH is <6.

Embodiment 6:PVA and EO combination is on stain resistance and clean impact

In this embodiment, tensio-active agent and the PVA of different ratios is compared.

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt %	contact angle	at the gloss of 60 °
									q	0.6	0.6	0.1	0.80	0.1	0	85	122
ex12	0.6	0.6	0.1	0.75	0.1	0.05	85	127
									ex13	0.6	0.6	0.1	0.65	0.1	0.15	84	129
ex14	0.6	0.6	0.1	0.55	0.1	0.25	83	130
									ex15	0.6	0.6	0.1	0.45	0.1	0.35	69	131
ex16	0.6	0.6	0.1	0.35	0.1	0.45	67	131
									ex17	0.6	0.6	0.1	0.25	0.1	0.55	62	132
ex18	0.6	0.6	0.1	0.15	0.1	0.65	56	132
									ex19	0.6	0.6	0.1	0.05	0.1	0.75	49	134.

Upper table display is for clean, and the nonionogenic tenside of minimum quantity is clean required.

Although acceptable hydrophobicity can be obtained under higher surfactant concentration, be less than the PVA of 0.5% tensio-active agent and at least 1:1: under Surfactant Ratio, obtain optimum.

The ratio of embodiment 7:PAC and soap

In this embodiment, PAC and the soap of different ratios is compared.

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt %	contact angle	at the gloss of 60 °
									r	0.2	0.6	0.1	0.05	0.1	0.25	35	128
ex20	0.4	0.6	0.1	0.05	0.1	0.25	72	126
									ex21	0.6	0.6	0.1	0.05	0.1	0.25	79	127
ex22	0.6	0.4	0.1	0.05	0.1	0.25	76	125
									s	0.6	0.2	0.1	0.05	0.1	0.25	52	113.

Upper table display is as PAC: the good result simultaneously obtaining contact angle (hydrophobicity) and clean (gloss) when the ratio of soap is 3:2 (Ex 22) to 2:3 (Ex20).Best result is obtained under 1:1 (Ex21).

Embodiment 8: the comparison of silicone oil

In this embodiment, the benefit of different silicone oil is confirmed.

group	pAC wt %	soap wt %	silicone oil (0.1%w)	pVA wt%	abrasive material wt%	eO3:EO7 (1:1, wt%)	contact angle	at the gloss of 60 °
									ex23	0.6	0.6	pMHS	0.05	0.1	0.1	81	128
ex24	0.6	0.6	decamethylcyclopentasiloxane	0.05	0.1	0.1	80	129
									ex25	0.6	0.6	simethicone (DC 200)	0.05	0.1	0.1	82	129.

Upper table display, when using different siloxanes (silicone oil as defined in the present invention), obtains the good result of contact angle (hydrophobicity) and clean (gloss) simultaneously.

Embodiment 9: hybrid metal embodiment (calcium)

In this embodiment, within the scope of shown pH and outside scope, the effect of mixed metal compositions (PAC and calcium chloride) is compared.

Composition provides as follows.All compositions all contain 0.55% PVA, 0.1% PDMS, 0.1% abrasive grain and 0.25% nonionogenic tenside (1:1 EO3:EO7).

Group	PAC wt %	CaCl ₂ wt %	Soap wt %	PAC:Ca	pH	Contact angle	At the gloss of 60 °
								Ex26	0.6	0	0.6		4	81	129
Ex27	0.54	0.06	0.6	9:1	4	82	126
								*Ex28	0.3	0.3	0.6	1:1	4	80	123
*Ex29	0.36	0.24	0.6	3:2	4	80	122
								T	0.24	0.36	0.6	2:3	4	56	123
U	0.06	0.54	0.6	1:9	4	38	112
								V	0.54	0.06	0.6	9:1	6	43	121
W	0.3	0.3	0.6	1:1	6	39	118
								X	0.36	0.24	0.6	3:2	6	45	116
Y	0.24	0.36	0.6	2:3	6	32	122
								Z	0.06	0.54	0.6	1:9	6	36	121

* outside scope of the present invention

The tangible PAC of upper illness that has not attacked the vital organs of the human body: the ratio of metal-salt is that the hybrid metal system within 9:1 to 3:2 shows well within pH scope 3-5, and other ratio or higher pH do not obtain required water contact angle (that is, not obtaining required hydrophobicity).

Embodiment 10: hybrid metal embodiment (zinc)

In this embodiment, within the scope of shown pH and outside scope, the effect of mixed metal compositions (PAC and zinc nitrate) is compared.

Group	PAC wt %	Zinc nitrate wt %	Soap wt %	PAC:Zn	pH	Contact angle	At the gloss of 60 °
								Ex30	0.6	0	0.6		4	81	128
Ex31	0.54	0.06	0.6	9:1	4	83	128
								*Ex32	0.3	0.3	0.6	1:1	4	80	125
*Ex33	0.36	0.24	0.6	3:2	4	81	124
								AA	0.24	0.36	0.6	2:3	4	48	121
AB	0.06	0.54	0.6	1:9	4	35	119
								AC	0.54	0.06	0.6	9:1	6	45	118
AD	0.3	0.3	0.6	1:1	6	42	122
								AE	0.36	0.24	0.6	3:2	6	36	120
AF	0.24	0.36	0.6	2:3	6	30	118
								AG	0.06	0.54	0.6	1:9	6	35	123

* outside scope of the present invention

Embodiment 11: hybrid metal embodiment (iron)

In this embodiment, within the scope of shown pH and outside scope, the effect of mixed metal compositions (PAC and iron(ic) chloride) is compared.

Group	PAC wt %	Iron(ic) chloride wt %	Soap wt %	PAC:Fe	pH	Contact angle	At the gloss of 60 °
								Ex34	0.6	0	0.6		4	81	128
Ex35	0.54	0.06	0.6	9:1	4	81	123
								*Ex36	0.3	0.3	0.6	1:1	4	82	120
*Ex37	0.36	0.24	0.6	3:2	4	80	126
								AH	0.24	0.36	0.6	2:3	4	39	119
AI	0.06	0.54	0.6	1:9	4	35	114
								AJ	0.54	0.06	0.6	9:1	6	46	121
AK	0.3	0.3	0.6	1:1	6	45	128
								AL	0.36	0.24	0.6	3:2	6	37	120
AM	0.24	0.36	0.6	2:3	6	35	121
								AN	0.06	0.54	0.6	1:9	6	36	124

* outside scope of the present invention

Claims

1. Hard surface treatment composition, it comprises:

The polymerize aluminum chloride (PAC) of a 0.01-1%w;

The soap of the C8-C18 lipid acid of b 0.01-1%w;

The tensio-active agent of c 0.05-1%w, is selected from nonionogenic tenside or quaternary ammonium cation tensio-active agent;

The PVA (polyvinyl alcohol) of d 0.05-1%w; With

The season silicone oil of e 0.1-1%w;

Wherein:

The pH that composition described in a has is 3 to 5; And

B PAC: the ratio of soap is 3:2 to 2:3.

2. composition according to claim 1, wherein PVA: the ratio of tensio-active agent is at least 1:1.

3. the composition any one of aforementioned claim, wherein said tensio-active agent is for having C9-C15 alkyl chain and comprising the ethoxylized fatty alcohol nonionogenic tenside of 3 to 12 ethylene oxide groups (EO).

4. composition according to claim 1, wherein said composition comprises abrasives further.

5. composition according to claim 4, wherein said abrasive material be selected from comprise silicon-dioxide, silicate inorganic abradant or comprise the polymer abrasive of polyethylene, polypropylene and polycarbonate.

6. composition according to claim 1, it comprises second metal-salt being selected from divalence and trivalent metal salt of 0.01-1 % by weight further, and the ratio of wherein said PAC and described second metal-salt is in the scope of 9:1 to 3:2.

7. process the method for base material, it comprises following step successively:

Composition as claimed in one of claims 1-5 is applied to hard surface by a,

B makes this surface drying,

Between step (a) and (b), wherein there is no this surface of rinsing.

8. bottled cleaning compositions, it comprises composition as claimed in one of claims 1-6.

9. bottled cleaning compositions according to claim 8, it is equipped with trigger spray dispensers.