CN102307981A - Multi-coloured laundry products - Google Patents

Abstract

A transparent fluid composition in packaging, the composition: (a) comprising 10 to 85% by wt. of a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwittehonic surfactants and mixtures thereof; and (b) having about 50% light transmittance or greater using a 1 cm cuvette at wavelength of 410-800 nanometers; and being contained within a deformable, bottom-dispensing packaging comprising: (c) having a viscosity of at least 100 Pa. s at rest or up to a shear stress of 10 Pa being contained within a deformable, bottom-dispensing packaging comprising: (i) a container comprising a front wall and opposing rear wall, (ii) each wall comprising an inner layer which is transparent such that its light transmittance is greater than 25% at wavelength of about 410- 800 nm, (iii) and an outer layer which is opaque such that its light transmittance is less than 25% at wavelength of about 410-800 nm; characterised in that at least a portion of the inner surface of the rear outer wall is coloured and the outer layer of the front wall incorporates one or more windows through which the coloured portion of the inner surface is visible.

Description

The polychrome laundry product

The present invention relates to the polychrome laundry product (multi-coloured laundry products) of distribution in the deformable packing.

Bright, pleochroic laundry product visually brings very big magnetism to the human consumer, and can be used in some function aspects of hint, and for example fabric color keeps, strengthens or improves.The bottom distribution package provides many benefits that are easy to the distribution aspect for the human consumer.Viscous fluid can be stored in this packing because higher viscosity reduced from the bottom towards dispensing orifice or the leakage of valve.But possibly there is technological challenge in the polychrome laundry liquid in some type of package (being deformable bottom distribution package).When extruding deformable packing, the multiple and color that separate that for example realizes through being separated with chemical mode can affect adversely, because extruding can cause the mixing of said phase.For viscous fluid, blended can spend mutually some times to be separated, and has weakened the visual effect that consumer experience arrives when using said product.

The purpose of this invention is to provide the polychrome viscosity laundry composition in the deformable bottom distribution package, it can arbitrarily push and not mix different colours, and need not change prescription.

Correspondingly, in first aspect, the invention provides the transparent fluid composition in packing, said composition is included in the distribution package of deformable bottom, said composition:

(a) contain 10 to the 85wt.% tensio-active agents that are selected from the group of forming by negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and their mixture; With

(b) use the 1cm cuvette to have about 50% or bigger transmittance at the wavelength measurement of 410-800 nanometer; With

(c) shear-stress at static or maximum 10Pa has the viscosity of 100Pa.s at least;

Said packing comprises:

(i) comprise the container of antetheca and relative rear wall,

(ii) thereby each wall comprises transparent its transmittance of wavelength at about 410-800nm greater than 25% internal layer,

Thereby (iii) with opaque its transmittance of wavelength at about 410-800nm less than 25% skin;

At least a portion of internal surface that it is characterized in that the back outer wall is painted, and the skin of said antetheca comprises one or more windows, can see the coloured part of said internal surface through said window.

The advantage of above-mentioned configuration be said fluid laundry composition can be enough dark, bright-coloured and different color dyes to be to produce beautiful effect, still make it possible to push simultaneously said deformable bottle, and this can't influence color effects unfriendly.

Preferably, the total inner surface of said rear wall is colored.Preferably, with the said internal surface of outer wall afterwards of multiple color dyes.

The preferably bright chromatic colour of said color, and through the definition of the CIE L*C*H* color space.The said L*C*H* color space is the form of spheroid (sphere).

Vertical L* axle is represented brightness or lightness: from the no lightness of bottom representative (black fully) 0,50 in the centre, to represent 100 of maximum lightness (promptly complete white) at the top.

H* or H ^oAxle is represented tone, and is the ring-type transverse axis through the center.Unit degree of being ^oForm, scope is from 0 ^o(redness) is through 90 ^o(yellow), 180 ^o(green), 270 ^o(blueness) gets back to 0 ^o

The C* axle is represented colourity or " saturation ratio ": at 0 of ring center is undersaturated fully (being neutral gray, black or white), until at 100 of said ring edge, it is maximum chrominance or saturation ratio.

Preferably, C* is greater than 20.

The color of said rear wall or every kind of color can be positioned at the zone of said L*C*H* spheroid, and said zone forms the equator shell, and this equator shell is through said center and asymmetric and occupy 1/3rd the volume of being less than of said spheroid about said center.Therefore, the strong dyes/pigments that need in said composition, comprise high density does not make preparation be suitable for sensitive skin to obtain bright-coloured coloured composition.

Said packing can contain one or more internal layer and outer field sidewalls with above definition.Said one or more sidewall can as as described in be painted the rear wall.

Preferred said or each window is as much as possible little, thus said packing can provide protection for any photaesthesia component.But, simultaneously, preferably can clearly see number of colors and more preferably whole color through said or each window.These contradiction sexual demands advantageously realize through the window that comprises one or more elongated portions; Each elongated portion (when when the front is seen) on the position with at least three kinds; More preferably at least five kinds, even more preferably the color on the internal surface of at least seven kinds of said outer rear walls is corresponding.Preferably, said window all colours with said rear wall on the position is corresponding.

A plurality of windows can be set, thus said elongated portion together on the position all colours with said rear wall corresponding.

Said color can the subregion be provided with and said elongated portion through overlapping on the position a part of corresponding of (when at least when the front is seen) and said zone.

The suitable material that is used for the transparent internal layer of said packing includes but not limited to: polypropylene (PP), Vilaterm (PE), polycarbonate (PC), polyamide (PA) and/or polyethylene terephthalate (PETE), polyvinyl chloride (PVC); And polystyrene (PS).Said container can through extrude, moulding for example forms by preform blowing or through thermoforming or through injection molding.

Have in spectrographic visible light part (about 410-800nm) according to the transparent layer of packing of the present invention and to be preferably greater than 25%, more preferably greater than 30%, more preferably greater than 40%, the transmittance more preferably greater than 50%.

On the contrary, have less than 25% in spectrographic visible light part (about 410-800nm), be more preferably less than 20%, be more preferably less than 15%, be more preferably less than 5% transmittance according to the opaque layer of packing of the present invention.

As selection, the absorbancy of transparent layer can be measured as less than 0.6 (approximating 25% sees through) or have the transmittance greater than 25%, and wherein the % transmittance equals:

On the contrary, the absorbancy of said opaque layer can be measured as greater than 0.6.

For the object of the invention,, just think that this container is transparent as long as a wavelength in the visible-range has the transmittance greater than 25%.

Unless otherwise indicated, otherwise all percentage ratios all to be intended to be weight percentage.

Said packing is the bottom distribution package, and wherein said packing comprises container (holding said fluid composition) and distribution device, and said distribution device is positioned at the bottom of said packing.Preferred said distribution device is surrounded by securing device, and said securing device also provides the base for supporting of said packing.Said securing device can also comprise dosing device, is used for quantitative said composition.

Said packing can have curved top portion and be inverted the storage bottle to stop the user.In this way, said packing more maybe be with pretreater-loading position storage, and promptly said fluid laundry composition is accumulated in the bottom of said packing through gravity.

Laundry composition

Said composition preferably has the viscosity of 500Pa.s at least.

Said composition is the gel type composition of shear shinning preferably.Said viscosity can be less than 300Pa.s under shear-stress, preferably less than 100Pa.s be more preferably less than 5Pa.s, even more preferably it is 1Pa.s to the maximum and most preferably it is 0.5Pa.s to the maximum.

The shear shinning composition can contain polymer latex (polymer gum), for example xanthan gum maybe can form steady and continuous can suspended particle other glue of glue network.

Can use other external structure agent for example hydrogenated castor oil, Microcrystalline Cellulose.

Another kind of useful method is to change the preparation of non-gelling to form internal structure therein, the performance that the gel type washing composition that wherein said structure gives to form is like this wanted.Said composition can contain soap or lipid acid and sodium sulfate and can use one or more tensio-active agents to form the structure of gelation with the formation through lamellar phase.

Said composition can contain the lamellar phase dispersion from micellar surface promoting agent system, makes up layered structural agent mutually with containing extraly to be useful on, and wherein said structural agent can be a Fatty Alcohol(C12-C14 and C12-C18).

Composition of the present invention contains one or more surface-active agents (tensio-active agent) that are selected from the group of being made up of negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics or their mixture.Can be used in combination the mixture that to be used for preferred surfactants washing composition of the present invention be negatively charged ion and nonionogenic tenside separately or with any other one or more tensio-active agents although will be appreciated that any tensio-active agent.Said tensio-active agent should account for the 10wt.% at least of said composition, and for example 11% to 85%, at least 15% to 70% of preferred whole composition, more preferably 16% to 65%; Even more preferably 20% to 65%.

Nonionogenic tenside

Hereinafter described and to have combined to be used for the synthetic organic detergent of nonionic of the present invention separately or with other tensio-active agent.

Nonionic detergent is with the characteristic that exists for of organic hydrophobic grouping and organic hydrophilic group, and the condensation prepared through organic fatty family or alkyl aromatic hydrophobic compound and oxyethane (hydrophilic nmature) typically.The typical nonionogenic tenside that is fit to is those disclosed among the U.S. Pat. Nos. 4,316,812 and 3,630,929.Usually, said nonionic detergent is the lipophilic substance of poly-alkoxylation, wherein obtains the hydrophil lipophil balance wanted to the interpolation of lipophilic portion from the hydrophilic lower alkoxy groups of gathering.A kind of preferred nonionic detergent type is oxyalkylated alkanol, wherein said alkanol have 9 to 18 carbon atoms and wherein the mole number of oxyalkylene (having 2 or 3 carbon atoms) be 3 to 12.Among this type of material, preferably using wherein said alkanol is Fatty Alcohol(C12-C14 and C12-C18) and its every mole those that contain 5 to 8 or 5 to 9 alkoxy bases of 9 to 11 or 12 to 15 carbon atoms.

The illustrative example of this compounds is that wherein said alkanol has 12 to 15 carbon atoms and its every mole and contains those of the 7 ethylene oxide groups of having an appointment, for example Neodol ^TM25-7 and Neodol ^TM23-6.5 said product is by Shell Chemical Company, Inc. makes.The former be condensation product and the carbon content that the latter is wherein high fatty alcohol of mixture and about 7 mole ethylene oxides of the high fatty alcohol of average about 12 to 15 carbon atoms be 12 to 13 and the average number of the ethylene oxide group of existence be about 6.5 respective mixtures.Said higher alcohols is a primary alkanol.

Other useful nonionogenic tenside is representative with the nonionic surfactants type of under the Plurafac trade mark, selling.Plurafacs is the reaction product of the mixture of senior straight chain alcohol and ethylene oxide and propylene oxide, and it contains the combination chain of ethylene oxide and propylene oxide, with the oh group end-blocking.Example comprises the C with 6 mole ethylene oxides and 3 mole propylene oxide condensations ₁₃-C ₁₅Fatty Alcohol(C12-C14 and C12-C18), with the C of 7 mole propylene oxide and 4 mole ethylene oxide condensations ₁₃-C ₁₅Fatty Alcohol(C12-C14 and C12-C18), with the C of 5 mole propylene oxide and 10 mole ethylene oxide condensations ₁₃-C ₁₅The mixture of Fatty Alcohol(C12-C14 and C12-C18) or any above-mentioned substance.

Another kind of liquid nonionic surfactants can be from Shell Chemical Company, and Inc. is commercially available with the Dobanol trade mark: Dobanol 91-5 is the C that on average has the ethoxylation of 5mol ethylene oxide ₉-C ₁₁Fatty Alcohol(C12-C14 and C12-C18) and Dobanol 23-7 are the C that on average has the ethoxylation of 7mol ethylene oxide ₁₂-C ₁₅Fatty Alcohol(C12-C14 and C12-C18) is with respect to every mol Fatty Alcohol(C12-C14 and C12-C18).

In composition of the present invention, preferred nonionic comprises the have narrow relatively ethylene oxide content C of (about 7 to 9 moles) ₁₂-C ₁₅Uncle's Fatty Alcohol(C12-C14 and C12-C18) and with the C of about 5-6 mole ethylene oxide ethoxylation ₉To C ₁₁Fatty Alcohol(C12-C14 and C12-C18).

Another nonionogenic tenside kind that can be used according to the invention is to join sugar surfactant (glycoside surfactants).Be fit to the sugar surfactant of joining used according to the invention and comprise those of following formula:

RO-R’O- _y(Z) _x

Wherein R is an any monovalent organic radical group of containing the individual carbon atom in 6 to 30 (preferred 8 to 18); R ' is the divalent hydrocarbyl mission that contains 2 to 4 carbon atoms of having an appointment; O is a Sauerstoffatom; Y is the number that can have 0 to about 12 mean value, but it most preferably is zero; Z is the part derived from the reducing sugar that contains 5 or 6 carbon atoms; With x is to have 1 number to the mean value of about 10 (being preferably 1.5 to 10).

Be used for the particularly preferred sugar surfactant of joining of a type of the present invention practice and comprise those of following formula, wherein R is an any monovalent organic radical group (straight or branched) of containing the individual carbon atom of 6-18 (particularly about 8 to about 18); Y is zero; Z is a glucose or by its deutero-part; X is that mean value is 1 number to about 4 (preferably about 1-4).

The useful especially ionic surfactant pack of the application is drawn together but be not limited to: alcohol ethoxylate (for example available from Shell Chemical Co. Neodol 25-9), alkylphenol ethoxylate (for example available from Union Carbide Corp. Tergitol NP-9), alkyl poly glucoside (alkylpolyglucosides) are (for example available from the Glucapon of Henkel Corp. ^TM600CS), the polyoxypropylene diols of polyoxyethyleneization is (for example available from the Pluronic of BASF Corp. ^TML-65), sorbitol ester is (for example available from the Emsorb of Henkel Corp. ^TM2515), the sorbitol ester of polyoxyethyleneization is (for example available from the Emsorb of Henkel Corp. ^TM6900), alkanolamide is (for example available from the Alkamide of Rhone-Poulenc Co. ^TMDC212/SE) and the N-alkyl pyrrolidone (for example available from the Surfadone of ISP Technologies Inc. ^TMLP-100).

The nonionogenic tenside that uses in the prescription is for about 0% to about 70%, and is preferred 5% to 50%, more preferably 10-40wt%.

Can use the mixture of two kinds or more kinds of said nonionogenic tensides.

The anion surfactant washing composition

Can be used for anion surfactant of the present invention and be containing those surface active cpds of long chain hydrocarbon hydrophobic grouping and hydrophilic radical (being for example sulfonate radical or sulfate groups of water solubilization group) at their molecular structure.Said anion surfactant comprises the water-soluble senior alkyl benzene sulfonate of basic metal (for example sodium and potassium), alkylsulfonate, alkyl-sulphate and alkyl, polyether vitriol.They also can comprise lipid acid or fatty acid soaps.The preferred anionic surfactants tensio-active agent is basic metal, ammonium or the alkanolamide salt of senior alkyl Phenylsulfonic acid and basic metal, ammonium or the alkanolamide salt of senior alkyl sulfonic acid.Preferred senior alkyl sulfonate is that wherein said alkyl group contains 8 to 26 carbon atoms, preferred 12 to 22 carbon atoms and more preferably those of 14 to 18 carbon atoms.Alkyl group in the said alkylbenzene sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms.Particularly preferred alkylbenzene sulfonate is X 2073 or potassium, for example linear alkyl benzene sulphonate.Can pass through long-chain alpha-olefin and sulphite or hydrosulphite (for example sodium bisulfite) prepared in reaction primary and secondary alkylsulfonate.Can also be like U.S. Pat. Nos. 2; 503; 280,2; 507,088,3,372; 188 and 3; Described in 260,741 through long-chain normal alkane and sulfurous gas and oxygen reaction are prepared said alkylsulfonate, with obtain to be suitable as surfactant detergent just or secondary senior alkyl sulfonate.

Said alkyl substituent is straight chain preferably, and promptly positive alkyl can use branched-chain alkyl sulfonate, although they are also different good aspect biological degradability.Said alkane, i.e. alkyl, substituting group can be sulfonated endways or can for example be connected with the carbon atom of said chain, promptly can be secondary sulfonate.Should be appreciated that said in the art substituting group can be connected with any carbon on the said alkyl chain.Can be with said senior alkyl sulfonate as an alkali metal salt, for example sodium and potassium.Preferred salt is sodium salt.Preferred alkylsulfonate is C ₁₀To C ₁₈The positive alkyl sodium sulfonate of uncle and potassium, more preferably C ₁₀To C ₁₅The positive alkylsulfonate of uncle.

Can use the mixture of senior alkyl benzene sulfonate and senior alkyl sulfonate and the mixture of senior alkyl benzene sulfonate and senior alkyl polyether thiourea hydrochlorate.

Can be with 0 to 70wt%, preferred 10 to 50wt% and more preferably 10 to 20wt% amount use said basic metal alkylbenzene sulfonate.

Said alkali metal sulfonate can arrive 70wt% with 0 with institute's alkylbenzene sulfonate, and preferred 10 to 50wt% amounts are mixed use.

Positive alkyl and branched-chain alkyl vitriol (for example primary alkyl sulphates) also can be used as anionic group.

Senior alkyl polyether thiourea hydrochlorate used according to the invention can be just or branched-chain alkyl and contain the lower alkoxy that can comprise two or three carbon atoms.Preferred positive senior alkyl polyether thiourea hydrochlorate, because they compare the biological degradability with higher degree with branched-chain alkyl, and the said rudimentary preferably oxyethyl group group of alkoxyl group that gathers.

Preferred senior alkyl polyethoxye vitriol used according to the invention is represented through following formula:

R’-O(CH ₂CH ₂O) _P-SO ₃M，

Wherein R ' is C ₈To C ₂₀Alkyl is preferably C ₁₀To C ₁₈C more preferably ₁₂To C ₁₅P is 2 to 8, is preferably 2 to 6 and more preferably 2 to 4; With M be basic metal, for example sodium and potassium, or ammonium cation.

Preferred sodium and sylvite.

A kind of preferred senior alkyl polyethoxylated vitriol is the triethoxy C with following formula ₁₂To C ₁₅The alcohol sodium sulfate salt:

C _12-15-O-(CH ₂CH ₂O) ₃-SO ₃Na

The example of the alkyl ethoxy sulfate that is fit to that can be used according to the invention is C _12-15Just or primary alkyl triethoxy vitriol, sodium salt; Positive decyl diethoxy vitriol, sodium salt; C ₁₂Primary alkyl diethoxy vitriol, ammonium salt; C ₁₂Primary alkyl triethoxy vitriol, sodium salt: C ₁₅Primary alkyl tetraethoxy vitriol, sodium salt; Blended C _14-15Positive primary alkyl blended three-and tetraethoxy vitriol, sodium salt; Octadecyl five ethoxy sulfates, sodium salt; With blended C _10-18Positive primary alkyl triethoxy vitriol, sylvite.

Said positive alkyl ethoxy sulfate be readily biodegradable be preferred.Said alkyl gathers lower alkoxy vitriol and can be mixed with each other and use and/or mix use with above-mentioned senior alkyl benzene sulfonate, alkylsulfonate or alkyl-sulphate.

Said basic metal senior alkyl polyethoxye vitriol can use with 0 to 70wt%, preferred 10 to 50wt% and more preferably 10 amounts that arrive 20wt% of whole composition with said alkylbenzene sulfonate and/or with alkylsulfonate or vitriol.

The anion surfactant that is particularly useful for the application includes but not limited to: linear alkylbenzene sulfonate is (for example available from the Vista of Vista Chemical Co. ^TMC-500), alkyl-sulphate is (for example available from the Polystep of Stepan Co. ^TMB-5), the alkyl-sulphate of polyoxyethyleneization is (for example available from the Standapol of Stepan Co. ^TMES-3), alhpa olefin sulfonate is (for example available from the Witconate of Witco Corp. ^TMAOS), α sulfo group methyl ester is (for example available from the Alpha-Step of Stepan Co. ^TMMC-48) and isethionate (for example available from the Jordapon of PPG Industries Inc. ^TMCI).

In said prescription, arrive about 60wt% with about 0wt%, preferred 5wt% more preferably 8 to 25wt% uses anion surfactants to 40wt%.

Cats product

Many cats products known in the art, and almost any cats product with long chain alkyl group of at least one about 10 to 24 carbon atom all is fit to the present invention.This compounds is described in " Cationic Surfactants ", Jungermann, and in 1970, it incorporates this paper by reference into.The concrete cats product that can be used as tensio-active agent in the present invention is described in detail among the U.S. Pat. No. 4,497,718.

As said nonionic and anion surfactant, composition of the present invention can be used in combination the use cats product separately or with any other tensio-active agent known in the art.Certainly, said composition cation tensio-active agent not.

Amphoterics

The both sexes synthetic detergent can be described as the derivative of aliphatic secondary and tertiary amine widely or heterocycle is secondary and the aliphatic derivatives of tertiary amine; Wherein said aliphatic group can be a straight or branched; And wherein said aliphatics substituent one of them contain 8 to 18 carbon atoms of having an appointment and contain the negatively charged ion water solubilization group with at least one, for example carboxyl, sulfonate radical, sulfate radical.

The example that drops on the compound within this qualification is 3 (dodecyl is amino) Sodium Propionate, 3-(dodecyl is amino) propane-1-sodium sulfonate, 2-(dodecyl is amino) sodium ethyl sulfate, 2-(dimethylamino) sodium stearate, 3-(N-carboxymethyl dodecyl is amino) propane-1-disodium sulfonate, octadecyl-Iminodiacetic acid sodium salt, 1-carboxymethyl-2-undecyl imidazole sodium and N, two (2-the hydroxyethyl)-2-sulfatos (sulfato) of N--3-dodecyloxy propyl group amine sodium.Preferred 3-(dodecyl is amino) propane-1-sodium sulfonate.

Zwitterionics can be described as the derivative of derivative, the heterocycle second month in a season and the tertiary amine of secondary and tertiary amine widely, or the derivative of quaternary ammonium 、 quaternary phosphine or uncle's sulfonium compound.The cation atom of said quaternary compound can be a heterocyclic part.In all these compounds, all exist aliphatic group at least one straight or branched, that contain 3 to 18 carbon atoms of having an appointment and at least one to contain the aliphatics substituting group of negatively charged ion water solubilization group (for example carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical).

The object lesson of operable zwitterionics is described in U.S. Pat. No. 4,062,647.

The amount of the amphoterics that uses can preferably change from 1 to 30wt% from 0 to 50wt%.

Should be noted that compound of the present invention preferably isotropic (this is generally understood as when macroscopic observation is homogeneous) and be transparent or semitransparent.

The total surfactant that uses is necessary for 10wt% at least, preferred 15wt% at least, more preferably 20wt% at least.

Washing assistant/ionogen

Can comprise conventional inorganic or organic basic cleaning washing assistant by washing assistant used according to the invention, it can arrive about 50wt% with about 0wt% of said composition, and preferred 3wt% uses to the concentration of about 35wt%.

As using among this paper, the term ionogen is meant any water-soluble salt.

Preferred said composition contains 1.0wt% at least, more preferably 5.0wt% at least, the most preferably ionogen of 10.0wt% at least.Said ionogen can also be the cleaning washing assistant, inorganic builders tripoly phosphate sodium STPP for example, or it can be for example sodium sulfate or a sodium-chlor of non-functional electrolyte.Preferred said inorganic builders constitutes the said ionogen of all or part.

Said composition can contain 1wt% at least, preferred 3wt% at least, and preferred 3wt% is to the ionogen of 50wt% nearly.

Composition of the present invention can suspended particulate solids, although particularly preferably be those systems that in fact this type of solid wherein is in suspension.Said solid can be with solution in the identical or different undissolved ionogen of ionogen, the ionogen in the said solution is saturated ionogen.In addition, or the conduct selection, they can be the materials that is insoluble to independent water basically.This type of insoluble basically examples of material is aluminosilicate washing assistant and calcite abrasive grain.

The example that operable suitable inorganic alkaline cleans washing assistant is water-soluble alkali phosphoric acid salt, polyphosphate, borate, silicate and carbonate.The object lesson of this type of salt is triphosphate, pyrophosphate salt, orthophosphoric acid salt, hexametaphosphate, tetraborate, silicate and the carbonate of sodium and potassium.

The example of the organic basic cleaning builder salt that is fit to is: (1) water soluble amino multi-carboxylate, the for example edetate of sodium and potassium, nitrilotriacetic acid(NTA) salt and N-(2 hydroxyethyl)-nitrilo diacetin; (2) water-soluble phytate, the for example phytate of sodium and potassium (seeing U.S. Pat. No. 2,379,942); (3) water-soluble polyphosphonic acid salt is particularly including ethane-1-hydroxyl-1, the sodium of 1-di 2 ethylhexyl phosphonic acid, potassium and lithium salts; The sodium of methylenediphosphonate (MDP), potassium and lithium salts; The sodium of ethylidene diphosphonic acid, potassium and lithium salts; And ethane-1,1, the sodium of 2-tri methylene phosphonic acid, potassium and lithium salts.Other example comprises ethane-2-carboxyl-1,1-di 2 ethylhexyl phosphonic acid, hydroxyl methanebisphosphonic acid, carboxyl di 2 ethylhexyl phosphonic acid, ethane-1-hydroxyl-1,1; 2-tri methylene phosphonic acid, ethane-2-hydroxyl-1,1,2-tri methylene phosphonic acid, propane-1; 1,3,3-tetra methylene phosphonic acid, propane-1; 1; 2,3-tetra methylene phosphonic acid and propane-1,2; 2, an alkali metal salt of 3-tetra methylene phosphonic acid; (4) the multi-carboxylate's polymkeric substance described among the U.S. patent No. 3,308,067 and the water-soluble salt of multipolymer.

In addition; Can use the multi-carboxy acid salt washing agent satisfactorily; The water-soluble salt that comprises mellitic acid, Hydrocerol A and carboxy methoxy-succinic acid, the salt of the polymkeric substance of methylene-succinic acid and toxilic acid, tartrate monosuccinic acid ester salt, tartrate disuccinic acid ester salt and their mixture (TMS/TPS).

Can use some zeolite or aluminosilicate.A kind of this type of aluminosilicate that can be used in the composition of the present invention is formula Na _x[(AlO ₂) _y.SiO ₂] amorphous water-insoluble hydrated compound, wherein x is that 1.0 to 1.2 number and y are 1, said amorphous substance is further with about 50mg eq. CaCO ₃The Mg++ exchange capacity of/g and 0.01mm are characteristic to the particle diameter of 5mm.This ion-exchange washing assistant has in English Patent No. 1,470,250 more fully to be described.

The synthetic aluminosilicate ion exchange material of spendable second water-insoluble is crystalline and has formula Na among this paper _z[(AlO ₂) _y(SiO ₂)] _xH ₂O, wherein z and y are at least 6 integer; Z to the mol ratio of y be 1.0 to about 0.5 and x be 15 to 264 integer; Said aluminosilicate ion exchange material has the particle size diameter of 0.1mm to 100mm; The calcium ion-exchanged capacity is at least about 200 milligramequivalent CaCO on the anhydrous basis ₃Hardness per gram; Be at least 2 grains (grains)/gallon per minute/gram with calcium rate of exchange on the anhydrous basis.These synthetic aluminosilicates have in English Patent No. 1,429,143 more fully to be described.

Enzyme

Hereinafter described in more detail and can be used for enzyme of the present invention.

If use lipase; Said lipolytic enzyme can be and to dredge the fungal lipase that the thermophilic hyphomycete of cotton shape (Thermomyces lanuginosus) produces through pubescence detritus enzyme (Humicola lanuginosa), or the bacterium lipase of the positive immunological cross-reaction of the lipase antibody of demonstration and microorganism Chromobacter viscosum var. lipolyticum NRRL B-3673 generation.This microorganism is described in the dutch patent specification 154 of ToyoJozoKabushikiKaisha; In 269 and be preserved in FermentationResearchInstitute; AgencyofIndustrialScienceandTechnology; MinistryofInternationalTradeandindustry; Tokyo; Japan; And add permanent the collection with nr.KOHatsuKenKinKi137; And the public can be with nr.NRRLB-3673 at UnitedStatesDepartmentofAgriculture; AgriculturalResearchSevice; NorthernUtilizationandDevelopmentDivisionatPeoria, III., USA obtains.Lipase by this microorganisms can be from Toyo Jozo Co., Tagata, and Japan is purchased acquisition, hereinafter referred to as " TJ lipase ".Use is according to the standard and the known IDP of Ouchterlony (Acta. Med. Scan., 133. 76-79 pages or leaves (1930)), and these bacterium lipase should show the positive immunological cross-reaction with said TJ lipase antibody.

Sero-fast preparation is implemented as follows:

The antigen of isopyknic 0.1mg/ml and freund's adjuvant (Freund ' s adjuvant) (fully or not exclusively) are mixed up to obtaining emulsion.Inject two does 45 according to following scheme with the said emulsion sample of 2ml:

0 day: the antigen in the complete Freund's adjuvant

4 days: the antigen in the complete Freund's adjuvant

32 days: the antigen in the incomplete Freund's adjuvant

64 days: the antigen stimulation agent (booster) in the incomplete Freund's adjuvant

The serum that contains required antibody through the clotted blood preparation of collection in centrifugal the 67th day.

Anti--sero-fast titre of TJ-lipase (titre) is confirmed through the deposition inspection of antigen and sero-fast a series of diluents according to the Ouchteriony process.Sero-fast diluent is the diluent that visible precipitate still is provided for the antigen concentration of 0.1mg/ml.

As stated, show that with said TJ-lipase antibody all bacterium lipase of positive immunological cross-reaction all are the lipase that in this embodiment of the present invention, is fit to.Their exemplary is (can trade(brand)name Amano-P lipase from Amano Pharmaceutical Co. from the lipase of Pseudomonas fluorescens (Pseudomonas fluorescens) IAM 1057; Nagoya; Japan obtains); From the lipase of Pseudomonas fragi FERM P 1339 (can trade(brand)name Amano B obtain); Lipase from false unicellular fungi degradation fat mutation (Pseudomonas nitroreducens var. lipolyticum) the FERM P1338 of nitroreduction; From the lipase of Rhodopseudomonas (Pseudomonas sp.) (can trade(brand)name Amano CES obtain); Lipase from pseudomonas cepacia (Pseudomonas cepacia); From Chromobacter viscosum; The lipase of Chromobacter viscosum var. lipolyticum NRRL B-3673 for example; Can be from Toyo Jozo Co.; Tagata, Japan is purchased acquisition; Further from U.S. Biochemical Corp. USA and Diosynth Co., the Chromobacter viscosum lipase that The Netherlands obtains, and from the lipase of gladiolus pseudomonas (Pseudomonas gladioli).

More than Ding Yi fungal lipase example is the lipase from pubescence detritus enzyme (Humicola lanuginosa), can obtain from Amano by trade(brand)name Amano CE; Above-mentioned european patent application 0; 258; The lipase of describing among 068 (NOVO) from pubescence detritus enzyme, and through the lipase (can from NOVO industri A/S with trade(brand)name " Lipolase " be purchased acquisition) of clone from the gene of pubescence detritus enzyme and this gene acquisition of expression in aspergillus oryzae (Aspergillus oryzae).This lipase is to be used for preferred fat enzyme of the present invention.

Although more than described various concrete lipase, should be appreciated that and to use any lipase that to give the desirable lipolysis activity of said composition, and the present invention also is subjected to the restriction of the concrete selection of lipase never in any form.

The lipase of this embodiment of the present invention is so that final composition has 100 to 0.005LU/ml in cycles of washing; Be preferably 25 to the active amount of lipolytic enzyme of 0.05LU/ml (when preparation with about 0.1-10; More preferably 0.5-7, most preferably the concentration that rises of 1-2g/ adds fashionable) be included in the liquid detergent composition.

Lipase unit (LU) is the amount that under following condition, produces the lipase of the titratable lipid acid of 1/mmol at certain pH state per minute: 30 ℃ of temperature; PH=9.0; Substrate is at 13mmol/L Ca in the Trisbuffer of 5mmol/l ²⁺Emulsion with 3.3wt.% sweet oil and 3.3wt.% Sudan Gum-arabic under the existence of 20mmol/L NaCl.

Certainly, can use the mixture of above-mentioned lipase.Said lipase can use with their not purified form or use with purified form, for example by means of known absorption process, and phenyl sepharose absorption techniques purifying for example.

If use proteolytic enzyme, said proteolytic ferment can be plant, animal or microbe-derived.Preferably, it is a kind of source, back, and it comprises yeast, fungi, mould and bacterium.Particularly preferably be the proteolytic enzyme of bacterium subtilisin type, for example the specific bacterial strain from subtilis and Bacillus licheniformis obtains.The examples of proteases of the commercially available acquisition that is fit to is Alcalase ^TM, Savinase ^TM, Esperase ^TM, all NOVO Industri A/S; The Maxatase of Gist-Brocades ^TMAnd Maxacal ^TMThe Kazusase of Showa Denko ^TMBPN and BPN ' proteolytic enzyme etc.The amount of the proteolytic ferment that comprises in the said composition is 0.05-50 based on final composition, and 000GU/mg is preferably 0.1 to 50GU/mg.Certainly, can use the mixture of different proteolytic ferments.

Although more than described various concrete enzymes; But should be appreciated that any proteolytic enzyme that can give the desirable proteolytic activity of said composition can use, and this embodiment of the present invention also is subjected to the restriction of the concrete selection of proteolytic ferment never in any form.

Except lipase or proteolytic enzyme, should be appreciated that for example cellulase, oxydase, amylase, peroxidase etc. also can be used for composition of the present invention to other enzyme as known in the art.Said enzyme can use with the cofactor that promotes enzymic activity, and promptly they can be used for enzyme system if desired.Be also to be understood that the present invention has also considered to have at different positions the enzyme (for example being performance and/or the stable enzyme that improves through engineering approaches) of sudden change.Through engineering approaches can the commercial enzyme that obtains an example be Durazym available from Novo.

Said prescription can not contain enzyme, the i.e. enzyme of 0wt%.

Optional ingredients

Except the above enzyme of mentioning, can also use many other optional ingredients.

The ealkaline buffer that can add in the composition of the present invention comprises monoethanolamine, trolamine, borax, water glass etc.

Hydrotropic agent of the present invention be can add and ethanol, sodium xylene sulfonate, cumene sodium sulfonate etc. comprised.

Other material is clay for example, and particularly water-insoluble type can be the useful supplementary additive in the present composition.Useful especially is wilkinite.This material mainly is polynite, and polynite is the pure aluminium silicate of hydration, and wherein about 1/6 aluminium atom can be combined with it by loosely by the hydrogen of magnesium atom replacement and different amounts, sodium, potassium, calcium etc.The wilkinite (promptly not containing any gravel, sand etc.) that is suitable for the more purified form of washing composition contain at least 30% polynite and therefore its cation exchange capacity be at least about 50 to 75 meg/100g wilkinites.Particularly preferred wilkinite is Wyoming or Western U.S. wilkinite, and it is with Thixo-jels 1,2, and 3 and 4 are sold by Georgia Kaolin Co..As authorize the English Patent No. 401,413 and the English Patent No.461 that authorizes Marriott and Guam of Marriott, and described in 221, known these wilkinite softening fabrics.

In addition, in Betengent product, can exist various other washing composition supplementary additives giving its extra performance of wanting, or on the function or aesthetic properties.

The aluminium salt (for example aluminum stearate) of higher fatty acid from little significant quantity to said composition that can be through adding is realized the improvement of said physical stability of such mixtures and resistance to settling ability.Said aluminum stearate stablizer can be with 0 to 3%, and preferred 0.1 to 2.0% and more preferably 0.5 to 1.5% amount is added.

In prescription, can also comprise a spot of dirt suspension agent or anti redeposition agent, for example polyvinyl alcohol, fatty amide, Xylo-Mucine, Vltra tears.A kind of preferred anti redeposition agent is the Xylo-Mucine with CM/MC ratio of 2:1, and it is sold with trade(brand)name Relatin DM 4050.

Another kind of minor constituent is a stain remover, for example deflocculated polymkeric substance.Usually, deflocculated polymkeric substance contains hydrophilic backbone and one or more hydrophobic side chain.

Deflocculated polymkeric substance of the present invention has been described in U.S. Pat. No. 5,147,576 in more detail.

When using, said deflocculated polymkeric substance accounts for 0.1 to 5% of said composition usually, be preferably 0.1 to 2% with most preferably be 0.5 to 1.5%.

Can use white dyes for cotton, polymeric amide and polyester textile.The white dyes that is fit to comprises Tinopal ^TM, stilbene, triazole and the substituted triazinyl stilbene of benzidine sulfone composition, particularly sulfonation, sulfonated aphthotriazoles stilbene, benzidine sulfone etc., most preferably stilbene and triazole combination.A kind of preferred whitening agent is Stilbene Brightener N4, and it is a dimorpholine hexichol amido stilbene-sulphonic acid salt.

Can also add defoamer with little significant quantity, silicone compounds for example is like Silicane L 7604.

Can use sterilant (for example tetrachloro-salicylanilide and Hexachlorophene), mycocide, dyestuff, pigment (water dispersible), sanitas (for example formalin), uv-absorbing agent, anti-yellowing agent (for example Xylo-Mucine), pH regulator agent and pH buffer reagent, the SYNTHETIC OPTICAL WHITNER of not damaging color, spices and dyestuff and bluing agent (for example Iragon Blue L2D, Detergent Blue 472/372 and ultramarine).

And, can use soil release polymer and cationic softening agent.

The tabulation of above-mentioned optional member and to be not intended to be exhaustive can also contain in said composition and might not list but well-known in the art other optional ingredients.

Randomly, composition of the present invention can contain all or some following compositions: zwitterionics is (for example available from the Mirataine of Rhone-Poulenc Co. ^TMBET C-30), cats product (for example available from Scher Chemicals, the Schercamox of Inc. ^TMDML), fluorescence dye, antiredeposition polymkeric substance, anti-dye migration polymkeric substance, soil release polymer, proteolytic enzyme, lipase, amylase, cellulase, peroxidase, enzyme stabilizers, spices, opalizer, UV absorption agent, washing assistant and be of a size of the particles suspended of 300-5000 micron.

Use 1 centimetre cuvette, at the wavelength of the preferred 570-690nm of 410-800 nanometer, composition of the present invention has at least 50% transmittance, and wherein said composition is substantially free of dyestuff.

As selection, use above-mentioned cuvette and wavelength, the transparency of said composition can be measured as at visible wavelength (about 410 to 800nm) has the absorbancy less than 0.3, and it is equal at least 50% transmittance.For the object of the invention, if said visible-range in a wavelength have transmittance greater than 50%, just think transparent/translucent.

The measurement of absorbancy and transmittance

Instrument: Milton Roy Spectronic 601

Process:

1. open spectrophotometer and power supply box and made it preheating 30 minutes.

2. setting wavelength

-on keyboard, import necessary wavelength (promptly 590,640 etc.)

-press [second function] key

-press " go to 8 " [yes] key

-machine at any time can be in selected wavelength readings then.

3. said instrument makes zero

-press [second function] key

-press " zero A " [%T/A/C]

-instrument should reading " XXX NM 0.000A T " then.

4. uncap vertically and in the transmitter front is put into sample.

5. close cap and write down reading (for example 640NM 0.123A T)

* note: all readings are all with " A " type collection (absorbancy pattern)

* note: each new wavelength shift and/or the new sample instrument that all will make zero.

Various indefiniteness embodiment of the present invention will more specifically be described now.

Fig. 1 shows the frontview according to the bottle of embodiment of the present invention.

With reference to figure 1, show the packing that contains deformable Plastic Bottle 1, it comprises according to the transparent liquid of the high viscosity of following table 1 or gelatinous composition 17 (being filled into liquid level 19, although this is invisible).

Said composition is transparent, uses the 1cm cuvette to have 50% transmittance at the wavelength of 410-800 nanometer.

Said bottle 1 has the container 2 that comprises antetheca 10 and relative rear wall 11; Said rear wall 11 is a visible through uppermost part 13 (hereinafter describe) and sidewall (not shown), thereby thereby each wall 10,11 comprise transparent its transmittance of wavelength at about 410-800nm greater than 25% internal layer and opaque its transmittance of wavelength at about 410-800nm less than 25% skin.Said skin obtains through shrink sleeve (shrink sleeve).

The total inner surface scope of said back outer wall 11 band or zone 7 (having different bright-colored 7 separately) by painted bright-colouredly; Between the zone 7 is border 27; And the skin of said anterior layer has window 5a 5b (it is to dig to cut district (cut-outs) or through hole (through-holes) in this embodiment), passes the color that said window can be seen painted rear wall 11.

Said color is bright chromatic colour, and limits through the CIE L*C*H* color space.The said L*C*H* color space is the form of spheroid.

Vertical L* axle is represented brightness or lightness: from the no lightness of bottom representative (black fully) 0,50 in the centre, to represent 100 of maximum lightness (promptly complete white) at the top.

H* or H ^oAxle is represented tone, and is the ring-type transverse axis through the center.Unit degree of being ^oForm, scope is from 0 ^o(redness) is through 90 ^o(yellow), 180 ^o(green), 270 ^o(blueness) gets back to 0 ^o

The C* axle is represented colourity or " saturation ratio ": at 0 of ring center is undersaturated fully (being neutral gray, black or white), until at 100 of said ring edge, it is maximum chrominance or saturation ratio.

The said color of said rear wall or every kind of color can be positioned at the formation level intercepts ball within the zone of (horizontal spherical segment), and it is through center and asymmetric and occupy 1/3rd the volume of being less than of said spheroid about said center.

Each window comprises elongated portion 13, each elongated portion 13 (when when the front is seen, promptly as among Fig. 1) on the position with as described at least three kinds of colors on the internal surface of outer rear wall corresponding.Said window 5a 5b together on the position all colours with said rear wall corresponding.Through corresponding with 7 overlapping realization positions, zone.

For the visual stimulus that increases, said elongated region is a bifurcated.

The material that is fit to that is used for the layer of said packing includes but not limited to: polypropylene (PP), Vilaterm (PE), polycarbonate (PC), polyamide (PA) and/or polyethylene terephthalate (PETE), polyvinyl chloride (PVC); And polystyrene (PS).Said container is the form of moulding.

The opaque layer of said packing can be any suitable opaque material that has 5% transmittance in spectrographic visible light part (about 410-800nm).The transparent layer of said packing is the rigidity bottle and is the thick PET of 0.2mm and has 50% transmittance in spectrographic visible light part (about 410-800 nanometer).

Said opaque layer is the cover that tightly assembles and is applied to said bottle (after stretch-blow) through thermal contraction.Thereby said window can limit through perforated lines and after applying said cover, remove undesired material to form said window.

Said packing 1 is that the bottom is distributed and correspondingly contains the distribution device 9 that is positioned at said container 2 bottoms.The distribution device 9 that illustrates contains pretreater 11, but this chooses wantonly.Said distribution device 9 is impaled the base for supporting that said quantitative securing device 15 itself comprises said packing by quantitative securing device (dosing closure device) 15.Said bottle container 2 is connected to each other through threaded or buckle linker with distribution device 9.

Said bottle top 29 illustrates puts down, but it can be crooked storing to stop to be inverted shown in dotted line 31 in other embodiments.

Securing device 15 comprises what expansion (for the neck area of said at least bottle) was put down, usually planar basal surface 15.Through the flat top surface 15 that expansion is provided, said surface makes securing device 13 can play the effect of base for supporting 13 (said bottle 7 is in upside down position), thereby makes said composition between storage-life, accumulate (under gravity) at distribution device 9 places.

In addition, said securing device 15 comprises the reservoir part 17 that wherein impales pretreater 12.With said securing device towards the surface 15 tapping outside so that stable base to be provided.Said surperficial 15 area is greater than the area at said device top 21.

Said distribution device 9 comprises the aperture, can realize distributing through said aperture.Said aperture comprises the valve 21 that is communicated with through conduit 23 fluids.Said valve 21 comprises the film (membrane) that extends the whole aperture 25 in the said distribution portion 9.

In one embodiment, said film has arcuate section (arcuate portion) (not shown) towards said container 7.The arcuate section of said film provides crossing slit to limit a plurality of leg-of-mutton blades that are generally.When for the content of the said container of dispense pressurised, said triangular vane towards the opening end bending in said aperture 25 to allow product through said aperture 25.When having discharged dispense pressure, said triangular vane rebound they starting position and work to hinder product and pass through said aperture 25.The blade of said valve has enough elasticity, only if applied pressure surpasses the pressure of the hydraulic pressure statical head (hydraulic static head pressure) of the material generation that is full of, otherwise they can curved open.In use, fluid is pressurized flows through and part is collected on the pretreater part 12 and prepares to be used for cleaning.

Be retained in any fluid on the said pretreater part 12 can both be between storage-life from said pretreater drippage and be collected in the said reservoir part 17, wash being used for next time.This has reduced the waste of product.

At container described in two embodiments described herein all is inflexible (rigid).But, will be appreciated that the present invention can adapt to and be used for flexibility (flexible) packing, for example bag, capsule etc.

The clear detergent prescription that table 1 is exemplary

?	?
		Composition as 100% active substance	Wt%
Neodol 25-9*	6-8
		Alcohol ethoxy vitriol	12-15
Linear alkylbenzene sulfonate	6-9
		Trisodium Citrate, dihydrate	3-6
Ucar 35	4-8
		Sorbyl alcohol	3-6
Five water sodium tetraborates	2-4
		The additive of small number and water	To 100%

* C ₁₂-C ₁₅Oxyalkylated (9EO) chain group.

Although the advantage of this configuration is that said liquid 17 is transparent, but still present bright-coloured painted dark colour (being used to produce beautiful effect), still make this prescription be suitable for sensitive skin simultaneously.

Certainly, should be appreciated that the present invention also is not intended to the details that is limited to above-mentioned embodiment, above-mentioned embodiment is described as just example.

Claims (10)

1. the transparent fluid composition in packing, said composition is included in the distribution package of deformable bottom,

Said composition:

(a) contain 10 to 85wt% the tensio-active agent that is selected from the group of forming by negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and their mixture; With

(b) use the 1cm cuvette to have about 50% or bigger transmittance at the wavelength measurement of 410-800 nanometer; With

(c) shear-stress at stationary state or maximum 10Pa has the viscosity of 100Pa.s at least,

Said packing comprises:

(i) comprise the container of antetheca and relative rear wall,

(ii) thereby each wall comprises transparent its transmittance of wavelength at about 410-800nm greater than 25% internal layer,

Thereby (iii) with opaque its transmittance of wavelength at about 410-800nm less than 25% skin;

At least a portion that it is characterized in that the internal surface of back outer wall is painted, and the skin of said antetheca comprises one or more windows, can see the coloured part of said internal surface through said window.

2. according to the transparent fluid composition in the packing of claim 1, the total inner surface of wherein said rear wall is colored.

3. require the transparent fluid composition in any one packing according to aforesaid right, the multiple color dyes in surface of wherein said back outer wall.

4. require the transparent fluid composition in any one packing according to aforesaid right; Wherein said or each window comprises one or more elongated portions, each elongated portion (when when the front is seen) on the position with said outside at least three kinds of colors on the internal surface of rear wall corresponding.

5. require the transparent fluid composition in any one packing according to aforesaid right, wherein said packing comprises the distribution device that is positioned at said container bottom.

6. require the transparent fluid composition in any one packing according to aforesaid right, wherein said distribution device is surrounded by securing device, and said securing device also provides the base for supporting of said packing.

7. require the transparent fluid composition in any one packing according to aforesaid right, wherein said securing device also comprises dosing device, is used for quantitative said composition.

8. require the transparent fluid composition in any one packing according to aforesaid right, wherein said packing has curved top portion.

9. the combination of aforesaid right requirement arbitrarily, wherein said transparent layer has the transmittance greater than 25% at the spectrographic visible part.

10. the combination of aforesaid right requirement arbitrarily, wherein said opaque layer has the transmittance less than 25% at the spectrographic visible part.

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