JP2001523500A - Product applicator - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention is a flowable formulation in a hand held package, wherein the package includes an applicator (114) and a container (10), the container having flexible elastic walls and a flowable formulation. A dispensing tank (24), the applicator includes a plurality of elongate parting members (144) forming a dispensing section, and the dispensing of the applicator in a direction substantially perpendicular to the dispensing section to fluidly dispense to a constant volume. The dispensing agent can be dispensed, the dispensing cross section has a plurality of outlets (146), and dispensing of the flowable formulation from the outlets by applying pressure to the flexible resilient wall (12) to provide a flexible resilient wall (146). When a pressure of 1.5 Pa is applied to 12), 0.1 g or more and 0.5 g or less of a flowable preparation is dispensed per 1 cm ² of the cross-section in 1 ^second. Related. In a preferred embodiment, the preparation is a hair dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to packaged formulation applicators, in particular, but not exclusively, time-efficient, controlled and non-staining, on the hair and / or scalp, The present invention relates to an applicator used to apply the hair and / or scalp preparation.

In the hair dyeing process, it would be desirable to be able to precisely control the flow of the hair dyeing solution and to accurately target the area to be colored by the hair dyeing solution. It would also be desirable to be able to minimize fouling during application and operation and to achieve a uniform color distribution throughout the area to be colored by the hair dye solution.

[0003] These objectives must be achievable even when a person trying to apply the hair dyeing solution wants to operate the applicator himself.

From US Pat. No. 4,290,027, a hair treatment device is fixed to a squeeze bottle containing the hair treatment solution, and the hair treatment solution is supplied through the discharge orifices of various applicators provided simultaneously by the hair treatment device. It is known for the user to send out.

[0005] One of the applicators has an elongated tip that is used primarily as parting means, and the other applicator is a brush or comb that is used primarily as a diffusing means. A valve is provided to allow the processing liquid to be sent to the parting and / or diffusion means.

[0006] A practical disadvantage of this conventional hair treatment device is that it is difficult to handle it in a controlled and clean manner.

[0007] Many hair treatment devices have an applicator in the form of an elongated discharge spout that gradually narrows along its length to a free end provided with a discharge orifice.

[0008] As disclosed in Japanese Utility Model Publication No. 7-22951, such a hair treatment device includes an internal passage for feeding a hair preparation from a discharge orifice of a spout to a plurality of small holes of teeth of a comb. It may also have a comb-shaped applicator provided.

For use, the comb is placed over the spout and press-fitted, the comb is extended beyond the free end of the spout, and along the part of the length of the spout by friction. Hold the comb.

[0010] A similar structure is disclosed in Japanese Patent Application Laid-Open No. Hei 9-118375, in which two liquids can be mixed and then sent out through a comb that can be detachably fixed to a nozzle by appropriate means. A method is disclosed. The two parts can form a hair dye.

[0011] Hair treatment devices generally include different types of applicators to suit various hair treatment situations.

For example, a delivery spout that can apply the hair preparation linearly, a delivery water-permeable member such as a cloth that spreads the hair preparation over the entire hair, and the hair preparation over the entire length of the hair It would be advantageous to have a delivery comb or brush that could be completely distributed.

In fact, US Pat. No. 4,211,247 discloses such a dispensing applicator, and also a non-dispensing sponge which is used only to spread the hair preparation after the hair preparation has been applied with the dispensing applicator. Has been disclosed.

The present invention is a hand-held packaged formulation having a combination of a flowable formulation and a package for the formulation, the package including an applicator and a container, the container having a flexible elastic wall and With the reservoir for a flowable formulation, the applicator includes a plurality of elongated parting members that form a distribution cross section and displaces the applicator in a direction substantially orthogonal to the cross section. This allows dispensing of the fluid formulation in a volume, the dispensing section has a plurality of outlets, and the pressure of the formulation from the outlets is increased by applying pressure to the flexible wall of the container. distribution is performed, when a pressure of 1.5Pa deflection elastic wall of the container, the cross-section of 1 cm ² per 0.1g or more per second, the following formulation is 0.5g It relates handheld package filling preparations being arranged.

[0015] Handheld is understood to mean that the user can hold the package with one or both hands. However, it does not necessarily mean that the packaged preparation is held by hand at the time of use.

[0016] A flowable preparation is one in which the preparation can flow under the action of gravity, for example a liquid, a paste,
It is understood to be a gel or powder formulation.

The container has a flexible elastic wall. Note that such flexing means that displacement by hand or finger pressure causes displacement of the wall, and when the displacement force is removed, the wall is elastic and returns to its original state. I want to be.

The applicator includes a plurality of elongate parting members that form a dispensing cross-section, and dispenses the flowable formulation into a volume by displacing the applicator in a direction substantially orthogonal to the cross-section. It should be understood that a dispensing cross section is a surface across which a plurality of elongated parting members and the space between the elongated members traverse. When the applicator is displaced in a direction perpendicular to the cross-section, a volume corresponding to a value obtained by multiplying the displacement of the applicator by the cross-sectional area of the applicator is indicated. In other words, if the elongated members have a common direction and are arranged in one or more rows, such as in the case of a comb or a brush, the cross-sectional area is the length of the comb and brush multiplied by the length of the elongated member. Equal to Thereby, the numerical value of the effective area of the applicator can be obtained. The amount obtained by multiplying the cross-sectional area of the applicator by the amount of displacement of the applicator, in the example of combing hair, is equal to the volume of hair passing through the cross-section during a constant displacement of the cross-section.

The dispensing section has a plurality of outlets, and the dispensing of the preparation from the outlet is performed by applying pressure to the flexible elastic wall of the container, and a pressure of 1.5 Pa is applied to the flexible elastic wall of the container. In this case, 0.1 g or more and 0.5 g or less of the preparation are dispensed per 1 cm ² of the cross section per ^second . When dispensing a smaller weight formulation at that pressure, it has been found that higher pressures are required to properly dispense the formulation. further,
When used in hair treatment, the preparation will not be thin in texture enough to be applied evenly along the hair. It has also been found that when delivering a higher weight formulation, the formulation will run off the hair, for example due to too fine texture, resulting in a smearing or ineffective application. In fact, it has been found that application is easy when using the packaged product according to the invention. In a preferred embodiment, 1.5 Pa
Is applied, 0.15 g or more and 0.45 g or less of the preparation are dispensed per 1 cm ² of the cross section in 1 ^second . In a further preferred embodiment, the flexible elastic wall of the container has one
. When a pressure of 5 Pa is applied, 0.2 g or more per square centimeter of the cross section per 1 ^{second is} 0. Up to 4 g of the preparation are dispensed. In a very preferred embodiment, when a pressure of 1.5 Pa is applied to the flexible elastic wall of the container, more than 0.25 g and less than 0.35 g of the preparation are dispensed per cm ² of cross section per ^second .

In a preferred embodiment, the outlet has a cumulative surface (> 2% and <10% of the distribution cross section).
cumulated surface). Note that each outlet has a surface that is an open surface where dispensing of the formulation takes place, and the cumulative surface is the sum of each of these. Also, the surface of each outlet may not necessarily be on a plane parallel to the cross section,
There is no need to be on a plane parallel to it.

In a preferred embodiment, the preparation is a hair treatment preparation. It should be understood that in hair treatment, for example, the preparation may be a hair dye.

In a preferred embodiment, the formulation comprises 0.01 Pa.s as measured at a shear strain rate of 2000 s ^-1 . s or more and 5 Pa.s when measured at a shear strain rate of 10 s ^-1 . s. This further improves the distribution of the preparation.

In a preferred embodiment, the outlet is such that the cumulative surface is no less than 0.05% and no more than 0.4% of the square of the cumulated perimeter. Having. According to the invention, the cumulative perimeter is the sum of the perimeters of the outlets of the applicator. By squaring this cumulative perimeter, the number having the dimension of the surface that can be compared to the cumulative surface of the exit (number having the dimension)
of a surface). In fact, it has been found that ratios above that range allow good distribution of the preparation. In a further preferred embodiment, the cumulative surface is greater than or equal to 0.075% and less than or equal to 0.3% of the square of the cumulative perimeter. In an even more preferred embodiment, the cumulative surface is at least 0.1% and at most 0.25% of the square of the cumulative perimeter. In a highly preferred embodiment, the cumulative surface is 0.12 of the square of the cumulative perimeter.
5% or more and 0.2% or less. For example, most preferably 28 outlets of a 1 mm ² square (other shapes such as circular or annular would also be preferred) and 0.5
thirteen outlets of 0.5 mm diameter, the thirteen outlets of 0.5 mm diameter being located at the junction of the elongated member and the applicator, one between each elongated member and thus 1
All four elongate members are provided in the same direction, and each elongate member further comprises ^two 1 mm ² square outlets at the end opposite the base, these outlets being alternated. Face to face. Such an arrangement of elongated members is 5 cm long, 5
cm is the length between the elongated members at the two ends along the direction perpendicular to the direction in which the elongated members extend, and since the length of each elongated member is 1.5 cm, the cross-sectional area of the applicator is 1.5 × 5 = 7.5 cm ² are obtained.

In a preferred embodiment, when a pressure of 1.5 Pa is applied to the flexible elastic wall of the container for at least 2 seconds, 0.1 g or more and 0.5 g or less of the preparation are dispensed per 1 cm ² of the cross section in 1 ^second. Is done. In a further preferred embodiment, when a pressure of 1.5 Pa is applied to the flexible elastic wall of the container for at least 5 seconds, 0.1 g or more and 0.5 g or less of the preparation are dispensed per 1 cm ² of the cross section in 1 ^second. . In an even more preferred embodiment, when a pressure of 1.5 Pa is applied to the flexible resilient wall of the container for at least 10 seconds, 0.1 g or more and 0.5 g or less of the preparation are dispensed per 1 cm ² of cross section per ^second. You. In a very preferred embodiment, when a pressure of 1.5 Pa is applied to the flexible elastic wall of the container for at least 18 seconds, 0.1 g or more and 0.5 g or less of the preparation is dispensed per 1 cm ² of cross section per ^second. Is done. When applied continuously, such pressure can be applied using, for example, compressed air. In fact, during manual use, pressurization time is the sum of multiple uses.

In a preferred embodiment, each of the elongated parting members is in the form of a substantially rigid tooth, wherein the teeth are arranged in at least one row and at least one of the outlets at the free end of each tooth. One is provided. In another preferred embodiment, each of the elongated parting members is in the form of a substantially rigid tooth, wherein the teeth are arranged in at least one row,
At least one of the outlets is provided at the end of each tooth opposite the free end. In a very preferred embodiment, each tooth is provided with at least two outlets, one outlet at its free end and the other outlet at an end opposite the free end. This allows the preparation to be distributed more evenly over the distribution cross section.

In a preferred embodiment, the container is a bag-in-bottle container, and the flowable formulation can be delivered regardless of the orientation of the bag-in-bottle container. In fact, this allows the packaged product to be used in any orientation.

In a preferred embodiment, the container has a main longitudinal direction and the elongated parting member is oriented in a direction substantially perpendicular to the main longitudinal direction of the container.

Preferably, the foamed, flocked or sponge material is in the form of a pad located at or near one end of the carrier. For ease of assembly, the carrier can be press-fit, more preferably screw-on, detachable from the spout. The pad can extend along only a portion of the outer circumference of the carrier to facilitate application, particularly when targeting a particular area.

Preferably, each of the elongated parting members is in the form of a substantially rigid tooth. The teeth can be arranged in at least one row for ease of manufacture, especially when molded from plastic material. When viewed from the end of at least one row, the teeth are:
It may have a generally triangular profile with different lateral dimensions, but this need not be the case. The flowable formulation may be released from the teeth to facilitate subsequent dispersion, for example, at least one of the outlets may be provided at the free end of each tooth.

Preferably, the elongated parting member and the support are removably separable from the housing. This allows a plurality of supports to be provided and the user to select one of the plurality of supports, the elongated parting members of different supports being of different types. For example, instead of a comb support having considerably rigid teeth, a brush support having flexible filaments can be used.

Preferably, the elongated parting member and the support are formed as a unit that can be fixed to the housing by fixing means including a catch. The catch is
The catch is resiliently deflectable and engageable with an opening through the housing, and the catch is releasable at a location remote from the elongated parting member. Additional catches can be provided that function as pivots. The resiliently deflectable catch must be releasable by finger pressure, but simply by rolling the housing on a hard surface to release the resiliently deflectable catch, the elongated parting member and support It would also be possible to remove the body from the housing.

[0032] For ease of assembly and strength, the housing is detachably screwed to the container and snaps together when the housing is fully screwed to the container in a predetermined alignment position. The lug means may be formed on both the housing and the container.

The spout can be push-fit or more preferably screw-fit to the container.

Flowable formulation as it passes through an applicator in the form of a spout before it is delivered from an applicator formed by a housing and a support having a plurality of elongated parting members protruding therefrom. To facilitate delivery of the agent, a guide tube may be provided in the housing to receive the free end of the spout when the housing is placed over the spout.

[0035] Preferably, the container is a bag-in-bottle container, so that the flowable formulation can be delivered regardless of the orientation of the bag-in-bottle container.

In such a container, the inner collapsed layer forms a tank and the outer deformable layer is separated from the inner collapsed layer by a buffer region. The valve means includes a buffer region (
The flow of air into the bottle) and the flow of the flowable formulation out of the tank (bag) can be controlled. The valve means may include a one-piece valve member in order to simplify assembly and thus obtain commercial advantages.

In practice, the valve member includes an annular flapper valve that controls the opening of one or more air inlets of the spout, wherein the annular flap valve comprises a single annular flapper valve in the spout. Surrounding a central quadrolobe valve that controls the opening of the elongate passage, which is push-fit into a single elongate passage at the spout. Preferably, the valve is held in the spout by a preferably annular device.

It will be appreciated that the flowable formulation may be a hair and / or scalp formulation.

Next, an applicator system according to the present invention will be described in detail by way of example with reference to the accompanying drawings.

The accompanying drawings illustrate an example of a hair dye kit embodying all aspects of the present invention, and illustrate various inventive features sought protection in this patent application and in several concurrent patent applications. Aspects relate to various applicators and applicator systems, as well as the delivery system used in delivering the flowable formulation.

The flowable preparation is preferably a hair dye, but none of the embodiments of the invention is limited to such a specific flowable preparation. Other examples of flowable preparations are agents such as pet care, foods such as cake mixes, detergents such as clothing or carpet care, cosmetics such as body lotions or moisturizers, adhesives or lubricants.

The use of hair dyes will be problematic.

One problem is that the hair dye must be prepared from more than one compounding material immediately prior to use. This means that the ingredients must be stored separately, allowing the user to mix the ingredients when needed. Generally, one compounding material is hydrogen peroxide and another compounding material is a dye. However, when adding the dye to the hydrogen peroxide, there should be no risk of fouling to the user.

Another problem is that the hair dye must be able to be applied to the hair with the applicator at any angle. When feeding the applicator from a simple squeeze bottle, when the squeeze bottle is full, the applicator will be ready to use in any orientation. However, as the contents of the squeeze bottle gradually decrease, the applicator cannot be used immediately in either direction, and it is necessary to first prepare the supply in order to offset the effect of the hair dye reabsorption. There will be. This makes it difficult to control the application of the hair dye, especially to the hairline, while avoiding skin stains.

The present hair dyeing kit allows the preparation of a hair dye just before use, and the hair dye is released by a mechanically generated pressure difference (not an aerosol), and the hair dye in any orientation It can have an applicator supplied by a user controlled delivery system that can always release the agent immediately.

An omnidirectional delivery is preferably possible for all of the released hair dye, which can be more than 90% and even 95% of the prepared hair dye.

The present hair dyeing kit further allows the hair dye to be delivered in a user-adjusted amount via an applicator to a specific area, thereby achieving a uniform color distribution with minimal soiling.

[0048] Even with careful operation, no applicator is equally suitable for applying the hair dye to the base, hairline and the majority of the hair with one applicator . Accordingly, it is common to prepare different types of applicators selected from wire applicators, surface applicators and brush / comb applicators. The wire applicator can be a spout with one outlet and the surface applicator can be made of a porous material with multiple outlets. The brush / comb applicator can have a plurality of outlets for delivering hair dye, and the hair dye then has a plurality of elongate paring members.
ting member). As expected, the elongated parting member will resemble the bristle or comb teeth. All different types of applicators can be in fluid communication with a container of hair dye.

The possible advantages of the present hair dyeing kit are as follows. It comprises: (a) preferably one of three different types of applicators;
Only one is exposed during use, eliminating the risk of soiling being caused by hair dye remaining inside or on other applicators during hair treatment. (B) Preferably, the surface applicator of the three different types of applicators is foamed, sponged or floked with an elastically compressible porous structure to improve hair dye diffusion It is formed of a material. (C) Preferably, for a brush / comb applicator of three different types of applicators, at least two of the outlets are each formed in a corresponding elongated parting member to improve the dispersion of the hair dye. ing.

Another advantage of the present hair dyeing kit is that the integral valve simultaneously serves the dual function of controlling the inflow of air and the outflow of the hair dye, while the support of the elongated parting member is Fixed to the housing by at least one catch releasable at a location remote from the brush and, with the wire applicator attached to the container, the brush /
It is possible to place the comb applicator over the wire applicator and still attach it directly to the container.

Before describing the surface applicator with reference to FIGS. 7 and 8 and the brush / comb applicator with reference to FIGS. 9-12, the line applicator with reference to FIGS. The following describes a delivery system that incorporates.

The bottle 10 can be provided with a hollow body 12 having a substantially elliptical cross-section, closed at the lower end and provided with an open neck 14 at the upper end. An external thread 16 may be attached to the neck. Further, a pair of opposing lug means 18 can be formed on the neck 14, only one of which is shown in FIG. Each of the lug means 18 preferably has a gap 20 to which the ramp 22 approaches for the purpose described below.

At least the body 12 is formed of an elastically deformable plastic material, and the bottle 1
When 0 is released from the squeezed state, it can quickly return to the original shape. The plastic material is low density polyethylene or linear low density polyethylene (LL
DPE) or polypropylene and may be transparent. If not transparent, the plastic material is preferably translucent and may or may not be colored.

By sealing two superposed sheets 26 of the same shape along most of the common perimeter to form a side sealed pouch having an upper opening 28 and a lower V-shaped edge 30, the flexible bag 24 can be formed. Bag 24 forms a tank for the first material, such as hydrogen peroxide, and must therefore have good waterproofing. Each sheet 26 can be made of a laminated metallized material and is preferably LLD
Includes three layers of PE sealant / adhesive / metallized PET (polyethyl terephthalate).

By inserting the bag 24 from the neck 14 into the bottle 10, as shown in FIG. 4, the outer deformable layers (the body 12
) And an inner collapsed layer (sheet 26).

As shown in FIG. 4, support tube 34 can be inserted into bag 24 through opening 28. The tube 34 can have a plurality of holes 36 along its length and can form at least some rigid channels that are open in cross section. The lower end 38 of the tube 34 may be open or closed. The lower end 38 of the tube 34 may be in contact with the bag 24, but preferably the lower end 38 of the tube 34 is close to but not in contact with the V-shaped edge 30 of the bag 24. The upper end of tube 34 can be secured to bayonet 40 by any suitable method or means,
It can be simply pushed onto the plug 40.

The insert 40 is partially insertable into the bag 24 through the opening 28 and is also partially insertable into the bottle 10 from the neck 14. Preferably, the bayonet is permanently liquid tightly secured to the sheet 26 around the opening 28, such as by heat or ultrasonic welding. Alternatively, the insert 40 and the bag 24 can be made in one piece. The bayonet 40 is preferably immovably secured to the neck 14 by a simple push-fit or other suitable method or means, but can be removed by a user to make the system refillable. It may be.

As shown in FIGS. 2, 4 and 6, the insert 40 includes a tubular member 42 that forms an orifice and extends centrally of the side wall 44, and a pair of opposing transverse walls 46. It can be a one-piece plastic molding having a lower portion 48.

As shown, an outward flange 50 is provided at the upper end of the side wall 44 to limit insertion of the insert 40 into the bottle 10 and is substantially intermediate between the flange 50 and the transverse wall 46. Is provided with an inward rib 52. As shown,
A plurality of holes 54 are provided in the transverse wall 46 to couple the buffer region 32 to an annular channel 56 formed between the tubular member 42 and the side wall 44 and thus surrounding the tubular member 42.
Is pierced. The opposing lower portion 48 is illustrated as hollow and prevents sinking of the molded article, thereby facilitating a liquid-tight fixation of the insert 40 to the bag 24.

The lower end of the tubular member 42 is provided with an inward recess for accommodating the upper end of the tube 34, and the upper end of the tubular member 42 may be chamfered inward. it can.

Generally, the bag 24 is supplied to a user in a state where the bag 24 is partially filled with a first material such as hydrogen peroxide. Therefore, it is necessary to prevent the first material from escaping through the tube 34 and the tubular member 42. A removable flip top cap can be provided to close the upper end of the tubular member 42. Alternatively, the upper end of the tubular member 42 can be closed with a breakable film seal. But,
Preferably, a removable cap 58 is provided as shown in FIG.

The cap 58 can also be a one-piece plastic molding and can have a plug seal 60 for sealing and closing the upper end of the tubular member 42. Cap 5
The fixing part 62 of 8 can be fitted in an airtight manner on the neck 14 of the bottle 10. However, it is advantageous to form the fixed portion 62 of the cap 58 in a non-hermetic fit. For example, a female thread 64 can be provided that is threadably ventilated to the male thread 16 on the neck 14 of the bottle 10 to form an air passage from the annular channel 56 to the atmosphere.

One advantage is that if the hydrogen peroxide in the bag 24 becomes unstable and generates oxygen, the bag 24 will expand and the air in the buffer area 32 will pass through the holes 50 in the plug-in 40. , Between the screws 16 and 64.

Another advantage is that if the buffer region 32 experiences an undesired pressure change, for example due to the movement of air, air can still escape from or enter the buffer region 32 by the above-mentioned path. .

A hair dye kit as described above allows a user to prepare a hair dye or other flowable formulation immediately prior to use.

In practice, at least the second material is added to the first material in the tank. If the tank is supplied empty or has been emptied from a previous use, it will of course be necessary to first add some first material to the tank. In any case, it is necessary to be able to mix the initially separated materials.

As schematically shown in FIG. 4, the second material can be stored in a completely independent container 66. If the first material is hydrogen peroxide, the second material is likely to be a dye. If the dye reacts to oxygen, the container 66 must have excellent oxygen barrier properties. Further, if the dye is in a form such as a gel, cream or paste, the container 66 would have to be plastically deformable, for example, so that the user can squeeze the dye. On the other hand, if the dye is in a liquid state, it will be able to flow out of the container 66 under the effect of gravity.

If the container 66 is elastically deformable, the bag 24 is preferably inflated with air above the first material, and if the container 66 is not elastically deformable, the bag 24
Is preferably contracted.

The user is provided with a plurality of containers 66, each of which can include a different material, such as a different shade of hair dye, and which pours one or more contents of the container 66 into a tank. This makes it possible to form special flowable preparations, such as hair dyes, of a particularly selected shade.

The container 66 or each of the plurality of containers 66 desirably includes a long nozzle 68 that can extend completely through the tubular member 42 and into the tube 34. Thus, even when the user is squeezing the container 66 using both hands, the container 6
6 becomes difficult to separate from the bottle 10, so that a good connection can be obtained. In addition, since the contents of the container 66 are jetted directly into the contents of the bag 24 from a short distance, good mixing can be promoted. Of course, prior to insertion of the long nozzle 68 into the tubular member 42, the container 66 must be opened, and the opening may break, cut or twist the nozzle tip 70 (shown in dashed lines in FIG. 4). Can be done by taking.

As the second material is poured from the container 66 into the bag 24, the volume of air above the first material in the bag 24 gradually decreases, and such compressed air is used to prevent inflation of the bag 24. Need to promote escape.

If the nozzle 68 is loosely fitted to the tubular member 42, the compressed air will escape from the loosely fitted portion. Alternatively, one or more splines may be applied to the nozzle 68
And / or one or more castellations may be formed in the dye container near the base of the nozzle 68. Depending on the nature and bulk of the second material in the container 66, the compressed air may be directed upwardly through the second material to cause the air pockets in the bag 24 to expand as the air pockets shrink. , Container 66
Can be formed within.

Even if the bag 24 is inflated, air in the buffer area 32 will escape through the holes 54 in the transverse wall 46 of the bayonet 40, as described above.

After enough second material has been added to the first material, the container 66 is removed from the bottle 10 and discarded or resealed for future use.

Instead of adding the second material to the first material by pouring, it is formed in the bag 24 or placed inside it and can be broken by squeezing the barrel 12 of the bottle 10 or the like. The second material can be accommodated in a container in which the second material can be added to the first material by the above method.

When the second materials have been added to the first materials, they are preferably mixed by shaking the bottle 10 at this stage. While shaking, the user could place a gloved finger on the upper end of the tubular member 42 to prevent the contents of the bag 24 from escaping. However, it may be more convenient for the user to re-fit the cap 58 so that the plug seal 60 closes the upper end of the tubular member 42. In either case, the tube 34 acts to restrain the bag 24 during the swinging, reversing, or both, of the bottle 10 so that the contents of the bag 24 move more freely than the bag 24. This promotes mixing. If about 10% of the volume of the bag 24 is left as head space, it is believed that optimum mixing by shaking occurs. If both the bag 24 and the barrel 12 of the bottle 10 are translucent, a visual inspection can be made as to whether mixing is complete.

In order to prepare for the release of the flowable formulation formed by the first and second materials, more specifically the hair dye formed by hydrogen peroxide and the dye, the insert 40 is again exposed. As shown in FIGS. 5 and 6, the spout 72
Can be attached to the plug 40.

The spout 72 is also a one-piece plastic molding, here a cylindrical part 74 and
It has a subsequent dome-shaped portion 76 followed by a tapered portion 78. An outward rib 80 is formed at the bottom end of the cylindrical portion 74. The upper end of the cylindrical portion 74 is formed adjacent to a shoulder 82 provided by a dome-shaped portion 76. One or more, for example, three, air inlets 84 extend through the dome-shaped portion 76 and may be circumferentially equally spaced around the dome-shaped portion 76. An elongated passage 86 is defined in the tapered portion 78 which gradually narrows along its length from a large lower end to a single outlet 88 at a smaller upper end. An annular recess 90 is formed in the inner surface of the tapered portion 78 near the large lower end of the passage 86. An annular rib 92 is formed on the outer surface of the tapered portion 78 near the small upper end of the passage 86.

A valve member 94, which can be made of a silicone polymer and can be made in one piece, can be attached to the spout 72.

The valve member 94 preferably includes an inlet portion in the form of an annular flapper valve 96 that functions as a one-way check valve for controlling the flow of air from the air inlet 84.

The valve member 94 further comprises a central quadrolobe valve 9 which functions as a one-way check valve for controlling the outflow of the hair dye from the passage 86.
Preferably, it comprises an outlet section in the form of an eight. The four-lobe valve 98 is preferred because it opens the hair from the center rather than the sides, thereby further smoothing the flow of hair dye. However, as a modification of the four-lobe valve 98, the outlet portion of the valve member 94 may be a flap valve, an umbrella valve, or a duckbill valve.

The flap valve 96 and the four-lobe valve 98 include a transverse sealing wall 100 and a frustoconical positioning wall 102, on the outer surface of which an annular rib 104 is provided.

By pushing the four-lobe valve 98 into the passage 86 until the annular rib 104 on the valve member 94 engages the annular recess 90 in the spout 72, the valve member 94 engages the spout 72. Easy to install.

Next, until the rib 80 of the annular portion 74 of the spout 72 clicks over the rib 52 of the insert 40 or at least snaps into place with its feel.
The spout 72 is easily attached to the spigot 40 by pushing the cylindrical portion 74 of the spout 72 into the annular channel 56 of the spigot 40, with the shoulder 82 of the spout 72 being inserted. Abuts the flange 40 of the fitting 40 and the sealing wall 100 of the valve member 94 sealingly engages the upper end of the tubular member 42 of the bayonet fitting 40.

In the modified structure, the spout 7 is screwed instead of the push-fit type described above.
2 can be attached to the plug 40.

After attaching the spout 72 to the insert 40, the bottle 10 can be shaken to mix or remix the flowable formulation.

The user squeezes the body 12 of the bottle 10 in order to send the hair dye from the bag 24 to the outlet 88 of the spout 72, and to release the hair dye linearly at the base of the hair or the like. . This compresses the air in the buffer region 32, but this compressed air passes through the fluid passage including the hole 54, the annular channel 56 and the air inlet 84 because the flap valve 96 acts to close the air inlet 84. Can not escape. Instead, the compressed air partially shrinks the bag 24 so that some hair dye is open to allow the tube 34, tubular member 42, frustoconical positioning wall 102, and hair dye to be released. It is extruded through a fluid passage containing a shape valve 98. When the user stops squeezing the body 12 of the bottle 10, the bottle 10 quickly returns to its original shape and the buffer area 32 expands. Closing the four-lobe valve 98 prevents hair dye from being sucked back past the four-lobe valve 98 and the bag 24 partially maintains its compressed state. Instead, air is drawn into the buffer area 32 through a flap valve 96 that is open to allow air to flow in from the air inlet 84.

The user may press the barrel 1 of the bottle 10 at the pressure and frequency considered suitable for the situation.
Repeat the aperture of 2.

The holes 36 of the tube 34 can prevent the hair dye from being caught when the bag 24 gradually contracts and the sheets 26 of the bag 24 come into contact with each other, and the tube 34 itself also contracts. It will be appreciated that the flowable formulation in tube 34 can be released.

When delivering the hair dye, the user will be able to see that the bag 24 is deflated through at least the translucent body 12. This will reassure users who are afraid that the hair dye will suddenly run out.

The tank for the first material may be a side sealed pouch as described above,
Other shapes are possible, for example, an inverting-half-bag
It is also possible to provide an inner shrinkable layer distinguished from the outer deformable layer by a bottle or delaminating bottle, or by a compression blown bag integrally molded with the bayonet. In the case of a layered bottle, it is preferable that the bottle is sequentially peeled from the neck.

[0092] Further, as described above, the valve member is an integral structure but can have a dual function, but the valve member can also take other forms, for example, a hair dye agent. Separate valves can be provided for controlling the outflow and the inflow of air, the inflow of air being a simple air hole, probably located in the body of the bottle and closed by the user.

Referring now to FIGS. 7 and 8, the surface applicator 106 includes a spout 72.
Is fixed so as to be removable over the outlet 88. More specifically, the surface applicator 106 can include a pad 108 of foam, sponge, or flocking material having a resiliently compressible porous structure. Such a structure not only has a plurality of outlets, but also the hair dye coming out of outlet 88
And carefully manipulated so that it can be spread evenly along the hairline. The pad 108 can be located at or near the upper end of the carrier 110, with the lower half of the carrier 110 frustoconical in a direction from the smaller upper end to the larger lower end. An annular recess 1 is provided on the inner surface of the lower half of the carrier 110.
When the carrier 110 is pressed onto the spout 72 by providing the spout 12, the spout 72
The upper annular rib 92 can be detachably engaged. The carrier 110 and the spout 72 can have a mutual structure that can prevent relative rotation. To facilitate accurate application, pad 108 may have a curved surface that extends along only a portion of the circumference of the upper half of carrier 110. If the pad 108 is made of a plastic material and the carrier 110 is also made of a plastic material, the pad 108 can be fixed to the carrier 110 using an adhesive. Of course, if the original surface applicator 106 is not to be cleaned and reused, a similar series of disposable or a different series of replaceable surface applicators 106 can be provided.

As shown in FIGS. 9-12, instead of the surface applicator 106, a brush / comb applicator 114 can be removably secured over the outlet 88 of the spout 72, The brush / comb applicator 114 includes a housing 116
And a removable unit 118.

The brush / comb applicator 114 can be screwed or snapped onto the neck 14.

The housing 116 is also a one-piece plastic molded product. When viewed from the top, an opening 120, a tapered open chamber 122 provided with a series of slotted webs 124 on the main side walls on both sides, and a chamber 128 are formed as chambers 122. Guide tube 126 that is in open communication with
A slot 130 at the upper end of the chamber 28, a female screw 132 near the lower end of the chamber 128, and a pair of opposed lug means 134 at the lower end of the chamber 128 are formed.

The female screw 132 is preferably removable from the mold without twisting.

The housing 116 can be removably screwed to the bottle 10 by engaging the internal thread 132 in the chamber 128 with the external thread 16 of the neck 14.
As the housing 116 is sequentially screwed, the outlet 88 of the spout 72 enters the guide tube 126. Finally, the lug means 134 cams along the ramp 22 of the lug means 18 to snap into the gap 20 of the lug means 18. When the snap fits, a click or at least the feel is obtained and the housing 1
Reference numeral 16 indicates that the bottle 10 is completely screwed. In this final position, remembering that the cross section of the body 12 is substantially elliptical with the lug means 18 and 132 engaged with each other, the chamber 122 opens in the direction of the long axis of the body 12.

The detachable unit 118, which is the last component of the hair dyeing kit, can also be formed as an integrally molded article from a plastic material such as polypropylene to which silicone or the like is added to reduce the coefficient of friction. it can.

By making the removable unit 118 at least partially translucent,
The user can be notified that the flowable formulation is about to be delivered.

The unit 118 includes a support 136 that is tapered from a generally flat, narrow upper end to a wider lower end. The narrow upper end has a catch 13
8 extend from which a barbed tip 138a extends. A rigid catch 140 extends from the wide lower end, and a barbed tip 140a extends therefrom. Around the support 136, a skirt 1 having an outer shape corresponding to the opening of the chamber 122 is provided.
42 are formed. A plurality of elongate parting members, such as substantially rigid teeth 144, can be resiliently deflected from support 136, rigid catch 140, rigid catch 140
And the skirt 142 protrudes in the opposite direction. A plurality of outlets 146 for the flowable formulation can extend through the support 136.

As best shown in FIG. 9, the teeth 144 can be arranged in two rows. When viewed from the ends of the two rows, the teeth 144 can, but need not, have a generally triangular profile with different lateral dimensions. Tooth 14
The lateral dimension of 4 can gradually increase from the narrow upper end of support 136 to the wide lower end of support 136. In addition, the different rows of teeth 144 may be staggered, again having a generally triangular profile, but having approximately the same thickness when viewed from the side of the two rows.

As best shown in FIG. 11, at least two of the outlets 146,
Perhaps all extend further through each tooth 144. But exit 1
It may be desirable for one or more of 46 not to penetrate teeth 144. For example, at least one outlet 146 can be provided in support 136 between adjacent teeth 144. At least two, and perhaps all, of the outlets 146 passing through the teeth 144 can be exposed at the orifices 148 at the free ends of the teeth 144.

Indeed, it is convenient to state that the orifice 148 is at the free end of the tooth 144, but in part to avoid directly covering the scalp, As a result of a suitable shaping technique known as a passing face shut off technique which allows the orifice 148 to be formed by a simple two-piece mold without the need, the orifice 148 is free of teeth 144. It is in a position slightly retracted from the end.

In order to assemble the unit 118 into the housing 116, it is only necessary to fit the barbed tip 140a of the rigid catch 140 into the slot 130 and then rotate it. This allows the free edge of the skirt 142 to engage the slotted web 124 and allows the barbed tip 138 a of the catch 138 to flex so that the catch 138 fits into the opening 120. A barbed tip 138 a of the catch 138 emerges from the opening 120 and the housing 1 around the opening 120.
When snap-engaged with the sixteen materials, the unit 118 is fully secured to the housing 116.

To remove unit 118 from housing 116, the reverse procedure is followed.
The catch 138 can be released by being pushed away by finger pressure. Alternatively, the housing 116 may be rolled over a hard surface so that the hard surface
The catch 138 can also be released by pushing the barbed tip 138a of 38 back into the opening 120. Release of catch 138 is orifice 14
It will be understood that this takes place at a location remote from E.8.

One reason for removing the unit 118 from the housing 116 may be to make it easier to clean the residual hair dye.

Another reason for removing unit 118 from housing 116 would be to allow it to be replaced with another unit 118 of a different type. For example, a substantially rigid tooth 144 having a comb structure may be replaced with a brush-like structure having a plurality of resiliently deflectable bristles, a sponge-like structure, and teeth and orifices different in size and / or shape. It may be desirable to replace it with another comb structure having both or either of the following. This will facilitate complete dispersion of the delivered hair dye in different situations, such as different hair lengths or different hair types.

The size, location and shape of the orifices 148 can be adjusted for the flowability of the hair dye or for different hair dyeing results, such as root covering, streaking or highlighting, as individual units 118 are required. Will be changed. The different ingredients may be added separately or in combination to modify the flowability of the formulation,
Or it can make the prevention of hair tangling easier. Such components include the following, which are listed together with the preferred maximum proportions by weight of the components in the preparation.

Raw material name Preferred maximum ratio % W / W Rheology modifier name Hydroxyethylcellulose 7.0 Cetylhydroxyethylcellulose 7.0 Silica (7631-86-9) 7.0 Bacterial rubber 7.0 Hydroxypropyl starch phosphate 10 0.0 Carbomer 10.0 Acrylate / C10-30 Alkyl Acrylate Cloth 10.0 Polymer Hydroxypropyl Guar 5.0 Guar Hydroxypropyl Trimonium Chloride 5.0 Hydroxypropyl Guar Hydroxypropyl Trimonium Chloride 5.0 Peg-150 / stearyl Alcohol / SMDI copolymer 10.0 acrylate copolymer 10.0 acrylate / steareth-20 methacrylate copolymer 10.0 acrylate / cetes-20 copo Mer 10.0 Hydroxypropylcellulose 7.0 PVM / MA decadiene crosspolymer 10.0 Polyquaternium 32 + mineral oil + PPG-1 tridecess 6 7.0 Polyquaternium 37 + mineral oil + PPG-1 tridecess 6 7.0 Polyqua Ternium 32 + propylene glycol dicaprylate 7.0 Mineral PPG-1 Trideceth 6 Dextrin 7.0 Hydroxybutyl methylcellulose 7.0 Guar gum 7.0 PEG-2M to PEG-160M 7.0 Sodium carbomer 7.0 Tapioca starch 10. 0 Xanthan gum 7.0 Yeast polysaccharide 10.0 Trihydroxystearin 5.0 Polyacrylamide / isoparaffin of C13-14 / 7.0 Laureth-7 acrylamide copolymer / paraffin oil / isopara Infin / 7.0 Polysorbate 85 Succinoglycan 5.0 Conditioner / Tangle Prevention Aid Peg-150 Distearate 5.0 Peg 60 Hydrogenated Castor Oil 5.0 Quaternium-22 10.0 10.0 Quaternium 80 5.0 Polydecene 0 PEG (generic name covers PEG4 to PEG115M) 5.0 Panthenyl hydroxypropyl steardimonium chloride 4.0 Dimethicone copolyol midiformate 4.0 Polyquaternium 6 5.0 Polyquaternium 7 7.0 Acrylamidoproyltrimonium chloride / 7.0 Acrylamide copolymer PEG-2 dimidofomamidoethylmonium methsulfate 5.0 Octyldodecylmidformate 5.0 Octyldodecylmidformate 5.0 Cocamidopropyl Betaine 5.0 Dimethicone Copolyol 5.0 Dimethicone Copolyol Acetate 5.0 Glycine 5.0 Hydroxypropyl Trimonium Hydrolyzed Soy Protein 5.0 Hydroxypropyl Trimonium Hydrolyzed Wheat Protein 5.0 Hydroxypropyltrimonium hydrolyzed honey protein 5.0 Oleyl betaine 5.0 Oleyl alcohol 5.0 Polysilicone-1 to Polysilicone-10 5.0 Silicone quaternium-1 to Silicone quaternium-13 5.0 Quaternium-8, 14, 16, 22, 26, 27, 33, 5.0 52, 53, 56, 60, 61, 63, 70, 72, 75, 77, 78, 80, 81, 82, 83, 85, 86 Cetyl alcohol 5.0 Ceteareth-25 7.0 Stearyl alcohol 5.0 Polyquaternium-10 5.0 Polyquaternium 4 5.0

In another embodiment, the applicators for the packaged preparation are all screwed to the container, thus allowing for a better seal. In the case of a further conceivable use of a comb or nozzle, the comb is screwed onto the nozzle so that the comb is well fixed and 1
When changing one applicator to another, it is preferable to reduce the hassle. Furthermore, this may make the comb shorter. To further secure the comb on the nozzle, a propeller structure can also be integrated with the nozzle, preventing rotation of the comb associated with the nozzle in use. Other improvements include a spacing tip on the nozzle, which holds the valve by itself.

The comb has a structure having a shape that becomes thinner toward the tip, and contributes to reducing residuals in the comb after use and avoiding pressure loss toward the tip of the comb. It should also be noted that

The filling orifice for the container preferably has an ophthalmic shape so that venting during filling can easily occur. Another improvement is to have the tube made with a double "C" section instead of a closed "O" section, and therefore the product in the tube. To allow better access. This is preferably combined with a bag-in-bottle type container.

As a general matter, for all purposes herein, the first container to contain the first material includes a bottle when mated with any one of the different applicators, or a combination thereof. Can be interpreted as

As another general matter, for all purposes herein, a flowable formulation may demonstrate pseudoplastic flowability, which means that when subjected to shear, Once the viscosity of the flowable formulation has decreased and the shearing action has ceased, the internal structure of the flowable formulation (which can respond to the original viscosity) rebuilds very quickly to reach the internal structure of the original viscosity. To increase viscosity.

The flowable preparation is capable of exhibiting the above-mentioned pseudoplastic flowability within a range of a shear strain rate of 0.01 s ^{−1 to} 10,000 s ^−1. This is the most promising range of shear strain rates available when the agent is a hair dye.

One example of a flowable formulation has a pH of 0.2 when measured at a shear strain rate of 2000 s ⁻¹ . 01 Pa. s or more (preferably 0.15 Pa.s or more) and 5 Pa.s when measured at a shear strain rate of 10 s ^-1 . s or less (preferably 1.4 Pa.s or less).

The packaged preparations according to the invention preferably comprise a hair treatment preparation, more preferably a hair dye. As used herein, the term "hair dye" refers to the low pH (about 1 to about 4.5) of inorganic peroxygen based dye oxidants and oxidative colorants.
Used in the broad sense that it is intended to include preparations containing the combinations herein of mixtures. In addition, it is also intended to include multiple preparations that contain other components which may or may not be active ingredients. Thus, the term "hair dye" refers to a mixture of active oxidizing and oxidizing colorants, as well as, for example, oxidizing aids, sequestering agents, stabilizers, thickeners, buffers, carriers, surfactants, It is intended to apply to formulations containing such things as solvents, antioxidants, polymers, non-oxidative dyes and conditioners.

Preferably, the hair dye comprises an inorganic peroxygen-based oxidant (a) and an oxidative hair dye (b
) Wherein the pH of each of (a) and (b) is from about 1 to about 4
. 5 and the pH of the combined mixture of (a) and (b) is from about 1 to about 4
. 5 range. Preferably, the pH of (a) and / or (b) is about 1.5
To about 4.5, more preferably from about 2 to about 4.4, and most preferably from about 3.6 to about 4
. 3, particularly in the range of about 3.8 to about 4.2, and the preferred pH of the combined mixture of (a) and (b) is about 1.5 to about 4.5, more preferably about 2 to about 4. 4, most preferably in the range of about 3.6 to about 4.3, especially about 3.8 to about 4.2. In addition to the inorganic peroxygen oxidizer, the preparation may optionally include (among other components) a preformed organic peroxyacid oxidizer. Organic peroxyacid, as used herein, is intended to cover any organic peroxyacid material that can act alone or in combination with a peroxygen oxidizing agent to oxidize a dye precursor.

Methods of Dye Oxidation and Hair Dyeing Successful coloring of human or animal hair with oxidation dyes generally requires treating the hair with a mixture of an oxidizing agent and an oxidizing hair dye. Is understood.
As mentioned earlier herein, the most common oxidizing agent is hydrogen peroxide.

[0121] Hydrogen peroxide has a pKa in the range of about 11.2 to about 11.6, and about 9 to about 12
It is commonly used as a dye oxidizing agent at a pH in the range of Improvement of color development is about pH1
It is observed in combination with an improved wash fastness of the color at a pH ranging from about pH 4.5 to about pH 4.5, preferably from about pH 3.8 to about pH 4.3, more preferably from about pH 3.8 to about pH 4.2.

The inorganic oxidizing agent preparation preferably includes at least one inorganic oxidizing agent (hereinafter referred to as "inorganic peroxygen oxidizing agent"). Inorganic peroxygen oxidizing agents should be safe and effective for use in the formulations herein. Preferably, inorganic peroxygen oxidants suitable for use herein are soluble in the formulations of the present invention when in liquid form and / or in the form intended to be used. Preferably, inorganic peroxygen oxidants suitable for use herein are water-soluble. Water-soluble oxidizing agent such as described herein, refers to an agent that has a solubility to the extent of about 10g of deionized water in 1000ml at 25 ℃ ( "Chemistry" CE Mortimer , 5 th Edn. P
277).

The inorganic peroxygen oxidizing agents useful herein are generally inorganic peroxygen substances that can produce peroxides in aqueous solutions. Inorganic peroxygen oxidizing agents are well known in the art and include, for example, hydrogen peroxide, inorganic alkali metal peroxides such as sodium periodate, sodium perbromate and sodium peroxide, and inorganic perhydration. Hydrochloride compounds, for example, alkali metal salts such as perborate, percarbonate, perphosphate, persilicate and persulfate. These inorganic perhydrate salts can be incorporated as monohydrate, tetrahydrate and the like. Mixtures of two or more such inorganic peroxygen oxidants may be used if desired. Alkali metal bromates and iodates are suitable for use herein, with bromates being preferred. Highly preferred for use in the preparation is hydrogen peroxide.

Under low pH conditions, improved initial color development, color consistency, wash fastness and color intensity (using equal levels of peroxides and dyes) over conventional high pH systems, and Provides equivalent color development to conventional systems at high pH, while using low inorganic peroxygen oxidizing agents (down to 75%), as well as substantially low oxidation hair dyes (down to 50%) ), It is also possible to supply an equivalent color development to a conventional high pH system. Thus, low pH hair dyes can be formulated to reduce the level of hair damage, as well as the level of skin irritation and dyeing. Furthermore, since the low pH hair dyes can be formulated without ammonia, the negative nature of ammonia-related odor or skin irritation associated with these formulations is not observed.

The inorganic peroxygen oxidizing agent is preferably present in the formulations of the present invention at a molar level of from about 0.0003 mol (per 100 g of formulation) to less than about 0.09 mol (per 100 g of formulation), The peroxygen oxidizing agent is present in an amount of about 0.0003 mol to about 0.08 mol, more preferably about 0.0003 mol to about 0.06 mol,
More preferably from about 0.0003 mol to about 0.04 mol, most preferably from about 0.0003 mol to about 0.03 mol, especially from about 0.0003 mol to about 0.04 mol.
2 mol, more particularly about 0.0003 mol to about 0.015 mol (formulation 10
(At 0 g).

In preferred formulations, the inorganic peroxygen oxidizing agent comprises from about 0.01% to about 0.01% by weight of the formulation.
Less than about 3%, preferably about 0.01% to about 2.5%, more preferably about 0.0%
1% to about 2%, more preferably about 0.01% to about 1%, most preferably about 0.0%.
1% to about 0.8%, especially about 0.01% to about 0.55%, especially about 0.01% to about 0%
. Present at a level of 5% by weight.

The preformed organic peroxyacid preparation may optionally contain one or more preformed organic peroxyacid oxidizing agents in addition to the inorganic peroxygen oxidizing agent (s).

Yet another optional organic peroxyacid oxidizing agent suitable for use in the color formulation is of the general formula: R—C (O) OOH, wherein R is saturated or unsaturated, substituted or Unsubstituted, straight-chain or branched-chain alkyl, aryl or alkaryl groups having 1 to 14 carbon atoms).

One type of organic peroxyacid compound suitable for use herein is an amide-substituted compound of the general formula:

[0130]

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(Wherein, R ¹ is a saturated or unsaturated alkyl or alkaryl group or an aryl group having 1 to 14 carbon atoms, and R ² is a saturated or unsaturated alkyl or alkenyl group having 1 to 14 carbon atoms) An alkaryl group or an aryl group, and R ⁵ is H, or a saturated or unsaturated alkyl or alkaryl group having 1 to 10 carbon atoms, or an aryl group). Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0,170,386.

Other suitable organic peroxyacid oxidants include peracetic acid, pernanonic acid, nonylamidoperoxycaproic acid (NAPCA), perbenzoic acid, m-chloroperbenzoic acid, di-peroxy-isophthalic acid, mono- Peroxyphthalic acid, peroxylauric acid, hexanesulfonylperoxypropionic acid, N, N-phthaloylaminoperoxycaproic acid, monopersuccinic acid, nonanoyloxybenzoic acid, dodecandioyl monoperoxybenzoic acid, nonylamide of peroxyadipic acid, diacyl and tetraacyl Peroxides, especially diperoxide decanedioic acid, diperoxytetradecandioic acid and diperoxyhexadecandionic acid, and derivatives thereof, are mentioned. Mono- and diperazelaic acids, mono- and diperbrasyl acids and N-phthaloylaminoperoxycaproic acid, and their derivatives, are also suitable for use herein.

The preformed organic peroxyacid oxidizing agents should be safe and effective for use in the formulations herein. Preferably, the preformed organic peroxyacid oxidizer suitable for use herein is soluble in the formulation when in liquid form and in the form intended to be used. Preferably, organic peroxyacid oxidizing agents suitable for use herein are water-soluble. The water-soluble organic peroxyacid oxidizing agent is
As described herein, an active substance having a solubility in 1000 ml of deionized water at 25 ° C. of up to about 10 g (“Chemistry” CE Mortimer, 5 ^th Edn. P277).

Preferred peroxyacid materials suitable for use herein are selected from peracetic and pernanonic acids and mixtures thereof.

The preformed organic peroxyacid oxidizing agent, when present, is present in an amount of from about 0.0001 mol to about 0.1 mol per 100 g of hair dye (per 100 g of formulation), more preferably from about 0.001 mol to about 0 mol. 0.05 mol, most preferably about 0.0
It is present at a molar level of from 03 mol to about 0.04 mol, especially from about 0.004 mol to about 0.03 mol.

The preformed organic peroxyacid oxidizing agent, when present, is preferably from about 0.01% to about 8%, more preferably from about 0.1% to about 6%, most preferably from about 0.1% to about 6% by weight of the hair dye. Preferably it is present at a level of about 0.2% to about 4%, especially about 0.3% to about 3% by weight. The weight ratio of inorganic peroxygen oxidizing agent to preformed organic peroxyacid is preferably about 0.5.
0125: 1 to about 500: 1, more preferably about 0.0125: 1 to about 50:
1 range.

In addition to inorganic peroxygen oxidants suitable for use herein and yet another optional preformed organic peroxyacid oxidizer, preparations may include additional organic peroxides, such as urea peroxide, Melamine peroxide and mixtures thereof may optionally be included. The level of organic peroxide, when present, is from about 0.01% to about 3%, preferably from about 0.01% to about 2%, more preferably from about 0.1% to about 3% by weight of the formulation. About 1.5%, most preferably about 0.2% to about 1% by weight.

[0138] Hair dyes low pH hair dye may comprise an oxidizing hair dye. Such oxidative hair dyes are preferably used in combination with a peroxide-based oxidizing system to formulate permanent, partially permanent, semi-permanent or temporary hair dye formulations at low pH.

A permanent hair dye formulation, as described herein, is a formulation that is substantially resistant to rinsing, once applied to the hair. Partially permanent hair dye preparations, as described herein, are preparations that are substantially removed from the hair after up to 24 washes. A semi-permanent hair dye formulation, as described herein, is a formulation that, once applied to the hair, is substantially removed from the hair after up to 10 washes. Temporary hair dye preparations, as described herein, are preparations that, once applied to the hair, are substantially removed from the hair after up to two washes. These various types of hair dyes can be formulated with specific combinations of oxidizing agents and / or dyes at various levels and ratios. Rinse, as described herein, is the process by which hair color is removed from hair over time during a standard hair cleansing regimen. Wash fastness, as described herein, refers to the resistance of the dyed hair to rinsing. Wash fastness, as described herein,
It can be measured in terms of relative discoloration of the dyed hair through several washes.

The concentration of each oxidative hair dye in the low pH coloring formulation is from about 0.001% by weight to about 3%.
%, Preferably from about 0.01% to about 2% by weight.

[0141] The total combined level of oxidative hair dye in the formulation is from about 0.001% to about 5%, preferably from about 0.01% to about 4%, more preferably from about 0.1% to about 3%. %, Most preferably from about 0.1% to about 1% by weight.

Typically, for conventional hair dyes, the total level of oxidative hair dye present in the formulation ranges from about 0.2% to about 3.5% by weight. Thus, low pH formulations, when compared to conventional high pH systems with the same level of dye, show improved hair dye attributes, such as initial color development and initial color consistency, in combination with long term wash fastness improvement. obtain. Color consistency, as described herein, means both the relative predictability of initial color development through different hairstyles and improved color retention over time. It should also be noted that the packaged formulations of the present invention can relate to either high or low pH formulations, but low pH formulations are preferred.

The efficacy of oxidation dyes is improved at low pH so that the formulation is typically beneficial for providing good high intensity colors (dark colors) with reduced levels of dye. In particular, good hair dyeing results combined with equivalent color development (for high pH systems) can be achieved using inorganic peroxygen oxidants and substantially less dye than conventional high pH hair dyes. .

Thus, preferably, a hair dye comprising: (a) an inorganic peroxygen oxidizing agent, (b) an oxidative hair dye, and (c) a diluent suitable for application to hair. , (A) and (b) have a pH of about 1 to about 4.
5 wherein the pH of the formulation is in the range of about 1 to about 4.5.

As mentioned above, the combination of an inorganic peroxygen oxidizer at low pH and an oxidative hair dye, combined with an improved odor profile (versus a conventional high pH formulation), hair damage,
Combined with a reduction in the level of skin irritation and skin staining, it is beneficial in providing excellent hair dye attributes. A further advantage of low pH colored formulations is that, compared to traditional high pH formulations,
It is that a reduction in the level of skin staining can be observed from such preparations.

Thus, a light brown colored with 40% gray hair comprising: (a) an inorganic peroxygen oxidizing agent, (b) an oxidative hair dye, and (c) a diluent suitable for application to the hair. A hair dye capable of supplying light reddish brown to hair, wherein the pH of each of the components (a) and (b) is in the range of about 1 to about 4.5, and the pH of the preparation is about 1 to about 4 .5 is provided.

Without being limited to any particular theory, reduction of skin irritation and / or staining can be achieved by (a) reducing dye levels and low pH systems; (b) paraphenylenediamine (PPD) at low pH Reduction of contact sensitization (higher levels of PPD have been shown to exhibit contact sensitization at high pH but not at low pH); (c) elimination of formation of nitrobenzene contact sensitizer (this Can occur in high pH formulations)
(D) reducing the level of skin staining at low pH versus high pH; and (e) low pH
It is believed to be due to a combination of the elimination of ammonia in the dyeing formulation and the reduction of the negative properties of skin irritation and odor as a result of the use of alternative oxidants.

Oxidative Hair Dyeing Process Any oxidative hair dye can be used in the preparation. Typically, oxidative hair dyes are
It consists essentially of at least two components, which are collectively referred to as, but not limited to, dye-forming intermediates (or precursors). The dye-forming intermediate can react in the presence of a suitable oxidizing agent to produce a colored molecule.

Dye-forming intermediates used in oxidative hair dyes include the following:
Aromatic diamines, aminophenols, various heterocyclic substances, phenol, naphthol and various derivatives thereof. These dye-forming intermediates can be broadly classified as primary and secondary intermediates. Primary intermediates, also known as oxidation dye precursors, are chemical compounds that become activated upon oxidation and can subsequently react with each other and / or with coupling agents to form a colored dye complex. Secondary intermediates, also known as color modifiers or coupling agents, are generally colorless molecules capable of producing a color in the presence of an activating precursor / primary intermediate and, together with other intermediates, Used to produce a particular color effect or to stabilize color.

Primary intermediates suitable for use in the formulations and methods herein include the following: aromatic diamines, polyphenols, aminophenols and derivatives of these aromatic compounds ( For example, N-substituted derivatives of amines, and ethers of phenols). Such primary intermediates are generally colorless molecules before oxidation.

While not wishing to be bound by any particular theory, the manner in which color is generated from these primary and secondary coupling compounds is generally that the primary intermediate is activated (by oxidation) and then When combined with a ring agent to produce a dimeric conjugated colored species, which in turn is combined with another `` activated '' primary intermediate to produce a trimeric conjugated colored molecule, herein Proposed.

Although not wishing to be bound by any particular theory of oxidative hair dye chemistry over the entire pH range , conventional oxidative dyeing generally involves:
It is understood that typically occurs at high pH (8-10) between the oxidation precursor molecule, the oxidative coupling agent molecule and the peroxygen oxidant. Typical precursors include 1,4
Disubstituted benzene derivatives, and typical coupling agents include 1,2- or 1,3-disubstituted benzene derivatives.

[0153] The pH of the hair the hair in the trunk of the human is about pH5.5~pH6 (CR Robbins, Chemical and Physical Behaviour of Human Hair, 2 nd Ed. P157), and that hair, has an inherent buffering capacity It is generally accepted.

Oxidative hair dyeing with oxidizing agents and oxidative hair dyes at pH 1-4.5 improves long-term hair color and wash fastness, desirable chroma and sharpness attributes, hair damage In combination with reduced skin irritation, reduced skin dyeing and more efficient dyeing, it is beneficial for providing a good initial hair color. The effectiveness of color development from inorganic peroxygen oxidants and oxidative hair dyes (ie, increased discoloration) is improved under low pH conditions. Furthermore, low p
H hair dyes can provide these excellent hair dye attribute results with minimal hair damage.

[0155] About 1.5 to about 4.5, preferably about 2 to about 4.4, more preferably about 3.6.
It has also been found that at pH levels of from about 4.3 to about 4.3, most preferably from about 3.8 to about 4.2, further improvements in color development can be achieved.

Oxidation Dye Precursors Generally, oxidation dye primary intermediates include monomeric substances that, upon oxidation, produce oligomers or polymers having an electron extended conjugated system in their molecular structure. Because of the new electronic structure, the resulting oligomers and polymers show a shift in their electronic spectrum into the visible range and appear colored. For example, oxidized primary intermediates that can produce colored polymers have a single functional group,
Materials such as aniline, which upon oxidation produce a series of conjugated imines and quinoid dimers, trimers, etc. in the green to black color range. Compounds such as p-phenylenediamine having two functional groups are capable of oxidative polymerization to produce a polymeric colored substance having an extended conjugated electron system. Oxidation dyes known in the art can be used in low pH formulations. A list of representative primary intermediates and secondary coupling agents suitable for use herein can be found in Sagarin, “Cosmetic Science and Technology.
", Interscience, Special Ed. Vol. 2, pages 308-310. The primary intermediates detailed below are by way of illustration only and are not limiting of the preparations and methods herein. It should be understood that no.

The typical aromatic diamines, polyhydric phenols, aminophenols and derivatives thereof described above as primary intermediates also have additional substituents on the aromatic ring, such as halogens, aldehydes, carboxylic acids, nitro, sulfonic acids, And have substituted and unsubstituted hydrocarbon groups, and additional substituents on the amino nitrogen and on the phenolic oxygen, such as substituted and unsubstituted alkyl and aryl groups.

Examples of suitable aromatic diamines, aminophenols, polyhydric phenols and derivatives thereof are compounds having the following general formulas (I), (II) and (III), respectively.

[0159]

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Wherein Y is hydrogen, halogen (eg, fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl, O Ｏ—CH—COOM or —SO ₃ M, where M is hydrogen or alkali or R ₁ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ and R ₄ may be different from each other be the same, hydrogen, C ₁ -C ₄ alkyl or alkenyl and aryl C ₆ -C _9, is selected from the group consisting of alkaryl or aralkyl, R ₅ Is hydrogen, C ₁ -C ₄ unsubstituted or substituted alkyl or alkenyl (where the substituent is selected from the same as those described above for Y) Or C ₆ -C ₉ unsubstituted or substituted aryl, alkaryl or aralkyl, wherein the substituents are selected from those described above for Y. Since the precursors of formula (I) are amines, they are described herein as having a peroxide-compatible anion wherein X represents a peroxide-compatible anion of the type detailed above. It can be used in the form of a salt. It is understood that the general formula of the salts shown includes salts having one, two and three negative anions.

Specific examples of compounds of formula (I) are shown below: o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine , 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 1,3,5-triaminobenzene, 2-hydroxy-p-phenylenediamine, 2,4-diaminobenzoic acid, sodium 2,4 Diaminobenzoate, calcium di-2,4-diaminobenzoate, ammonium 2,4-diaminobenzoate, trimethylammonium 2,4-diaminobenzoate, tri- (2-hydroxyethyl) ammonium 2,4-diaminobenzoate, 2,4 -Diaminobenzaldehyde carbonate, 2, 4-diaminobenzenesulfonic acid, potassium 2,4-diaminobenzenesulfonate, N, N-diisopropyl-p-phenylenediamine bicarbonate, N, N-dimethyl-p-phenylenediamine, N-ethyl-N ′-(2-
Propenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, N-phenyl-N-benzyl-p-phenylenediamine, N-ethyl-N ′
-(3-ethylphenyl) -p-phenylenediamine, 2,4-toluenediamine, 2-ethyl-p-phenylenediamine, 2- (2-bromoethyl) -p-phenylenediamine, 2-phenyl-p-phenylenediamine Laurate, 4- (
2,5-diaminophenyl) benzaldehyde, 2-benzyl-p-phenylenediamine acetate, 2- (4-nitrobenzyl) -p-phenylenediamine,
2- (4-methylphenyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -5-methylbenzoic acid, methoxyparaphenylenediamine, dimethyl-p-phenylenediamine, 2,5-dimethylpara- Phenylenediamine, 2
-Methyl-5-methoxy-para-phenylenediamine, 2,6-methyl-5-methoxy-para-phenylenediamine, 3-methyl-4-amino-N, N-diethylaniline, N, N-bis (β- (Hydroxyethyl) -para-phenylenediamine, 3-methyl-4-amino-N, N-bis (β-hydroxyethyl) aniline, 3-chloro-4-amino-N, N-bis (β-hydroxyethyl) aniline ,
4-amino-N-ethyl-N- (carbamethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (carbamethyl) aniline, 4-amino-N-ethyl-
(Β-piperidnoethyl) aniline, 3-methyl-4-amino-N-ethyl- (
β-piperidonoethyl) aniline, 4-amino-N-ethyl-N (β-morpholinoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-morpholinoethyl) aniline, 4-amino-N -Ethyl-N- (β-acetylaminoethyl) aniline, 4-amino-N- (β-methoxyethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-acetylaminoethyl) aniline , 4
-Amino-N-ethyl-N- (β-mesylaminoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-mesylaminoethyl) aniline, 4-amino-N-ethyl-N -(Β-sulfoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-sulfoethyl) aniline, N- (4-aminophenyl) morpholine, N- (4-aminophenyl) piperidine, , 3-dimethyl-
p-phenylenediamine, isopropyl-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine sulfate.

In highly preferred preparations, substances having the general formulas (Ia) and (Ib) are preferred.

[0163]

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Wherein Y is hydrogen, halogen (eg, fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl, O‖—CH—COOM or —SO ₃ M (where M is hydrogen or alkali or R ₁ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ , R ₂ , R ₃ and R ₄ may be different from each other be the same, hydrogen, C ₁ -C ₄ alkyl or alkenyl and aryl C ₆ -C _9, is selected from the group consisting of alkaryl or aralkyl, R ₅ Is hydrogen, C ₁ -C ₄ unsubstituted or substituted alkyl or alkenyl (where the substituent is selected from the same as those described above for Y) Or C ₆ -C ₉ unsubstituted or substituted aryl, alkaryl or aralkyl, wherein the substituents are selected from those described above for Y. Since the precursors of formula (I) are amines, they are described herein as peroxide-compatible anions, where X represents a peroxide-compatible anion of the type detailed above. Used in salt form. It is understood that the general formula of the salts shown includes salts having one, two and three negative anions.

[0165]

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(Wherein X and Y are the same as in the case of the formula (I), R ₁ and R ₂ may be the same or different from each other, and are the same as in the case of the formula (I); R ₅ is the same as in formula (I) and R ₆ is hydrogen or C ₁ -C ₄ substituted or unsubstituted alkyl or alkenyl, wherein the substituents are the same as Y in formula (I). Selected from those)).

Specific examples of compounds of formula (II) are shown below: o-aminophenol, m-aminophenol, p-aminophenol, 2-iodo-p-aminophenol,
2-nitro-p-aminophenol, 3,4-dihydroxyaniline, 3,4-
Diaminophenol, chloroacetate, 2-hydroxy-4-aminobenzoic acid, 2-hydroxy-4-aminobenzaldehyde, 3-amino-4-hydroxybenzenesulfonic acid, N, N-diisopropyl-p-aminophenol, N-methyl -N- (1-propenyl) -p-aminophenol, N-phenyl-N-benzyl-p-aminophenol sulfate, N-methyl-N- (3-ethylphenyl) -p-aminophenol, 2-nitro -5-ethyl-p-aminophenol, 2-nitro-5- (2-bromoethyl) -p-aminophenol, (2-
(Hydroxy-5-aminophenyl) acetaldehyde, 2-methyl-p-aminophenol, (2-hydroxy-5-aminophenyl) acetic acid, 3- (2-hydroxy-5-aminophenyl) -1-propene, 3- ( 2-hydroxy-5-aminophenyl) -2-chloro-1-propene, 2-phenyl-p-aminophenol palmitate, 2- (4-nitrophenyl) -p-aminophenol, 2-benzyl-p-amino Phenol, 2- (4-chlorobenzyl-p-aminophenol) perchlorate, 2- (4-methylphenyl) -p-aminophenol,
2- (2-amino-4-methylphenyl) -p-aminophenol, p-methoxyaniline, 2-bromoethyl-4-aminophenyl ether phosphate, 2
-Nitroethyl-4-aminophenyl ether bromide, 2-aminoethyl-4
-Aminophenyl ether, 2-hydroxyethyl-4-aminophenyl ether, (4-aminophenoxy) acetaldehyde, (4-aminophenoxy) acetic acid, (4-aminophenoxy) methanesulfonic acid, 1-propenyl-4-aminophenyl Ether isobutyrate, (2-chloro) -1-propenyl-4-aminophenyl ether, (2-nitro) -1-propenyl-4-aminophenyl ether, (2-amino) -propenyl-4-aminophenyl ether , (2-hydroxy) -1-propenyl-4-aminophenyl ether, N-methyl-p-
Aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-amino Phenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3-hydroxymethyl-4-aminophenol.

Compounds having the following general formula are not preferred.

[0169]

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(Wherein, R₁Is alkyl, hydroxyalkyl, carboxyalkyl or aminoalkyl;_TwoIs a hydrogen, alkyl or hydroxyalkyl group; R_ThreeAnd R_FiveIs H or -OR (where R is alkyl or hydroxyalkyl)
R is a substituent); R_FourIs H, alkyl or NHR '; R₆Is H,
Alkyl, -OR or NHR '; R' is H, alkyl, hydroxyal;
Kill, provided that a) R_FourAnd R₆Is only NHR '; b) R_Two , R_FiveAnd R₆Is H and R_FourIs NH_TwoIf R_ThreeAnd -OR₁Hato
No longer methoxy; c) R_ThreeOr R_FourOr R_FiveOr R₆Is H; d)
R₆Is NH_TwoAnd R_TwoIs H and R₁Is methyl._Three, R_FourAnd R _Five Are not all H; e) R₁Is ethyl and R_Two, R_Three, R_FourAnd R₆But
If H, then R_FourIs NH_TwoNot; f) R₁R is carboxyalkyl or aminoalkyl;_FourIs NHR ').

[0171]

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(Wherein Y, R ₅ and R ₆ are as defined above in formula (II)).

Specific examples of compounds of formula (III) include: o-hydroxyphenol (catechol), m-hydroxyphenol (resorcinol), p-hydroxyphenol (hydroquinone), 4-methoxyphenol, 2-methoxyphenol Phenol, 4- (2-chloroethoxy) phenol, 4-
(2-propeneoxy) phenol, 4- (3-chloro-2-propeneoxy)
Phenol, 2-chloro-4-hydroxyphenol (2-chlorohydroquinone), 2-nitro-4-hydroxyphenol (2-nitrohydroquinone), 2-
Amino-4-hydroxyphenol, 1,2,3-trihydroxybenzene (pyrogallol), 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzenesulfonic acid, 3-ethyl-4- Hydroxyphenol, 3- (2-nitroethyl) -4-hydroxyphenol, 3-
(2-propenyl) -4-hydroxyphenol, 3- (3-chloro-2-propenyl) -4-hydroxyphenol, 2-phenyl-4-hydroxyphenol, 2- (4-chlorophenyl) -4-hydroxyphenol, 2-benzyl-
4-hydroxyphenol, 2- (2-nitrophenyl) -4-hydroxyphenol, 2- (2-methylphenyl) -4-hydroxyphenol, 2- (2-
Methyl-4-chlorophenyl) -4-hydroxyphenol, 3-methoxy-4
-Hydroxy-benzaldehyde, 2-methoxy-4- (1-propenyl) phenol, 4-hydroxy-3-methoxycinnamic acid, 2,5-dimethoxyaniline, 2-methylresorcinol, alpha naphthol and salts thereof.

Preferred formulations herein do not include the following compounds having the following general formula:

[0175]

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Secondary coupling compounds (color modifiers), as described in detail below, are preferably used with the primary intermediates herein, and during their formation, incorporate themselves into the colored polymer. It is believed to insert and cause a shift in its electronic spectrum, thereby causing a slight discoloration.

Secondary coupling compounds suitable for incorporation in the coloring preparations and processes described hereinbefore include those that do not produce color on their own, but are generated by a primary oxidation dye intermediate. Certain aromatic amines and phenols that modify the color shade, shade or intensity, and their derivatives. The above formulas (I) and (Ia)
, (Ib), (II) and (III), but not including some aromatic diamines and polyhydric phenols of the type known in the art to be not suitable primary intermediates Aromatic amines and phenolic compounds, and their derivatives, are suitable herein as coupling agents. Polyhydric alcohols are also suitable for use herein as coupling agents.

The aromatic amines and phenols and derivatives mentioned above as coupling agents have additional substituents on the aromatic ring, such as halogens, aldehydes, carboxylic acids,
It may also have groups that are substituted and unsubstituted by nitro, sulfonyl, and hydrocarbon groups, and additional substituents on amino nitrogens or phenolic oxygens, such as substituted and unsubstituted alkyl and aryl groups. Also, their peroxide-compatible salts are suitable for use herein.

Examples of aromatic amines, phenols and derivatives thereof are represented by the following general formula (IV)
) And (V).

[0180]

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Wherein Z is hydrogen, C ₁ and C ₃ alkyl, halogen (eg, fluorine, chlorine, bromine or iodine), nitro, O ‖ —CH—COOM or —SO ₃ M, where M Is hydrogen or a substituted ammonium in which one or more hydrogens on an alkali or alkaline earth metal, ammonium or ammonium ion is replaced by an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms); ₁ and R ₂ may be different from each other be the same, hydrogen, C ₁ -C ₄ alkyl or alkenyl and aryl C ₆ -C _9, is selected from the group consisting of alkaryl or aralkyl, R ₇ is hydrogen, C ₁ -C unsubstituted or substituted alkyl or alkenyl (wherein the _4, substituents selected from those selected in the same manner as described above for Z ), Or C ₆ unsubstituted or substituted aryl of -C _9, alkaryl, or aralkyl (wherein the substituents are the chosen from those described as Z in), X in the case of formula (I) And the same.)

Specific examples of compounds of formula (IV) are shown below: aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline,
p-aminobenzaldehyde, p-aminobenzoic acid, sodium-p-aminobenzoate, lithium-p-aminobenzoate, calcium di-p-aminobenzoate, ammonium-p-aminobenzoate, trimethylammonium-p-aminobenzoate, tri ( 2-hydroxyethyl) -p-aminobenzoate, p-aminobenzenesulfonic acid, potassium p-aminobenzenesulfonate, N-methylaniline, N-propyl-N-phenylaniline, N-methyl-N-2-propenylaniline, N-benzylaniline, N- (2-ethylphenyl) aniline, 4-methylaniline, 4- (2-bromoethyl) aniline,
-(2-nitroethyl) aniline, (4-aminophenyl) acetaldehyde,
(4-aminophenyl) acetic acid, 4- (2-propenyl) aniline acetate, 4
-(3-bromo-2-propenyl) aniline, 4-phenylalanine chloroacetate, 4- (3-chlorophenyl) aniline, 4-benzylaniline, 4- (
4-iodobenzyl) aniline, 4- (3-ethylphenyl) aniline, 4- (
2-chloro-4-ethylphenyl) aniline.

[0183]

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(Wherein Z and R ₇ are the same as in formula (IV), and R ₈ is hydrogen or C ₁ -C ₄ substituted or unsubstituted alkyl or alkenyl (wherein the substituent is a group represented by the formula (IV) IV) selected from those defined as Z))).

Specific examples of compounds of formula (V) are given below: phenol, p-chlorophenol, p-nitrophenol, p-hydroxybenzaldehyde, p-hydroxybenzoic acid, p-hydroxybenzenesulfonic acid, ethylphenyl Ether, 2-chloroethylphenyl ether, 2-nitroethylphenylether, phenoxyacetaldehyde, phenoxyacetic acid, 3-phenoxy-1-propene, 3-phenoxy-2-nitro-1-propene, 3-phenoxy-2-bromo- 1-propene, 4-propylphenol, 4- (3-bromopropyl) phenol, 2- (2-nitroethyl) phenol, (4-hydroxyphenyl) acetaldehyde, (4-hydroxyphenyl) acetic acid, 4- (
2-propenyl) phenol, 4-phenylphenol, 4-benzylphenol, 4- (3-fluoro-2-propenyl) phenol, 4- (4-chlorobenzyl) phenol, 4- (3-ethylphenyl) phenol, -(2-chloro-3-ethylphenyl) phenol, 2,5-xylenol, 2,5-diaminopyridine, 2-hydroxy-5-aminopyridine, 2-amino-3-hydroxypyridine, tetraaminopyrimidinedi, , 2,4-trihydroxybenzene, 1
, 2,4-Trihydroxy-5- (C ₁ -C ₆ alkyl) benzene, 1,2,3
-Trihydroxybenzene, 4-aminoresorcinol, 1,2-dihydroxybenzene, 2-amino-1,4-dihydroxybenzene, 2-amino-4-methoxy-phenol, 2,4-diaminophenol, 3-methoxy-1 , 2-Dihydroxy-benzene, 1,4-dihydroxy-2- (N, N-diethylamino)
Benzene, 2,5-diamino-4-methoxy-1-hydroxybenzene, 4,6
-Dimethoxy-3-amino-1-hydroxybenzene, 2,6-dimethyl-4-
[N- (p-hydroxyphenyl) amino] -1-hydroxybenzene, 1,5
-Diamino-2-methyl-4- [N- (p-hydroxyphenyl) amino] benzene and salts thereof.

Preferred preparations suitable for use herein exclude the following combinations of primary intermediates and coupling agents.

[0187]

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And m-aminophenol, resorcinol, 2-methyl-5-aminophenol, 2-methylresorcinol and mixtures thereof.

Still other primary intermediates suitable for use herein include catechol species, particularly catechol "DOPA (DOPA)" species, including dopa itself and homologs, analogs and derivatives of dopa. Is included. Examples of suitable catechol species include
Cysteinyl dopa, alpha alkyl dopa having an alkyl group of 1-4, preferably 1-2, epinephrine, and dopa alkyl ester having an alkyl group of 1-6, preferably 1-2, No.

In general, a suitable catechol is represented by the following formula (VI).

[0191]

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Wherein R ₁ , R ₂ and R ₃ may be the same or different and are H, lower (C ₁ -C ₆ ) alkyl, OH, OR, COOR, NHCOR, CN, COOH , Halogen, NO ₂ , CF ₃ , SO ₃ H or NR ₄ R _5, provided that only one of R ₁ , R ₂ or R ₃ is CN, CO
R ₄ and R ₅ may be the same or different and may be H, lower (C ₁ -C ₆ ) alkyl, or substituted lower; OH, halogen, NO ₂ , CF ₃ or SO ₃ H; (C ₁ -C ₆ ) alkyl (where the substituents are OH, OR, NHCOR ₆ , NHCO NH ₂ , NHCO ₂ R ₆ , NHCSNH ₂ , CN, COOH, SO ₃ H, SO ₂ NR ₆ , SO ₂ R ₆ or CO ₂ R ₆ ); R ₆ is lower (C ₁ -C ₆ ) alkyl, lower (C ₁ -C ₆ ) hydroxyalkylphenyl, phenyl or substituted phenyl (C ₁ -C ₆ ) linked to nitrogen by an alkylene chain. The substituents are represented by R ₁ ) and R is C ₁ -C ₆ alkyl or C ₁ -C ₆ hydroxyalkyl).

The following formula:

[0194]

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(Wherein, R ₁ = substituted or unsubstituted benzene ring, tertiary butyl, etc .; R = substituted or unsubstituted benzene ring), and the following formula:

[0196]

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Wherein R = aminoalkyl, amidoalkyl, aminobenzene (substituted or unsubstituted), amidobenzene (substituted or unsubstituted), alkyl, substituted or unsubstituted benzene ring; R ₁ = substituted or unsubstituted benzene (Ring) is also included in the present specification.

A primary intermediate is used herein, alone or in combination with other primary intermediates, one or more of which is used in combination with one or more coupling agents. The choice of the primary intermediate and the coupling agent is determined by the desired hue, shade and color intensity. There are nineteen preferred primary intermediates and coupling agents herein that can be used alone or in combination to provide dyes with varying shades ranging from ash blonde to black. These include pyrogallol, resorcinol, p-toluenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p -Phenylenediamine, N-phenyl-p-phenylenediamine, m-aminophenol, 2-amino-3-hydroxypyridine, 1-naphthol, N, N-bis (2-hydroxyethyl) p-phenylenediamine, 4-amino -2-hydroxytoluene, 1,
5-dihydroxynaphthalene, 2-methylresorcinol and 2,4-diaminoanisole. These can be used in molecular form or in the form of peroxide-compatible salts as described above.

[0199] The primary intermediate and the coupling agent are combined to provide a wide range of shades to the hair, as described herein above. Hair color can vary depending on both the intensity of the color and the intensity of the color. As mentioned above, the preparation is preferably beneficial for providing high intensity colors. By color intensity, as described herein, is meant the amount of a color compound produced on and retained in hair. Generally, high strength means
As used herein, dark or deep colors, such as dark red, dark brown or black, are meant. By adjusting the initial level of each of the oxidative dyes in accordance with the foregoing, hair dyes of various color intensities can be formulated.

For example, low intensity colors, such as natural blond to light brown hair shades, are generally about 0.001% to about 5%, preferably about 0.1% to about 2%, by weight of the colored formulation. More preferably, about 0.2% to about 1% by weight of total oxidative hair dye is included, and primary intermediates such as 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminoanisole, -Aminophenol, 2,5-diaminobenzyl alcohol and 2
It can be achieved by a combination of-(2 ', 5'-diamino) phenylethanol and a coupling agent such as resorcinol, 2-methylresorcinol or 4-chlororesorcinol.

Similar combinations of said primary intermediates and coupling agents, for example 5-amino-2-
Methylphenol and 1,3-diamino-benzene derivatives, such as 2,4-diamino-anisole, can produce medium intensity red at about 0.5% to about 1% total hair dye level. A high intensity color, for example, a shade of blue to violet hair, can be obtained by combining the primary intermediate with a coupling agent, for example, 1,3-diamino-benzene or a derivative thereof, for example, 2
, 5-diamino-toluene combinations can be produced at levels of about 1% to about 6% by weight of the formulation of total hair dye. Black hair color is obtained by combining the primary intermediate with a coupling agent such as 1,3-diaminobenzene or a derivative thereof.

However, problems have been raised with respect to the physiological compatibility of para-aminophenol, which is commonly used to impart red color to hair. Similarly, the physiological compatibility of some drugs provided to produce black color, such as paraphenylenediamine (PPD), was questioned. Accordingly, a need exists for oxidative hair dyes that exhibit improved safety profiles, and in particular, oxidative hair dyes that provide darker, ie, high color strength, dyes that exhibit improved safety profiles. As mentioned above, low pH formulations provide excellent hair dye attributes in combination with hair damage and reduced levels of skin dyeing and / or irritation.

As such, these preparations, especially when used in the grip-type containerized preparations of the present invention, have good besides reduced hair damage and irritation levels and / or skin dyeing. It is beneficial to provide improved hair condition attributes in combination with improved initial color development and consistency, and long wash speed.

The non-oxidative dyes and other dye hair dyes may optionally contain non-oxidative dyes and other dye substances in addition to the essential oxidative hair dyes. Any non-oxidizing dyes and other dyes suitable for use in hair dyes and hair dyeing methods include semi-permanent, temporary and other dyes.
Non-oxidizing dyes as described herein include so-called "direct-acting dyes", metal dyes, metal chelate dyes, fiber-reactive dyes, and other synthetic and natural dyes. Various types of non-oxidizing dyes are detailed below: 'Chemical and Physical Behavior of Human Hair' 3rd Ed. By Clarence Robbins (pp250-259); 'The Chemistry and Manufacture of Cosmetics', Vol.
^{ume IV, 2 nd Ed. Maison} G. De Navarre at chapter 45 by GS Kass (pp841-9
.. 20); 'cosmetics: Science and Technology' 2 nd Ed, Vol II Balsam Saga
rin, Chapter 23 by FEWall (pp279-343); 'The Science of Hair Care' edite
d by C. Zviak, Chapter 7 (pp235-261) and 'Hair Dyes', JC Johnson, Noy
es Data Corp., Park Ridge, USA (1973), (PP3-91 and 113-139).

Direct-acting dyes that do not require an oxidizing effect for color formation are also called hair dyes and have long been known to those skilled in the art. They are usually applied to the hair in a base containing surfactants. Direct acting dyes include nitro dyes such as derivatives of nitroaminobenzene or nitroaminophenol; disperse dyes such as nitroarylamine, aminoanthraquinone or azo dyes; anthraquinone dyes, naphthoquinone dyes; basic dyes such as acridine orange CI46005. Can be

Nitro dyes are added to hair dyes to enhance the color of the colorant and add an appropriate aesthetic color to the dye mixture before application.

Further examples of direct acting dyes are given below: Arianor Dye Basic Brown 17, CI (Color Index) -no. Basic red 76, CI-12,245; basic brown 16, CI-12,250; basic yellow 57, CI-12,719 and basic blue 99, CI-56,059, and further direct acting dyes, for example. Acid yellow 1, CI-10,316 (D & C yellow no. 7); Acid yellow 9, CI-13,015; Basic violet CI-45,170; Dispersible yellow 3, CI-11,855; Basic yellow 57, CI-1
2,719; dispersible yellow 1, CI-10,345; basic violet 1, CI-42,535; basic violet 3, CI-42,555; green blue, CI-42,090 (FD & C blue no. 1); yellow red, CI
-14700 (FD & C red no.4); yellow, CI-19140 (FD & C yellow no.5); yellow-orange, CI-15985 (FD & C yellow no.6); bluish green, CI42053 (FD & C green no.3)
Yellow-red, CI-16035 (FD & C red no. 40); green-blue, CI-61570 (FD & C green no. 3); orange, CI-45370 (D & C orange no. 5); red, CI-15850 (D & C
Red no. 6); blue red, CI-15850 (D & C red no. 7); pale blue red, CI-45
380 (D & C red no. 22); blue-red, CI-45410 (D & C red no. 28); blue-red, CI-73360 (D & C red no. 30); magenta, CI-17200 (D & C red no. 3)
3); dark blue red, CI-15880 (D & C red no. 34); light yellow red, CI-12085 (D & C red no. 36); light orange, CI-15510 (D & C orange no. 4); green yellow, CI- 47005 (D & C yellow no. 10); bluish green, CI-59040 (D & C green no. 8);
Blue violet, CI-60730 (Ext. D & C violet no. 2); Green yellow, CI-10316 (Ext. D & C)
Yellow no. 7).

The fiber-reactive dyes include Procion (trade name), Dorimalen (trade name), Cibacron (trade name), Levafix (trade name) and Remazol (trade name) dyes (ICI, Sandoz, Ciba-, respectively). Geigy, available from Bayer and Hoechst).

Natural and vegetable dyes as specified herein include extracts of henna (Lawsonia alba), chamomile (Matricaria chamomila or Anthemis nobilis), indigo, logwood and walnut shells.

Temporary hair dyes or hair dye rinses are generally too large to diffuse into the hair shaft and are composed of dye molecules acting on the outside of the hair. They are usually applied by a standing method in which the dye solution is dried on the hair surface. Thus, these dyes
Typically, it has low resistance to the cleaning and cleaning action of hair by surfactants,
It is relatively easily washed off the hair. Any temporary hair dye can be suitably used, and examples of preferred temporary hair dyes are shown below.

[0211]

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Semi-permanent hair dyes are dyes that are generally smaller in size and effect on temporary hair dye rinses, but are generally larger in size than permanent (oxidation) dyes. Typically,
Semi-permanent dyes work similarly to oxidation dyes in that they have the ability to diffuse into the hair shaft. However, semi-permanent dyes are generally smaller in size than the conjugated oxidative dye molecules described above, and as such, are pre-treated to gradually diffuse out of the hair again. A simple hair washing and cleansing action facilitates this process and, in general,
The semi-permanent dye is largely washed off after about 5 to 8 washes. Any semi-permanent dye system may be suitably used. Semipermanent dyes suitable for use in the preparation are H
C blue 2, HC yellow 4, HC red 3, dispersible violet 4, dispersible black 9, HC blue 7
, HC yellow 2, dispersible blue 3, dispersible violet 1, and mixtures thereof.

The following are examples of semi-permanent dyes:

[0214]

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Typical semi-permanent dye systems incorporate a mixture of both large and small color molecules.
Because the dimensions of the hair are not uniform from root to tip, small molecules diffuse both at the root and tip, but are not retained inside the tip, while large molecules can generally only diffuse to the ends of the hair. is there. This combination of dye molecule dimensions is used both during the initial dyeing step and during subsequent washing to help produce a consistent tone from the root to the tip of the hair.

Buffering agents Preferably, the coloring preparation is from about 1 to about 4.5, preferably from about 1.5 to about 4.5.
More preferably, it has a pH in the range of about 2 to about 4.4, most preferably about 3.6 to about 4.3, especially about 3.8 to about 4.2.

The pH of the preferred coloring preparation is kept within a desired pH range by the action of an inorganic peroxygen oxidizing agent. However, if so desired, the preparation may contain one or more optional buffers and / or hair swelling agents (HSA).
Several different pH modifiers may be used to adjust the pH of the final formulation or any component thereof.

The pH adjustment may be effected by acidifying agents well known in the field of treating keratinous fibers, especially human hair, such as inorganic and organic acids, such as hydrochloric, tartaric, citric, succinic, phosphoric and carboxylic acids or Sulfonic acids such as ascorbic acid, acetic acid,
Lactic acid, sulfuric acid, formic acid, ammonium sulfate and sodium dihydrogen phosphate / phosphoric acid, disodium hydrogen phosphate / phosphoric acid, potassium chloride / hydrochloric acid, potassium dihydrogen phthalate / hydrochloric acid, sodium citrate / hydrochloric acid, potassium dihydrogen citrate / hydrochloric acid Potassium dihydrogen citrate / citric acid, sodium citrate / citric acid, sodium tartrate / tartaric acid, sodium lactate / lactic acid, sodium acetate / acetic acid, disodium hydrogen phosphate / citric acid, and sodium chloride / glycine / hydrochloric acid, succinic acid and It can be performed with a mixture thereof.

Examples of alkaline buffers are ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines such as 1,3-diaminopropane, anhydrous alkaline alkanolamines such as mono- or di-ethanolamine, preferably amine Completely substituted on groups, such as dimethylaminoethanol, polyalkylenepolyamines such as diethylenetriamine or heterocyclic amines such as morpholine, and alkali metal hydroxides such as sodium and potassium hydroxide, alkaline earths Hydroxides of metals such as hydroxides of magnesium and calcium, basic amino acids such as L-arginine, lysine, alanine, leucine, isoleucine, oxylysine and histidine; And alkanolamines, such as dimethylaminoethanol and aminoalkylpropanediol, and mixtures thereof. Compounds that generate HCO ₃ ^— upon dissociation in water (hereinafter “ion forming compounds”) are also suitable for use herein. Examples of suitable are ionic product _{compound, Na 2 CO 3, NaHCO 3} , K 2 CO 3, (NH 4) 2 CO 3, NH 4 HCO 3, CaC
O ₃ and Ca (HCO ₃ ), and mixtures thereof.

Preferred for use herein as buffers are organic and inorganic acids having a primary pKa below pH 6, and their conjugate bases. As described herein, first order pKa refers to the negative logarithm (relative to base 10) of the equilibrium constant K, where K is acid dissociation. The following are organic and inorganic acids suitable for use herein: aspartic acid, maleic acid, tartaric acid, glutamic acid, glycolic acid, acetic acid, succinic acid, salicylic acid, formic acid, benzoic acid, malic acid, lactic acid, malonic acid. Acids, oxalic acid, citric acid, phosphoric acid and mixtures thereof. Particularly preferred are acetic, succinic, salicylic and phosphoric acids, and mixtures thereof.

The low pH coloring preparation may consist of a final solution containing the peroxide and the oxidative hair dye incorporated before application to the hair, or a single component system. As such,
The preparation may include a number of separate component coloring kits.

In oxidation and coloring kits that include some of the inorganic peroxygen oxidants, such as hydrogen peroxide, which may be in solid or liquid form, a buffer solution may be used to stabilize the hydrogen peroxide. Since hydrogen peroxide is stable at a pH in the range of 2 to 4, pH within this range
Must be used. Dilute acid is a suitable hydrogen peroxide buffer.

For oxidation and coloring kits that include an oxidizing agent (which can be in solid or liquid form) in combination with one or more coloring agents, the buffering agent will increase the solution pH from about 1 to about 4.5.
Preferably from 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, especially from about 3.8 to about 4.2. Can hold. Therefore, it is necessary to use a buffer having a pH within this range.

Catalyst The coloring formulation herein comprises a transition metal containing catalyst for an inorganic peroxygen oxidizing agent,
Any preformed peroxyacid oxidizing agent (s) may optionally be included. One suitable type of catalyst is a heavy metal cation having limited bleaching catalytic activity, such as a copper, iron or manganese cation, an auxiliary metal cation having little or no bleaching catalytic activity, such as zinc or aluminum. A sequestering agent having a limited stability constant with respect to the cation, and the catalyst and auxiliary metal cation;
Particularly, the catalyst system includes ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and a water-soluble salt thereof. Such catalysts are disclosed in U.S. Pat.
No. 30,243.

[0225] Other types of suitable catalysts include the manganese-based complexes disclosed in US Patent Nos. 5,246,621 and 5,224,594. Preferred examples of these catalysts include Mn ^IV ₂ (u—O) ₃ (1,4,7
- _{trimethyl-1,4,7-triazacyclononane) 2 - (PF 6) 2} , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7- trimethyl-1,4, _{7-triazacyclononane) 2 - (ClO 4) 2} , Mn IV 4 (u-O) 6 (1,4,7- triaza _{cyclononane) 4 - (ClO 4) 2} , Mn III Mn IV 4 (u- O) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (ClO ₄ ) ₃ and mixtures thereof. Others are described in EP 0,549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-
Methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and And mixtures thereof.

See US Pat. No. 4,246,612 and US Pat. No. 5,227,084 for examples of suitable catalysts. Mononuclear manganese (IV) complex,
For example, Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (
OCH _{3) 3} - (a this PF ₆₎ See also U.S. Pat. No. 5,194,416 which teaches. Yet another type of suitable catalyst, such as that disclosed in U.S. Pat. No. 5,114,606, is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups with a ligand. Manganese (III) and / or (
IV) is a water-soluble complex. Other examples include tetra -N- dentate and bi -N- dentate ligand forming a complex with the binuclear Mn, for example, N ₄ Mn ^III (u-
^{_{O) 2 Mn IV N 4)}} + and ^{_{[Bipy 2 Mn III (u-}} O) 2 Mn IV bipy 2] - ( include ClO _{4) 3.}

Further suitable catalysts are, for example, EP 0,408,131 (cobalt complex catalysts), EP 0,384,503 and EP 0,3.
No. 06,089 (metal porphyrin catalyst), U.S. Pat. No. 4,728,455 (
Manganese / polydentate ligand catalyst), US Pat. No. 4,711,748 and EP 0,224,952 (absorbed manganese catalyst on aluminosilicate), US Pat. No. 4,601,845 ( Aluminosilicate supported by manganese and zinc or magnesium salts), US Pat. No. 4,626,373 (manganese / ligand catalyst), US Pat. No. 4,119,557 (ferric complex catalyst), German patent Publication No. 2,054,019 (Cobalt chelating agent catalyst), Canadian Patent No. 86
No. 6,191 (transition metal containing salt), US Pat. No. 4,430,243 (chelating agent of manganese cation and non-catalytic metal cation), and US Pat.
No. 28,455 (manganese gluconate catalyst).

The heavy metal ion sequestering agent coloring preparation may contain a heavy metal ion sequestering agent as an optional component. By heavy metal sequestrant is meant herein a component that acts to sequester (chelate or scavenge) heavy metal ions. These components also have calcium and magnesium chelation abilities, but preferentially they show selectivity for binding of heavy metal ions such as iron, manganese and copper.
Such sequestering agents are beneficial in hair dyes as described herein for providing a controlled oxidative action, as well as for providing good storage stability of the hair dye product.

Heavy sequestering agents generally comprise from about 0.005% to about 20% of the weight of the formulation,
Preferably it is present at a level of from about 0.01% to about 10%, more preferably from about 0.05% to about 2%.

A variety of sequestering agents are known for such uses, including aminophosphonates (available from Monsanto as Quest ™), nitriloacetate, hydroxyethylethylenetriamine, and the like. Heavy sequestering agents suitable for use herein include organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxydisphosphonates and nitrilotrimethylene phosphonates.

Among the above species, preferred are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene 1,1 diphosphonate.

Preferred biodegradable phosphorus-free heavy sequestering agents suitable for use herein include nitrilotriacetic acid, and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, Ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid or any salts thereof may be mentioned. Particularly preferred is ethylenediamine-N, N
'-Disuccinic acid (EDDS) (see U.S. Patent No. 4,704,233), or an alkali metal, alkaline earth metal, ammonium or substituted ammonium salt thereof, or a mixture thereof.

Other suitable heavy sequestering agents for use herein are iminodiacetic acid derivatives such as EP 317,542 and EP 399.
133, 2-hydroxyethyl diacetate or glyceryl iminodiacetic acid. Iminodiacetic acid described in EP-A-516,102-
N-2-hydroxypropyl sulfonic acid and N-carboxymethyl aspartate N-2-hydroxypropyl-3-sulfonic acid sequestrants are also suitable herein. Β-alanine-N, N′-diacetic acid, aspartic acid-N, N′-diacetic acid, aspartic acid-N described in EP 509,382
-Monoacetic acid and iminodisuccinate sequestering agents are also suitable.

EP 476,257 describes suitable amino-based sequestrants. EP 510,331 describes suitable sequestering agents obtained from collagen, keratin or casein. European Patent Publication No. 52
No. 8,859 describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N'-succinic acid (GADS), ethylenediamine-
N, N'-Diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-succinic acid (HPDDS) are also suitable.

[0235] Heavy sequestering agents can be used with their alkali or alkaline earth metal salts.

The thickener coloring preparation is present in an amount of about 0.05% to about 20% by weight, preferably about 0.1% by weight.
It may additionally contain a thickener at a level of from about 10% to about 10%, more preferably from about 0.5% to about 5% by weight. Thickeners suitable for use in the formulations herein include oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, synthetic thickeners such as carbopol, acrine and acrosil and Selected from a mixture thereof. Preferred thickeners for use herein are Acrylin 22 (trade name), Steareth-20 methacrylate copolymer; Acrylin 44 (trade name), polyurethane resin and Axol 830 (trade name), acrylate copolymer (Rohm and Haas, Philadelphia, PA, USA). Still other thickening agents suitable for use herein include sodium alginate or gum arabic, or a cellulose derivative such as methylcellulose, or the sodium salt of carboxymethylcellulose, or an acrylic polymer.

Diluent water is a preferred diluent for the preparation. However, the preparation may contain one or more solvents as additional diluent. Generally, suitable solvents for use in the coloring preparation are selected to be miscible with water and harmless to the skin.
Suitable solvents for use herein as additional diluents include C ₁ -C ₂₀ monohydric or polyhydric alcohols and their ethers, glycine, monohydric and dihydric alcohols and their Ethers are preferred. In these compounds, alcoholic residues having 2 to 10 carbon atoms are preferable. Thus, preferred groups include ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether, and mixtures thereof. Water is the preferred primary diluent in the formulation. Main diluent, as described herein, means that the level of water present is higher than the total level of any other diluent.

The diluent may comprise from about 5% to about 99.98%, preferably from about 15% to about 99.5%, more preferably at least about 30% to about 99% by weight of the formulation herein. Especially at a level of about 50% to about 98%.

Still another substance useful in enzyme hair dyes is one or more enzymes.

Suitable enzymatic substances include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases customarily incorporated into detergent formulations. Suitable enzymes are described in U.S. Patent Nos. 3,519,570 and 3,533,139.
(The contents of which are incorporated herein by reference).
.

[0241] Peroxidase is a peroxide-specific hemoprotein, but uses a wide range of substrates as donors. Catalase, which decomposes peroxide, is included here in view of the fact that it is generally similar in structure and properties, and can cause some oxidation by H ₂ O ₂ . The decomposition of H ₂ O ₂ can be considered as the oxidation of one molecule by another. It is ubiquitous in aerobic cells and may have some more important functions. The coenzyme peroxidase is not a hemoprotein, one is at least a flavoprotein. Other flavoprotein such as xanthine oxidase nor used H ₂ O ₂ in the other receptors, coenzyme peroxidases, in that no specific to H ₂ O _2, are similar to those rather than classical peroxidase . Suitable peroxidases for the preparations of the present invention include horseradish peroxidase, Japanese horseradish peroxidase, milk peroxidase, rat liver peroxidase, linginase and haloperoxidases such as chloro- and bromo-peroxidase.

The enzymes are optionally incorporated at a level sufficient to provide up to about 50 mg, more typically about 0.01 mg to about 10 mg, of active enzyme per gram of the hair treatment preparation. Unless otherwise noted, peroxidase enzyme is used at about 0.0
001% to about 5%, preferably about 0.001% to about 1%, more preferably about 0%.
. At levels of from 01% to about 1% active enzyme, they can be incorporated into the preparation.

[0243] Commercially available protease enzymes include alcalase, sabinase, primase,
Durazyme and Esperase trade names sold by Novo Industries A / S (Denmark), Maxatase, Maxacal and Maxapen trade names
These include those sold by Gist-Brocades, those sold by Genencor International, and those sold by Solvay Enzymes under the trade names Opticlean and Optimase. Protease enzymes are present in 0.0001% to 4% of the weight of the preparation.
% Active enzyme can be incorporated into the preparation.

As the amylase, for example, α-amylase obtained from a specific strain of B. licheniformis
Amylases are described in more detail in GB 1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold by Gist-Brocades under the trade name rapidase, and those sold by Novo Industries A / S under the trade names Termamyl and BAN. The amylase enzyme can be incorporated into the preparation at a level of 0.0001% to 2% active enzyme by weight of the preparation.

The lipolytic enzyme is present in an amount of 0.0001% to 2% by weight of the preparation, preferably 0.001%.
% To 1%, most preferably 0.001% to 0.5% by weight of active lipolytic enzyme.

Lipases are of fungal or bacterial origin, for example, Humicola sp., Thermomyces sp. Or Pseudomonas sp.
Obtained from lipase-producing strains of Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipases from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is obtained from Pseudomonas pseudoalcaligenes, which is described in issued European Patent No. 0218272.

Another preferred lipase herein is to clone a gene from Humicola lanuginosa and express the gene in Aspergillus oryza as host, as described in EP-A-0258068. And is commercially available from Novo Industri A / S, Bagsvaerd, Denmark under the trade name Lipolase. This lipase is disclosed in U.S. Pat. No. 4,810,414 (Huge-Jensen et al.
, Issued March 7, 1989).

The surfactant preparations may additionally contain a surfactant system. Surfactants suitable for inclusion in the formulations generally have a lipophilic chain length of about 8 to about 22 carbons, anionic,
It may be selected from cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof.

(I) Anionic Surfactant Examples of the anionic surfactant suitable for inclusion in the preparation include alkyl sulfate, ethoxylated alkyl sulfate, alkyl glyceryl ether sulfonate, and methyl acyl tau. Rates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxy sulfosuccinates, alpha-sulfonated fatty acids, their salts and / or
Or their esters, alkyl ethoxycarboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl sulfates, acyl sarcosinates and fatty acid / protein condensates, and mixtures thereof. Alkyl for these surfactants and / or acyl chain length is C ₁₂ -C _22, preferably C ₁₂ -C _18, more preferably a C ₁₂ -C _14.

(Ii) Nonionic Surfactants The preparation may also include a water-soluble nonionic surfactant (s). As this kind of the surfactant, the fatty acid mono- C ₁₂ -C ₁₄ - and diethanolamides, sucrose polyester surfactants and polyhydroxy fatty acid amide surfactants include having the following general formula.

[0251]

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Preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants of the above formula include those wherein R _{8 includes} straight and branched chain alkyl and alkenyl, or mixtures thereof. A C ₅ -C ₃₁ hydrocarbyl, preferably a C ₆ -C ₁₉ hydrocarbyl, wherein R ₉ is typically hydrogen, C ₁ -C ₈ alkyl or hydroxyalkyl, preferably methyl, or in the formula -R ¹ -O-R ² (wherein, R ¹ is linear, C ₂ -C ₈ hydrocarbyl including branched and cyclic (include aryl), preferably C ₂ -C ₄ alkylene, R ² is a straight-chain, branched-chain and cyclic hydrocarbyl C ₁ -C _8, including aryl and oxyhydrocarbyl, preferably an alkyl of C ₁ -C _4, especially Is methyl or phenyl). Z ₂ has at least two (in the case of glyceraldehyde) or at least three hydroxyls (directly linked to the chain)
Polyhydroxyhydrocarbyl moieties having a linear hydrocarbyl chain with other reducing sugars), or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated). Z ₂ is preferably derived from a reducing sugar in a reductive amination reaction, most preferably Z ₂ is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose, and glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be used as well as the individual sugars described above. These corn syrups may produce a mixture of sugar components for Z _2. It should be understood that it does not exclude other suitable ingredients. Z ₂ is preferably —CH ₂ — (CHOH) _n —CH ₂ OH, —CH (CH ₂ OH) — (CHOH) _n-1 —CH ₂ H, CH ₂ (CHOH) ₂ (CH OR ′) CHOH—CH ₂ OH, where n is an integer from 1 to 5 (inclusive), and R ′ is H or a cyclic monosaccharide or polysaccharide and alkoxylated derivatives thereof. Selected. As mentioned above, most preferred is n
Glycityls There is 4, particularly -CH ₂ - is (CHOH) ₄ -CH ₂ OH.

Most preferred polyhydroxy fatty acid amides have the formula R₈(CO) N (CH_Three) CH _Two (CHOH)_FourCH_TwoOH (where R₈Is C₆~ C₁₉Is a straight-chain alkyl or alkenyl group). In compounds of the above formula, R₈-CO-N <is, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, caprica
Mido, palmamide, tallowamide and the like.

Oil-derived nonionic surfactants suitable for use herein include water-soluble plant and animal derived emollients, such as triglycerides with inserted polyethylene glycol chains; ethoxylated mono and di -Glycerides, polyethoxylated lanolin and ethoxylated butter derivatives. One preferred class of oil-derived nonionic surfactants for use herein has the general formula:

[0255]

Embedded image

(Wherein n is about 5 to about 200, preferably about 20 to about 100, more preferably about 30 to about 85, and R is about 5 to about 20, preferably about 7 to 7 carbon atoms.) ~ About 1
8 aliphatic groups).

Suitable ethoxylated oils and fats of this type include glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate, derived from triglycerides such as coconut, almond and corn oils. Glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate and glyceryl fatty esters, preferably polyethylene glycol derivatives of glyceryl tallowate and glyceryl cocoate are included.

Preferred for use herein is an average of about 5 to about 5 moles per surfactant
Fatty alcohol nonionic surfactants of the polyethylene glycol based polyethoxylated C ₉ -C ₁₅ containing about 50 ethyleneoxy moieties.

Polyethylene glycol based polyethoxylated C ₉ -C ₁₅ fatty alcohols suitable for use herein include C ₉ -C ₁₁ Palace-3, C ₉ -C ₁₁ Palace-4. , Palace -5 C ₉ -C _11, Palace -6 C ₉ -C _11, Palace -7 C ₉ -C _11, Palace -8 _{C 9 ~C 11, C 11 ~C} 15 Palace -3 , C ₁₁ Palace -4 -C _15, C ₁₁ -C Palace -5 _15, Palace -6 C ₁₁ -C _15, Palace -7 _{C 11 ~C 15, C 11 ~C} 15 Palace -8 , Palace -9 of C ₁₁ ~C _15, C ₁₁ ~C Palace -10 _15, Palace -11 C ₁₁ ~C _15, C ₁₁ ~C ₁₅ Palace -12, C ₁₁ ~
Palace -14 Palace -13 and C ₁₁ -C ₁₅ in C ₁₅ and the like. PEG40
Hardened castor oil is commercially available from BASF under the trade name Cremophor.
PEG7 glyceryl cocoate and PEG20 glyceryl laurate are commercially available from Henkel under the trade names CETIOL (trade name) HE and Ramacit (trade name) GML20, respectively. Palace of C ₉ ~C ₁₁ -8 is commercially available from Shell Ltd under the trade name Dobanol (trade name) 91-8. Particularly preferred for use herein are polyethylene glycol ethers of ceteryl alcohol, such as ceteareth 25, which is available from BASF under the trade name Cremaphor A25.

Nonionic surfactants derived from complex vegetable fats and their derivatives extracted from shea tree (Butyrospermum Karkii Kotschy) fruits are also suitable for use herein. Similarly, ethoxylated derivatives of mango, cocoa and Illipe butter can be used in the formulations of the present invention. Although these are classified as ethoxylated nonionic surfactants, it is understood that some portions may remain as non-ethoxylated vegetable oils or fats.

Other suitable oil-derived nonionic surfactants include almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, apricot kernel, walnut, coconut, pistachio nut , Sesame seeds, rapeseed oil, pine oil, corn oil, peach kernel oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil,
Ethoxylated derivatives of coconut oil, hazelnut oil, olive oil, grape seed oil and sunflower seed oil.

(Iii) Amphoteric surfactants Amphoteric surfactants suitable for use in the preparations of the present invention include the following. (A) an imidazolinium surfactant of the formula (VII):

[0263]

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Wherein R ₁ is C ₇ -C ₂₂ alkyl or alkenyl, R ₂ is hydrogen or CH ₂ Z, and each Z is independently CO ₂ M or CH ₂ CO ₂ M, Is H, an alkali metal, alkaline earth metal, ammonium or alkanol ammonium); and / or is an ammonium derivative of the formula (VIII):

[0265]

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(Wherein R ₁ , R ₂ and Z are the same as described above)

(B) Aminoalkanoate of the following formula (IX): R ₁ NH (CH ₂ ) _n CO ₂ M Imino dialkanoate of the following formula (X): R ₁ N [(CH ₂ ) _m CO ₂ M ₂ ] and an iminopolyalkanoate of the following formula (XI):

[0268]

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Wherein n, m, p and q are numbers from 1 to 4 and R ₁ and M are independently selected from the groups described above; and (c) mixtures thereof.

Suitable amphoteric surfactants of type (a) are sold under the trade names Milanol and Empigen and are understood to encompass complex mixture species. Traditionally, Milanol is described as having the general formula (VII), but the CTFA Cosmetic Ingredient Dictionary 3rd edition shows an acyclic structure (VIII), while 4th edition shows that R ₂ is N-linked. Rather, they represent additional structural isomers that are O-linked. In practice, it is believed that there is a complex mixture of cyclic and acyclic species, and for completeness both definitions are given here for completeness. However, preferred for use herein are acyclic species.

Examples of suitable amphoteric surfactants of the type (a) include those of the formulas XII and / or XI
II, wherein R ₁ is C ₈ H ₁₇ (particularly iso-capryl), C ₉ H ₁₉ and C ₁₁ H ₂₃ alkyl. Particularly preferred are compounds wherein R ₁ is C ₉ H ₁₉ , Z is CO ₂ M, and R ₂ is H, R ₁ is C ₁₁ H ₂₃ , Z is CO ₂ M, and R ₂ is CH ₂ CO ₂ M, compound and R ₁ is C ₁₁ H _{2 3,} Z is CO ₂ M, and a compound wherein R ₂ is H.

In the CTFA nomenclature, suitable substances to be used are cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, and especially cocoamphoacetate and cocoamphodiacetate (cocoamphocarboxyglycate). Nit). Specific commercial products include Amphorax 7TX (sodium carboxymethyl tallow polypropylamine), Empigen CDL60 and CDR60 (Albright & Wilson), Milanol H2M Conc. , Milanor C2M Conc. N. P. , Milanor C2M
Conc. O. P. , Milanol C2M SF, Milanol CM Special (Rhone-Poulenc); Alcateric 2CIB (Alkaril Chemicals); Amphotage W-2 (Lonza, Inc.); Monateric CDX-38, Monatelic CSH-32 (Mona Industries); 2C (Rewo Chemical Group); and those sold under the trade name SHERCOTIC MS-2 (Scher Chemicals). Further examples of amphoteric surfactants suitable for use herein include octoxynol-1 (trade name), polyoxyethylene (1) octyl phenyl ether; nonoxynol-4 (trade name), Examples include polyoxyethylene (4) nonyl phenyl ether and nonoxynol-9, and polyoxyethylene (9) nonyl phenyl ether.

A number of commercially available amphoteric surfactants of this type are, for example, in the form of electroneutral complexes with hydroxide counterions or with anionic sulphate or sulphonate surfactants, especially sulfuric acid. of C ₈ -C ₁₈ ones alcohols, C ₈ -C ₁₈ ethoxylated alcohols or C ₈ -C ₁₈ acyl glyceride types are manufactured, it is understood to be sold. Concentrations and weight ratios of amphoteric surfactants are herein based on the uncomplexed form of the surfactant, with all anionic surfactant counterions comprising all anionic surfactant components. It is considered part of the content.

Examples of preferred amphoteric surfactants of the type (b) include the N-alkylpolytrimethylene poly-, carboxymethylamine sold by Berol Nobel under the trade names Amphorac X07 and Amphorac 7CX And salts, especially triethanolammonium salts, and salts of N-lauryl-beta-aminopropionic acid and N-lauryl-imino-dipropionic acid. Such substances are sold by Henkel under the trade name Derifat and by Rhone-Poulenc under the trade name Milatine.

(Iv) Zwitterionic Surfactants Water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the preparation include those of the formula R ₅ R ₆ R ₇ N ⁺ (CH ₂ ) _n CO 2 ₂ M alkyl betaines, and amides betaine following formula (XII):

[0276]

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Wherein R ₅ is C ₁₁ -C ₂₂ alkyl or alkenyl, R ₆ and R ₇ are independently C ₁ -C ₃ alkyl, M is H, an alkali metal, an alkaline earth metal,
Ammonium or alkanol ammonium, and n and m are each a number from 1 to 4). Preferred betaines include cocoamidopropyldimethylcarboxymethylbetaine, laurylamidopropyldimethylcarboxymethylbetaine and Tegobetaine (trade name).

Suitable water-soluble auxiliary sultaine surfactants for inclusion in the formulations of the present invention include alkyl sultaines of the formula (XIII):

[0279]

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Wherein R ₁ is C ₇ -C ₂₂ alkyl or alkenyl, R ₂ and R ₃ are independently C ₁ -C ₃ alkyl, M is H, an alkali metal, an alkaline earth Metal, ammonium or alkanol ammonium, and m and n are numbers from 1 to 4). Preferred for use herein is cocoamidopropylhydroxysultaine.

Suitable water-soluble auxiliary amine oxide surfactants for inclusion in the preparation include alkylamine oxides R ₅ R ₆ R ₇ NO and amidoamine oxides of the formula (XIV):

[0282]

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Wherein R ₅ is C ₁₁ -C ₂₂ alkyl or alkenyl, R ₆ and R ₇ are independently C ₁ -C ₃ alkyl, M is H, an alkali metal, an alkaline earth metal,
Ammonium or alkanolammonium, m is a number from 1 to 4)
. Preferred amine oxides include cocoamidopropylamine oxide, lauryl dimethylamine oxide and myristyl dimethylamine oxide.

Optional Materials A number of additional optional materials may each comprise from about 0.001% to about 5%, preferably from about 0.01% to about 3%, more preferably about 0.05%, by weight of the formulation. % To about 2% may be added to the coloring preparations described herein. Such substances include:
Proteins and polypeptides and their derivatives; water-soluble or solubilizing preservatives, such as DMDM hydantoin, Germar 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA, Oixil K400, natural preservatives, For example, benzyl alcohol, potassium sorbate and bisavalol, benzoic acid, sodium benzoate, and 2-phenoxyethanol; antioxidants such as sodium sulfite, hydroquinone, sodium disulfite, sodium metabisulfite and thioglycolic acid, sodium dithionite, erythrobin Acids and other mercaptans; dye removers,
For example, oxalic acid, sulfated castor oil, salicylic acid and sodium thiosulfate; H ₂ O ₂ stabilizers such as tin compounds such as sodium stannate, stannic hydroxide and stannous octoate, acetanilide, phenacetin colloidal silica For example, magnesium silicate, oxyquinoline sulfate, sodium phosphate, and tetrasodium pyrophosphate; and p-hydroxybenzoate; a moisturizer, such as hyaluronic acid, chitin, and a starch-grafted sodium polyacrylate, such as Sunwet. IM-1000, IM-1500 and I
M-2500 (Celanese Superabsorbent Materials, Portsmith, VA, USA) (described in U.S. Pat. No. 4,076,663), and methylcellulose, starch, higher fatty alcohols, paraffin oil, fatty acids and the like; solvents; antibacterial agents such as Oxeco (phenoxyisopropanol); low-temperature phase modifiers such as ammonium ion source (eg NH ₄ Cl); viscosity modifiers such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl. −
Di-hardened tallow, dimethylammonium chloride, dicetyldiethylammonium ethylsulfate, ditallow dimethylammonium methylsulfate, soybean oil dimethylammonium chloride and dicocodimethylammonium chloride; hair conditioning agents such as silicones, higher alcohols, Ionic polymers and the like; enzyme stabilizers, such as aqueous sources of calcium or borate species;
Coloring agents; TiO ₂ and TiO ₂ - coated mica; perfumes and perfume solubilizers;
The zeolites such Barufoa BV400 and derivatives thereof, and Ca ^{2 +} / Mg ²⁺ metal ion sequestrants such as polycarboxylates, amino polycarboxylates Kishireto, polyphosphonates, amino polyphosphonate like, as well as water softeners, such as sodium citrate Is mentioned.

The preparations are represented by, but not limited to, the following examples. In the examples, all concentrations are based on 100% activity and all percentages are by weight unless otherwise specified. The abbreviations have the following names: oxidizing agent hydrogen peroxide oxidation dye 1 para-phenylenediamine oxidation dye 2 para-aminophenol oxidation dye 3 meta-aminophenol oxidation dye 4 2-amino-3-hydroxypyridine oxidation dye 5 4 -Amino-2-hydroxytoluene Non-oxidative dye Basic Red 76 Chelating agent Ethylenediaminetetraacetic acid Surfactant 1 Ceteareth-25 Surfactant 2 Cocoamidopropyl betaine Thickener 1 Cetyl alcohol Thickener 2 Stearyl alcohol Antioxidant Sodium sulfite buffer acetic acid

Examples I to VII The following are hair treatment preparations in the form of hair dyes representative of the present invention. Component I II III IV V VI VII Oxidizing agent 0.7 0.7 0.7 0.7 1.0 1.5 2.5 Oxidizing dye 1 0.24 0.14 0.24 0.24 0.24 0.24 0.3 Oxidizing dye 2 0.09 0.05 0.009 0.09--0.1 Oxidizing dye 3 0.006 0.004 0.006 0.006 0.006 0.006-Oxidizing dye 4 0.06 0.03 0.06 0.06 0.06 0.06 0.06 Oxidative dye 5-----0.5-Non-oxidative dye----0.1--Surfactant 1 1.5 1.7 1.5 1.5 1.5-3.0 Surfactant 2-----1.5-Chelate Thickener 0.1 0.06 0.09 0.1 0.1 0.1 0.1 Thickener 1 2.3 2.6 2.3 2.3 2.3 2.3 2.0 Thickener 2 2.3 2.6 2.3 2.3 2.3 2.3 4.0 Antioxidant 0.1 0.06 0.1 0.1 0.1 0.1 0.1 Buffer---0.5--- Water ............ Amount to make the whole 100 ...... pH 4.0 3.8 3.9 2.7---

In an embodiment, water is used as a diluent. However, in a variation herein, the water is partially replaced by a diluent, such as a lower alcohol, such as ethylene glycol, ethylene glycol, by about 0.5% to about 50% by weight of the total water content of the examples. Monoethyl ether, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol, 1,3-propanediol, ethanol, isopropyl alcohol, glycerin, butoxyethanol, ethoxydiglycol, hexylene glycol, polyglyceryl-2-oleyl ether and mixtures thereof Be replaced.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a cap, a bottle, a flexible bag, a support tube, a plug, a valve, a spout, a sponge or flocked pad, a comb-shaped housing, and a comb which are constituent members of a hair dyeing kit embodying the present invention. FIG.

FIG. 2 is a cutaway enlarged sectional view showing the cap when fixed to a bottle.

FIG. 3 is a plan view of the plug-in device.

FIG. 4 is a schematic cross-sectional view in a direction perpendicular to the cross-sectional view of FIG. 2, showing the dye container when connected to a bayonet so that the dye in the dye container can be added to the flexible bag.

FIG. 5 is a perspective view showing a spout when fixed to a bottle.

FIG. 6 is an enlarged cross-sectional view of FIG.

FIG. 7 is a perspective view similar to FIG. 5, showing the sponge or flocked pad when fixed to the spout.

FIG. 8 is a sectional view of FIG. 7;

FIG. 9 is a perspective view showing the comb housing when the comb portion is fixed to the comb housing and fixed to the bottle.

FIG. 10 is a sectional view of FIG. 9;

FIG. 11 is a cross-sectional view of the comb portions before they are fixed to each other.

FIG. 12 is a sectional view of the comb housing before being fixed to each other.

────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number 9724715.9 (32) Priority date November 21, 1997 (November 21, 1997) (33) Priority claim country United Kingdom (GB) (31) Priority claim number 9724716.7 (32) Priority date November 21, 1997 (November 21, 1997) (33) Priority claiming country United Kingdom (GB) (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD) , RU, TJ TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX , NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Diaz, Louis Carlos Weybridge, Katy UK, 13, 8, UWY, Bull Clans, Lane, Brooklands, Farm, House (72) Inventor Rainey, Rosemary Jane United Kingdom, Sussex, R.H. 20, 2B, West, Tiltington, Sunset, Lane, Cranford (72) Inventor Oaks , Laura Ann United Kingdom, Surrey, Katie 16, 9th H, Chart Sea, Masonic, Hall, Road 9

Claims (10)

[Claims] 1. A hand-held packaged formulation comprising a combination of a flowable formulation and a package for the flowable formulation, wherein the package includes an applicator and a container, the container having a flexible elastic wall. And a tank for the flowable formulation, wherein the applicator includes a plurality of elongated parting members forming a dispensing section, and displacing the applicator in a direction substantially perpendicular to the dispensing section to achieve a constant volume. The flowable formulation can be dispensed, wherein the dispensing section has a plurality of outlets, and dispensing the flowable formulation from the outlets by applying pressure to the flexible wall of the container. , One on the flexible wall of the container
. When a pressure of 5 Pa is applied, 0.1 g or more per 1 cm ² of the cross-section per 1 ^{second is not} less than 0.1 g. A hand-held packaged preparation in which no more than 5 g of flowable preparation is dispensed. 2. The hand-held packaged preparation according to claim 1, wherein the outlet has a cumulative surface of 2% to 10% of the distribution cross section. 3. The hand-held packaged preparation according to claim 1, wherein the preparation is a hair dye. 4. The composition of claim 1, having a viscosity of 0.01 Pa.s when measured at a shear strain rate of 2000 s ^-1 . s or more and 5 Pa.s when measured at a shear strain rate of 10 s ^-1 . 2. The hand-held packaged preparation according to claim 1, having a viscosity of not more than s. 5. The method of claim 1, wherein the outlet has a cumulative surface and a cumulative perimeter, the cumulative surface being no less than 0.05% and no more than 0.4% of the square of the cumulative perimeter. Hand-held packaged preparation. 6. When a pressure of 1.5 Pa is applied to the flexible elastic wall of the container for at least 2 seconds, 0.1 g or more and 0.5 g or less of a flowable preparation is distributed per 1 cm ² of a cross section in 1 ^second. The hand-held packaged preparation according to claim 1, wherein 7. Each of said elongated parting members is in the form of a substantially rigid tooth, said teeth being arranged in at least one row and having at least one of said outlets at a free end of each of said teeth. The hand-held packaged preparation according to claim 1, wherein one is provided. 8. Each of said elongated parting members is in the form of a substantially rigid tooth, said teeth being arranged in at least one row and having an end opposite the free end of each of said teeth. The hand-held packaged preparation according to claim 1, wherein at least one of the outlets is provided. 9. The container according to claim 1, wherein the container is a bag-in-bottle container, and the flowable preparation can be delivered regardless of the orientation of the bag-in-bottle container. Hand-held packaged preparation. 10. The container has a major longitudinal direction, and the elongated parting member is oriented in a direction substantially orthogonal to the major longitudinal direction of the container.
A hand-held packaged preparation as described.