CN1283968A - Product applicator - Google Patents

Abstract

The invention relates to a hand-held packaged flowable composition, the package comprising an applicator (114) and a container (10), the container having flexible and resilient walls and comprising a reservoir for the flowable composition (24), the applicator having a plurality of elongated parting members (144) forming a distribution cross section for distributing the flowable composition in a volume by displacement of the applicator in a direction substantially normal the the cross section, the distribution cross section comprising a plurality of outlet (146), the composition distribution through the outlets being actuated by application of a pressure to the flexible and resilient walls (12), whereby at least 0.1 g and up to 0.5 g of composition are distributed per cm<2> of the cross section and per second when a pressure of 1.5 Pa is applied to the flexible and resilient walls (12). In a preferred embodiment, the composition is a hair dye composition.

Description

Product applicator

The present invention relates to a kind of packaged composition applicator, more specifically and not exclusively, the present invention relates to be used to smear hair and/or the scalp composition applicator to hair and/or the scalp in effective, controlled and not mixed and disorderly mode.

In the hair dyeing processing procedure, hope can accurately be controlled flowing of hair dye fluid and can point to the zone of being dyeed by hair dye fluid accurately.Equally, also wish smear with operating period the chien shih hair be kept to minimum in a jumble, and in by the whole zone of hair dye fluid dyeing, realize even distribution of color.

Even under situation, also require to reach these above-mentioned purposes by people oneself the operation applicator that uses the hair rinse hair dyeing.

US-A-4209027 discloses a kind of hair care devices, and this device can be fixed on the squeeze bottle that hair nursing liquid is housed, described hair nursing liquid will flow through in each applicator tap and extruded by the user, and be coated with by the hair care device simultaneously.

An elongated top that has main as separator in these applicators, other applicator or brush shape or pectination, main as dispersal device, and be provided with a valve, this valve makes hair nursing liquid can be directed into separator or dispersal device, perhaps is directed into separator and dispersal device simultaneously.

The actual defects of this known hair treatment device is that it is difficult to controlled handling with unruffled mode.

Many hair treatment devices all have the applicator of elongated dispense spout form, and described spout narrows to its end gradually along its length direction, and this end is provided with discharge orifice.

As JP (UM)-A-7-22951 was disclosed, this type of hair treatment device also can have the comb shape applicator, and described comb has the inner passage, was used for the hair composition from the spout discharge orifice is directed in a plurality of apertures in the broach.

In use, comb is urged and is assemblied on the spout, and this comb extends beyond the free end of spout, and is held in place by friction along the partial-length of spout.

Similarly structure is disclosed among the JP-A-9-118375, and how the document mixes two kinds of liquid if disclosing, subsequently they are carried through comb, and this comb removably is fixed on the nozzle by any suitable device.Described two kinds of liquid can form composition for hair dying.

Hair treatment device is typically provided with dissimilar applicators to adapt to different hair treatment situations.

For example, preferably have: dispense spout, so that can be coated with a hair care composition line; Permeable distribution member (as fabric) is so that can be with the hair care composition obliterating on hair; And distribute comb or distribute brush, so that make hair care composition on the whole length of hair, play effect up hill and dale.

In fact, disclose this distribution applicator in US-A-4211247, and also disclose the sponge of non-distributivity, this sponge only is used for after applying hair care composition with the distribution applicator these compositions being spread apart.

The present invention relates to a kind of hand-held packaging compositions, but it comprises flow composition and the combination that is used for the said composition packing, but flow composition and the combination that is used for the said composition packing, described packing comprises an applicator and a container, described container has flexible and resilience wall, but and comprise the storage of a flow composition, described applicator has the lengthening separating element in a plurality of formation distributions cross section, be used for flowable composition being distributed by moving of the applicator on vertical with the cross section basically direction, described distribution cross section comprises a plurality of outlets, ordering about composition by the flexibility of container and resilience wall are pressed distributes through these outlets, wherein, when the pressure with 1.5Pa put on the flexibility of container and the resilience wall, 0.1g at least distributed on every square centimeter cross section each second, the composition of 0.5g at the most.

So-called " hand-held " should be understood to, and the user can be on the other hand or two held and pack.But it is not to be meant that necessarily packaging compositions is in use with holding.

So-called " but flow composition " should be understood to, and composition is flowable under gravity, for example liquid, paste, gel, even particulate composition.

Described container has flexible and resilience wall.Should be appreciated that this flexibility is meant with hand or with finger pressure will cause wall shift moving, and because of it has resilience, described wall will restPose after pressure is removed.

Applicator has the lengthening separating element in a plurality of formation distributions cross section, is used for by moving of the applicator on vertical with the cross section basically direction flowable composition being distributed.Should be appreciated that the distribution cross section is such surface, it is passed by a plurality of lengthening separating elements and the space between these extending parts.When applicator was mobile on the direction vertical with the cross section, described volume was corresponding to the cross section and the applicator displacement product of applicator.That is to say that if the parts of lengthening have common direction and place as being used for those forms of comb or brush with a row or multi-row arrangement, then the cross section is corresponding to the product of the length and the elongated portion length of comb or brush.Thus, can obtain evaluation to the effective useful cross section of applicator.In the example of combing hair, the volume that is obtained by the product in the cross section of applicator displacement and applicator is corresponding to the volume that carries out at pair cross-section in the given moving process by the hair in cross section.

Described distribution cross section comprises a plurality of outlets, ordering about composition by the flexibility of container and elastic wall are pressed distributes through these outlets, wherein, when the pressure with 1.5Pa puts on the flexibility of container and the elastic wall, the 0.1g that on every square centimeter cross section, distributes each second at least, the composition of 0.5g at the most.Have found that if the composition weight that distributes is few, then suitably the assign group compound just requires higher pressure under this pressure.And then when being used for hair treatment, composition can not fully approach to smear along hair equably in structure.Find that also if the composition that transmits is too many, composition can flow down along hair, for example,, therefore mean and smear confusion or can not smear effectively because it is too thin in structure.Really, when using packaged products of the present invention, then find and to smear expediently.In a preferred embodiment, when the pressure with 1.5Pa puts on the flexibility of container and the elastic wall, the 0.15g that on every square centimeter cross section, distributes each second at least, the composition of 0.45g at the most.In preferred embodiment, when the pressure with 1.5Pa puts on the flexibility of container and the elastic wall, the 0.2g that on every square centimeter cross section, distributes each second at least, the composition of 0.4g at the most.In most preferred embodiment, when the pressure with 1.5Pa puts on the flexibility of container and the elastic wall, on every square centimeter cross section, distribute at least 0.25 each second, the composition of 0.35g at the most.

In a preferred embodiment, outlet has cumulative surface, and it is at least 2%, at the most 10% of the distribution cross section.Should be pointed out that each outlet all has a surface, it is the surface of an opening, distributes by this surface composition, and cumulative surface is each this type of surperficial summation.Should be appreciated that each outlet the surface needn't with the cross section in one plane, even must be on the plane parallel with the cross section.

In a preferred embodiment, composition is a hair-treatment composition.So-called hair-treatment composition, said composition can be hair dye for instance.

In preferred embodiments, with the shear strain rate 2000S ^-1Under when measuring, the viscosity of composition is not less than 0.01Pa.S, when being 10S at shear strain rate ^-1Under when measuring, the viscosity of composition is not higher than 5Pa.S.This will further improve the distribution of composition.

In preferred embodiments, the outlet have cumulative surface and the accumulation girth, thereby make cumulative surface be the accumulation girth square value at least 0.05%, at the most 4%.According to the present invention, the accumulation girth is the summation of girth of all outlet ports of applicator.The numerical value of this accumulation girth square acquisition is had the dimension on surface, and its cumulative surface with outlet compares.Have found that the ratio that is included in the above-mentioned scope can make composition have excellent the distribution.In a more preferred embodiment, cumulative surface is at least 0.075%, at the most 0.3% of accumulation girth square value.In a more preferred embodiment, cumulative surface is at least 0.1%, at the most 0.25% of accumulation girth square value.In the most preferred embodiment, cumulative surface is at least 0.15%, at the most 0.2% of accumulation girth square value.For example, most preferred embodiment comprises 28 1mm ²Square outlet (preferred other shape, as circular or annular) and the outlet of 13 0.5mm diameters, the outlet that 13 diameters are 0.5mm is arranged on the joint of extending part and applicator, between the parts that is arranged on each lengthening, thereby provide the parts of 14 lengthenings, all on identical direction, the parts of each prolongation further comprise two 1mm in the end relative with its bottom for they ²Square outlet, this outlet faces with each other.This extending part to be set to 5cm long, 5cm be between the extending part of two ends along with the distance of the perpendicular direction of the prolonging direction of extending part, each extending part is that 1.5cm is long, thus the cross section of applicator is 1.5 * 5=7.5cm ²

In preferred embodiments, on the pressure with 1.5Pa puts on the flexibility and resilience wall of container, exert pressure at least 2 seconds the time, the 0.1g that on every square centimeter cross section, distributes each second at least, the composition of 0.5g at the most.In a more preferred embodiment, on the pressure with 1.5Pa puts on the flexibility and resilience wall of container, exert pressure at least 5 seconds the time, the 0.1g that on every square centimeter cross section, distributes each second at least, the composition of 0.5g at the most.In embodiment preferred more, on the pressure with 1.5Pa puts on the flexibility and resilience wall of container, exert pressure at least 10 seconds the time, the 0.1g that on every square centimeter cross section, distributes each second at least, the composition of 0.5g at the most.In the most preferred embodiment, on the pressure with 1.5Pa puts on the flexibility and resilience wall of container, exert pressure at least 18 seconds the time, the 0.1g that on every square centimeter cross section, distributes each second at least, the composition of 0.5g at the most.When exerting pressure continuously, for example can adopt compressed air to press.Really, when manual the use, exerting pressure is the increment of various use.

In preferred embodiments, each lengthening separating element is the tooth of rigidity basically, and described tooth is arranged to a row at least, and the free end of each tooth has an outlet at least.In another preferred embodiment, each lengthening separating element is the tooth of rigidity basically, and described tooth is arranged to a row at least, and the other end that each tooth is relative with free end has an outlet at least.In the most preferred embodiment, each tooth has two outlets at least, and one at free end, and another is at an end relative with free end.This makes the distribution on the distribution cross section of composition more even.

In preferred embodiments, described container is that a kind of bottle contains bag-type container, thereby flowable composition can be transmitted on bottle contains arbitrary orientation of bag-type container.This can use packaged products really on all orientations.

In preferred embodiments, container has vertically main, and the lengthening separating element points to the main vertically perpendicular direction with container.

Preferably, foam, flocked fabric or sponge material are at carrier one end place or near the mat at this place.Be ease of assembly, described carrier can push separably and be assembled on the spout, or more preferably is assembled on the spout by screw thread.For being easy to smear, particularly when target was special area, this mat can only partly extend around the carrier circumference.

Preferably, each lengthening separating element is the tooth of rigidity basically.For easy to manufacture, particularly carrying out with plastic material when molded, described tooth can be arranged at least one row.When at least one row's end is observed, tooth can but and nonessential triangle profile with different lateral dimensions.For ease of later distribution, flowable composition can be transmitted by tooth, and for example the free end of each tooth can have at least one outlet.

Preferably, the lengthening separating element can be removed, separate with support member from shell.This allows to provide a plurality of support members, and the user can select one from these support members, and the lengthening separating element of different support members has different types.For example, the brush and sac like support member that can be had a flexible filament of the comb shape support member with substantially rigid tooth replaces.

Preferably, lengthening separating element and support member form a cover, and it can be fixed by the fixture and the shell that comprise clamp.Flexibly deflection of described clamp, and can being meshed with the hole that extends through shell, thus make the clamp can be from released away from the position of lengthening separating element.A clamp that plays pivot action can be set in addition.Flexibly the clamp of deflection should be able to unclamp by the pressure of finger, still, but only unclamps the clamp of elastic deflection by rolling shell on crust, and it also is possible that the lengthening separating element is separated from shell with support member.

For the convenience of assembling and guarantee assembling intensity, shell can be removable screw thread assembling with container, and shell and container all are formed with projection portion, and when shell is screwed on the container fully, when being in the predetermined aligned position, these projection portions pass over each other the ground interlock.

Spout can push and be assembled on the container, perhaps more preferably is assembled on the container by screw thread.But for after the applicator of flow composition by the spout form, through shell and support member form (stretching out a plurality of lengthening separating elements) from support member but applicator be convenient to the conveying of flow composition before scattering, shell can have guiding tube, in the time of on shell is positioned at spout, described guiding tube engages the free end of spout.

Preferably, container makes that for bottle contains bag-type container flowable composition can transport out when bottle contains bag and is in arbitrary orientation.

In this container, can collapse flat layer and define storage device in inside, and outside deformable layer can be collapsed flat layer by buffering area and inside and be separated.Valve gear can be operated with to air to buffering area (bottle) but in inflow and flow composition control simultaneously from the outflow of storage device (bag).In order to simplify assembling, and for the advantage of thing followed economy, valve gear can comprise integrally-built valve member.

In fact, valve member can comprise: the ring-shaped baffle valve of unlatching that is used for being controlled at one or more air intakes of spout, the ring-shaped baffle valve collar is around central authorities' four lobe-shape valves (quardrolobe valve) of the unlatching of the single elongated channel that is used for controlling spout, and described central four lobe-shape valves are urged in the single elongated channel that is engaged in spout.

Can understand, but flow composition is hair nursing and/or skin of head care composition.

Describe in detail with reference to the accompanying drawings according to applicator system of the present invention, but these descriptions only are illustrative.In the accompanying drawing:

Fig. 1 is the decomposition diagram that lid, bottle, flexible pouch, stay pipe, intubate, valve, spout, sponge or flocking pad, comb shell and comb are shown, and these elements are members of having implemented in the hair dyeing kit utility of the present invention;

Fig. 2 is local amplification view, shows the lid that is fixed on the bottle;

Fig. 3 is the plane of intubate;

Fig. 4 is perpendicular to the schematic cutaway view of the cutaway view intercepting of Fig. 2, adds wherein dyestuff in the flexible pouch dye reservoir thereby show to dock with intubate;

Fig. 5 shows the perspective view that is fixed on the spout on the bottle;

Fig. 6 is the cutaway view of Fig. 5;

Fig. 7 is the perspective view that is similar to Fig. 5, but shows sponge or the flocking pad that is fixed on the spout;

Fig. 8 is the local amplification view of Fig. 7;

Fig. 9 illustrates the perspective view that is installed in comb shell on the bottle and that comb is housed;

Figure 10 is the cutaway view of Fig. 9;

Figure 11 and 12 is respectively the comb before being installed to together and the cutaway view of comb shell.

Accompanying drawing shows the hair dyeing kit utility; each different aspect that this device has been implemented all aspects of the invention-promptly be in the present invention and will sought to protect in the patent application of some same periods, the various applicators and the applicator system that relate to induction system and be used to carry flowable composition.

Although flowable composition is composition for hair dying preferably, but either side of the present invention all is not limited in this specific flow composition.But the example of other flow composition comprises: the medicament that for example is used for pet nursing; The food of cake mix for example; The cleaning agent that for example is used for the nursing of laundry care and carpet; The cosmetics of body lotion and NMF for example; Lubricant or bonding agent.

In the use of composition for hair dying, there are some problems.

One of them problem is: needed with two kinds or two or more composition material preparation composition for hair dying before soon using.This just means needs separate storage composition material, and the mode of its storage should allow the user when needed can the blending constituent material.General, a kind of composition material is a hydrogen peroxide, and another kind of composition material is a dyestuff.But, when adding to dyestuff in the hydrogen peroxide, should not have any danger of being polluted, perhaps risk to the user.

Another problem is: composition for hair dying need can be applied on the hair with any angle by applicator.If applicator is to supply with hair dye by simple squeeze bottle, squeeze bottle be the situation of full bottle next under any orientation applicator all be useful.But, along with squeeze bottle by crowded empty gradually, find that then applicator is not can both use immediately under any orientation, but at first need applicator is poured into to offset the back suction effect of any composition for hair dying.This has brought difficulty for using of composition for hair dying controlled (particularly using) on hair when avoiding polluting skin.

Hair dyeing kit utility of the present invention not only allows to prepare composition for hair dying before closing on use, and have by being subjected to induction system that the user controls to supply with the applicator of composition for hair dying, wherein composition for hair dying is discharged in the following manner by the pressure differential (non-aerosol) that machinery produces, this mode be induction system when being in any orientation composition for hair dying always be in the state of preparing discharge.

Preferably, for all composition for hair dying that are discharged from (can surpass the composition for hair dying be produced 90% even 95%), the conveying of all orientations all is possible.

Hair dyeing kit utility of the present invention also allows composition for hair dying can being transported on the specific zone through applicator by the amount that the user adjusts, thereby obtains more uniform distribution of color, and makes to subtract in a jumble and put minimum.

Be used for to the root of hair of hair, when sending out the tip and administered composition for hair dying, it is always suitable not having a kind of applicator, even if operation also is like this carefully.Therefore dissimilar applicators is provided is ten minutes usefulness, and these applicator types can be selected from the line applicator, surperficial applicator and brush shape/pectination applicator.The line applicator can be the spout with single outlet, and surperficial applicator can comprise the porous material with a plurality of outlets.Brush shape/pectination applicator can have a plurality of outlets that are used to distribute composition for hair dying, and these composition for hair dying are distributed by a plurality of lengthening separating elements subsequently.Can estimate that the lengthening separating element can be similar to the hair of brush or the tooth of comb.All dissimilar applicators can with the container of composition for hair dying fluid connection mutually.

The concrete advantage of hair dyeing kit utility of the present invention is:

Therefore (a) preferably, have only a selected applicator to expose in three kinds of applicators in use, in the processing procedure of hair, do not exist by in the applicator that remains in other or the caused mixed and disorderly danger of the composition for hair dying on the applicator.

(b) preferably, the surperficial applicator in three dissimilar applicators is to be made by the foam with elasticity, compressible loose structure, sponge or flocked material, thereby the better distribution of composition for hair dying can be provided.

(c) preferably, the brush shape/pectination applicator in three dissimilar applicators has two outlets at least, and these two outlets are respectively formed on its separating element that respectively extends, thereby the better dispersion of composition for hair dying can be provided.

The concrete advantage of another of hair dyeing kit utility of the present invention is: the monolithic valve has been realized dual-use function simultaneously, promptly controls entering and the discharge of composition for hair dying of air; The support member of separating element of being used to extend can be installed in shell from the clamp that unclamps away from the position of composition for hair dying by at least one; By the line applicator is installed on the container, brush shape/pectination applicator can be located on the online applicator, and can directly be installed on the container.

Before describing surperficial applicator with reference to figure 7 and 8, describing brush shape/pectination applicator, at first referring to figs. 1 through 6 induction systems of describing in conjunction with wired applicator with reference to figure 9 to 12.

Bottle 10 is formed with the bottle 12 of hollow, and bottle 12 has the cross section of substantially elliptical, in lower end closed, has the neck 14 of opening in the upper end.Neck can be formed with external screw thread 16.Neck 14 also is formed with a pair of relative projection portion 18, only shows this to one in the projection portion in Fig. 1.Each projection portion 18 preferably includes the gap 20 near inclined-plane 22, and its purpose is described hereinafter.

At least bottle 12 can be by flexible deformable plastic material manufacturing, thereby bottle 10 can be restored to the original state rapidly after being extruded and when unclamping.Plastic material can be low-density polyethylene, LLDPE (LLDPE) or polypropylene, and transparent.If not transparent, this plastic material is preferably translucent, can be colored, also can be not colored.

Flexible pouch 24 can be made by having identical shaped two overlapping lamellas 26, and these two lamellas are closed round their most common peripheries, thereby forms the pouch of side seal, and pouch has the opening 28 on top and the V-arrangement edge 30 of bottom.Bag 24 defines the storage device that is used to deposit first material (as hydrogen peroxide), therefore should provide moist preferably barriers.Can comprise metallized laminated material in each lamella 26, and preferably include following three layers: LLDPE sealant/bonding agent/metallized PET (PETG).

Bag 24 can be inserted in the bottle 10 by neck 14, form the container that have outside deformable layer (bottle 12) and inside can shrivel layer (lamella 26) with this, above-mentioned outside deformable layer and inside can shrivel floor and be cushioned the district and 32 be separated from each other, as shown in Figure 4.

As shown in Figure 4, stay pipe 34 can be inserted in the bag 24 by opening 28.Stay pipe 34 can have a plurality of holes 36 along its length, and to form be the passage of local stiffness at least, and this passage is opening in the cross section.Pipe 34 lower end 38 can be opening or sealing.Pipe 34 lower end 38 can contact with bag 24, and perhaps managing 34 lower end 38 can be approaching with the V-arrangement edge 30 of bag 24, but does not contact.The upper end of pipe 34 can be fixed on the intubate 40 by any suitable manner or device, perhaps can be press fit into simply in the intubate 40.

Intubate 40 partly is inserted in the bag 24 through opening 28, and can partly be inserted in the bottle 10 through neck 14.Preferably, intubate for good and all is fixed on the lamella 26 around opening 28 in the close mode of liquid, for example by hot joining or ultrasonic bonding.Perhaps, intubate 40 and bag 24 can be whole structures.Intubate 40 is preferably by simply press-fiting or being fixed on the neck 14 in the mode that can't remove by other suitable method or device, perhaps, can be removed system to obtain to fill again by the user.

Shown in Fig. 2,4 and 6, intubate 40 can be the plastic mould of single-piece, has tubular piece 42, and this tubular piece 42 defines a perforate, and extend at the center of passing sidewall 44, transverse wall 46 and a pair of relative bottom 48.

The sidewall 44 that illustrates has the flange 50 of the outward extending insert action that is used to limit 40 pairs of bottles 10 of intubate in the top and is in flange 50 and rib 52 that the direction in the roughly centre position of transverse wall 46 is inside.As shown in the figure, transverse wall 46 has a plurality of holes 54 of passing itself, be used for buffering area 32 with between tubular piece 42 and sidewall 44, limit and be connected around the annular channel 56 of tubular piece 42 thus.Illustrated relative lower end 48 is a hollow, to prevent occurring depression in molded, helps thus intubate 40 liquid thickly are inserted on the bag 24.

The lower end of tubular piece 42 can be inwardly recessed, so that the upper end of receiving tube 34, and inwardly cut sth. askew in the upper end of tubular piece 42.

General, when bag 24 was fed in user's hand, this bag partly had been filled with first material (as hydrogen peroxide).Therefore need avoid first material from manage 34 and tubular piece 42 overflow.Removable pushing (flip) top cover can be set seal the upper end of tubular piece 42.Perhaps, the upper end of tubular piece 42 can be by rupturable diaphragm seal sealing.But preferably, the lid 58 that can remove is set, as shown in Figure 2.

Lid 58 also can be the plastic mould of single-piece, and it can have the plug sealing 60 of hermetically enclosed tubular piece 42 upper ends.The standing part 62 of lid 58 can cooperate airtightly with the neck 14 of bottle 10.But, the standing part 62 that covers 58 is made into non-airtight cooperation also has some advantages.For example, can form with bottle 10 neck 14 on external screw thread 16 internal thread 64 of breathable threaded engagement is arranged, so that the air flue that leads to atmosphere from annular channel 56 to be provided.

An advantage is, if the hydrogen peroxide in bag 24 becomes unstable and produces oxygen, then bag 24 can expand, and the air in buffering area 32 will be overflowed by the hole in the intubate 40 54, enters into subsequently between screw thread 16 and 64.

Another advantage is, if to be subjected to not be to be that the pressure of wishing changes to buffering area, for example is the mobile result who causes by air, and then air can be overflowed through the above-mentioned path that indicates or from buffering area 32 again, perhaps flow into buffering area 32.

Aforesaid hair dyeing kit utility allows user preparation hair coloring preparation composition or other flowable composition before contiguous the use.

In practice, be that second material is added in first material in the storage device at least.If storage device is to supply with at the state of sky, or emptied in preceding once use, then at first need certainly some first materials are added in the storage device.In either case, all need to make the material of these initial separation to mix mutually.

As schematically illustrating in Fig. 4, second material can be stored in fully independently in the container 66.If first material is a hydrogen peroxide, then second material may be a dyestuff.Because dyestuff may be oxysensible, so container 66 may need to provide the oxygen barrier performance of excellence.And if dyestuff is for example gel, emulsion form or pasty state, then needing container 66 is shaping distortion, with allow the user with dyestuff from wherein extruding.On the other hand, if dyestuff is a liquid form, then dyestuff can be under the influence of gravity flow container 66.

If container 66 can strain,, then bags 24 preferably discharge gas and be retracted if then bag 24 is not an elastically deformable by the charge of air expansions-container 66 of first material top preferably.

The user has a plurality of containers 66, and each container 66 can accommodate the different materials such as the hair dye of different tones, purpose is but that the material in one or more container 66 is emptied in the storage device to form specific flow composition, such as the composition for hair dying with concrete tone of selecting.

Comparatively ideally be, container 66 or each container 66 comprise long nozzle 68, and this nozzle 68 can extend fully through tubular piece 42 and enter pipe 34.Can provide good butt joint like this, thereby when even the user with the hands removes squeeze receptacle 66, container 66 can not separate yet with bottle 10.But also can promote better mixing, because the material in the container 66 is directly to advance to inject in the material of bag 24 from close scope.Obviously, before will long nozzle 68 being inserted in the tubular piece 42, container 66 need be opened, can realize that this opens by fractureing, cut off or twist into two parts nozzle top 70 (shown in broken lines in Fig. 4).

Can understand that in the time of in second material is emptied to bag 24 from container 66, the volume of air that is positioned at above first material is dwindled gradually in bag 24, and should promote these compressed air to overflow, expand to prevent bag 24.

If nozzle 68 is loose fit in tubular piece 42, then compressed air will be overflowed from this loose fit.Perhaps, can form one or more keyway, and/or on the position of the substrate of dye reservoir adjacent nozzles 68, be formed with one or more air effusion notch (castellations) along the length of nozzle 68.According to second properties of materials in the container 66 and relevant size, compressed air may pass second material and upwards spray, thereby forms air bag in container 66, and along with the air bag in the bag 24 shrinks, the air bag in this container rises greatly.

Even bag 24 does not expand, overflow in the hole from the transverse wall 46 of intubate 40 like that 54 that the air in buffering area 32 also can be as indicated above.

After adding to the second enough material in first material, container 66 is shifted out from bottle 10, this container or be dropped perhaps is sealed again in order to use next time.

As adding second material in first material alternative by decant(-ation), second material can be contained in the container that forms with bag 24, perhaps be contained in the container that is arranged in bag 24, this container can break by the bottle 12 of for example squeeze bottle 10, perhaps this container has other feature, allows second material to be added in first material.

After second material has been added in first material, then preferably by rocking bottle 10 thirty years of age these materials mixing soon.The user can prevent that the material in the bag 24 from overflowing by the upper end that gloved hands is referred to be placed on tubular piece 42 when rocking.But, be that the user can cover lid 58 again, so that plug envelope 60 closes the upper end of tubular piece 42 more easily.In either case, when rocking and/or overturning bottle 10, pipe 34 plays the effect of restriction bag 24, mixes than more free help of motion of bag 24 by allowing the material in the bag 24.It is believed that if 10% volume of bag 24 reserved as head space and will occur mixing by rocking the optimum of realizing.If the bottle 12 of bag 24 and bottle 10 all is translucent, then can mix whether fully by visual inspection.

But in order to prepare to discharge the flow composition that forms by first material and second material, the perhaps composition for hair dying that forms by hydrogen peroxide and dyestuff specifically, then intubate 40 is come out again, be fixed on the intubate 40, just as illustrated in Figures 5 and 6 to allow spout 72.

Spout 72 also can be the plastic mould of single-piece, comprises cylindrical part 74 here, and this part extends to dome shape part 76, and this dome part 76 extends to tapering part 78.Be formed with rib 80 toward the outer side in the bottom of cylindrical part 74.The top of cylindrical part 74 forms near the shoulder 82 that dome shape part 76 produces.One or more (for example three) air intake 84 extends through dome shape part 76, and these inlets are circumferentially evenly spaced apart around dome shape part 76.Tapering part 78 is formed with elongated path 86, and this path 86 narrows down along its length towards being in less high-end single outlet 88 gradually from its bigger low side.Annular groove 90 forms on the inner surface of the big low side of the close path 86 of tapering part 78.Circumferential rib 92 forms on the less high-end outer surface of the close path 86 of tapering part 78,

Valve member 94 can be affixed on the spout 72, and this valve member can be made by silicone polymer, and can have overall structure.

Preferably, valve member 94 is included as the intake section of ring-shaped baffle valve 96 forms, and this part is passed the one way stop peturn valve of the air inflow of air intake 84 as control.

Preferably, valve member 94 also is included as the exit portion of central four lobe-shape valves, 98 forms, and this part is controlled the outflow of the composition for hair dying that passes passage 86 as one way stop peturn valve.Four lobe-shape valves 98 are preferred, because it opens from central authorities, rather than open from side, make the composition for hair dying that passes this valve produce level and smooth flowing thus.But as the alternative of four lobe-shape valves 98, the exit portion of valve member 94 also can be flapper valve, umbrella valve or duckbill valve.

Flapper valve 96 can be by comprising that the intermediate member of transverse sealing wall 100 with truncated cone-shaped location wall 102 is connected with four lobe-shape valves 98, and the outer surface of described truncated cone-shaped location wall 102 has circumferential rib 104.

Can engage and at an easy rate valve member 94 is affixed in the path 86 with annular groove 90 in the spout 72 by four lobe-shape valves 98 being inserted the circumferential rib 104 on valve member 94 in the passages 86.

Subsequently, by following manner spout 72 is fixed on the intubate 40 at an easy rate, the cylindrical part 74 that is about to spout 72 pushes in the circular passage 56 of intubate 40, rib 80 on cylindrical part 74 with can hear or be at least certain click cross intubate 40 rib 52 and with it the engaging, the shoulder 82 of spout 72 leans with the flange 50 of intubate 40 this moment, and sealed engagement takes place in the upper end of the tubular piece 42 of the sealed wall 100 of valve member 94 and intubate 40.

In an alternate configurations, spout 72 can be secured on the intubate 40 by screw assembling rather than above-mentioned pushing assembling.

After being fixed to spout 72 on the intubate 40, can rock bottle 10 so that mix or mixed flow composition again.

For composition for hair dying is transported to outlet 88 in the spout 72 (from composition for hair dying here with the linear for example root of hair of hair that is discharged to) from bag 24, need the bottle 12 of user's squeeze bottle 10.This action compresses be in air in the buffering area 32, but because flapper valve 96 has played the effect of sealing inlet 84, compressed air can't be overflowed by the fluid passage that comprises hole 54, circular passage 56 and air intake 84.On the contrary, compressed air partly plays the effect that bag 24 is shriveled, thus make some composition for hair dying pass to comprise pipe 34, tubular piece 42, truncated cone-shaped location wall 102 and four lobe-shape valves 98 (described four lobe-shape valves 98 are opened so that composition for hair dying passes this valve) fluid passage and be extruded.When the user stopped the bottle 12 of squeeze bottle 10, bottle 10 recovered its shape rapidly, thereby buffering area 32 is expanded.Four lobe-shape valves 98 cut out, and avoiding the composition for hair dying back suction and to cross four lobe-shape valves 98, and make bag 24 remain on the state that it is shriveled by the part.Air passes flapper valve 96 and is inhaled in the buffering area 32, thereby described flapper valve 96 is opened air is introduced through air intake 84.

Any pressure that the user thinks with it and situation at that time adapts and frequency repeat the extruding to the bottle 12 of bottle 10.

Can understand, can avoid, and the contacting with each other of lamella 26 of the bag 24 and composition for hair dying that cause be absorbed in the situation at dead angle flat along with collapsing gradually of bag 24 in the hole 36 of pipe in 34, and manage 34 itself can collapse flat, but be discharged from the flow composition that allows to be in the pipe 34.

Along with composition for hair dying is scattered gradually, it is that translucent bottle 12 sees that bag 24 is flattened at least that the user can see through.This can give up about the composition for hair dying worry that quilt is used up under the situation that does not have caution for the user.

Although the storage device that is used for first material can be the pouch of side seal (as mentioned above), storage device can also adopt other form, for example, can be by half bag of bottle of upset, or layering bottle (preferably from it neck is peeled off gradually), perhaps provide the inside of clearly separating can shrivel layer with outside deformable layer by blowing bag with the Unitarily molded pressure of intubate.

And, although can be as indicated above make valve member have whole structure like that but realize dual-use function, but valve member also can adopt other form, for example, can provide the valve of separation to control the outflow of composition for hair dying and the inflow of air, and can realize with the airport of finger sealing by on bottle, leaving the user for the latter's control.

Referring now to Fig. 7 and 8, wherein show the surperficial applicator 106 in the outlet 88 that removably is fixed on spout 72.Say that more specifically surperficial applicator can comprise: by pad 108 foam with elasticity, compressible loose structure, that sponge or flocked material are made.This structure not only has a plurality of outlets, and allows to pass pad 108 from exporting 88 composition for hair dying of extruding, and by careful operation it is coated with equably along hair.Pad 108 can be positioned at or near the upper end of support 110, and the Lower Half of support 110 is truncated cone-shaped, and its direction is to extend to bigger lower end from less upper end.The inner surface of the Lower Half of support 110 is formed with annular groove 112, and when being pushed to support 110 on the spout 72, this annular groove is used for engaging with circumferential rib 92 removable turning up the soil on the spout 72.Support 110 and spout 72 can be interworkings each other, relatively rotate avoiding.Pad 108 can have the surface of curve, so that accurately use, and curvilinear surface only centers on the periphery extension of the first half of support 110 partly.Make by plastic material if fill up 108, and support 110 also is to be made by plastic material that then filling up 108 can be by using adhesive securement to support 110.Obviously, if initial surperficial applicator will no longer be cleaned and reuse, then can provide a series of surperficial applicator 106, these surperficial applicators or similar (is disposable if wish), or different (is interchangeable if wish).

As shown in Fig. 9 to 12, brush shape/pectination applicator 114 can replace surperficial applicator 106 and can be fixed in the outlet 88 of spout 72 with pulling down, and brush shape/pectination applicator 114 comprises shell 116 and can unclamp assembly 118.

Brush shape/pectination applicator 114 can spiral cooperates or the bullet card is coupled on the neck 14.

Shell 116 is plastic moulds of another part single-piece, it defines perforate 120, cone-shaped open chamber 122 (it has a series of fluting web 124 on the opposite major sides wall) from top to bottom, guarantee from chamber 128 to chamber the internal thread 132 of the lower end of the guiding tube 126 of 122 open communication, the groove 130 that is positioned at chamber 128 upper ends, adjacent cavity 128, and a pair of relative projection portion 134 that is positioned at chamber 128 lower ends.

Internal thread 132 is preferably molded from mould, and is not to be tapping thread.

By the effect that the internal thread in chamber 128 132 is meshed with external screw thread 16 on the neck 14, shell 116 and bottle 10 have realized that removable screw thread installs.Along with shell 116 is screwed gradually, the outlet 88 of spout 72 progresses in the guiding tube 126.At last, projection portion 134 is similar to along the inclined-plane 22 of projection portion 18 by the moving of cam jack-up, and is engaged to subsequently in the gap 20 of projection portion 18.This engaging preferably has the sound that can hear, perhaps is definite click at least, has been screwed to fully on the bottle 10 with indication shell 116.On this last position, projection portion 18 and projection portion 134 are meshing with each other, and this moment, chamber 122 was open on the direction of the main shaft of bottle 12 (this bottle is roughly elliptic cross-section).

Releasable assembly 118 also can be made into the molded of plastic material part of single-piece, this element is have hair dyed last assembly of kit utility of the present invention, described plastic material can be as having the polypropylene of silicone additive, and the effect of silicone additive is to produce lower coefficient of friction.

Can unclamp assembly 118 is translucent in the part at least, thinks that the user makes the indication that flowable composition is about to be output.

Assembly 118 comprises support member 136, and this support member is roughly smooth, and the lower end to broad enlarges tapered gradually from narrower upper end.Narrower upper end has the deflectable clamp 138 of elasticity, and this clamp begins to extend and have hook-shaped leading end 138a from here.The lower end of broad has the clamp 140 of rigidity, and this clamp begins to extend and have hook-shaped leading end 140a from here.Periphery at support member 136 has shirt rim 142, and this shirt rim has the profile with the opening complementation of chamber 122.A plurality of lengthening separating elements for example are roughly the tooth 144 of rigidity, and are outstanding in the direction opposite with the detachable clamp 138 of elasticity, rigidity clamp 140 and shirt rim 142 from support member 136.But a plurality of outlets that are used for flow composition extend through support member 136.

Know as Fig. 9 to illustrate that tooth 144 can be arranged in two row.When from the ends of two row when looking, tooth 144 can but be not the triangular-shaped profile roughly that must have the varying cross-section size.The lower end of the cross sectional dimensions of tooth 144 from the narrower upper end of support member 136 to the broad of support member 136 increases gradually.And the tooth 144 in the different rows can relative to each other be staggered, and can have triangular-shaped profile, when still when looking from the sides of two row being (as figure), then has roughly the same thickness.

As shown in Figure 11, at least two but can be that all outlets 146 further extend through each tooth in the tooth 144.But, wish to have one or more outlet 146 not extend through tooth 144.For example, have at least the outlet 146 can be on the position between the adjacent teeth on the support member 136 144.Extend through at least two of tooth 144 but can be that all outlet 146 can be at each free end of tooth 144 through the hole 148 and reveal.

In fact, although hole 148 is very easily when being positioned at the free end of tooth 144, but the rear can also be partial to a little from the free end of tooth 144 in hole 148, be for fear of being applied directly on the skin of head on the one hand, be that preferred molding technique by so-called " through face cut-out technology (passing face shut off technique) " causes on the other hand, this technology can need not to use lateral pin can form hole 148 by simple dissection type mould.

For assembly 118 is assembled into shell 116, only the hook-shaped leading end 140a of rigidity clamp 140 need be navigated in the groove 130, subsequently with its pivot.This action makes the free end of shirt rim 142 engage with fluting web 124, and makes the hook-shaped leading end 138a deflection of clamp 138, so that clamp 138 enters perforate 120.When the hook-shaped leading end 138a of clamp 138 stretches out from perforate 120 when finishing with the engaging of the material of shell 116 around perforate 120, assembly 118 promptly is completely fixed on the shell 116.

For assembly 118 is taken off from shell 116, then need carry out opposite step.The pressure of clamp 138 by finger is unclamped.Perhaps, make rigid surface that the hook-type leading end 138a of clamp 138 is struck back perforate 120 by the mode that shell 116 is rolled across rigid surface and roll.More preferably, the action of unclamping of clamp 138 takes place away from hole 148.

The reason that assembly 118 is pulled down from shell 116 is that this will help to remove any residual composition for hair dying.

The Another reason that assembly 118 is pulled down from shell 116 is to allow that former assembly 118 is replaced with another and have dissimilar assembly 118.For example, may wish that the roughly rigid teeth 144 that will present pectinate texture with another brush shape structure replaces, described another structure or comprise the brush shape structure of a plurality of elasticity, flexible mane, or spongelike structure, perhaps or even another pectinate texture, tooth in this structure and/or hole are of different sizes and/or configuration.This distribution that will impel (such as different hair lengths or different hair types) composition for hair dying under different situations more completely.

In different assemblies 118, can size, position and the shape in hole 148 be changed, this depends on the rheological behavior of composition for hair dying, perhaps depends on the needs of different hair dyeing effects, for example root covers, requirement streak or highlight.Can add or be mixed into different compositions individually with the rheological behavior of improving hair dye or in order more easily to allow hair not tangle.Composition like this comprises following ingredients, and following table has been listed the maximum weight ratio of the best of each composition in mixture:

Material name	Best maximum weight ratio
			％w/w
The rheology modifier title	7.0
		Hydroxyethylcellulose	7.0
The cetyl hydroxyethylcellulose	7.0
		Silica (7631-86-9)	7.0
Sclerotium natural gum (Sclerotium Gum)	7.0
		The hydroxypropul starch phosphate	10.0
Carbomer	10.0
		Acrylate/C10-30 alkyl acrylate cross-linked copolymer	10.0
HPG	5.0
		The guar gum hydroxypropyl-trimethyl ammonium chloride	5.0
The hydroxypropyl guar hydroxypropyl-trimethyl ammonium chloride	5.0
		Peg-150/ stearyl alcohol/SMDI copolymer	10.0
Acrylate copolymer	10.0
		Acrylate/octadecyl APEO-20 methacrylate copolymer	10.0
Acrylate/ceteth-20 copolymer	10.0
		Hydroxypropyl cellulose	7.0
PVM/MA decadinene cross-linked copolymer	10.0
		Polyquaternium 32+ mineral oil+PPG-1 Tridecem 6	7.0
Polyquaternium 37+ mineral oil+PPG-1 Trideceth 6	7.0
		Polyquaternium 32+ propane diols dicaprylate mineral PPG-1 Trideceth 6	7.0
Dextrin	7.0
		Hydroxy butyl methyl cellulose	7.0
Guar gum	7.0
		PEG-2M to PEG-160M	7.0
Carbomer sodium	7.0
		Tapioca	10.0
Xanthans	7.0
		Zymosan	10.0
The trihydroxy tristerin	5.0
		Polyacrylamide/C13-14 isoparaffin/laureth-7	7.0
Acrylamide copolymer/paraffin oil/isoparaffin/polysorbate 85	7.0
		The succinyl group glycan	5.0

		Conditioner/the go auxiliary agent that tangles
The Peg-150 distearate	5.0
		Peg 60 rilanit specials	5.0
Quaternium-22	0.0
		Quaternium?80	5.0
Poly decene	3.0
		PEG (generally comprising PEG4 to PEG115M)	5.0
General thiazolinyl hydroxypropyl stearyl alkyl dimethyl ammonium chloride	5.0
		Dimethicone?copolyol?meadowfoamate	4.0
Polyquaternium?6	5.0
		Polyquaternium?7	7.0
Acrylamido oxypropyl trimethyl ammonium chloride/acrylamide copolymer	7.0
		PEG-2 two Dow formamido ethyl methane sulfonate ammoniums	5.0
Octyldodecyl?meadowformate	5.0
		Octyldodecyl?meadowfoamate	5.0
The cocounut oil amido betaines	5.0
		The alkoxylate dimethyl silicone polymer	5.0
Alkoxylate dimethyl silicone polymer acetic acid esters	5.0
		Glycine	5.0
The soybean protein of Hydroxyproyl Trimethyl ammonium hydrolysis	5.0
		The wheat gluten of Hydroxyproyl Trimethyl ammonium hydrolysis	5.0
The honey albumen of Hydroxyproyl Trimethyl ammonium hydrolysis	5.0
		Oil-based betaine	5.0
Oleyl alcohol	5.0
		Polysilicone-1 to Polysilicone-10	5.0
Silicone Quatemiurm-1 to Silicone Quatemium-13	5.0
		Quaternium- 8，14，16，22，26，27，33，52，53，56，60，61，63，70，72，75，77，78，80，81，82，83， 85，86	5.0
Cetanol	5.0
		16/octadecyl APEO-25 (Ceteareth-25)	7.0
Stearyl alcohol	5.0
		Polyquaternium-10	5.0
Polyquaternium?4	5.0

In another embodiment, the applicator of the packaging compositions that is useful on all can be screwed on the container, thereby, it is sealed better.And then, under the situation that may use comb or nozzle, preferably comb is screwed on the nozzle so that it is fixed better and reducing Operating Complexity when a kind of applicator is changed to another kind of applicator.In addition, can make comb shorter like this.For comb further is fixed on the nozzle, also can designs and make propeller and nozzle integrated, thereby prevent that comb rotates with nozzle in use.Other improvement comprises break connector to nozzle, retention valve and nozzle self.

Should be noted that comb can have shape-designing, thereby it reduces to reduce the waste liquid that uses in the comb of back on its end direction, avoid the pressure loss towards comb end.

The filling mouth of container is preferably eyes shape, thereby ventilates easily when filling.Other improvement comprises having the pipe that replaces " O " section of sealing to make with two " C " section, and product is easier to be entered in the pipe thereby make, and thisly advantageously combines with box bag Container Type.

In general, relevant with existing all open source literatures is, first container that is used for taking in first kind of material can be thought and comprises bottle, is assemblied on one or more different applicators.

Perhaps, in general, relevant with existing all open source literatures is, flowable composition can demonstrate the pseudoplastic fluid dynamic characteristic, this be meant flowable composition work as its when being sheared viscosity reduce, and in case shear stop after, but the internal structure of flow composition (producing the reason of initial viscosity) is rebuild very fast, make viscosity increase, near its material viscosity value.

Flowable composition should be able to have above-mentioned pseudoplastic fluid dynamic characteristic, and shear strain rate is 0.01s ^-1To 10,000s ^-1, this is when flowable composition is composition for hair dying, the most probable shear strain rate scope that can run into.

But an example of suitable flow composition is 2000s at shear strain rate ^-1Viscosity should be not less than 0.01Pa.s (preferably being not less than 0.15Pa.s) when Shi Jinhang measured, and was 10s at shear strain rate ^-1When Shi Jinhang measured, viscosity was no more than 5Pa.s (preferably being no more than 1.4Pa.s).

Of the present inventionly preferably comprise hair-treatment composition, more preferably comprise composition for hair dying through packaged composition.Herein, term " composition for hair dying " broadly is meant following composition, and it comprises the mixture of the low pH value (about 1 to about 4.5) of inorganic peroxy radical dye oxidant and oxidative staining agent.And then it can also comprise compound composition, wherein comprises the component that other can be active component or non-active ingredient.Therefore, term " composition for hair dying " is meant described composition except that the mixture that comprises active oxidizer and oxide hair dye, also comprise other reagent, for example oxidation promoter, chelating agent, stabilizing agent, thickener, buffer, carrier, surfactant, solvent, antioxidant, polymer, non-oxidizable dyestuff and conditioner.

Preferred composition for hair dying comprises a kind of inorganic peroxy base oxidant (a) and a kind of oxide hair dye (b), wherein, is about 1 to about 4.5 with (b) separately pH value (a), and the pH value of (a) after the merging and mixture (b) also is about 1 to about 4.5.(a) and/or pH value (b) be preferably about 1.5 to about 4.5, more preferably from about 2 to about 4.4, most preferably from about 3.6 to about 4.3, particularly about 3.8 to about 4.2, and, wherein (a) with (b) merge after the pH value of mixture be preferably about 1.5 to about 4.5, more preferably from about 2 to about 4.4, most preferably from about 3.6 to about 4.3, particularly about 3.8 to about 4.2.Except the inorganic peroxy oxidant, composition of the present invention optionally comprises (in other composition) a kind of preformed organic peroxy acid oxidant.Be used for herein organic peroxide acid and comprise that any can work separately or with crossing the organic peroxide acid that peroxygen oxidising agent works oxidation dye precursors.

Dyestuff oxidation and hair colouring methods

Those of ordinary skills know, in order successfully to dye with the hair of oxidative dyestuff to the human or animal, need the mixture process hair with oxidant and oxide hair dye usually.As previously mentioned, the most frequently used oxidant is a hydrogen peroxide.

The pKa value of hydrogen peroxide is about 11.2 to about 11.6, thus usually in about 9 to about 12 pH value scope as the dyestuff oxidant.To about pH4.5, preferably about pH3.8 is to about pH4.3 at about pH1, and more preferably from about pH3.8 can be observed the colour rendering of improvement and the color washability of improvement to the pH scope of about pH4.2.

Inorganic oxidizer

Composition preferably comprises at least a inorganic oxidizer (hereinafter being referred to as " inorganic peroxy oxidant ").The inorganic peroxy oxidant should be used for composition of the present invention safely and effectively.Be applicable to that preferably inorganic peroxy oxidant of the present invention should be dissolved in the composition of the present invention of liquid form and/or final type of service.Be applicable to that preferably inorganic peroxy oxidant of the present invention is a water-soluble oxidizers.Water-soluble oxidizers as herein described is meant that in the time of 25 ℃ solubility is the oxidant (" Chemistry ", C.E.Mortimer, the 5th edition, 277 pages) of about 10g in the 1000ml deionized water.

Be used for inorganic peroxy oxidant of the present invention and be generally the inorganic peroxy material that can produce peroxide at the aqueous solution.The inorganic peroxy oxidant is known in the art, comprise hydrogen peroxide, inorganic base metal peroxide and inorganic perhydrate salt oxide, wherein inorganic base metal peroxide such as sodium periodate, perbromic acid sodium and sodium peroxide, are crossed the alkali metal salt of silicic acid, persulfuric acid etc. at inorganic perhydrate salt oxide such as perboric acid, percarbonic acid, peroxophosphoric acid.These inorganic perhydrate salt can monohydrate, the form of tetrahydrate etc. is mixed.As required, can use the mixture of two or more this inorganic peroxy oxidants.When alkali metal bromate and iodate all are applicable to when of the present invention preferred bromate.What be particularly preferred for the present composition is hydrogen peroxide.

Have found that, compare, under the low ph condition, can provide initial colour rendering, colour consistency, washability and the color intensity of improvement with the high pH value of routine system (adopting the peroxide and dyestuff of equivalent); And, compare with the high pH value of routine system, though adopt still less inorganic peroxy oxidant (at the most 75% or lower), but can provide identical colour rendering, in addition, compare with the high pH value of routine system,, can provide identical colour rendering though adopt still less oxide hair dye (at the most 50%).Therefore, the composition for hair dying of low pH value be can prepare, thereby the extent of damage and the stimulation and the pollution level that reduce skin reduced hair.And then, owing to can prepare low pH value composition for hair dying of the present invention without ammonia, thereby these compositions just do not have peculiar smell relevant with ammonia or skin irritatin defective yet.

The preferred molar content of inorganic peroxy oxidant in composition is that about 0.0003 mole (composition of every 100g) is extremely less than about 0.09 mole (composition of every 100g), the molar content of preferred inorganic peroxy oxidant is about 0.0003 mole to about 0.08 mole, more preferably from about 0.0003 mole to about 0.06 mole, also preferred about 0.0003 mole to about 0.04 mole, most preferably from about 0.0003 mole to about 0.03 mole, especially about 0.0003 mole to about 0.02 mole, most particularly about 0.0003 mole to about 0.015 mole (composition of every 100g).

In preferred compositions, the content of inorganic peroxy oxidant is about 0.01% to being lower than about 3%, preferred about 0.01% to about 2.5%, more preferably from about 0.01% to about 2%, also preferred about 0.01% to about 1%, and most preferably from about 0.01% to about 0.8%, especially about 0.01% to about 0.55%, most particularly about 0.01% to about 0.5%, in the weight of composition.

Preformed organic peroxide acid

Except that the inorganic peroxy oxidant, the composition alternative comprises one or more preformed organic peroxy acid oxidants.

Suitable other that is applicable to composition for hair dying optionally organic peroxy acid oxidant has following general formula:

R-C(O)OOH

Wherein, R be selected from have 1-14 carbon atom saturated or unsaturated, replace or do not replace, alkyl, aryl or the alkaryl of straight or branched.

Be applicable to that a class organic peroxy acid compound of the present invention is the compound with acid amides replacement of following general formula:

Wherein, R ¹For having saturated or undersaturated alkyl or the alkaryl or the aryl of 1-14 carbon atom, R ²For having saturated or undersaturated alkyl or the alkaryl or the aryl of 1-14 carbon atom, R ⁵For H or have saturated or undersaturated alkyl or the alkaryl or the aryl of 1-10 carbon atom.The organic peroxy acid compound that such acid amides replaces is at EP-A-0, states in 170,386.

Other suitable organic peroxide acid oxidant comprises peracetic acid; cross n-nonanoic acid; nonyl-amido is crossed oxy hexanoic acid (PAPCA); benzylhydroperoxide; metachloroperbenzoic acid; the diperoxy M-phthalic acid; monoperphthalic acid; the peroxide laurate; hexane sulfonyl Perpropionic Acid; N; N-O-phthalic acylamino-peroxide caproic acid; single oxydisuccinic acid of crossing; the nonanoyl p-methoxybenzoic acid; dodecyl diacyl list benzoyl hydroperoxide; the nonyl acid amides of peroxide adipic acid; diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid; diperoxy tetracosandioic acid and diperoxy hexadecandioic acid (hexadecane diacid) and its derivative.Single and two cross that azelaic acid and two is crossed tridecandioic acids and N-O-phthalic acylamino-peroxide caproic acid also can be used among the present invention with its derivative.

Preformed organic peroxy acid oxidant should be used for composition of the present invention safely and effectively.Be applicable to that preferably preformed organic peroxy acid oxidant of the present invention dissolves in the composition of the present invention of liquid form and/or final type of service.Be applicable to that preferably preformed organic peroxy acid oxidant of the present invention is a water-soluble oxidizers.Water miscible preformed organic peroxy acid oxidant as herein described is meant that in the time of 25 ℃ solubility is the oxidant (" Chemistry ", C.E.Mortimer, the 5th edition, 277 pages) of about 10g in the 1000ml deionized water.

Be applicable to that preferred peroxy acid material of the present invention is selected from peracetic acid and crosses n-nonanoic acid and composition thereof.

When adopting preformed organic peroxy acid oxidant, its molar content is about 0.0001 mole to about 0.1 mole (composition of every 100g), be preferably about 0.001 mole to about 0.05 mole, more preferably from about 0.003 mole to about 0.04 mole, first-selected about 0.004 mole to about 0.03 mole, the composition for hair dying of every 100g.

When adopting preformed organic peroxy acid oxidant, its preferred content in the present invention is about 0.01% to about 8%, and more preferably from about 0.1% to about 6%, also more preferably from about 0.2% to about 4%, most preferably from about 0.3% to about 3%, based on the weight of composition for hair dying.The weight ratio of inorganic peroxy oxidant and preformed organic peroxide acid is preferably about 0.0125: 1 to about 500: 1, more preferably from about 0.0125: 1 to about 50: 1.

Except the optionally preformed organic peroxy acid oxidant that is applicable to inorganic peroxy oxidant of the present invention and adds, composition also optionally comprises other organic peroxide, as urea peroxide, melamine peroxide and its mixture.When adopting organic peroxide, with composition weight meter, its content is about 0.01% to about 3%, preferred about 0.01% to about 2%, and more preferably from about 0.1% to about 1.5%, most preferably from about 0.2% to about 1%.

Hair dye

Low pH value composition for hair dying can comprise oxide hair dye.This oxide hair dye preferably is used in combination with peroxide-based oxidation system, to be mixed with permanent, inferior forever (demi-permanent), semipermanent (semi-permanent) or the temporary transient composition for hair dying under low pH value.

In this article, described permanent composition for hair dying is meant the washable basically composition that removes after being coated on the hair; Inferior permanent composition for hair dying is meant after reaching 24 washings, can be substantially the composition of eccysis from the hair; Semipermanent composition for hair dying is meant after reaching 10 washings, can be substantially the composition of eccysis from the hair; Temporary transient composition for hair dying is meant after proceeding to many 2 washings, can be substantially the composition of eccysis from the hair.These dissimilar composition for hair dying can be formulated by the particular combinations of the oxidant of different content and ratio and/or dyestuff.Described herein eccysis is meant a kind of process, by this process under common hair washing condition through removing hair color from hair after a while.Washability is meant the hair that the dyed tolerance degree to the eccysis process herein.Herein, washability can be measured with the relative change color of washing times according to the hair that dyed.

The concentration of each oxide hair dye in low pH value composition for hair dying is about 0.001% to about 3% weight, and preferably about 0.01% to about 2% weight.

Total content in the composition after the oxide hair dye combination is about 0.001% to about 5%, preferred about 0.01% to about 4%, and more preferably from about 0.1% to about 3%, and most preferably from about 0.1% to about 1% weight.

Usually, in conventional composition for hair dying, the total content of oxide hair dye in composition is about 0.2% to about 3.5% weight.Thereby the system that has the high pH value of similar dyestuff content with routine is compared, and low pH composition can demonstrate the hair dyeing performance of improvement, as the long-time washability of initial colour rendering and priming color uniformity and improvement.Herein, colour consistency is meant different hair types, the relative predictability of initial colour rendering and the long-time color retention of improvement.Should be noted in the discussion above that packaging compositions of the present invention can relate to high pH value composition or low pH value composition, but preferred low pH value composition.

The usefulness of oxidation dye improves when low pH value, thereby composition of the present invention only adopts a spot of dyestuff that excellent high strength color (furvous) can be provided.Particularly, with respect to the composition for hair dying of the high pH value of routine, adopt inorganic peroxy oxidant of the present invention can obtain excellent hair dyeing effect and identical colour rendering (comparing) with high pH value system with the dyestuff that significantly reduces consumption.

Therefore, the present invention preferably provides a kind of composition for hair dying, and it comprises:

(a) a kind of inorganic peroxy oxidant;

(b) a kind of oxide hair dye; With

(c) a kind of diluent that is coated on the hair that is applicable to;

Wherein, (a) be about 1 to about 4.5, and wherein the pH value scope of composition is about 1 to about 4.5 with (b) separately pH value.

As previously mentioned, found that the combination when hanging down the pH value of inorganic peroxy oxidant and oxide hair dye is valuable, can be used for providing the hair dyeing performance of excellence, and can reduce hair damage, minimizing skin irritatin and skin contamination, also can improve smell (with respect to the high pH value of routine composition).Another effect of low pH composition for hair dying is, compares with the high pH value of routine composition, uses this composition to can observe the reduction of skin contamination degree.

Therefore, the invention provides a kind ofly can provide shallow russet with the 40% grey composition for hair dying to the light brown hair, and it comprises:

(a) a kind of inorganic peroxy oxidant;

(b) a kind of oxide hair dye; With

(c) a kind of diluent that is coated on the hair that is applicable to;

Wherein, component (a) and (b) separately pH value are about 1 to about 4.5, and wherein the pH value scope of composition is about 1 to about 4.5.

Although be not subjected to the restriction of any theory, the reduction that it is believed that these skin irritatins and/or be infected with degree is the combined result of following means: (a) reduced the content of dyestuff and adopted low pH value system; (b) hanging down the tactiosensible property (PPD of high-load shows to have tactiosensible property under high pH value, and does not have) that has reduced p-phenylenediamine (PPD) (PPD) under the pH value when hanging down pH; (c) eliminated tactiosensible dose of nitrobenzene (coming across in the high pH value composition); (d) compare the skin contamination when having reduced low pH value with high pH value; (e), skin irritatin and peculiar smell have been reduced owing to using alternative oxidant without ammonia in the low pH composition for hair dying of the present invention.

The oxidation hair-dye method

Can use any oxide hair dye in the composition of the present invention.Usually, but be not bound by any theory, oxide hair dye is made up of at least two kinds of components basically, and they are referred to as dyestuff and form intermediate (or precursor).Dyestuff forms intermediate can react the coloured molecule of formation in the presence of suitable oxidant.

The dyestuff that is used for oxide hair dye forms intermediate and comprises: aromatic diamine, amino phenols, various heterocyclic compound, phenol, naphthols and its various derivatives.It is primary intermediate and secondary intermediate that but these dyestuffs form the intermediate rough classification, primary intermediate also is referred to as oxidation dye precursors, it is to activate by oxidation, reacts to each other then and/or forms the compound of coloured dye composition with colour coupler (coupler) reaction.Secondary intermediate also is referred to as color modifier or colour coupler, it typically is colourless molecule, can in the presence of the precursor/primary intermediate of activation, form color, and use to produce specific color effects or to play the effect of stable color with other intermediate.

The primary intermediate that is applicable to the present composition and method comprises: the derivative of aromatic diamine, polyhydric phenols, amino phenols and these aromatic compounds (as, the N-substitutive derivative of amine and the ether of phenol).This primary intermediate is colourless molecule usually before oxidation.

Be not bound to any specific theory although do not wish, but propose herein to generally include sequential steps by these primary intermediate and the colorific method of secondary colour coupler compound, thereby, primary intermediate becomes activated form (by oxidation), then, obtain a kind of coloring matter of conjugation of dimerization with the colour coupler effect, this material produces trimerization conjugation coloured molecule with another kind of " activation " primary intermediate effect again.

Oxidative coloration of hair effect chemistry under various pH values

Although do not wish to be subjected to the restriction of any theory, can understand so usually: conventional oxidative coloration effect normally takes place between oxidisability precursor molecule, oxidisability colour coupler molecule and mistake peroxygen oxidising agent when high pH (8-10).Typical precursor comprises 1, the dibasic benzene derivative of 4-, and typical colour coupler comprises 1,2-or 1, the dibasic benzene derivative of 3-.

Usually acceptable is, the pH value during human hair is dry is approximately 5.5-6 (C.R.Robbins, Chemical and Physical Behaviour of Human Hair, the 2nd edition, 157 pages), and known person is sent out itself and had buffer capacity.

The oxidative coloration of hair effect of carrying out with oxidant and oxidative coloration of hair agent under pH1-pH4.5 is important for following effects is provided: the excellent initial hair color and the color of improvement and the washability of hair color that changes in time, desirable color full and verisimilitude, minimizing hair damage, minimizing skin irritatin, minimizing skin contamination and more effectively hair dyeing.Under low ph condition, improved colour developing usefulness (that is the change color of increase) from inorganic peroxy oxidant and oxidative coloration of hair agent.In addition, find also that low pH value composition for hair dying can provide the hair dyeing performance and the hair damage of excellence very little.

Having found that, can be about 1.5 to about 4.5 scope in the pH value, and preferred pH value about 2 is to about 4.4, and more preferably from about 3.6 to about 4.3, and most preferably from about 3.8 to about 4.2, further improves colour rendering.

The oxidative dyestuff precursor

In general, the oxidative dyestuff primary intermediate comprises those monomeric substances by oxidation formation oligomer or polymer, has the electron conjugated system of prolongation in these oligomer or the polymer molecular structure.Because this new electronic structure, the oligomer of gained and polymer are moved to the visible light scope and demonstrate color in electronic spectrum.For example, the oxidisability primary intermediate that can form colored polymeric comprises the material such as aniline, and it has a functional group, after it is oxidized, can form a series of conjugated imines and quinoid dimer, tripolymer etc., color from green to black.Can oxidation polymerization such as the compound with two functional groups of p-phenylenediamine (PPD), obtain the coloring matter of HMW, it has the conjugated electrons system of prolongation.Oxidation dye well known in the art can be used in the low pH value composition.The representative example that is applicable to primary intermediate of the present invention and secondary colour coupler is stated in following document: Sagarin, " CosmeticScience and Technology ", Interscience, Special Ed. the 2nd volume, 308-310 page or leaf.Being appreciated that following primary intermediate only is some examples, is not the restriction to the present composition and method.

Typical aromatic diamine, polyhydric phenols, amino phenols and its derivative as primary intermediate also can have other substituting group on its aromatic ring as previously mentioned, as halogen, aldehyde, carboxylic acid, nitro, sulfonic acid and replacement or unsubstituted alkyl, and can on the oxygen of ammonia nitrogen and phenol, have other substituting group, as replacement or unsubstituted alkyl and aryl.

The example of suitable aromatic diamine, polyhydric phenols, amino phenols and its derivative be respectively have following general formula (I), the compound of (II) and (III):

Wherein, Y be hydrogen, halogen (as fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl,

-COOM or-SO ₃M (wherein, M is the ammonium of hydrogen or alkali metal or alkaline-earth metal, ammonium or replacement, and wherein, the one or more hydrogen atoms on ammonium ion can replace with the alkyl or the hydroxyalkyl of 1-3 carbon atom), wherein R ₁, R ₂, R ₃And R ₄Identical or different, be selected from hydrogen, C ₁-C ₄Alkyl or alkenyl and C ₆-C ₉Aryl, alkaryl or aralkyl, R ₅Be hydrogen, C ₁-C ₄Replacement or unsubstituted alkyl or alkenyl, wherein substituting group is selected from those substituting groups in the as above Y definition, or C ₆-C ₉Replace or unsubstituted aryl, alkaryl or aralkyl, wherein substituting group is selected from those substituting groups in the as above Y definition.Because the precursor of formula (I) is an amine, they can use with the salt form of peroxide compatible, the X representative in the past that described in detail with anion peroxide compatible.The general formula of described salt is interpreted as having one-, two-and three-negative anionic those salt.

The instantiation of formula (I) compound is: o-phenylenediamine; m-phenylene diamine (MPD); p-phenylenediamine (PPD); 2-chloro-p-phenylenediamine (PPD); 2-iodine p-phenylenediamine (PPD); 4-nitro o-phenylenediamine; the 2-nitro p-phenylenediamine; 1; 3; the 5-triaminobenzene; 2-hydroxyl-p-phenylenediamine (PPD); 2; the 4-diaminobenzoic acid; 2; 4-diaminobenzoic acid sodium; two-2; 4-diaminobenzoic acid calcium; 2; 4-diaminobenzoic acid ammonium; 2; 4-diaminobenzoic acid trimethyl ammonium; 2; 4-diaminobenzoic acid three-(2-ethoxy) ammonium; 2; 4-diaminobenzene formaldehyde carbonate; 2; the 4-diamino benzene sulfonic acid; 2; 4-diamino benzene sulfonic acid potassium; N; N-diisopropyl-p-phenylenediamine (PPD) bicarbonate; N; the N-dimethyl-p-phenylenediamine; N-ethyl-N '-(2-acrylic)-p-phenylenediamine (PPD); N-phenyl-p-phenylenediamine (PPD); N-phenyl-N-benzyl p-phenylenediamine (PPD); N-ethyl-N '-(3-ethylphenyl) p-phenylenediamine (PPD); 2; the 4-toluenediamine; 2-ethyl-p-phenylenediamine (PPD); 2-(2-bromoethyl) p-phenylenediamine (PPD); 2-diphenyl-para-phenylene diamine laruate; 4-(2; the 5-diamino-phenyl) benzaldehyde; 2-benzyl-p-phenylenediamine (PPD) acetate; 2-(4-nitrobenzyl) p-phenylenediamine (PPD); 2-(4-aminomethyl phenyl) p-phenylenediamine (PPD); 2-(2; the 5-diamino-phenyl)-the 5-methyl benzoic acid; the methoxyl group p-phenylenediamine (PPD); the dimethyl-p-phenylenediamine; 2; the 5-dimethyl-p-phenylenediamine; 2-methyl-5-methoxyl group p-phenylenediamine (PPD); 2; 6-methyl-5-methoxyl group p-phenylenediamine (PPD); 3-methyl 4-amino-N; the N-diethylaniline; N; two (beta-hydroxyethyl) p-phenylenediamine (PPD) of N-; 3-methyl 4-amino-N; two (beta-hydroxyethyl) aniline of N-; 3-chloro-4-amino-N; two (beta-hydroxyethyl) aniline of N-; 4-amino-N-ethyl-N-(carbonic acyl radical methyl (carbamethyl)) aniline; 3-methyl-4-amino-N-ethyl-N-(carbonic acyl radical methyl) aniline; 4-amino-N-ethyl-(β-piperidino ethyl) aniline; 3-methyl-4-amino-N-ethyl-(β-piperidino ethyl) aniline; 4-amino-N-ethyl-N-(β-morpholino ethyl) aniline; 3-methyl-4-amino-N-ethyl-N-(β-morpholino ethyl) aniline; 4-amino-N-ethyl-N-(β-acetylamino ethyl) aniline; 4-amino-N-('beta '-methoxy ethyl) aniline; 3-methyl-4-amino-N-ethyl-N-(β-acetylamino ethyl) aniline; 4-amino-N-ethyl-N-(β-mesyl amino-ethyl) aniline; 3-methyl-4-amino-N-ethyl-N-(β-mesyl amino-ethyl) aniline; 4-amino-N-ethyl-N-(β-sulfo group ethyl) aniline; 3-methyl-4-amino-N-ethyl-N-(β-sulfo group ethyl) aniline; N-(4-aminophenyl) morpholine; N-(4-aminophenyl) piperidines; 2; 3-dimethyl-p-phenylenediamine (PPD); the isopropyl p-phenylenediamine (PPD); N, N-pair-(2-ethoxy) p-phenylenediamine sulfate.

In particularly preferred composition, (I a) and the material of (I b) preferably to have formula. Wherein, Y be hydrogen, halogen (as fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl,

-COOM or-SO ₃M (wherein, M is the ammonium of hydrogen or alkali metal or alkaline-earth metal, ammonium or replacement, and wherein, the one or more hydrogen atoms on ammonium ion can replace with the alkyl or the hydroxyalkyl of 1-3 carbon atom), wherein, R ₁, R ₂, R ₃And R ₄Identical or different, be selected from hydrogen, C ₁-C ₄Alkyl or alkenyl and C ₆-C ₉Aryl, alkaryl or aralkyl, R ₅Be hydrogen, C ₁-C ₄Replace or unsubstituted alkyl or alkenyl, or C ₆-C ₉Replace or unsubstituted aryl, alkaryl or aralkyl, wherein, substituting group is selected from those substituting groups in the as above Y definition.Because the precursor of formula (I) is an amine, so they can use with the salt form of peroxide compatible, the X representative in the past that described in detail with anion peroxide compatible.The general formula of described salt is interpreted as having list, two and three negative anionic those salt.

Wherein, X and Y are suc as formula definition in (I), R ₁And R ₂Can be identical or different, and identical with the definition in the formula (I), R ₅Identical with the definition in the formula (I), R ₆Be hydrogen or C ₁-C ₄Replacement or unsubstituted alkyl or alkenyl, wherein substituting group is selected from those that in the formula (I) Y are limited.

The instantiation of formula (II) compound is:

O-aminophenol, m-aminophenol, para-aminophenol, 2-iodo-para-aminophenol, 2-nitro para-aminophenol, 3,4-dihydroxy aniline, 3, the 4-diaminophenol, chloracetate, 2-hydroxyl-4-amino benzoic Acid, 2-hydroxyl-4-aminobenzaldehyde, 3-amino-4-hydroxy benzene sulfonic acid, N, N-diisopropyl-para-aminophenol, N-methyl-N-(1-acrylic)-para-aminophenol, N-phenyl-N-benzyl p-aminophenol sulfate, N-methyl-N-(3-ethylphenyl) para-aminophenol, 2-nitro-5-ethyl para-aminophenol, 2-nitro-5-(2-bromoethyl)-para-aminophenol, (2-hydroxyl-5-aminophenyl) acetaldehyde, 2-methyl-para-aminophenol, (2-hydroxyl-5-aminophenyl) acetate, 3-(2-hydroxyl-5-aminophenyl)-1-propylene, 3-(2-hydroxyl-5-aminophenyl)-2-chloro-1-propylene, 2-phenyl-para-aminophenol palmitate, 2-(4-nitrobenzophenone)-para-aminophenol, 2-benzyl-para-aminophenol, 2-(4-benzyl chloride base-para-aminophenol) perchlorate, 2-(4-aminomethyl phenyl)-para-aminophenol, 2-(2-amino-4-aminomethyl phenyl)-para-aminophenol, P-nethoxyaniline, 2-bromoethyl-4-aminophenyl ether phosphate, 2-nitro-ethyl-4-aminophenyl ether bromide, 2-amino-ethyl-4-aminophenyl ether, 2-hydroxyethyl-4-aminophenyl ether, (4-amino-benzene oxygen) acetaldehyde, (4-amino-benzene oxygen) acetate, (4-amino-benzene oxygen) methanesulfonic acid, 1-acrylic-4-aminophenyl ether isobutyrate, (2-chlorine)-1-acrylic-4-aminophenyl ether, (2-nitro)-1-acrylic-4-aminophenyl ether, (2-amino)-1-acrylic-4-aminophenyl ether, (2-hydroxyl)-1-acrylic-4-aminophenyl ether, N-methyl-para-aminophenol, 3-methyl-4-amino-phenol, 2-chloro-4-amino-phenol, 3-chloro-4-amino-phenol, 2,6-dimethyl-4-amino-phenol, 3,5-dimethyl-4-amino-phenol, 2,3-dimethyl-4-amino-phenol, 2,5-dimethyl-4-amino-phenol, 2-hydroxymethyl-4-amino-phenol, 3-hydroxymethyl-4-amino-phenol.

Compound with following general formula is not preferred:

Wherein, R ₁Be alkyl, hydroxy alkyl, carboxyalkyl or aminoalkyl; R ₂Be hydrogen, alkyl or hydroxy alkyl; R ₃And R ₅For H or-OR, wherein, R is alkyl or hydroxy alkyl substituting group; R ₄Be H, alkyl or NHR '; R ₆For H, alkyl ,-OR or NHR '; R is H, alkyl, hydroxy alkyl, and condition is: a) R ₄And R ₆In only one be NHR ＇; B) work as R ₂, R ₅And R ₆Be H and R ₄Be NH ₂The time, R ₃With-OR ₁Be not methoxyl group simultaneously; C) R ₃Or R ₄Or R ₅Or R ₆Be H; D) work as R ₆Be NH ₂And R ₂Be H and R ₁During for methyl, R ₃, R ₄And R ₅Not all be H; E) if R ₁Be ethyl and R ₂, R ₃, R ₄And R ₆Be H, R ₄Be not NH ₂F) if R ₁During for carboxyalkyl or aminoalkyl, R ₄Be NHR '.

Wherein, Y, R ₅And R ₆As the definition in the above-mentioned formula (II).

The instantiation of formula (III) compound is:

O-hydroxy phenol (catechol), between hydroxyl phenol (resorcinol), para hydroxybenzene phenol (quinhydrones), the 4-metoxyphenol, the 2-metoxyphenol, 4-(2-chloroethoxy) phenol, 4-(2-propenyloxy group) phenol, 4-(3-chloro-2-propenyloxy group) phenol, 2-chloro-4-hydroxyl phenol (2-chlorohydroquinone), 2-nitro-4-hydroxyl phenol (2-nitro quinhydrones), the amino 4-hydroxyl phenol of 2-, 1,2,3-trihydroxy benzene (pyrogallol), 2, the 4-4-dihydroxy benzaldehyde, 3, the 4-dihydroxy-benzoic acid, 2, the 4-dihydroxy benzenes sulfonic acid, 3-ethyl-4-hydroxyl phenol, 3-(2-nitro-ethyl)-4-hydroxyl phenol, 3-(2-acrylic)-4-hydroxyl phenol, 3-(3-chloro-2-acrylic)-4-hydroxyl phenol, 2-phenyl-4-hydroxyl phenol, 2-(4-chlorphenyl)-4-hydroxyl phenol, 2-benzyl-4-hydroxyl phenol, 2-(2-nitrobenzophenone)-4-hydroxyl phenol, 2-(2-aminomethyl phenyl)-4-hydroxyl phenol, 2-(2-methyl 4-chlorphenyl) 4-hydroxyl phenol, 3-methoxyl group 4-hydroxyl-benzaldehyde, 2-methoxyl group-4-(1-acrylic) phenol, 4-hydroxyl-3-methoxy cinnamic acid, 2, the 5-dimethoxyaniline, 2-methyl resorcinol, α naphthols and its salt.

In preferred compositions of the present invention, the listed compound of following formula does not comprise:

Preferably be used in combination such as the secondary coupling compound that will describe in detail later on (color modifier) with primary intermediate, these compounds are considered to and can in its forming process himself be got involved in coloured polymer, and cause that electronic spectrum is subjected to displacement, thereby produce slight change color.

Be applicable to that the secondary coupling compound that is included in previously described composition for hair dying and the method comprises some aromatic amine and phenol and its derivative, they can not produce color separately, but it can change color and luster or intensity by the shown color of the dyestuff intermediate of primary oxidation, color.Some aromatic amine and phenolic compound and its derivative, comprise by above-mentioned formula (I), (I a), some aromatic diamine and the polyhydric phenols of (I b), (II) and (III) described type, be known in the art the material that is not suitable for as primary intermediate and be suitable for use as colour coupler of the present invention.Polyalcohol also is applicable to makes colour coupler of the present invention.

Also can on its aromatic ring, have other substituting group as the aromatic amine of colour coupler and phenol and derivative as mentioned above; as halogen, aldehyde, carboxylic acid, nitro, sulfonyl; and can be replaced by alkyl or not replace; and can on ammonia nitrogen or phenolic group oxygen, have other substituting group, for example replacement or unsubstituted alkyl and aryl.In addition, their salt with peroxide compatible also is applicable to the present invention.

The compound of the example of aromatic amine, phenol and its derivative for having following general formula (IV) and (V): Or Wherein, Z is hydrogen, C ₁And C ₃Alkyl, halogen (as fluorine, chlorine, bromine or iodine), nitro,

-COOM or-SO ₃M (wherein, M is the ammonium of hydrogen or alkali metal or alkaline-earth metal, ammonium or replacement, and wherein, the one or more hydrogen atoms on ammonium ion can replace with the alkyl or the hydroxyalkyl of 1-3 carbon atom), wherein, R ₁And R ₂Identical or different, be selected from hydrogen, C ₁-C ₄Alkyl or alkenyl and C ₆-C ₉Aryl, alkaryl or aralkyl, R ₇Be hydrogen, C ₁-C ₄Replacement or unsubstituted alkyl or alkenyl, or C ₆-C ₉Replace or unsubstituted aryl, alkaryl or aralkyl, wherein, substituting group is selected from those substituting groups that as above Z defined, and wherein X is suc as formula the definition in (I).

The instantiation of formula (IV) compound is:

Aniline, parachloroanilinum, para-fluoroaniline, paranitroanilinum, para aminotenzaldehyde, p-aminobenzoic acid, para aminobenzoic acid sodium salt, the p-aminobenzoic acid lithium, two p-aminobenzoic acid calcium, the p-aminobenzoic acid ammonium, the p-aminobenzoic acid trimethyl ammonium, three-(2-hydroxyethyl)-para-aminobenzoate, sulfanilic acid, sulfanilic acid potassium, methylphenylamine, N-propyl group-N-phenylaniline, N-methyl-N-2-acrylic aniline, Phenhenzamine, N-(2-ethylphenyl) aniline, the 4-methylaniline, 4-(2-bromoethyl) aniline, 2-(2-nitro-ethyl) aniline, (4-aminophenyl) acetaldehyde, (4-aminophenyl) acetate, 4-(2-acrylic) phenylglycine salt, 4-(3-bromo-2-acrylic) aniline, 4-phenylaniline chloracetate, 4-(3-chlorphenyl) aniline, the 4-benzylaniline, 4-(4-benzyl iodide) aniline, 4-(3-ethylphenyl) aniline, 4-(2-chloro-4-ethylphenyl) aniline.

Wherein, Z and R ₇Suc as formula the definition in (IV), R ₈Be hydrogen or C ₁-C ₄Replacement or unsubstituted alkyl or alkenyl, wherein substituting group is selected from those that define Z in the formula (IV).

The instantiation of formula (V) compound is:

Phenol, parachlorophenol, p-nitrophenol, parahydroxyben-zaldehyde, P-hydroxybenzoic acid, p-hydroxybenzenyl sulfonate, ethylphenyl ether, 2-chloroethyl phenyl ether, 2-nitro-ethyl phenyl ether, phenoxy acetaldehyde, phenoxyacetic acid, 3-phenoxy group-1-propylene, 3-phenoxy group-2-nitro-1-propylene, 3-phenoxy group-2-bromo-1-propylene, the 4-propylphenol, 4-(3-bromopropyl) phenol, 2-(2-nitro-ethyl) phenol, (4-hydroxy phenyl) acetaldehyde, (4-hydroxy phenyl) acetate, 4-(2-acrylic) phenol, the 4-phenylphenol, the 4-benzylphenol, 4-(3-fluoro-2-acrylic) phenol, 4-(4-benzyl chloride base) phenol, 4-(3-ethylphenyl) phenol, 4-(2-chloro-3-ethylphenyl) phenol, 2, the 5-xylenols, 2, the 5-diamino-pyridine, 2-hydroxyl-5-aminopyridine, 2-amino-3-pyridone, tetraminopyrimidine, 1,2, the 4-trihydroxy benzene, 1,2,4-trihydroxy-5-(C1-C6 alkyl) benzene, 1,2, the 3-trihydroxy benzene, the amino resorcinol of 4-, 1, the 2-dihydroxy benzenes, 2-amino-1, the 4-dihydroxy benzenes, 2-amino-4-metoxyphenol, 2, the 4-diaminophenol, 3-methoxyl group-1, the 2-dihydroxy benzenes, 1,4-dihydroxy-2-(N, the N-diethylamino) benzene, 2,5-diaminourea-4-methoxyl group-1-hydroxy benzenes, 4,6-dimethoxy-3-amino-1-hydroxy benzenes, 2,6-dimethyl-4-[N-(p-hydroxybenzene) amino]-the 1-hydroxy benzenes, 1,5-diaminourea-2-methyl-4-[N-(p-hydroxybenzene) amino] benzene and its salt.

In being applicable to preferred compositions of the present invention, do not comprise the combination of following primary intermediate and colour coupler:

R wherein ₁And R ₂Not H

And with m-aminophenol, resorcinol, 2-methyl-5-amino-phenol, 2-methyl resorcinol and its mixture.

Be applicable to that other primary intermediate of the present invention comprises pyrocatechol, catechol " DOPA (dihydroxyphenylalanine) " class material particularly, comprise DOPA self with and homologue, analog and derivative.The example of suitable pyrocatechol material comprises that half Guang ammonia DOPA, alkyl have 1-4 carbon atom, and α alkyl DOPA, adrenaline and the alkyl of preferred 1-2 carbon atom have 1-6 carbon atom, the DOPA Arrcostab of preferred 1-2 carbon atom.

Usually, Shi Yi catechol is represented by following formula (VI):

Wherein, R ₁, R ₂And R ₃Can be identical or different, be electron donor or acceptor substituting group, be selected from H, rudimentary (C ₁-C ₆) alkyl, OH, OR, COOR, NHCOR, CN, COOH, halogen, NO ₂, CF ₃, SO ₃H or NR ₄R ₅, condition is, only R ₁, R ₂Or R ₃One of can be CN, COOH, halogen, NO ₂, CF ₃Or SO ₃H; R ₄And R ₅Can be identical or different, be H, rudimentary (C ₁-C ₆) rudimentary (C of alkyl or replacement ₁-C ₆) alkyl, wherein, substituting group can be OH, OR, NHCOR ₆, NHCONH ₂, NHCO ₂R ₆, NHCSNH ₂, CN, COOH, SO ₃H, SO ₂NR ₆, SO ₂R ₆Or CO ₂R ₆R ₆Be rudimentary (C ₁-C ₆) alkyl, be connected to rudimentary (C on the nitrogen-atoms by alkylidene chain ₁-C ₆) hydroxy alkyl phenyl, phenyl or substituting group definition be as R ₁The phenyl of replacement, R is C ₁-C ₆Alkyl or C ₁-C ₆Hydroxy alkyl.

The present invention also comprises the oxidative coloration of hair agent of following formula:

Wherein, R ₁For replacing or unsubstituted phenyl ring the tert-butyl group etc.; R is for replacing or unsubstituted phenyl ring; Also comprise the oxidative coloration of hair agent of following formula:

Wherein, R is aminoalkyl, amidoalkyl, aminophenyl (replacement or unsubstituted), amido phenyl (replacement or unsubstituted), alkyl, replacement or unsubstituted phenyl ring; R ₁For replacing or unsubstituted phenyl ring.

Primary intermediate can be used separately or be used in combination with other primary intermediate, and one or more primary intermediate can be used in combination with one or more colour couplers.The selection of primary intermediate and colour coupler will be depended on color, color and luster and the intensity of required color.Exist 19 kinds preferably to can be used for primary intermediate of the present invention and colour coupler, they can be used singly or in combination to obtain having by the dyestuff of linen (ashb1onde) to the various color and luster scopes of black (black); They are: pyrogallol, resorcinol, to toluenediamine, p-phenylenediamine (PPD), o-phenylenediamine, m-phenylene diamine (MPD), o-aminophenol, para-aminophenol, 4-amino-2-nitrophenol, nitro p-phenylenediamine, N-phenyl-p-phenylenediamine (PPD), m-aminophenol, 2-amino-3-pyridone, 1-naphthols, N, N-pair-(2-hydroxyethyl) p-phenylenediamine (PPD), 4-amino-2-hydroxy-methylbenzene, 1,5-dihydroxy naphthlene, 2-methyl resorcinol and 2, the 4-diamino anethole.As previously mentioned, these compositions can use or use with the salt form with peroxide compatible by molecular forms.

Aforesaid primary intermediate and quality compound can make up to provide shades of colour to hair.Hair color can change aspect the intensity of the degree of depth of color and color.As previously mentioned, the value preferred body of composition of the present invention provides high strength color aspect now.Herein, the intensity of color is meant the quantity that forms and remain in the colored compound in the hair on hair.Usually, high strength is meant dead color or dark as kermesinus, burgundy or black etc. herein.According to the above, by regulating the initial content of each oxidative coloration material, the hair dye that just might make shades of colour intensity comes.

For example, low-intensity color such as natural linen to light brown hair color and luster comprises usually and accounts for composition for hair dying weight about 0.001% to about 5%, preferred about 0.1% to about 2%, more preferably from about total oxidative coloration of hair agent of 0.2% to about 1%, this can make by making up following primary intermediate and colour coupler, primary intermediate is as 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diamino anethole, 4-amino-phenol, 2,5-diaminourea-benzyl alcohol and 2-(2 ', 5 '-diaminourea) phenylethanol, colour coupler such as resorcinol, 2-methyl resorcinol or 4-chlorine resorcinol.

The similar combination of above-mentioned primary intermediate and colour coupler, as 5-amino-2-methyl phenol and 1,3-diaminourea-benzene derivative is as 2, and 4-diaminourea-anisole is to account for the redness that total hair dye about 0.5% to about 1% content can obtain moderate strength.High strength color such as Lan Zhilan-purple hair color and luster can be by making above-mentioned primary intermediate and colour coupler as 1, and 3-diaminobenzene or derivatives thereof is as 2, and the 5-diaminotoluene is realized with the amount that accounts for composition for hair dying weight about 1% to about 6%.Black hair dye can by with above-mentioned primary intermediate and colour coupler as 1,3-diaminobenzene or derivatives thereof makes up and obtains.

Yet, the physiology compatibility that also needs to consider to be generally used for to give the para-aminophenol of hair redness.Similarly, also need to consider to be usually used in to produce the physiology compatibility of some reagent such as the p-phenylenediamine (PPD) (PPD) of black dyes.Therefore, need the improved oxidation hair-dye composition of security, need particularly that security is improved to be used to provide the oxidation hair-dye composition that black dyes is high color intensity dyestuff.As previously mentioned, low pH value composition provides excellent hair dyeing characteristic, and can reduce damage, minimizing skin contamination and/or stimulation to hair.

Therefore these compositions can advantageously provide the hair conditioning characteristic of improvement, and have excellent initial color developing and a uniformity, and the long-time washability of improving, also can reduce the hair damage degree, reduce skin irritatin and/or reduce skin contamination, particularly when these compositions are used for hand-held packaged composition of the present invention.

Non-oxide dyestuff and other dyestuff

Composition for hair dying also optionally comprises non-oxide dyestuff and other dyestuff except that containing basic oxide hair dye.Be applicable to that the non-oxide dyestuff of selectivity and other dyestuff in composition for hair dying and the method comprise semipermanent dyestuff, temporary transient dyestuff and other dyestuff.Non-oxide herein dyestuff comprises so-called " directly acting on dyestuff ", metal dye, metal-chelator dyestuff, fibre-reactive dye and other synthetic and natural dye.Various types of non-oxide dyestuffs have in following document to be stated: " chemistry that the people sends out and physical characteristic " (Chemical and Physical Behviour of Human Hair), the 3rd edition, ClarenceRobbins (250-259 page or leaf); " cosmetic chemistry and production " (The Chemistry and Manufacture), IV, the 2nd edition, Maison G.De Navarre, 45 chapters, G.S.Kass (841-920 page or leaf); " cosmetic science and technology " (Cosmetics:Science and Technology), the 2nd edition, II volume, Balsam Sagarin, 23 chapters, F.E.Wall (279-343 page or leaf); " hair nursing science " (The Scienceof Hair Care), C.Zviak edits, 7 chapters (235-261 page or leaf); " hair dye " (Hair Dyes), J.C.johnson, Noyes Data Corp., Park Ridge, U.S.A. (1973), (3-91 page or leaf and 113-139 page or leaf).

Need not the direct effect dyestuff that oxidation can Show Color and be also referred to as hair coloring agent (hairtint), is this area known dyestuff early.Usually they can be coated on the hair with the base matrix that comprises surfactant material.Directly the effect dyestuff comprises nitro dye, as the derivative of nitro amino benzene or nitro amino phenol; Disperse dyes are as nitro arylamine, amino anthraquinones or azo dyes; Anthraquinone dye, naphthoquinone dyestuff; Basic-dyeable fibre such as acridine orange C.I.46005.

Adding nitro dye before coating in dye composite can strengthen the color of dyestuff and can bring suitable aesthetic colors to dye mixture.

Directly the example of effect dyestuff comprises: Arianor dyestuff bismarck brown 17, C.I. (color index)-12, No. 251; Alkalescence is red 76, C.I.-12,245; Bismarck brown 16, C.I.-12,250; Basic yellow 57, C.I.-12,719 and alkali blue 99, C.I.56.059 and other directly act on dyestuff, as Indian yellow 1, C.I.-10,316 (D﹠amp; Yellow No. 7 of C); Indian yellow 9, C.I.-13,015; The purple C.I.-45 of alkalescence, 170; Disperse yellow 3, C.I.-11,855; Basic yellow 57, C.I.-12,719; Disperse yellow 1, C.I.-10,345; Alkaline purple 1, C.I.-42,535, alkaline purple 3, C.I.-42,555; Turquoise, C.I.-42,090 (FD﹠amp; Blue l number of C); Huang Hong, C.I.-14700 (FD﹠amp; Red No. 4 of C); Huang, C.I.-19140 (FD﹠amp; Yellow No. 5 of C); Yellow orange, C.I.-15985 (FD﹠amp; Yellow No. 6 of C); Bluish-green, C.I.-42053 (FD﹠amp; Green No. 3 of C); Huang Hong, C.I.-16035 (FD﹠amp; Red No. 40 of C); Bluish-green, C.I.-61570 (D﹠amp; Green No. 3 of C); Orange, C.I.-45370 (D﹠amp; No. 5, C orange); Red, C.I.-15850 (D﹠amp; Red No. 6 of C); Lan Hong, C.I.-15850 (D﹠amp; Red No. 7 of C); Light blue red, C.I.-45380 (D﹠amp; Red No. 22 of C); Lan Hong, C.I.-45410 (D﹠amp; Red No. 28 of C); Lan Hong, C.I.-73360 (D﹠amp; Red No. 30 of C); Purple, C.I.-17200 (D﹠amp; Red No. 33 of C); Dirty (dirty) Lan Hong, C.I.-15880 (D﹠amp; Red No. 34 of C); Bright orange red, C.I.-12085 (D﹠amp; Red No. 36 of C); Bright orange, C.I.-155l0 (D﹠amp; No. 4, C orange); Greenish-yellow, C.I.-47005 (D﹠amp; Yellow No. 10 of C); Bluish-green, C.I.-59040 (D﹠amp; Green No. 8 of C); Royal purple, C.I.-60730 (Ext.D﹠amp; Purple No. 2 of C); Greenish-yellow, C.I.-10316 (Ext.D﹠amp; Yellow No. 7 of C).

Fibre-reactive dye comprises Procion (RTM), Drimarene (RTM), Cibacron (RTM), Levafix (RTM) and the Remazol (RTM) that is purchased from ICI, Sandoz, Ciba-Geigy, Bayer and Hoechst respectively.

Natural dye defined herein and vegetable colour comprise henna (Lawsonia alba), chamomile dyestuff (Matricaria chamomila or Anthemis nobilis), indigoid dye, logwood and walnut shell extract dyestuff.

Temporary hair dye or hair dyeing purificant are too big so that can not to diffuse into hair dry and form with the dye molecule that the outside of hair acts on by molecule usually.They apply through disposable (1eave-in) process usually, and wherein, dye solution can be dry on hair surface.Like this, these dyestuffs are not usually to having resistance with surfactant washing and cleaning hair, are easy to eccysis from the hair relatively.Any temporary hair dye all is suitable for, and the example of preferred temporary transient dyestuff is as follows:

Semipermanent hair dye is the dyestuff of the usually less and anti-temporary transient hair rinse of size, but its molecule is usually greater than permanent (oxidation) dyestuff.Generally speaking, semipermanent dyestuff adopts the mode of similar oxidation dye to work, they can diffuse into hair dry in.But the semipermanent dyestuff oxidation dye molecule than above-mentioned conjugation usually is little, thereby their can be at first processed and diffuse out hair once more gradually.Simple hair washing and cleaning course will promote this process, and usually, the most meetings of semipermanent dyestuff are in eccysis from the hair after washing for 5-8 time.Any semipermanent dye system is all applicable.The semipermanent dyestuff that is applicable to composition is that HC indigo plant 2, HC Huang 4, HC are red 3, disperse violet 4, disperse black 9, HC indigo plant 7, HC Huang 2, disperse blue 3, disperse violet 1 and its mixture.The example of semipermanent dyestuff is: Typical semipermanent dye system contains the mixture of big dye molecule and primary dye molecule.Because hair is that thickness is uneven from root of hair to sending out a tip, thereby subclass will and be sent out tip diffusion at root of hair in little minute, send out in the tip but can not rest on, and the branch subclass only can diffuse into the end of hair usually greatly.The combination of this dye molecule size will help to obtain from root of hair to the hair dyeing effect of sending out tip uniformity in initial hair dyeing process and washing process subsequently.

Buffer

Preferably, the pH value of composition for hair dying is about 1 to about 4.5, and preferred about 1.5 to about 4.5, and more preferably from about 2 to about 4.4, most preferably from about 3.6 to about 4.3, first-selected about 3.8 to 4.2.

Through the effect of inorganic peroxy oxidant, the pH value of preferred composition for hair dying remains in the required pH scope.Yet, work if desired, composition can comprise one or more selectivity buffers and/or hair sweller (HSAs).Can use some kinds of different pH conditioning agents to regulate the pH value of final composition or its arbitrary part composition.

This pH adjustment process can adopt that known acidulant carries out in handling cutin fiber (particularly the people sends out) field, for example, inorganic acid and organic acid, example hydrochloric acid, tartaric acid, citric acid, butanedioic acid, phosphoric acid and carboxylic acid or sulfonic acid such as ascorbic acid, acetate, lactic acid, sulfonic acid, formic acid, ammonium sulfate and sodium dihydrogen phosphate/phosphoric acid, sodium hydrogen phosphate/phosphoric acid, potassium chloride/hydrochloric acid, phthalic acid potassium dihydrogen/hydrochloric acid, natrium citricum/hydrochloric acid, potassium citrate dihydrogen/hydrochloric acid, potassium citrate dihydrogen/citric acid, natrium citricum/citric acid, sodium tartrate/tartaric acid, sodium lactate/lactic acid, sodium acetate/acetate, sodium hydrogen phosphate/citric acid and sodium chloride/glycerine/hydrochloric acid, butanedioic acid and its mixture.

The example of ealkaline buffer is an ammonium hydroxide, ethamine, di-n-propylamine, triethylamine and alkane diamines are as 1, the 3-diaminopropanes, anhydrous alkali alkanolamine such as list or diethanol amine, preferred amino those that are replaced fully, as DMAE, polyalkylenepolyamines such as diethylenetriamines or heterocyclic amine such as morpholine, and alkali-metal hydroxide, as NaOH and potassium hydroxide, the hydroxide of alkaline-earth metal, as magnesium hydroxide and calcium hydroxide, basic amino acid such as L-arginine, lysine, alanine, leucine, isoleucine, oxygen lysine and histidine and alkanolamine such as DMAE and aminoalkyl propane diols and its mixture.Be equally applicable to of the present invention for by being dissolved in the compound that forms HCO3 in the water (hereinafter be referred to as ion and form compound).It is sodium carbonate, sodium acid carbonate, potash, ammonium carbonate, carbonic hydroammonium, calcium carbonate and calcium bicarbonate and its mixture that suitable ion forms examples for compounds.

Being preferred for buffer of the present invention is organic and inorganic acid and the conjugate base thereof with the one-level pKa value that is lower than about pH6.Herein, one-level pKa is meant the negative logarithm (is the end with 10) of equilibrium constant K, and wherein, K is an acid ionization constant.Be applicable to that organic acid of the present invention and inorganic acid are: asparatate, maleic acid, tartaric acid, glutamic acid, glycolic, acetate, butanedioic acid, salicylic acid, formic acid, benzoic acid, malic acid, lactic acid, malonic acid, oxalic acid, citric acid, phosphoric acid and its mixture.Preferred especially acetate, butanedioic acid, salicylic acid and phosphoric acid and composition thereof.

Low pH composition for hair dying can comprise a kind of final solution, and it comprises peroxide and oxide hair dye, and they mixed before being coated on the hair or are the one-component system.Like this, composition can comprise the dyeing bag of multiple component of separating.

In oxidation that comprises part inorganic peroxy oxidant such as hydrogen peroxide (the inorganic peroxy oxidant can be solid or liquid form) and hair dyeing bag, can adopt buffer agent solution to come stable peroxide hydrogen.Because hydrogen peroxide is stable, therefore, need to adopt the buffer of pH value in this scope in the pH of 2-4 value scope.Diluted acid is suitable for the buffer as hydrogen peroxide.

In oxidation that comprises oxidant (oxidant can be solid or liquid form) and one or more hair dyes and hair dyeing bag, buffer can make the pH value of solution remain about 1 to about 4.5, preferred about 1.5 to about 4.5, more preferably from about 2 to about 4.4, most preferably from about 3.6 to 4.3, first-selected about 3.8 to 4.2.Therefore, need to use the buffer of pH value within described scope.

Catalyst

Composition for hair dying optionally comprises a kind of catalyst that contains transition metal, being used for catalysis inorganic peroxy oxidant, and optionally preformed peroxy acid oxidant.A kind of catalyst of suitable type contains the catalyst system of the heavy metal cation with definite bleach catalyst activity, does not almost have or do not have the assistant metal cation of bleach catalyst activity and a chelating agent that catalysis and assistant metal cation are had definite stability constant, heavy metal cation such as copper, iron or manganese cation, assistant metal cation such as zinc or aluminium cations, chelating agent is ethylenediamine tetra-acetic acid, ethylenediamine tetraacetic (methylene phosphonic acid) and water soluble salt thereof especially.This catalyst is disclosed in U.S. Pat-A-4, in 430,243.

The suitable catalyst of other type comprises and is disclosed in U.S. Pat-A-5, the manganese-basigamy compound in 246,621 and US-A-5,244,594.The preferred embodiment of such catalyst comprises Mn ^IV ₂(u-O) ₃(1,4,7-trimethyl-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) 1 (u-OAc) ₂(1,4,7-trimethyl-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethyl-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃And their mixture.Other catalyst is to be described in EP-A-549, those in 272.Be applicable to that other parts of the present invention comprise 1,5,9-trimethyl-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-7-triazacyclononane and their mixture.

The example of suitable catalyst is referring to U.S. Pat-A-4, and 246,612 and US-A-5,227,084.Also referring to U.S. Pat-A-5,194,416, mention monokaryon manganese (IV) complex such as Mn (1,4,7-trimethyl-1,4,7-7-triazacyclononane) (OCH in this patent ₃) ₃-(PF ₆).The suitable catalyst of another kind of type as at U.S. Pat-A-5, as described in 114,606, is the water-soluble complexes of the part of manganese (III) and/or (IV) and the non--carboxylate polyol with at least three consecutive C-OH groups.Other example comprises the double-core Mn complex that has four-N-dentate and two-N-dentate part, comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Other suitable bleaching catalyst is described in, for example, and EP-A-408,131 (cobalt complex catalyst), EP-A-384,503 and EP-A-306089 (metal-porphyrin catalyst), US4,728,455 (manganese/polygamy position ligand catalyst), US4,711,748 and EP-A-224952, (being adsorbed onto the Mn catalyst on the alumino-silicate), US4,601,845 (aluminosilicate carrier and manganese and zinc or magnesium salts), US4,626,373 (manganese/ligand catalysts), US4,119,557 (iron complex catalyst), German patent DE 2,054,019 (cobalt chelating agent catalyst), Canadian Patent CA-A-866,191 (containing transition metal salt), US4,430,243 (chelating agent and manganese cation and on-catalytic metal cations), and US4,728,455 (managanese gluconate catalyst).

Heavy metal ion chelating agent

Colouring compositions can comprise a kind of heavy metal ion chelating agent as optional ingredient.So-called heavy metal ion chelating agent is meant that it can be used as the component of chelating (chelating or purification) heavy metal ion.These components also can have calcium and magnesium sequestering power, but preferably they demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.This chelating agent is valuable in foregoing composition for hair dying, is that they can be used for providing controllable oxidation and the storage-stable of the hair dye product that is used to provide good.

With composition weight meter, the content of heavy metal ion chelating agent is generally about 0.005% to about 20%, and preferred about 0.01% to about 10%, and more preferably from about 0.05% to about 2%.

Known amino phosphonates do (DEQUEST (RTM) is available from Monsanto), nitrilo-acetate, the ethoxy ethylidene triamines etc. of comprising all can use at interior various chelating agents.Be suitable for heavy metal ion chelating agent of the present invention and include organic phosphonates, as amino alkylidenyl many (alkylene phosphonic acids salt), alkali metal ethane 1-hydroxyl diphosphonate and nitrilo-trimethylene phosphonic salt.

Preferred diethylenetriamines five (methylene phosphonic acid salt), ethylene diamine three (methylene phosphonic acid salt), hexamethylene diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1 in the above-mentioned substance, the 1-diphosphonate.

Be applicable to that preferred biodegradable non-phosphorus heavy metal ion chelating agent of the present invention comprises NTA and polyamino carboxylic acid such as ethylenediamine tetra-acetic acid, second pentaacetic acid, EDDS, ethylenediamine two glutaric acids, 2-hydroxyl propane diamine disuccinic acid or its salt.Preferred especially ethylenediamine-N, N '-disuccinic acid (EDDS) (referring to United States Patent (USP) 4,704,233) or its alkali metal salt, alkali salt, ammonium salt or substituted ammonium salt, or its mixture.

Other is applicable to that heavy metal ion chelating agent of the present invention is iminodiacetic acid derivatives such as 2-hydroxyethyl oxalic acid or glyceryl iminodiacetic acid, as EP-A-317, and 542 and EP-A-399,133 is described.EP-A-516,102 described iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and asparatate N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agent also are applicable to the present invention.EP-A-509,382 described Beta-alanine-N, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic butanedioic acid chelating agent also are that the present invention is suitable for.

EP-A-476,257 disclose the suitable chelating agent based on amino.EP-A-510,31 disclose from collagen, keratin or caseic suitable chelating agent.EP-A-528,859 disclose a kind of suitable alkyl imino oxalic acid chelating agent.Pyridinedicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also can adopt.Glycine amide-N, N '-disuccinic acid (GADS), ethylenediamine-N, N '-two glutaric acid (EDDG) and 2-hydroxyl propane diamine-N, N '-disuccinic acid (HPDDS) also can adopt.

Heavy metal ion chelating agent can its alkali metal or the form of alkali salt use.

Thickener

Colouring compositions also can comprise thickener, and its content is about 0.05% to about 20%, and preferred about 0.1% to about 10%, and more preferably from about 0.5% to about 5% weight.The thickener that is applicable to composition is selected from oleic acid, cetanol, oleyl alcohol, sodium chloride, 16/18 alcohol, stearyl alcohol, synthetic thickening agent such as Carbopol, Aculyn and Acrosyl and composition thereof.The thickener that the present invention preferably adopts is Aculyn22 (RTM), laureth-20 methacrylic acid copolymer (RTM); Aculyn44 (RTM), polyurethane resin and Acusol 830 (RTM), acrylate copolymer, available from Rohm andHaas (Philadelphia, PA, USA).Other is applicable to that thickener of the present invention comprises mosanom or Arabic gum, or cellulose derivative, as the sodium salt or the acrylate copolymer of methylcellulose or carboxymethyl cellulose.

Diluent

Water is the composition preferable absorbent.But composition can comprise one or more solvents as additional diluents.Usually, the solvent that is applicable to colouring compositions should be selected the solvent miscible and harmless to skin with water.Suitable solvent as additional diluent comprises C ₁-C ₂₀Monohydric alcohol or polyalcohol and its ether, glycerine, preferred monohydric alcohol and dihydroxylic alcohols and its ether.In these compounds, the preferred alcohols residue comprises 2-10 carbon atom.Therefore, preferable absorbent is ethanol, isopropyl alcohol, normal propyl alcohol, butanols, propane diols, ethylene glycol monomethyl ether and its mixture.Water is preferred main diluent in the composition.Herein, main diluent is meant the total content of the content of water greater than any other diluent.

With composition weight meter, the content of preferred diluent about 5% is to about 99.98%, and preferred about 15% to about 99.5%, more preferably at least about 30% to about 99%, first-selected about 50% to about 98%.

Enzyme

Another other composition that can be used in the colouring compositions is one or more enzymes.

Suitable enzyme comprises that routine can mix commercially available lipase, cutin enzyme, amylase, neutrality and alkali protease, esterase, cellulase, pectase, lactase and the peroxidase in the composition of detergent.Suitable enzyme is at US3, states in 519,570 and 3,533,139, and this paper introduces above-mentioned patent as a reference.

Peroxidase is that peroxide is had the specific enzyme of hemalbumin, but can adopt multiple material as donor.But the catalase decompose hydroperoxide has similar structure and character usually and can produce certain oxidation by hydrogen peroxide according to this enzyme, thereby comprises in the present invention.The decomposition of hydrogen peroxide can be counted as a molecule by another molecular oxidation.It is widely distributed and have some prior function in aerobic cell.The coenzyme peroxidase is not a hemalbumin, is a kind of flavoprotein at least.Other flavoprotein such as xanthine oxidase also will adopt the hydrogen peroxide in other acceptor, and coenzyme peroxidase and these flavoproteins are similar, and hydrogen peroxide not had the peroxidase that is different from conventional meaning aspect the specificity.The peroxidase that is suitable for composition comprises horseradish peroxidase, Japanese radish peroxidase, milk peroxidase, rats'liver peroxidase, linginase and halo peroxidase such as chloro and bromoperoxidase.

The addition of enzyme should be enough to make the gram number in composition for hair dying unit of the present invention, contains about at the most 50mg, and preferably about 0.01mg is to the organized enzyme of about 10mg.In addition, the addition of peroxidase in the present composition be, organized enzyme account for composition weight about 0.0001% to about 5%, preferred about 0.001% to about 1%, more preferably from about 0.01% to about 1%.

Commercially available protease comprises: available from Novo Industries A/S (Denmark) under commodity by name Alcalase, Savinase, Primase, Durazym and Esperase, sell those; Be called those that sell under Maxatase, Maxacal and the Maxapem available from Gist-Brocades at commodity; Available from those of Genencor Intemational; Available from Solvy Enzymes under trade name Opticlean and Optimase, sell those.With composition weight meter, the addition of protease is 0.0001% to 4% organized enzyme.

Diastatic example comprises that more detailed description is at GB-1, among 269,839 (Novo) by the AMS of the special bacterium pearl acquisition of lichens bacillus.Preferred commercially available amylase comprises: for example available from Gist-Brocades those under trade name Rapidase; Available from Novo Industries A/S those under trade name Termamyl and BAN.With composition weight meter, diastatic addition is 0.0001% to 2% organized enzyme.

It is 0.0001% to 2% of composition weight that the content of lipolytic ferment can be active lipolytic ferment, preferred 0.001% to 1%, first-selected 0.001 to 0.5%.

Lipase can derive from fungi or bacterium, for example produces bacterial strain by the lipase of Humicola (Humicola sp.), Thermomyces sp. or pseudomonas (Pseudomonas sp.) (comprising pseudomonas pseudoalcaligenes or Pseudomonas fluorescens) and obtains.Mutant from these bacterium pearls of chemical modification or gene modification also can be used among the present invention.Preferred lipase is obtained by pseudomonas pseudoalcaligenes (Pseudomonaspseudoalcaligenes), and it is described among the EP-B-218272 of mandate.

The preferred lipase of another kind of the present invention is by to cloning from the gene of fetal hair humicola lanuginosa and expressing the lipase that obtains as the host with aspergillus oryzae, as described in EP-A-0258 068, this lipase can (Bagsvaerd Denmark) be purchased under trade name Lipolase from Novo Industri A/S.This lipase also is described in US4, in 810,414 (being issued to Huge-Jensen etc. on March 7th, 1989).

Surfactant

Composition also can comprise a kind of surfactant system.It is the about 8 oleophylic chains to about 22 carbon atoms that the surfactant that is applicable to composition has length usually, and described surfactant is selected from anion surfactant, cationic surfactant, non-ionic surface active agent, amphoteric surfactant, zwitterionic surfactant and its mixture.

(ⅰ) anion surfactant

Be applicable to that the anion surfactant in the composition comprises alkyl sulfate, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonate, methyl-acyl taurine salt, fat acidyl glycine salt, N-acyl glutamate, acyl isethinate, alkyl sulfo succinate, alkyl ethoxy sulfosuccinate, α-sulfonated aliphatic acid; their salt and/or ester; alkyl ethoxy carboxylate, alkyl phosphate, ethoxylated alkyl phosphate ester, alkyl sulfate, acyl sarcosinates and aliphatic acid/protein condensation product and its mixture.The alkyl of these surfactants and/or acyl chain length are C ₁₂-C ₂₂, preferred C ₁₂-C ₁₈, more preferably C ₁₂-C ₁₄

(ⅱ) non-ionic surface active agent

Composition also can comprise water soluble nonionic surfactant.This type of surfactant comprises C ₁₂-C ₁₄Aliphatic acid list and diglycollic amide, SPE surfactant and have the polyhydroxy fatty acid amide surfactant of following formula:

Be R wherein according to the preferred N-alkyl of following formula, N-alkoxyl, N-aryloxy group, polyhydroxy fatty acid amide surfactant ₈Be C ₅-C ₃₁Those of alkyl, preferred C ₆-C ₁₉Alkyl comprises straight or branched alkyl or alkenyl, or its mixture, R ₉Be generally hydrogen, C ₁-C ₈Alkyl or hydroxyalkyl, preferable methyl, or formula-R ¹-O-R ²Group, wherein, R ¹Be C ₂-C ₈Alkyl comprises straight chain, side chain and cyclic group (comprising aryl), preferred C ₂-C ₄Alkylidene, R ²Be C ₁-C ₈Straight chain, side chain and cyclic hydrocarbon group comprise aryl and oxygen alkyl, preferred C ₁-C ₄Alkyl, particularly methyl or phenyl.Z ₂For having the polyhydroxy alkyl part of straight-chain alkyl chain, it has at least 2 (during glyceraldehyde) or at least 3 (during other reduced sugar) hydroxyls that are connected directly on the chain, or its alkoxy derivative (preferred ethoxylated derivative or propoxylated derivative).Z ₂Preferably in reductive amination process, obtain, most preferably Z by reduced sugar ₂It is glycosyl (glycityl) part.Suitable reduced sugar comprises glucose, fructose, maltose, lactose, galactolipin, mannose and wood sugar and glyceraldehyde.As raw material, high glucose corn syrup, high-fructose corn syrup and high malt sugar corn syrup can with the same employing of independent sugar of listing above.These corn syrup can obtain for Z ₂Sugared mixture of ingredients.Be appreciated that this is not to mean to get rid of other suitable raw material.Z ₂Be preferably selected from :-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂H, CH ₂(CHOH) ₂(CHOR ') CHOH-CH ₂OH, wherein, n is the integer of 1-5, R ' is H or ring-type list or polysaccharide base and its alkoxy derivative.Should be pointed out that most preferably glucityl, wherein, n is 4, particularly, and-CH ₂-(CHOH) ₂-CH ₂OH.

Most preferred polyhydroxy fatty acid amide has following formula: R ₈(CO) N (CH ₃) CH ₂(CHOH) ₄CH ₂OH, wherein, R ₈Be C ₆-C ₁₉Straight chained alkyl or alkenyl.In the following formula compound, R ₈-CO-N＜can be is coconut oleoyl amine, stearmide, oleamide, lauramide, myristamide, decyl amide, palmitamide, butter acid amides etc. for example.

Be used for the ionic surfactant pack that suitable oil of the present invention derives and draw together the lubricant of water-soluble plant and animal derived, as have the triglycerides of the polyglycol chain of insertion; The list of ethoxylation and two glyceride, the cream derivative of the lanolin of polyethoxylated and ethoxylation.The non-ionic surface active agent that one class oil preferred for the present invention is derived has following general formula: Wherein, n is about 5 to about 200, and preferred about 20 to about 100, and more preferably from about 30 to about 85, and wherein, R comprises the aliphatic group with average about 5-20 carbon atom, preferably has about 7-18 carbon atom.

The polyethyleneglycol derivative that such suitable ethyoxyl carburetion and fat comprise following substances: coconut oil glyceride, caproin, caprylin, tallow acid glyceride, tristerin, glyceryl laurate ester, olein, castor oil acid glyceride, and from the fatty acid glyceride of triglyceride, as palm oil, apricot kernel oil, corn oil, preferably glycerine butter acid esters and glyceryl cocoate.

Being preferred for of the present invention is polyethylene glycol groups polyethoxylated C ₉-C ₁₅Fatty alcohol nonionic surfactant contains in every mole of surfactant and has an appointment 5 to about 50 inferior ethoxyl parts.

Be applicable to suitable polyethylene glycol groups polyethoxylated C of the present invention ₉-C ₁₅Fatty alcohol comprises: C ₉-C ₁₁Pareth-3, C ₉-C ₁₁Pareth-4, C ₉-C ₁₁Pareth-5, C ₉-C ₁₁Pareth-6, C ₉-C ₁₁Pareth-7, C ₉-C ₁₁Pareth-8, C ₁₁-C ₁₅Pareth-3, C ₁₁-C ₁₅Pareth-4, C ₁₁-C ₁₅Pareth-5, C ₁₁-C ₁₅Pareth-6, C ₁₁-C ₁₅Pareth-7, C ₁₁-C ₁₅Pareth-8, C ₁₁-C ₁₅Pareth-9, C ₁₁-C ₁₅Pareth-10, C ₁₁-C ₁₅Pareth-11, C ₁₁-C ₁₅Pareth-12, C ₁₁-C ₁₅Pareth-13 and C ₁₁-C ₁₅Pareth-14.PEG 40 rilanit specials can be purchased with trade name Cremophor (RTM) from BASF.PEG 7 glyceryl cocounut oil acid esters and PEG 20 glyceryl laurates can be purchased with trade name Cetiol (RTM) HE and Lamacit (RTM) GML 20 respectively from Henkel.C ₉-C ₁₁Pareth-8 can be purchased with trade name Dobanol (RTM) 91-8 from Shell Ltd.The present invention particularly preferably is the polyglycol ether of 16/18 alcohol, and as Ceteareth 25, it can be purchased with trade name Cremaphor A25 from BASF.

Also being applicable to of the present invention is the non-ionic surface active agent that derives from composite plant fat and derivative thereof, and described composite plant fat is that the fruit by Shea Tree (Butyrospermum Karkii Kotschy) obtains through extraction.Similarly, the ethoxylated derivative of mango (Mango), coconut (cocoa), Illipe butter also can be used in the composition of the present invention.Though these materials can be sorted in the ethoxylated non-ionic surface active agent, be appreciated that some part still can divide in non-ethoxylated vegetable oil or lipid.

The ionic surfactant pack that other suitable oil is derived is drawn together the ethoxylated derivative of following oil: apricot kernel oil, peanut oil, rice bran oil, wheat-germ oil, Linseed oil, jojoba oil, Apricot kernel oil (oil of apricotpit), nut oil, palm-kernel oil, pistachio oil, sesame oil, rape seed oil, cade oil, corn oil, persic oil, poppy seed oil, pine tar, castor oil, soya-bean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grape-kernel oil and sunflower seed oil.

(ⅲ) amphoteric surfactant is applicable to that the amphoteric surfactant in the composition comprises: (a) imidazoline surfactant of formula (VII)

Wherein, R ₁Be C ₇-C ₂₂Alkyl or alkenyl, R ₂Be hydrogen or CH ₂Z, each Z are CO independently ₂M or CH ₂CO ₂M, M are H, alkali metal, alkaline-earth metal, ammonium or alkanol ammonium; And/or the ammonium derivative of formula (VIII) Wherein, R ₁, R ₂With Z such as preceding definition; (b) the amino-alkane hydrochlorate of formula (IX)

R ₁NH (CH ₂) _nCO ₂The iminodiacetic alkanoate of M formula (X)

R ₁N[(CH ₂) _mCO ₂M] ₂The imino group multichain alkyl salt of formula (XI)

Wherein, n, m, p and q are 1-4, R ₁Be independently selected from above-mentioned group with M;

(c) its mixture.

The suitable amphoteric surfactant of type (a) can trade name Miranol and Empigen be purchased, they are compound mixtures of multiple material.Usually, Miranol is described to have general formula (VII), though CTFA cosmetic ingredient dictionary (the 3rd edition) shows that it is non-ring structure (VIII), and the 4th edition also pointed out to also have another kind of constitutional isomer, wherein, and R ₂For O-connects but not the N-connection.In fact, may have the compound mixture of ring-type and non-annularity material, for the purpose of complete, two kinds of definition all provide at this paper.Yet, preferred acyclic material among the present invention.

The suitable examples of amphoteric surfactants of type (a) comprises the compound of formula X II and/or X III, wherein, and R ₁Be C ₈H ₁₇(particularly iso-octyl), C ₉H ₁₉And C ₁₁H ₂₃Alkyl.Particularly preferably be following compound: R wherein ₁Be C ₉H ₁₉, Z is CO ₂M and R ₂Compound for H; R wherein ₁Be C ₁₁H ₂₃, Z is CH ₂CO ₂M and R ₂Compound for H; And R ₁Be C ₁₁H ₂₃, Z is CO ₂M and R ₂Compound for H.

In the CTFA nomenclature, be applicable to that material of the present invention comprises cocounut oil both sexes carboxyl propionate, cocounut oil both sexes carboxyl propionic acid, particularly cocounut oil both sexes acetate and cocounut oil both sexes diacetin (also can be referred to as cocounut oil both sexes carboxyl glycinate).The concrete product that is purchased comprises those products of selling with following trade name: Ampholak 7TX (sodium carboxymethyl butter gather propyl group amine), Empigen CDL 60 and CDR60 (Albright﹠amp; Wilson), Miranol H2M Conc.Miranol C2M Conc.N.P., Miranol C2M Conc.O.P., Miranol C2M SF, Miranol CM Special (Rhone-Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona Industries); RewotericAM-2C (Rewo Chemical Group); Schercotic MS-2 (Scher Chemicals).Be applicable to that other examples of amphoteric surfactants of the present invention comprises Octoxynol-1 (RTM), polyoxyethylene (1) octyl phenyl ether; Nonoxynol-4 (RTM), polyoxyethylene (4) nonylplenyl ether and Nonoxynol-9 (RTM), polyoxyethylene (9) nonylplenyl ether.

Be appreciated that many these type of commercially available amphoteric surfactantes can with for example hydroxide counter ion counterionsl gegenions or anion sulfate or sulfosalt surfactant (sulphation C particularly ₈-C ₁₈Alcohol, C ₈-C ₁₈Ethoxylated alcohol or C ₈-C ₁₈Those of acyl glyceride type) the form production and the sale of formation electroneutral compound.It shall yet further be noted that the concentration of amphoteric surfactant and the not complex form that weight ratio is based on surfactant in this article, any anion surfactant counter ion counterionsl gegenions are considered to the part of overall anion surfactant constituent content.

The examples of amphoteric surfactants of preferred type (b) comprises poly-carboxymethyl amine of N-alkyl polytrimethylene and salt, sell with trade name Ampholak X07 and Ampholak 7CX by Berol Nobel, particularly the salt of tri ethanol ammonium salt and N-lauryl-Beta-alanine and N-lauryl-imino-diacetic propionic acid.This class material is sold with trade name Mirataine with trade name Deriphat with by RHone-Poulenc by Henkel.

(ⅳ) zwitterionic surfactant

The water-soluble auxiliary zwitterionic surfactant that is suitable for being included in the composition comprises formula R ₅R ₆R ₇N ⁺(CH ₂) _nCO ₂The amido betaines of the alkyl betaine of M and formula (X II):

Wherein, R ₅Be C ₁₁-C ₂₂Alkyl or alkenyl, R ₆And R ₇Be C independently ₁-C ₃Alkyl, M are H, alkali metal, alkaline-earth metal, ammonium or alkanol ammonium, and n and m are respectively the number of 1-4.Preferred betaine comprises cocounut oil acylamino-propyl-dimethyl carboxyl methyl betaine, lauryl acylamino-propyl-dimethyl carboxyl methyl betaine and fatty acid acyl aminoalkyl betaine (RTM).

Be suitable for adding the alkyl sulfobetaines that water-soluble auxiliary sulfobetaines surfactant in the composition comprises formula (X III):

Wherein, R ₁Be C ₇-C ₂₂Alkyl or alkenyl, R ₂And R ₃Be C independently ₁-C ₃Alkyl, M are H, alkali metal, alkaline-earth metal, ammonium or alkanol ammonium, and n and m are respectively the number of 1-4.Preferred betaine comprises cocounut oil acylamino-propyl hydroxy sulfobetaines.

The water-soluble assisted oxidation amine surfactant that is suitable for adding in the composition comprises formula R ₅R ₆R ₇The acylamino-amine oxide of the alkyl amine oxide of NO and following formula (X IV):

Wherein, R ₅Be C ₁₁-C ₂₂Alkyl or alkenyl, R ₆And R ₇Be C independently ₁-C ₃Alkyl, M are H, alkali metal, alkaline-earth metal, ammonium or alkanol ammonium, and m is the number of 1-4.Preferred amine oxide comprises cocounut oil acylamino-propyl group amine oxide, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide.

The selectivity composition

Also can comprise many other selectivity compositions in the colouring compositions, with composition weight meter, every kind content is about 0.001% to about 5%, preferred about 0.01% to about 3%, more preferably from about 0.05% to about 2%.Specific examples of such components comprises protein and polypeptide and its derivative: but the anticorrisive agent of water-soluble or solubilising such as DMDM hydantoins, Germall 115, the methyl ester of hydroxybenzoic acid, ethyl ester, propyl diester and butyl ester, EDTA, Euxyl (RTM) K400, natural antiseptic agent such as benzylalcohol, potassium sorbate and bisabol (bisabalol) benzoic acid, Sodium Benzoate and 2-phenoxetol; Antioxidant is as sodium sulfite, quinhydrones, sodium hydrogensulfite, sodium metabisulfite and TGA, sodium dithionite, erythronic acid (erythrobic acid) and other mercaptan; Dye scavenging agent such as oxalic acid, sulfated castor oil, salicylic acid and sodium thiosulfate: stabilizer of hydrogen peroxide such as tin compound, as sodium stannate, stannic hydroxide and stannous octoate, antifebrin, N-acetyl group p-Phenetidine, colloidal silica such as magnesium silicate, hydroxyquinoline sulfate, sodium phosphate and tetrasodium pyrophosphate; And p-hydroxybenzoate; Moisturizing agent such as hyaluronic acid, chitin and starch-grafted Sodium Polyacrylate, as Sanwet (RTM) IM-1000, IM-1500, IM-2500, be purchased Materials from Celanese Superabsorbent, Portsmith, VA, USA, it is at US4, state in 076,663, and methylcellulose, starch, higher aliphatic, paraffin oil, aliphatic acid etc.; Solvent; Antiseptic such as Oxeco (phenoxy group isopropyl alcohol); Low temperature phase modifier such as ammonium ion source (as ammonium chloride); Viscosity-control additive such as magnesium sulfate and other electrolyte; Quaternary ammonium compound such as distearyl, dilauryl, dihydro tallow alkyl, alkyl dimethyl ammonium chloride, two cetyl diethylmethyl ammonium sulfate, ditallow dimethyl methyl ammonium sulfate, two soybean-based (soya) alkyl dimethyl ammonium chloride, two cocoyl alkyl dimethyl ammonium chlorides: hair conditioner such as siloxanes, higher alcohol, cationic polymer etc.; Colouring agent; The mica of titanium dioxide and titanium dioxide coating; Spices and spices solubilizer; Zeolite such as Valfour BV 400 and its derivative, and Ca ²⁺/ Mg ²⁺Chelating agent such as multi-carboxylate, aminopolycanboxylic acid's salt, polyphosphonic acid salt, aminopolyphosphonic acid salt etc.; Water softener is as natrium citricum.

Following non-limiting embodiment has exemplified composition.In these embodiments, except as otherwise noted, all concentration all is as the criterion with 100% active group, and all percentage number averages are percetages by weight, writes a Chinese character in simplified form to have following definitions:

Oxidants hydrogen peroxide

Oxidation dye 1 p-phenylenediamine (PPD)

Oxidation dye 2 para-aminophenol

Oxidation dye 3 m-aminophenols

Oxidation dye 4 2-amino-3-pyridone

Oxidation dye 5 4-amino-2-hydroxy-methylbenzene

Non-oxide dyestuff alkalescence red 76

The chelating agent ethylenediamine tetra-acetic acid

Surfactant 10 six/octadecyl APEO-25

Surfactant 2 cocoamidopropyl

Thickener 1 cetanol

Thickener 2 stearyl alcohols

The antioxidant sodium sulfite

Buffer acetate

Embodiment I-VII

Below be the hair-treatment composition of composition for hair dying form, they are representatives of the present invention. Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅶ 0.7 0.7 0.7 0.7 1.0 1.5 2.51 0.24 0.14 0.24 0.24 0.24 0.24 0.32 0.09 0.05 0.009 0.09--0.13 0.006 0.004 0.006 0.006 0.006 0.006-4 0.06 0.03 0.06 0.06 0.06 0.06 0.065-----0.5-----0.1--1 1.5 1.7 1.5 1.5 1.5-3.02-----1.5- 0.1 0.06 0.09 0.1 0.1 0.1 0.11 2.3 2.6 2．3 2．3 2．3 2.3 2.02 2.3 2.6 2．3 2．3 2．3 2.3 4.0 0.1 0.06 0.1 0.1 0.1 0.1 0.1---0.5--- pH 4.0 3.8 3.9 2.7---

In these embodiments, water is as diluent.But, in other cases, water also can partly replace with other diluent that accounts for water gross weight about 0.5% to about 50%, these diluents for example are lower alcohol such as ethylene glycol, ethylene glycol monoethyl ether, diethylene glycol (DEG), diethylene glycol monoethyl ether, propane diols, 1, ammediol, ethanol, isopropyl alcohol, glycerine, butyl cellosolve, ethoxydiglycol, hexylene glycol, polyglyceryl-2-oleyl ether and its mixture.

Claims (10)

1, a kind of hand-held packaged composition, but it comprises flow composition and the combination that is used for the packing of said composition, described packing comprises applicator and container, but described container has flexibility and resilience wall and comprises the storage of storage flow composition, described applicator has the lengthening separating element in a plurality of formation distributions cross section, be used for flowable composition being distributed by the displacement of the applicator on vertical with the cross section basically direction, described distribution cross section comprises a plurality of outlets, ordering about composition by the flexibility of container and resilience wall are pressed distributes through these outlets, wherein, when the pressure with 1.5Pa put on the flexibility of container and the resilience wall, 0.1g at least distributed on every square centimeter cross section each second, the composition of 0.5g at the most.

2, hand-held packaged composition according to claim 1, wherein, the cumulative surface of outlet be the distribution cross section at least 2%, be at most 10%.

3, hand-held packaged composition according to claim 1, wherein, composition is a hair-treatment composition.

4, hand-held packaged composition according to claim 1 wherein, is 2000S at shear strain rate ^-1Under when measuring, the viscosity of composition is not less than 0.01Pa.s, when being 10S at shear strain rate ^-1Under when measuring, the viscosity of composition is not higher than 5Pa.s.

5, hand-held packaged composition according to claim 1, wherein, the outlet have cumulative surface and the accumulation girth, make cumulative surface be the accumulation girth square value at least 0.05%, at the most 0.4%.

6, hand-held packaged composition according to claim 1, wherein, on the pressure with 1.5Pa puts on the flexibility and resilience wall of container, exert pressure 2 seconds the time 0.1g that on every square centimeter cross section, distributes each second at least, the composition of 0.5g at the most at least.

7, hand-held packaged composition according to claim 1, wherein, each lengthening separating element is the tooth of rigidity basically, and described tooth is arranged to a row at least, and the free end of each tooth has at least one outlet.

8, hand-held packaged composition according to claim 1, wherein, each lengthening separating element is the tooth of rigidity basically, and described tooth is arranged to a row at least, and the other end relative with free end of each tooth has at least one outlet.

9, hand-held packaged composition according to claim 1, wherein, container is that a kind of bottle contains bag-type container, is transmitted when bag is on arbitrary orientation thereby flowable composition can be contained at bottle.

10, hand-held packaged composition according to claim 1, wherein, container has vertically main, and the master of sensing of lengthening separating element and container is perpendicular direction vertically.

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