CN103492544A

CN103492544A - Hard surface treatment composition

Info

Publication number: CN103492544A
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: 2014-01-01
Anticipated expiration: 2032-04-03
Also published as: EA201301192A1; ZA201307836B; WO2012146464A1; EP2702129B1; AR086479A1; CN103492544B; 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

The hard surface treatment compositions

Invention field

The invention belongs to hard surface treatment compositions field.The present invention be more particularly directed in the follow-up more hard surface treatment compositions of easy cleaning that provides when clean.

Background of invention

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

When clean at once after deposition, more difficult the removing that may become of the dirt on hard surface.When not cleaning immediately, it is upper that dirt may be attached to surface more, more tacky and usually more tough and tensile, needs more effort clean.Although not bound by theory, this more difficult dirt of removing may be due to chemical transformation in dirt exsiccation effect, dirt, dirt and environmental factors such as reacting of oxygen etc.Malleableize (toughening) reaction and process more easily occur than other in some dirts.The dirt that comprises 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 so fatty dirt pass in time and toughen.Except environmental factors, the character on the residing surface of 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 antioxidant, processes this surface, then makes this surface dirty, subsequently clean this surface.Before making dirty, use the 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 clean in.In addition, the preferred cleaning compositions that comprises antioxidant with the concentration of 0.1-10 % by weight is disclosed.Tannic acid is exemplified as especially effective.

WO 2006/108475 A1 discloses the method except the degrease dirt from hard surface, and described method comprises following consecutive steps: (a) with liquid cleansing composition, process hard surface; (b) make fatty dirt deposition; Reach and (c) clean this surface to remove the degrease dirt.

WO 2010/069731 A1 discloses the processing fabric substrate and has made this base material repel various dirts and spot and make it be hydrophobic method and composition.A kind of method of processing base material by the composition with soap and water-soluble trivalent or tetravalent metal is wherein disclosed, and wherein said composition by adding pH adjusting agent to keep pH to be less than 6.

Disclose self-cleaning surface in WO04037944 A1, wherein disclose for the preparation of by the method and composition on the self-cleaning surface of water, disclose especially the water-based system that is used to form the transparent self-cleaning surface.In the method for WO04037944 A1, a kind of aqueous mixture is provided, and it comprises the nano particle with the particle diameter that is less than 300 nanometers and is selected from and can forms the water insoluble 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 to surface upper, forms the automatically cleaning Clear coating after the water evaporation on described surface.In one embodiment, this aqueous mixture is not substantially containing the organic solvent except agglomerated solvent.

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

This area discloses the sanitising agent based on microemulsion that comprises metallic soap and silicon materials (for example US 5,759,983 and US 5,741,760).Yet, when using said composition, owing to lacking surface hydrophobicity, these compositions do not provide required spot repellency.

Therefore, still expectation makes surface be hydrophobicity 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, yet tensio-active agent makes surface be wetting ability, this makes surface that water-based spot deposition more easily occur rather than the water-based spot is repelled.

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

A kind of good clean composition that provides is provided another object of the present invention.

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

The invention summary

Therefore, the invention provides a kind of hard surface treatment compositions, the soap of the C8-C18 lipid acid of its polymerize aluminum chloride that comprises 0.01-1%w (PAC), 0.01-1%w, the season silicone oil (quaternary silicon oil) of the tensio-active agent that is 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 of processing base material, it comprises the step successively that composition according to the present invention is applied to hard surface and makes this surface drying, wherein between these steps, there is no this surface of rinsing.

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

For those of ordinary skills, by reading following detailed description and claims, the aspects, features and advantages of these and other will become apparent.For fear of causing query, any feature of one aspect of the present invention can be used for any other side of the present invention.Word " comprise " be intended to mean " comprising " but not necessarily " by ... form " 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 does not plan to limit the invention to these examples itself.Similarly, except as otherwise noted, otherwise all per-cent is weight/weight percent.Except in operation embodiment and comparative example or explicitly pointing out in addition, in this specification sheets, indication quantity of material or reaction conditions, the physical properties of material and/or all numerical value of purposes should be understood to be modified by word " approximately ".The numerical range meaned with " x to y " form is understood to include x and y.When for special characteristic, during with a plurality of preferable range of " x to y " format description, should be appreciated that all scopes of also considering the different end points of combination.

Detailed Description Of The Invention

The soap that the present invention comprises polymerize aluminum chloride (PAC), C8-C18 lipid acid, the tensio-active agent that is 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 preferably in 1.5 to 1.9 scope, b preferably in 1.1 to 1.5 scope, a+b=3 wherein.Aluminium content is generally 12-20%.

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

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

In addition, at context of the present invention, consider to there is the hybrid metal system, the second metal-salt that it comprises aluminium (from PAC) and 0.01 to 1 % by weight.Described the second metal-salt is selected from divalence and trivalent metal salt, is preferably selected from calcium, zinc and iron (III).When having described the second metal-salt, the ratio of described PAC and described the 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 consider the salt of the combination of saturated fatty acid and unsaturated fatty acids.

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

For fear of causing query, " mainly " refers 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% of described soap weight.

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

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

Suitable glass or plastic containers and quaternary ammonium cation tensio-active agent in the context of the invention.Also consider the two the combination of quaternary ammonium cation tensio-active agent and nonionogenic tenside.

Those skilled in the art this area fully aware of is known tensio-active agent usually, and the textbook of knowing as be described in is as " Surface Active Agents ", the 1st volume, Schwartz & Perry, Interscience 1949, the 2 volumes, 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, 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 usually by water-soluble poly alkylene oxide group (polyalkoxylene) (preferably 3 to 10 oxyethyl groups and/or propoxy-) or single-or two-alkylolamide base and organic hydrophobic group chemical combination and form, wherein said organic hydrophobic group derived from, for example, have 9 to 15 carbon atoms fatty alcohol (optional side chain, methyl branch for example), wherein alkyl is containing having an appointment 6 to the about alkylphenol of 12 carbon atoms (preferably 12 to 20 carbon atoms), the dialkyl phenol that wherein each alkyl contains 6 to 12 carbon atoms, alkyl has 10 to primary of about 24 carbon atoms, the second month in a season or tertiary fatty alcohol (or its alkyl-blocked derivative) monocarboxylic acid, and polyoxypropylene (polyoxypropylene).

Wherein fatty acid-based alkyl contain 10 to approximately 20 carbon atoms and silane alcohol base (alkyloyl) have the lipid acid list of 1 to 3 carbon atom-and two-alkylolamide be also common.Single-and any of two-alkylolamide derivative in, optionally, may have polyoxyalkylene (polyoxyalkylene) part in conjunction with the hydrophobic parts of back group and molecule.

In all tensio-active agents that contain poly-alkylene oxide group, poly-alkylene oxide group part is usually by average 2 to 20 ethylene oxides (ethylene oxide) group, propylene oxide (propylene oxide) group or its compositions of mixtures.Mentioned kind is included in European patent specification EP-A-0, describes those that particularly use as all liquid phases or its part in 225,654.

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

cats product

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

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

In quaternary ammonium salt according to the present invention, R1 is preferably the 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 described composition is the 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 0.4 % by weight even at the most.

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 exist concentration of PVA in described composition is the 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 the PVA polymkeric substance can improve the clean effect of tensio-active agent, and can not cause surface hydrophilicity.

season silicone oil

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

a. cyclomethicone

Cyclomethicone is defined by following general formula I, and wherein m is 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 part.

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

b. Simethicone

simethicone is defined by following general formula III:

Wherein R or R1 usually be selected from straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, alkenyl or alkynyl part ,-H ,-OH.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, n=1-100 wherein, 000, preferably 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 that is less than 1 % by weight in composition.Described composition preferably comprises and is less than 0.5 % by weight, but is preferably greater than 0,1 % by weight.

abrasives

Optionally, also can comprise abrasives 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 compositions, the maximum of particle is 20%, preferably 10%, more preferably 5%.

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

Alternatively, described abrasive grain can be by softer material such as hard wax and fat, hard fatty acids, hard fatty acids soap etc. are made.Such material also can or mix with other material (preferably solid material, be applicable to the particle that improves cleaning course and form thus desired size) with the fine particle of any known abrasive material.

In translucent composition, for the human consumer is had to visual attraction, described particle is preferably macroscopic, obviously visible respectively with naked eyes.These are different from most of abrasive powders particles, the median size that most of abrasive powders particles have usually is far below 0.3mm and be 0.1mm (100 μ m) at the most in most cases, or even being less than 0.05mm, it is also for opaque composition, to consider in context of the present invention.

Therefore, for translucent composition, 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 particle diameter quite uniformly, they all have the particle diameter in median size ± 70% scope, preferably ± 50%, the particle diameter in more preferably ± 30% scope, the visual attraction of said composition significantly strengthens.

If it is spherical that described particle has definite minimum, particle and therefore all the visual attraction of compositions can further strengthen, make ratio between the longest and the shortest diameter of particle on 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 the particulate material melting, converts it into drop, after this cooling drop in gas (air) stream.Therefore, the whole bag of tricks and suitable equipment are known in the art, and can be applied to organic abrasive material (prerequisite is that they have enough low fusing point).By various condensing methods known in the art, use if necessary the cohesion tackiness agent, can be by dystectic powder such as the inorganic abradant powder is made the particle of suitable shape.

Although can be formed by 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, said composition is understood remarkable more attractive to the human consumer.They can have the different colourities of same color, the mazarine particle in light blue liquid for example, perhaps preferably, described liquid and described particle have contrasting colour, the white particle in blue, green or yellow liquid for example, perhaps vice versa, or the coloured particle in different colored liquids.

Optional member

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

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

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

pH

According to the pH of composition of the present invention, be 3 to 5.

Do not wish to be bound by theory, it is believed that when preparation during described composition, PAC and fatty acid separation and part combination, obtain the mixture of acid PAC and basic soap, to give 3 to 5 whole pH.

It is believed that aluminium salt forms different positively charged hydration kinds under acid pH in water, for example: Al ₂(OH) ₂ ⁴⁺and Al ₃(OH) ₄ ⁵⁺.Polymerize aluminum chloride also can form Al in solution ₁₃o ₄(OH) ₂₄ ⁷⁺, and the pKa that lipid acid has is 4.5, causing the pH scope in mixture is 3-5.Think that this can cause hydrophobic compound deposition from the teeth outwards.

solvent

Described composition is preferably waterborne liquid, yet, also consider the preparation prepared in comprising the alcohol mixed solvent of (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 of processing base material, it comprises the step successively that composition according to the present invention is applied to hard surface and makes this surface drying, wherein between these steps, there is no this surface of rinsing.

Usually, dirt deposition is stood in described surface after processing.

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

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

product form

Described composition can be with the form of any commercially available obtainable liquid composition, usually with the packaged of the bottle that comprises liquid.

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

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

Now, will set forth the present invention 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-methyl hydrogen-containing siloxane (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 of 25 microlitres (Bertolli) is coated on glass slide equably.The preparation of 0.5 mL is applied on glass surface.Liquid level is stopped approximately 30 seconds on glass surface.Surperficial until its complete drying with the paper handkerchief cleaning glass window.

water repellency (hydrophobicity) test:

Use the Kruss protractor to be placed on glass slide and to measure seat (sessile droplet) contact angle by the distillation water droplet by 10 microlitres.Analyze this angle 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 being greater than 75.

cleaner assay (measuring except oiliness by gloss):

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

Embodiment 1: on contact angle and the clean impact of oily dirt of glass slide

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

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	eO wt %	contact angle	gloss at 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.

It is better that this table shows that composition according to the present invention shows than any combination that does not contain one of described composition.

Embodiment 2: the type of nonionic EO is on spot repellency and clean impact:

In this embodiment, PAC and the soap of comparing embodiment composition Ex2a-Ex4 and different amounts, 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	gloss at 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 that soap changes spot repellency (contact angle).

Embodiment 3: the amount of nonionic EO is on spot repellency and clean impact:

In this embodiment, confirm to compare with comparing embodiment J, in embodiment E x5-Ex8, non-ionic amount should be greater than 0.05%.Show nonionic and PVA in described scope but containing another comparing embodiment (K) of PAC and soap, also do not show 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	gloss at 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 variation of nonionogenic tenside is presented under at least 0.05% tensio-active agent and obtains best cleaning, and the tensio-active agent of 0.05-0.5% obtains best spot repellency, 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 of a large amount (amphipathic molecule) more.

Embodiment 4: the type of tensio-active agent is on spot repellency and clean impact:

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

group	pAC wt%	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	tensio-active agent	tensio-active agent wt%	contact angle	gloss at 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 shows that anion surfactant can not provide sufficiently high contact angle or clean (gloss).

Embodiment 5: the pH of described treatment agent is on spot repellency and clean impact:

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

group	pAC wt%	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt %	pH	contact angle	gloss at 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.

The spot repellency reduces under high pH, thereby preferred pH is<6.

Embodiment 6:PVA and EO combination are on spot repellency and clean impact

In this embodiment, the tensio-active agent and the PVA that compare different ratios.

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt %	contact angle	gloss at 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 demonstration is for clean, and the nonionogenic tenside of minimum quantity is clean required.

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

The ratio of embodiment 7:PAC and soap

In this embodiment, the PAC and the soap that compare different ratios.

group	pAC wt %	soap wt %	pDMS wt %	pVA wt%	abrasive material wt%	eO3:EO7 (1:1) wt %	contact angle	gloss at 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 shows as PAC: the ratio of soap obtains the good result of contact angle (hydrophobicity) and clean (gloss) simultaneously while being 3:2 (Ex 22) to 2:3 (Ex20).In the best result of the lower acquisition of 1:1 (Ex21).

Embodiment 8: the comparison of silicone oil

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

group	pAC wt %	soap wt %	silicone oil (0.1%w)	pVA wt%	abrasive material wt%	eO3:EO7 (1:1, wt%)	contact angle	gloss at 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 shows when using different siloxanes (as the silicone oil 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, shown in the pH scope and outside scope, the effect of mixed metal compositions (PAC and calcium chloride) relatively.

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	Gloss at 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

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, shown in the pH scope and outside scope, the effect of mixed metal compositions (PAC and zinc nitrate) relatively.

Group	PAC wt %	Zinc nitrate wt %	Soap wt %	PAC:Zn	pH	Contact angle	Gloss at 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

Embodiment 11: hybrid metal embodiment (iron)

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

Group	PAC wt %	Iron(ic) chloride wt %	Soap wt %	PAC:Fe	pH	Contact angle	Gloss at 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

Claims

1. hard surface treatment compositions, it comprises:

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

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

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

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

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

Wherein:

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

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

2. according to the composition of claim 1, PVA wherein: the ratio of tensio-active agent is at least 1:1, preferably 1:1 to 15:1.

3. according to the composition of any one in aforementioned claim, wherein said tensio-active agent is the ethoxylized fatty alcohol nonionogenic tenside that has the C12-C18 alkyl chain and comprise 1 to 12 ethylene oxide group (EO).

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

5. according to the composition of claim 4, wherein said abrasive material is selected from the inorganic abradant that comprises silicon-dioxide, silicate or comprises the polymkeric substance abrasive material of polyethylene, polypropylene and polycarbonate.

6. according to the composition of any one in aforementioned claim, it further comprises second metal-salt that is selected from divalence and trivalent metal salt of 0.01-1 % by weight, and the ratio of wherein said PAC and described the 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:

A will be applied to hard surface according to the composition of any one in claim 1-5,

B makes this surface drying,

Wherein in step (a) with (b), there is no this surface of rinsing.

8. bottled cleaning compositions, it comprises the composition according to any one in claim 1-6.

9. bottle according to Claim 8, it is equipped with the trigger spray divider.