CN102355833A - A packaging and applicator device for at least one solid cosmetic composition - Google Patents
A packaging and applicator device for at least one solid cosmetic composition Download PDFInfo
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- CN102355833A CN102355833A CN2010800127712A CN201080012771A CN102355833A CN 102355833 A CN102355833 A CN 102355833A CN 2010800127712 A CN2010800127712 A CN 2010800127712A CN 201080012771 A CN201080012771 A CN 201080012771A CN 102355833 A CN102355833 A CN 102355833A
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- composition
- block
- applicator
- acid
- core
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D40/00—Casings or accessories specially adapted for storing or handling solid or pasty toiletry or cosmetic substances, e.g. shaving soaps or lipsticks
- A45D40/26—Appliances specially adapted for applying pasty paint, e.g. using roller, using a ball
- A45D40/262—Appliances specially adapted for applying pasty paint, e.g. using roller, using a ball using a brush or the like
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D40/00—Casings or accessories specially adapted for storing or handling solid or pasty toiletry or cosmetic substances, e.g. shaving soaps or lipsticks
- A45D40/26—Appliances specially adapted for applying pasty paint, e.g. using roller, using a ball
- A45D40/262—Appliances specially adapted for applying pasty paint, e.g. using roller, using a ball using a brush or the like
- A45D40/265—Appliances specially adapted for applying pasty paint, e.g. using roller, using a ball using a brush or the like connected to the cap of the container
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B9/00—Arrangements of the bristles in the brush body
- A46B9/005—Arrangements of the bristles in the brush body where the brushing material is not made of bristles, e.g. sponge, rubber or paper
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B9/00—Arrangements of the bristles in the brush body
- A46B9/02—Position or arrangement of bristles in relation to surface of the brush body, e.g. inclined, in rows, in groups
- A46B9/021—Position or arrangement of bristles in relation to surface of the brush body, e.g. inclined, in rows, in groups arranged like in cosmetics brushes, e.g. mascara, nail polish, eye shadow
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B9/00—Arrangements of the bristles in the brush body
- A46B9/06—Arrangement of mixed bristles or tufts of bristles, e.g. wire, fibre, rubber
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B2200/00—Brushes characterized by their functions, uses or applications
- A46B2200/10—For human or animal care
- A46B2200/1046—Brush used for applying cosmetics
- A46B2200/1053—Cosmetics applicator specifically for mascara
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- Cosmetics (AREA)
Abstract
The present invention provides a packaging and applicator device for at least one solid cosmetic composition for application to the eyelashes, the eyebrows, or the hair, the device comprising: a handle member (2); a stem (3) connected to the handle member; and an applicator member (4) connected to the stem, and comprising: a core (5) secured to the stem; an applicator elements (6) extending transversely to an axis of the stem from a base secured to the stem to an end opposite to said base, at least some of the applicator elements having their bases disposed inside a solid block (7) of said composition, said block presenting an outer envelope extending part or all of the way around the axis (X), and situated, prior to first use of the device, between the bases and the opposite ends of the applicator elements, at a non-zero distance therefrom; the composition being dispersible while dry, with or without assistance from heat.
Description
Technical field
The present invention relates to the packagings and Unit for applying a product that are applied to eyelashes, eyebrow, at least one care product of hair (including artificial hair or false eyelashes) and/or cosmetic cosmetic composition.
Term " cosmetic composition " is for referring to the composition as defined in the Council Directive 93/35/EEC on June 14th, 1993.
The cosmetic composition can be mascara, the substrate for make-up eyelash, the skin combined object applied on mascara.
Background technique
It in the prior art, is known for packaging mascara and many packagings applied it on eyelashes and Unit for applying a product.Those devices mainly provide in two forms, the quality depending on mascara.
When mascara is liquid, it includes in the container for being provided with contact brush and the applicator including applicator element, the use of mascara is by taking out composition from container using the applicator, so that applicator element is passed through the contact brush to remove extra composition, contacts the applicator element full of mascara with eyelashes.
Application WO 2008/068337 describes a kind of mascara packaging and Unit for applying a product including heater assembly.
When mascara is solid, usually using solvent or heating so that mascara is suitable for the application of.
Therefore, the mascara of the open solid form of patent disclosure US 2007245 or FR 2833163 needs to be contacted in water phase before being applied to eyelashes, to dissolve some mascaras.
Application FR 2733398 describes the mascara Unit for applying a product of elongated shape block form, and it is suitable for dispersing in water.The block can be overmolded on brush.
Application WO 2006/057439 describes mascara, is at ambient temperature solid, and using heater assembly softening at being suitable for the application of to eyelashes.Once the mascara of softening is applied to eyelashes,
It is quickly cooled down, to solidify, thus, it is possible to form the film of covering eyelashes.
Application FR 2914161 describes a kind of packaging and Unit for applying a product, and wherein mascara is included in rod handle with bar form, and the heater assembly being resiliently forced toward in applicator element.
Another method for preparing mascara includes becoming the block form for being suitable for the composition being administered on eyelashes by the transfer of direct dry type.
Composition can be made particularly to be disclosed in patent disclosure FR 2888735,1913835 A1 of EP 1785055 A1 and EP by the device of dry type transfer application.
Exploitation has difficulties when applicable such composition when dry, these difficulties are particularly that the amount of material, the quality of attachment material and the user that obtain the controllable block of hardness, adjustment is attached on keratin fiber can apply the speed and easy degree of the cosmetics.
Too hard block cannot make composition be adequately applied to eyelashes, and too soft block may cause in the presence of the non-uniform danger of attachment is made and leave not beautiful fritter on eyelashes.In addition, too soft composition prevents block from absorbing impact and pressure, especially when it is being applied.
In above-mentioned application, the block is the form of stick, starts to apply via its distal end.
Using required gesture and user using difference more often usually used with brush, and some users of conventional brush accustomed to using can be prevented to use such device.
Summary of the invention
In the presence of disadvantages mentioned above and the needs by packing and Unit for applying a product is benefited entirely or partly are solved, the packaging and Unit for applying a product are easy to use, and cause satisfactory dressing effect.
The present invention seeks to meet the needs.
Illustrative embodiment of the invention provide be applied to eyelashes, eyebrow, hair at least one Solic cosmetic composition packaging and Unit for applying a product, described device includes:
● handle component;
● it is connected to the rod handle of handle component;With
● it is connected to the applicator component of rod handle comprising:
● it is fixed to the core of rod handle;With
● the axis relative to the rod handle laterally extends to the applicator element of the opposite end of the base from the base portion for being fixed to the core, the base portion of at least some applicator elements is arranged in inside the solid mass of the composition, the block have around axis it is whole around some or all of the upper outer envelope face extended, such as continuously extend along the segment angle around at least 30 ° of axis, preferably completely around axis, and before first time is using the device, it is located between base portion and the opposite end of applicator element with the distance apart from base portion and the opposite end non-zero of applicator element;
● when dry with the help of with and without being heated, the composition is dispersible.The shear stiffness that the composition can have is 200 grams ms (g/m) to 5000g/m, preferably 375g/m to 5000g/m.
For example, when for the first time in use, the length thereof of the applicator element of covering in the composition can for example be greater than or equal to the 30% of applicator element total length.
The block can at least partly cover whole applicator elements.
The block extends to all or part of core.
Term " before first time use " should be understood as referring to before user uses described device for the first time.For example, this can be equivalent to the state of the device when user's purchase.It can particularly be equivalent to the device in packaging, or in being presented to state of the consumer without packaging.
The embodiment of other examples of the invention also provides the packaging and Unit for applying a product for being applied at least one Solic cosmetic composition of eyelashes, eyebrow or hair, and described device includes::
● handle component;
● it is connected to the rod handle of handle component;With
● it is connected to the applicator component of rod handle comprising:
● it is fixed to the core of rod handle;With
● the axis relative to the rod handle laterally extends to the applicator element of the opposite end of the base portion from the base portion for being fixed to the core, the base portion of at least some applicator elements is arranged in inside the solid mass of the composition, the block have around axis it is whole around some or all of the upper outer envelope face extended, preferably completely around axis, and in first time using before the device, with the distance apart from base portion and the opposite end non-zero of applicator element be located at base portion and applicator element opposite end it
Between;The shear stiffness that the composition has is 200g/m to 5000g/m, preferably 375g/m to 5000g/m.
Applicator element outstanding can be stretched out from core at least three different angle directions, so that angle between any two is more than 60 °, preferably more than 90 °, or even 120 °.
Term " can be dispersed when drying " should be understood as referring to that the composition suitably forms the attachment for being adhered to or being covered on eyelashes, eyebrow or hair under environment temperature (20 DEG C) or when heating, without making the composition be in contact with solvent before, in water and need to be partly dissolved before use opposite to be applied to the mascara of the bulk form of fiber with dispersible.The composition is dispersible when can be dry under environment temperature (20 DEG C), and described device need not be combined with the tool of heating the composition.
The composition can optionally be heated for applying, when especially non-dispersible when it is dried at ambient temperature.In such a case, it is possible to which temperature is heated to 40 DEG C to 95 DEG C, preferably 45 DEG C to 75 DEG C.
Preferably, the hardness that the Solic cosmetic composition used in device in accordance with an exemplary embodiment of the invention has can be such that the composition obtains to become the hardness in the form of block enough, while have sufficiently soft to can be easy to be applied to the quality of eyelashes.
Term " solid mass " is used to refer to the compacting block of predetermined shape, and there is no under stress, its original shape is kept under environment temperature and atmospheric pressure.
The present invention has the advantages that the ergonomics and hand motion of most common conventional application device in reserved market, i.e. comprising for immersing in the container containing liquid composition, brush or comb to carry the composition, while the also offer advantage related with the composition of solid form.
The block can have the cross section of any shape, such as round or non-circular, polygon, square, rectangle, triangle, rhomboid, star, ellipse, however it is not limited to this.Certain shapes can make composition be easier to be supported on eyelashes and to bigger contact area is provided between composition and eyelashes.In certain embodiments of the invention, the element of the core and/or protrusion can serve as reinforcing element, so as to using composition it is more crisp, which mechanically reinforced by the applicator element of core and/or protrusion.
The block can be tubular form, such as cylindrical, can surround core with its whole length.
The block can be symmetrically placed with respect to the longitudinal axis of core.The longitudinal axis of the block can be optionally overlapped with the longitudinal axis of applicator element.
The block can be evenly distributed in around the core of applicator component.In a variant, the block can be unevenly distributed over around core.For example, the longitudinal axis of the block need not be overlapped with the longitudinal axis of the core of applicator component, however, for example can be with its keeping parallelism.Therefore, the block on the side of core can be thick than on another side.
Before the first use, as long as that is, the block uses not yet, the block can have the substantially matched outer surface of shape of the outer envelope face structure limited substantially in the free end with protrusion applicator element.
The block can continuously extend around applicator component, especially continuously extend its whole length around the core of applicator component.In a variant, which can extend to a part of applicator component profile only with its at least part length.
The block can be optionally with its whole length, or with the core of only its partial-length contact applicator component.The block is preferably placed directly on core.
The block can first partially or completely covering protrude element.For example, for the first time in use, protrude element can contact at least 30% of the block more than its height, or at least 50%, 70% or 90% of even more than its height.
The block can completely or partially cover at least 20% or 40%, 60%, 80% or 90% protrusion applicator element.All protrude elements can be contacted with the block.
In its at least part length, rod handle can have the cross section of following shape: circle, square, rectangle, triangle, rhomboid, star, ellipse, polygon, however it is not limited to this.Rod handle can have maximum transversal diameter, particularly smaller or equal than 6 millimeters (mm) of diameter.
The core of applicator component can be straight line, curve, torsion or any other shape.
The core of applicator component may include the tool for promoting to connect with the block of composition.The core of applicator component, which can have hydrophily or hydrophobic nature or its, can be subjected to any suitable processing for being suitable for that the block is promoted to be retained in core.
The longitudinal axis of the applicator component core can be overlapped with the longitudinal axis of rod handle or it can be relative to rod handle bias.Particularly, the axis of applicator component core can be parallel with the axis of rod handle.
The core of applicator component can be formed together single component with rod handle, may be by being overmolding in rod handle
Type.In a variant, the core of applicator element can be fixed to rod handle, can be removably, such as connect or block by adhesive, fastener, screw and order.
Applicator component can be rotated relative to rod handle and/or handle component.Particularly, the apparatus may include motor, such as are placed in handle component, and applicator component can be made to be rotated.
Described device may include the cap for covering applicator component when applicator component is not used.The cap need not have contact brush element.In a variant, the cap may include the element for cleaning the end of protrusion applicator element.The cap may include heater system.
Protrude element can all length having the same or they can have different length.
The cross section or longitudinal section of the enveloping surface limited by the free end of protrude element may exist various shapes, such as shape: circle, square, rectangle, triangle, rhomboid, star, ellipse, polygon, however it is not limited to this.
Protrude element is different from the embossed section formed on the Solic cosmetic composition surface of block form.
Protrude element can be made of the impervious material of the composition.For example, it can be made of the material of thermoplastic material, such as polyolefin such as polypropylene (PP) or polyethylene (PE), acronitrile-butadiene-styrene (ABS), thermoplastic elastomer (TPE), polyamide, it is without being limited thereto.
The protrude element can be the carding element suitable for being suitable for separating eyelashes.For example, protrude element can be tooth or natural or synthetic mane.When appropriate, protrude element can be thin flat blade form.The quantity for the protrude element that the core of applicator component is loaded with can be 20 to 500.
Protrude element can be fixed with respect to the core of applicator component.When appropriate, composition block can be movable relative to protrude element.
The protrude element can be spaced apart along core with rule or variable.For example, two continuous protrude elements can be in contact or they can be spaced no more than 2mm.
Protrude element can have fixed or variable height.Height between the connection first end and free second end for being connected to core and referred to as proximal end can be 0.5mm to 15mm.
The single global facility with applicator component together can be made by molding material or machining in protrude element.Thus, protrude element moulds together with core.In a variant, they can be fixed to core,
Or they can be (dual-injected) form with the dual injection molding of core.Protrude element can be the mane being for example loaded in the core of torsion.Protrude element can be made of the material identical or different with the material of core.
The block may include at least two different compositions, such as can make device in accordance with an exemplary embodiment of the invention for a variety of purposes.In terms of described two compositions can have different property, especially hardness or they can become liquid at different temperatures.These different compositions can be coaxially or angularly about core juxtaposition.
The composition can heat advantageous by application and become liquid.For example, the composition can have the fusion temperature less than or equal to 60 DEG C.
Therefore, the apparatus may include heater system, it is for example suitable for softening or melting the heater system at least Solic cosmetic composition surface.The heater system can be separated particularly with applicator component, so that applicator component can be used.Therefore, heater system can be separated with applicator component, so that applicator is contacted with eyelashes, eyebrow or hair.
Heater system can be optionally housed in interior of shell, and packaging in accordance with an exemplary embodiment of the invention and Unit for applying a product at least partly may be accommodated in the shell.The shell can limit protective cap as described above.
Heater system may include the control tool that user can be made to control its operation, such as setting heating temperature.
In order to make its heating, by the outer surface of heat application to block, local temperature can for example be made to rise at least 5 DEG C.
The block can be heated by being exposed to infra-red radiation, radio radiation, it can be heated by blowing hot-air, it can be heated by being exposed to ultrasonic vibration, or it can heated by with hotlist face contact or leading to heat transfer in its vicinity.Hot surface can axially and/or radially be fixed against the surface of block or near the block.When appropriate, hot surface can be flexible.
It can be by being locally heated to the temperature heating composition more than or equal to 40 DEG C or greater than 45 DEG C or even greater than 50 DEG C.The temperature on the block surface must not have any danger for causing to burn during applying.The reason of heating block and the waiting time being applied between keratin fiber can optionally be needed here it is it.
The temperature T that the surface of the block is initially heatedfIt can be 40 DEG C to 95 DEG C, preferably 45 DEG C to 85 DEG C, more preferable 45 DEG C to 75 DEG C.When the composition is applied to eyelashes, the core of the block can be solid.
The composition can have reversible solid/liquid states of matter variation.Caused by the solid/liquid states of matter variation can be due to fusion-crystallization part (such as one or more waxes).
Illustrative embodiment of the invention also provides the packaging and Unit for applying a product for being applied at least one Solic cosmetic composition of eyelashes, eyebrow or hair, and the composition is dispersible when drying, and described device includes:
● handle component;
● it is connected to the rod handle of handle component, which, which does not have, is applied to its external composition;
● it is connected to the applicator component of rod handle comprising:
● extend the core of the elongated shape of rod handle;With
● the protrusion applicator element that the longitudinal axis relative to core laterally extends from core;With
● the block of the elongated shape of at least one composition of at least some protrusion applicator elements and/or core is at least partly covered before at least one composition is applied to eyelashes, eyebrow or hair for the first time, its at least part height is fully inserted into the block by most of protrude element;
The composition is dispersible when drying, and when cold or heating, then the device includes that at least outer surface reaches the system that can make the composition that temperature can be dispersed for composition to be heated to it.
The embodiment of other examples of the invention also provides the packaging and Unit for applying a product for being applied at least one Solic cosmetic composition of eyelashes, eyebrow or hair, and described device includes:
● handle component;
● it is connected to the rod handle of handle component, which, which does not have, is applied to its external composition;
● it is connected to the applicator component of rod handle comprising:
● extend the core of the elongated shape of rod handle;With
● the protrusion applicator element that the longitudinal axis relative to core laterally extends from core, and the longitudinal axis of core is set to extend from least three different directions;With
● at least portion before at least one composition is applied to eyelashes, eyebrow or hair for the first time
Divide the block of at least part of at least one composition of ground covering protrusion applicator element and/or core;
When drying, when cold or heat when, the composition be it is dispersible, then the device include for by composition be heated to its at least outer surface reach can make the composition can be dispersed temperature system.The block may extend continuously to all or part of core along a part of at least its length, and/or be fixed on applicator element, and be fixed to carrier, which extends continuously to all or part of core along a part of at least its length.
When composition is applied to eyelashes or other keratin fibers by applicator component, heater system does not need to be fixed to the applicator component.
The present invention also provides kits comprising:
● it is applied to the packaging and Unit for applying a product of at least one Solic cosmetic composition of eyelashes, eyebrow or hair, described device includes:
● handle component;
● it is connected to the rod handle of handle component, which, which does not have, is applied to its external any composition;
● it is connected to the applicator component of rod handle comprising:
● extend the core of the elongated shape of rod handle;
● the protrusion applicator element that the longitudinal axis relative to core laterally extends from core, and the longitudinal axis of core is set to extend from least three different directions;
● at least partly the block of at least part of at least one composition of applicator element and/or core is protruded in covering before at least one composition is applied to eyelashes, eyebrow or hair for the first time;
● when drying, when cold or hot, the composition is dispersible;With
● for heating the heater system of the composition, the heater system is not incorporated in described device, or separable with applicator component, so that applicator component can be used.
Heater system
Heater system may include resistive element.Heater system may include the source of infrared radiation that setting makes the block receive infrared ray to heat to it.The tool that heater system may also comprise transmitting radio radiation (such as microwave radiation), improve the temperature of the block.Heater system may include to the bulk
Object blows the fan of hot-air.The heater system may include heating the supersonic source of the block.Heater system also may include at least two components, and exothermic reaction can be generated when mixing.The heat so generated can be transferred to the block surface.
Heater system can be assembled into the whole length for heating applicator component or only its partial-length.Particularly, the whole length or only part length of the block can receive the heat of heater assembly releasing, around it or only part.
Heater system can pass through any kind of power supply power.For example, heater assembly may include battery or power supply adaptor, can be attached directly to electric power socket or independent generator such as solar generator etc..In a variant, it can also mechanically apply the heat of heater system generation, such as pass through scraping.
Applicator component need not have the heater system in it, especially near block or the heater system that is in contact with it.
The block of composition can be rotated with relative heater device, allow it to be heated in its whole outer surface.
Method
Another exemplary implementation scheme of the invention provides a kind of method to the fiber coat selected from eyelashes, eyebrow or hair, and the method comprising the steps of:
● make at least part surface of the composition block of fiber contacts device as defined above;With
● start that the surface of the block and fiber is made to move relative to each other, to cause the block to disperse and at least one layer of cosmetic composition of formation on fiber.
In method defined above, the composition can be applied before and after not heating or heating.
During application, the composition block can be retained in solid core.
During manufacturing device, the composition and applicator component can be fluid state when contacting.
It is administered in the case where not advancing with wet with solvent the composition block.
Detailed description of the invention
After the description for reading its following nonlimiting embodiments, and the illustrating graphical of research attached drawing, the present invention may be better understood, in which:
● Fig. 1 shows the embodiment of packaging and Unit for applying a product according to the present invention;
● Fig. 2 is the cross section of the II-II of Fig. 1;
● Fig. 3 is the longitudinal section of the modified embodiment of applicator component of the invention;
● the cross section of other modified embodiments of Fig. 4 to 8 applicator components;
● Fig. 9 is the view similar to Fig. 1 of modified embodiment;
● Figure 10 is the cross section of applicator component and composition block;
● Figure 11 be shown in applicator component assembling before, the embodiment of the carrier of composition block;
● Figure 12 shows the modified embodiment of composition block;
● Figure 13 is the section of the XIII-XIII of Figure 12;
● Figure 14 shows heater system;
● Figure 15 is the diagram for remolding the discontinuous view of the system of applicator component
● Figure 16 is the longitudinal section of the modified embodiment of applicator component;
● Figure 17 is the perspective view of modified embodiment;With
● Figure 18 is the cross section of modified embodiment;
Specific embodiment
Composition
When being measured using the method for following definitions, the shear stiffness that the present invention is suitable for being applied to the cosmetic product of keratin fiber when drying and/or make-up composition can have is 200g/m to 5000g/m, preferably 375g/m to 5000g/m.
With such hardness, the composition " soft " enough allows it to direct and is easy to be administered to eyelashes, material can be made to adhere to especially by it is simply contacted with eyelashes, and does not have to apply eyelashes edge excessive pressure.
In order to determine " shear stiffness " of block according to the present invention, can be used " cheese silk (cheese wire) method ", this method is the rigid tungsten wire for the use of diameter being 250 microns (μm), makes the silk with 100mm/min's
Speed is promoted to the block, and the cylindrical bar with diameter 8mm is crosscutting.The maximum shear stress that the hardness applies corresponding to the metal wire described at 20 DEG C, the DFGS2 force measuring machine sold using Indelco-Chatillon company measure this power.Duplicate measurements six times.By the average value for six values for using above-mentioned dynamometer to measure with gram indicating.These obtained values are 3 grams (g) to 40g, preferably 4g to 20g, more preferably 6g to 12g.Accordingly, with the diameter of block, i.e. 8mm will use gram value indicated a standardization, so as to the value obtained grams m.
In specific exemplary embodiment, the composition is characterized in that its shear stiffness for 500g/m to 2500g/m, especially 750g/m to 1500g/m.
Dry matter
In the meaning of the present invention, " dry matter content " refers to the content of nonvolatile matter.
The amount of the dry matter (DE) of composition of the invention is to be measured using Mettler Toledo with the halogen lamp drier that title " halogen lamp moisture analyzer HR83 (Halogen Moisture Analyzer HR83) " is sold.The measurement is what the weight saving based on heat by lalonge lamp drying sample carried out, after moisture and volatile materials evaporation, can obtain the degree of surplus materials.
The technology is described in detail in the instrument file of Mettler Toledo offer.
The experimental design of the measurement is as follows:
By the composition of about 2g, it is known as " sample " as follows, is laid down into metallic crucible, crucible is placed in above-mentioned halogen lamp drier.Then, by sample 120 DEG C at a temperature of place 1 hour.Utilize the weight in wet base (initial mass that the weight in wet base is equivalent to sample) of precision balance measurement sample and the dry weight of measurement sample (dry weight is equivalent to its weight after heat by lalonge lamp).
The numerical value measured using above-mentioned experimental design may and corresponding theoretical value have ± 1% deviation.
Dry matter (DE) content indicated with % weight is calculated as follows:
DE=100 × dry weight/weight in wet base
The dry matter content DE that the composition can have be based on the composition total weight be greater than or equal to 45% weight and be less than or equal to 55% weight, specifically greater than or equal to 48% weight and be less than or
Equal to 52% weight, or even greater than or equal to 49% weight and less than or equal to 51% weight.
The composition can be emulsion form, especially have the lotion for the oily phase being dispersed in water phase, especially water packet wax pattern lotion.Therefore, the composition has continuous aqueous phase and the oily phase comprising at least one wax.
Water phase
The composition may include a kind of water phase, the water phase can be substantially made of water, or it can wrap that aqueous and mixed with water soluble or " water solubility " is (i.e. at 25 DEG C, be greater than 50% weight with the compatibility of water) solvent mixture, the solvent is such as: the lower polyol (such as ethyl alcohol, isopropanol) with 1 to 5 carbon atom, glycol (such as propylene glycol, ethylene glycol, 1,3-BDO, dipropylene glycol), C with 2 to 8 carbon atoms3-C4Ketone, C2-C4Aldehyde, glycerol and its mixture.
In an exemplary embodiment, the aqueous phase content that the composition includes is greater than 40% weight relative to the total weight of composition, preferably more than 45% weight, more preferably larger than 50% weight, and/or content is less than 80% weight, preferably less than 75% weight, it is therefore preferable to 40% to 80% weight, in particular 50% to 75% weight.
Composition of the invention also may include at least one emulsifier.
Emulsifier
In the present invention, generalling use emulsifier is selected with obtaining the suitable method of water packet wax or emulsion oil-in-water.Particularly, it can be used with the emulsifier for being greater than or equal to 8 according to Griffin theory hydrophile-lipophile balance (HLB) value at 25 DEG C.
Griffin HLB value is defined on J.Soc.Cosm.Chem.1954 (volume 5), in the 249-256 pages.
These emulsifiers can be selected from nonionic, anion, cation, amphoteric surfactant or even polymeric surfactant.It can be referring in particular to document " Encyclopedia of Chemical Technology; Kirk-Othmer ", volume 22, the 333-432 pages, the 3rd edition, 1979, Wiley, there is defined (emulsification) characteristics and function of surfactant, especially in 347-377 pages of above-mentioned document, describe anion, both sexes and nonionic surfactant.
In the present compositions it is preferable to use surfactant be selected from:
A) nonionic surfactant of the HLB more than or equal to 8 at 25 DEG C, is used alone or uses as a mixture;It can particularly refer to:
● the ester and ether of monosaccharide, for example, hexadecane stearoyl glucosides mixture and hexadecanol and stearyl alcohol mixture, for example, the Montanov 68 from Seppic;
● oxyethylation and/or oxypropylation glycerin ether (including 1 to 150 oxyethylene group and/or oxypropylene group);
● oxyethylation and/or oxypropylation (including 1 to 150 oxyethylene group and/or oxypropylene group) fatty alcohol (especially C8-C24Alcohol, preferably C12-C18Alcohol) ether, for example, the oxyethylation ether (INCI entitled " stereth (Steareth) -20 ") of the oxyethylation ether (INCI entitled " Ceteareth-30 ") of the cetanol with 30 oxyethylene groups, stearyl alcohol with 20 oxyethylene groups, particularly by Shell Chemicals with title Neodol 25-7The C with 7 oxyethylene groups of sale12-C15Oxyethylation ether (entitled " the C of INCI of the mixture of fatty alcohol12-15Pareth-7");
● aliphatic ester (the especially C of polyethylene glycol (with 1 to 150 ethylene glycol unit)8-C24Acid, preferably C16-C22Acid), for example, particularly by supplier ICI Uniqema with title Myrj 52PThe PEG-50 stearate and PEG-40 monostearate of sale, or even particularly by supplier Evonik Goldschmidt with title Tagat SThe PEG-30 tristerin of sale;
● aliphatic ester (the especially C of oxyethylation and/or oxypropylation glycerin ether (with 1 to 150 oxyethylene group and/or oxypropylene group)8-C24Acid, preferably C16-C22Acid), for example, particularly by supplier Seppic with title Simulsol 220TMThe PEG-200 glycerol monostearate of sale;Poly-ethylene oxide stearine with 30 oxyethylene groups, for example, the product Tagat S sold by supplier Evonik GoldschmidtPoly-ethylene oxide glyceryl oleate with 30 oxyethylene groups, for example, the product Tagat O sold by supplier Evonik GoldschmidtPoly-ethylene oxide glyceryl cocoate with 30 oxyethylene groups, for example, the product Varionic LI 13 sold by supplier SherexPoly-ethylene oxide iso stearic acid of glycerine ester with 30 oxyethylene groups, for example, the product TagatL sold by supplier Evonik GoldschmidtWith with 30 oxyethylene groups poly-ethylene oxide glycerol monolaurate, for example, by supplier Evonik Goldschmidt sell product Tagat I
● aliphatic ester (the especially C of oxyethylation and/or oxypropylation sorb alcohol ether (with 1 to 150 oxyethylene group and/or oxypropylene group)8-C24Acid, preferably C16-C22Acid), for example, particularly by supplier Croda
With title Tween 20The polysorbate20 of sale, and particularly by supplier Croda with title Tween60The polysorbate60 of sale;
● the copolymer of propylene oxide and ethylene oxide, also referred to as EO/PO condensation polymer;With
● its mixture.
EO/PO condensation polymer is more particularly due to the copolymer that polyethylene glycol and polyethylene glycol block form, for example, polyethylene glycol propylene glycol-polyethylene glycol three block condensation polymer.For example, these three block condensation polymers have following chemical structure:
H-(O-CH2-CH2)a-(O-CH(CH3)-CH2)b-(O-CH2-CH2)a- OH, wherein a 2-120, b 1-100.
The weight average molecular weight that the EO/PO condensation polymer has is preferably 1000 to 15000, and more preferably 2000 to 13000.Preferably, in the case where being greater than or equal to 20 DEG C, preferably greater than or equal to 60 DEG C, the EO/PO condensation polymer has the cloud temperature of 10 grams per liters (g/l) in distilled water.The cloud temperature is measured according to iso standard 1065.As can be used for EO/PO condensation polymer of the invention, it can be mentioned that by supplier ICI with title SynperonicSuch as Synperonic PE/L44With Synperonic PE/F127Polyethylene glycol propylene glycol-polyethylene glycol three block condensation polymer of sale.
B) at 25 DEG C, nonionic surface active agent of the HLB less than 8, can optionally with 25 DEG C at one or more nonionic surface active agent (as described above) of the HLB greater than 8 be used in mixed way;It can particularly refer to:
● the ester and ether of monosaccharide, for example, sucrose stearate, sucrose cocounut oil acid esters, sorbitan stearate and its mixture, for example, the Arlatone 2121 sold by supplier ICI
● fatty alcohol (especially C8-C24Acid, preferably C12-C18Acid) oxyethylation and/or oxypropylation ether (have 1 to 150 oxyethylene group and/or oxypropylene group), for example, there are two the oxyethylation ethers (INCI title " Steareth-2 ") of the stearyl alcohol of oxyethylene group for tool;
● aliphatic ester (the especially C of polyalcohol8-C24Acid, preferably C16-C22Acid), the especially aliphatic ester of the aliphatic ester of glycerol or D-sorbite, for example, tristerin, such as by supplier Evonik Goldschmidt with title Tegin MThe product of sale;Glyceryl laurate ester, for example, by supplier H ü ls with title Imwitor 312Product, polyglyceryl -2- stearate, sorbitan tristearate and the castor-oil plant oil glyceride of sale;
● lecithin, for example, soybean lecithin (such as the Emulmetik 100J from Cargill, or the Biophilic H from Lucas Meyer);
● by Dow Corning company, supplier with title Q2-3225CCyclomethicone/dimethicone copolyol mixture of sale.
C) anionic surfactant, such as:
●C16-C30The salt of fatty acid, the especially salt as derived from amine, for example, triethanolamine stearate and/or 2-Amino-2-methyl-1,3-propanediol stearate.Triethanolamine stearate is usually to be obtained by the way that stearic acid and triethanolamine is simply mixed;
● the salt of polyoxyethylated fatty acid, especially by those of amine or alkali metal salt derivative and its mixture;
● phosphide and its salt, for example, " DEA oleth-10phosphate (phosphate) " (the Crodafos N 10N from supplier Croda) or single hexadecanyl phosphate list potassium (monocetyl monopotassium phosphate) or potassium cetyl phosphate (potassium cetyl phosphate) (the Amphisol K from Givaudan);
● sulfosuccinate, such as " PEG-5 citric acid lauryl disodium sulfosuccinate " and " castor oil MEA sulfosuccinate disodium ";
● alkyl ether sulfate, for example, sodium laureth sulfate;
● isethionate;
● acyl glutamate, for example, " hydrogenated tallow acyl disodium glutamate " (Amisoft HS-21 R sold by supplier Ajinomoto) and stearoyl-glutamic acid sodium (the AmisoftHS-11 PF sold by supplier Ajinomoto) and its mixture;
● soybean derivatives, such as soybean potassium oleate (potassium soyate);
● citrate, for example, glyceryl stearate citrate (62 Pellets of Axol C from Degussa);
● proline derivative, for example, palmityl Sodium proline (the Sepicalm VG from Seppic) or palmitoyl sarcosine sodium, palmityl psicosoma, palmitinic acid and palmityl proline mixture (the Sepifeel One from Seppic);
● lactoyl base ester (lactylates), for example, stearoyl lactate (the Akoline SL from Karlshamns AB);
● sarcosinate, for example, 75/25 mixture (the Crodasin SM from Croda) of palmitoyl sarcosine sodium (Nikkol sarcosine PN) or Hamposyl S and myristoyl sarcosinate;
● sulfonate, for example, anhydrous C14-C17Sodium alkyl sulfonate (the Hostapur SAS60 from Clariant);With
● glycinate, for example, sodium cocoyl glycinate (the Amilite GCS-12 from Ajinomoto).
Composition according to the present invention can also include one or more amphoteric surfactantes; such as; N- acylamino acid (such as; N- p dialkylaminobenzoic acid ester and cocounut oil acyl both sexes base diethyl acid disodium) and amine oxide (such as; stearic amine oxide), or even silicone surfactant, such as; dimethicone copolyol phosphate, such as by supplier Phoenix Chemical with title Pecosil PS 100The product of sale.
The emulsifier used may be the surfactant of polymerization, especially hot initiation gel polymer.
In special illustrative embodiments according to the present invention, the emulsifier is selected from: the i) salt of C16-C30 fatty acid, especially as derived from amine, for example, triethanolamine stearate;Ii) fatty alcohol (especially C8-C24Alcohol, preferably C12-C18Alcohol) oxyethylation/and/or oxypropylation ether (including 1 to 150 oxyethylene group and/or oxypropylene group), for example, with 2 oxyethylene groups stearyl alcohol ethylene oxide ether (INCI title " Steareth-2 ");Iii) fatty acid (especially C8-C24Acid, preferably C16-C22Acid) ester and polyalcohol (especially glycerol or sorbierite) ester, for example, tristerin, such as by supplier Evonik Goldschmidt with title Tegin MThe product of sale;Iv) the salt of its phosphate and they, for example, potassium cetyl phosphate (the Amphisol K from Givaudan);And/or v) fatty acid (especially C8-C24Acid, preferably C16-C22Acid) and oxyethylation and/or oxypropylation glycerol ether (there is 1 to 150 oxyethylene group and/or oxypropylene group) ester, such as, poly-ethylene oxide tristerin with 30 oxyethylene groups, for example, the product Tagat sold by supplier EvonikGoldschmidtS;And vi) its mixture.
It is more specifically suited for according to the present invention as emulsifier being stereth -2 (Steareth-2), tristerin, Triethanolamine Esters of Stearic Acid, poly-ethylene oxide tristerin, potassium cetyl phosphate and its mixture with 30 oxyethylene groups.
In an exemplary embodiment, composition of the invention includes at least one anionic surfactant and at least one nonionic surfactant, nonionic surfactant especially at 25 DEG C with HLB more than or equal to 8, the surfactant are preferably chosen from above-mentioned surfactant.
In an exemplary embodiment, composition of the invention includes at least one emulsifier selected from potassium cetyl phosphate, stereth -2 and its mixture.It advantageously, is the mixture of potassium cetyl phosphate and stereth -2.
Composition of the invention may include the emulsifier of 0.01% to 30% weight of total weight relative to the composition, preferably 1% to 15% weight, more preferably 2% to 10% weight.
In other exemplary embodiments, composition of the invention includes the emulsifier of at least one ester selected from fatty acid and polyalcohol, the especially ester (especially PEG-30 stearate) and its mixture of tristerin, fatty acid and polyethylene glycol.
Composition of the invention may also comprise at least one hydrophilic gelling agent.
Hydrophilic gelling agent
Available hydrophilic gelling agent can be selected from the present compositions:
● the homopolymer or copolymer of acrylic or methacrylic acid, its salt and ester, especially by supplier AlliedColloid with title Versicol FOr Versicol KThe product of sale, by supplier Ciba-Geigy with title Ultrahold 8The product and Synthalen K of saleThe polyacrylic acid of type;
● by supplier Hercules with title RetenThe sodium-salt form of the copolymer of the acrylic acid and acrylamide of sale, the sodium polymethacrylate sold by supplier Vanderbilt with title Darvan N ° 7, by supplier Henkel with title Hydagen FThe sodium salt of the polyhydroxycarboxyliacid acid of sale;
● the AMPS such as sold by supplier Clariant (by amino moiety neutralization and highly cross-linked polyacrylamide base methyl propane sulfonic acid);
● the copolymer (optionally cross-linked) and its mixture of AMPS and polyoxyethylated alkylmethacrylate.
Following water-soluble film forming polymers are also used as hydrophilic gelling agent.
The dry matter content of the hydrophilic gelling agent in the present compositions can be 0.01 to 30% weight relative to the composition total weight, preferably 0.5 to 20% weight, more preferable 1 to 15% weight.
Oily phase
Composition of the invention includes oily phase, wax of the oil mutually comprising at least one composition forming agent effect for being suitable for composition.Term " texturizer " is used for the compound for referring to assign composition institutional framework, arranges especially by the aggregation for forming particle.
Such texturizer keeps unmixability in water phase, can be the form being dispersed in the water phase.When there are sufficient amount, texturizer will form semisolid or solid quality at this time.
Wax
It is lipophilic, solid, deformable or non-deformable compound that the wax referred in context of the invention, which is preferably under environment temperature (25 DEG C), change with reversible solid-liquid state, fusing point is greater than or equal to 30 DEG C, can be up to 200 DEG C, especially be up to 120 DEG C.
When there are liquid oil phase, it can be made to dissolve each other with one or more oil to form wax+oil mixture of macroscopically homogeneous by the way that one or more waxes according to the present invention are added into the liquid phase (melting), but the temperature of the mixture is once restored to environment temperature, then obtain the recrystallization of the oil packet wax mixture.
Particularly, it is suitable for the invention the fusing point that wax can have and is greater than or equal to 45 DEG C, specifically greater than or equal to 55 DEG C.
In the sense of the invention, as by iso standard 11357-3, differential scanning calorimetry described in 1999 (DSC) observes fusion temperature corresponding with the maximum temperature of endothermic peak in heat analysis.The fusing point of differential scanning calorimetry wax can be used, for example, by supplier TA Instruments with title " MDSC 2920 "
The calorimeter of sale.
The experimental design of the measurement is as follows:
According to the rate of 10 DEG C/min, the first time temperature for making the waxy product of the 5mg being placed in crucible be warming up to from -20 DEG C 100 DEG C increases, then -20 DEG C are cooled to from 100 DEG C with the rate of 10 DEG C/min, are finally increased with second of temperature that the rate of 5 DEG C/min be warming up to from -20 DEG C 100 DEG C.During second of temperature rises, the variation as temperature funtion is being measured by the difference between the crucible of sky and the absorption heat of the crucible containing waxy product.The fusing point of compound is comparable to draw the temperature value of the vertex peak value of the curve of the variation of the absorption heat difference of the function as temperature.
Wax in composition is suitable for the invention to be selected from ambient temperature as wax and its mixture of solid, animal sources, plant source, mineral sources or synthesis.
Particularly, alkyl wax can be used, for example, natural beeswax (or cera alba), synthetic bees wax, Brazil wax, lanolin wax and insect wax, rice wax, candelila wax, ouricury wax, alfa wax, cork fibrous wax, sugarcane wax, Japan tallow and sumac wax;Lignite wax, microwax, paraffin and ceresine;Polyethylene wax, wax and wax copolymer and its ester by Fischer-Tropsch Synthesis acquisition.
It may also be mentioned that by the animal or plant C of the aliphatic chain with linear chain or branched chain8-C32The wax that the catalytic hydrogenation of oil obtains.
Among these waxes, it can particularly refer to: hydrogenated jojoba oil, hydrogenated sunflower oil, rilanit special, hydrogenated coconut oil and hydrogenated lanolin oil, the two (trihydroxy methyls -1 sold by supplier Heterene with title " Hest 2T-4S ", 1,1- propane) tetrastearate, the two (trihydroxy methyls -1 sold by supplier Heterene with title Hest 2T-4B, 1,1- propane) four behenates.
It can also refer to: silicone wax, for example, alkyl or oxy-dimethicone with 16 to 45 carbon atoms, and fluorination wax.
It can also use by hydrogenating the wax that esterification olive oil obtains with stearyl alcohol, particularly such as by supplier Sophim with title " 18 L 57 of Phytowax Olive " sale, or it is even particularly sold by the wax obtained with the castor oil of cetanol hydrogenation esterification by supplier Sophim with title " Phytowax ricin 16L64 and 22L73 ".Such wax description is in patent application FR-A-2792190.
In specific exemplary embodiment, composition according to the present invention may include at least one so-called " viscous " wax, and the viscosity having is greater than or equal to 0.7 N second (Ns), and hardness is less than or equal to 3.5 megapascal (MPa).
The cosmetic composition for being easy to be administered on eyelashes can be particularly obtained using sticky wax, is adhered well on eyelashes, smooth, uniform and thickening makeup is obtained.
The sticky wax used has viscosity can be in particular 0.7Ns to 30Ns, particularly greater than or equal to 1Ns, especially 1Ns to 20Ns, particularly greater than or equal to 2Ns, especially 2Ns to 10Ns, especially 2Ns to 5Ns.
The viscosity of wax be by measure exert oneself at 20 DEG C (wherein the power can be compressing force or drawing force) change with time and measure, using by supplier Rheo with title " TA-TX2i" sell and equipped with angle at 45 ° cone acrylate copolymer made of movable body (moving body) texturometer.
The experimental design of the measurement is as follows:
By wax be equal to+10 DEG C of fusing point of wax at a temperature of melt.The wax of melting pours into diameter is 25mm, depth is in the container of 20mm.The wax is recrystallized 24 hours for (25 DEG C) at ambient temperature, so that the smooth surface of wax saves the wax at least 1 hour then before measurement viscosity at 20 DEG C.
Move the movable body of texturometer with the speed of 0.5 mm/second (mm/s), then penetrating in wax and arriving penetration depth is 2mm.When it is 2mm that movable body, which penetrates in wax to penetration depth, stabilized 1 second of movable body (being equivalent to relaxation time) is then taken out with the speed of 0.5mm/s.
In relaxation time, (compressing force) power is greatly reduced until becoming zero, and then, during the taking-up of movable body, (drawing force) power becomes negative value, then increases to 0 value again.Viscosity is equivalent to the integral that curved portion when power (drawing force) is negative value is corresponded in the curve for the power for drawing the function as the time.Viscosity number is expressed as Ns.
The hardness that the sticky wax being usually applicable in has is less than or equal to 3.5Mpa, especially 0.01MPa to 3.5MPa, especially 0.05 to 3MPa, or even 0.1MPa to 2.5MPa.
The hardness of sticky wax is determined by measuring compressing force at 20 DEG C, use the texturometer sold by supplier Rheo with title TA-XT2, diameter equipped with the measuring speed movement with 0.1mm/s is the stainless steel cylinder of 2mm, and penetrating in wax and arriving penetration depth is 0.3mm.
The experimental design of the measurement is as follows:
By wax be equal to+10 DEG C of fusing point of wax at a temperature of melt.The wax of melting pours into diameter is 25mm, depth is in the container of 20mm.(25 DEG C) at ambient temperature recrystallize wax 24 hours, so as to the smooth surface of wax, then store the wax at 20 DEG C at least 1 hour before measuring hardness.
Move the movable body of texturometer with the speed of 0.1mm/s, then penetrating in wax and arriving penetration depth is 0.3mm.When it is 0.3mm that movable body, which penetrates in wax to penetration depth, stabilized 1 second of the movable body (phase one is inferior to relaxation time) is then taken out with the speed of 0.5mm/s.
Hardness number is the area that the maximum compression measured is contacted divided by texturometer with wax.
As sticky wax, C can be used20-C40Alkyl (hydroxy stearate acyloxy) stearate (that is, the alkyl has 20 to 40 carbon atoms), is used alone or as a mixture, especially has C shown in formula (II)20-C40Alkyl 12- (12 '-hydroxy stearate acyloxy) stearate:
The wherein mixture of the compound of integer or formula (II) of the m between 18-38.
Wax as a kind of is particularly by supplier Koster Keunen with title " Kester Wax K 82P" and " KesterWax K 80" sale.
The microwax sold by supplier Strahl & Pitsch with title SP18 can also be used, hardness is about 0.46Mpa, and viscosity number is about 1Ns.
The wax can exist in the form of water wax fine dispersion.Term " water wax fine dispersion " refers to the aqueous dispersion of wax particle of the size less than or equal to about 1 μm of the wherein Wax particles.
Wax fine dispersion is the stabilising dispersions of colloidal state Wax particles, they are particularly described in " Microemulsions Theory and Practice ", L.M.Prince is edited, academic press (Academic Press) (1977), and the 21-32 pages.
Particularly, then wax fine dispersion can be added slowly with stirring hot water and obtain by the presence of surfactant and optionally water, wax is melted.Observe the intermediate lotion for forming water-in-oil type, then
Inversion of phases ultimately produces the micro emulsion of oil-in-water type.When cooled, the stabilising dispersions of solid state wax colloidal particles are obtained.
Wax fine dispersion can also be obtained by using the mixture of stirring tool (such as ultrasound, high pressure homogenizer or turbine) stirring wax, surfactant and water.
The average-size that the particle of wax fine dispersion has is preferably less than 1 μm (especially 0.02-0.99 μm), and preferably less than 0.5 μm (especially 0.06 μm to 0.5 μm).
These particles are mainly made of the mixture of wax or wax.However, they may include the liposoluble additive or activating agent of a small amount of fat, oiliness and/or viscosity additives, surfactant and/or routine.
In advantageous exemplary implementation scheme, the composition also has at least one synthetic bees wax and/or Brazil wax, and particularly content is at least 2% weight, more particularly at least 3% based on the composition total weight, or even at least 4% weight.
The total content for the wax that composition of the invention can have is 2% to 35% weight of total weight relative to the composition, preferably 5% to 30% weight.
In advantageous exemplary implementation scheme, composition of the invention includes Brazil wax and/or synthetic bees wax, and particularly content is at least 2% weight, advantageously at least 3% weight, more particularly at least 4% weight based on the composition total weight.
Composition of the invention may include 2% to 30% weight of total weight (such as 2% to 25% weight) relative to the composition, or the Brazil wax and/or synthetic bees wax of even 2% to 10% weight (especially when the composition further comprises the wax other than synthetic bees wax and/or Brazil wax), or even 15% to 25% weight (especially when the composition does not contain the wax other than synthetic bees wax and/or Brazil wax), or even 5% to 30% weight.
In still other specific exemplary implementation schemes, composition of the invention includes the wax phase being made of the mixture of hydrogenated jojoba oil and beeswax.
Term " Brazil wax and/or synthetic bees wax " in the context of the present invention is for referring to or mixtures thereof Brazil wax, synthetic bees wax.
Brazil wax
Relative to the total weight of wax, Brazil wax generally comprises aliphatic ester (such as comprising 80% to 85% weight), fatty alcohol (such as comprising 10% to 15% weight), sour (such as comprising 3% to 6% weight) and hydrocarbon chain (such as comprising 1% to 3% weight).Particularly, the diol ester that can have high-content, especially with respect to the hydroxy fatty acid of about 20% weight of total weight of wax, the particularly from about cinnamic acid of 6% weight and high-content, especially with respect to about 10% weight of total weight of wax.
Content is that the aliphatic ester of 80% to 85% weight may include the monoesters of 36% to 40% weight, the hydroxy ester of the diester of the cinnamic acid of 26% to 34% weight and 10% to 14% weight.
Its fusing point is about 78 DEG C to 85 DEG C.
Brazil wax is in particular by supplier Strahl & Pitsch with trade name Carnauba Wax SP 63Or by supplier Baerlocher with trade name CeraubaTl sale.
Synthetic bees wax
The wax as known to INCI title " synthetic bees wax " generally comprises C16-C36Fatty acid and fatty alcohol.Its fusing point is about 50 DEG C to 60 DEG C.
Synthetic bees wax is in particular by supplier Evonik Goldschmidt with trade name Cyclochem326A sale.
Composition of the invention can also include at least one other optional tissue structure disperses agent, can be selected from: i) semi-crystalline polymer;Ii) lipophilic gelling agent;And iii) its mixture.
The content that the other dispersing agent can have is 1% to 40% weight of total weight relative to the present composition, preferably 2.5% to 30% weight, more preferably 5% to 25% weight.The amount of other dispersing agent can be adjusted according to the function of the topographic characteristics of the reagent by those skilled in the art.
Composition of the invention also may include at least one semi-crystalline polymer.
Semi-crystalline polymer
Term " semi-crystalline polymer " has crystallizable part, crystallizable side chain or crystallizable sequence for referring on its main chain, there is pars amorpha on main chain, and also with the polymer of level-one reversible transition temperature (especially fusion temperature, solid-liquid phase change).When crystallizable part is the shape of the crystallizable sequence of main polymer chain
When formula, the pars amorpha of polymer is the form of amorphous sequence.So the semi-crystalline polymer is sequential copolymer, for example, diblock type, three block type or more block types at least one crystallizable sequence and at least one amorphous sequence.Term " sequence " is often referred at least five identical repetitive units.The difference of the chemical property of crystallizable sequence and amorphous sequence.
The fusion temperature that semi-crystalline polymer has is greater than or equal to 30 DEG C, especially 30 DEG C to 80 DEG C, and preferably 30 DEG C to 60 DEG C.The fusion temperature is the temperature of first order phase change.
The fusion temperature can be measured by any of method, especially by using differential scanning calorimetry (DSC) (DSC).
Advantageously, the number-average molecular weight that the semi-crystalline polymer that the present invention applies has is greater than or equal to 1000.Advantageously, the number-average molecular weight Mn that the semi-crystalline polymer of composition of the invention has is 2000 to 800000, it is therefore preferable to 3000 to 500000, more preferably 4000 to 150000, particularly less than 100000, more particularly 4000 to 99000.Preferably, the number-average molecular weight that semi-crystalline polymer has is greater than 5600, that is, it is 5700 to 99000.The term " crystallizable chain or sequence " being used in the present invention refers to if it is individual chain or sequence, whether be higher or lower than fusion temperature according to temperature, can reversibly be converted to crystalline state from amorphous state." chain " in meaning of the present invention is one group of atom vertical or horizontal relative to main polymer chain.Sequence is the one group of atom to form main chain, a repetitive unit of polymer described in this group of atomic building.Advantageously, " crystallizable side chain " can be the chain at least six carbon atoms.
The semi-crystalline polymer can be selected from including that the sequential copolymer, each repetitive unit of at least one crystallizable sequence and at least one amorphous sequence contain the homopolymer and copolymer and its mixture of at least one crystallizable branch or side chain.
For example, such polymer description is in document EP 1 396 259.
In particular exemplary embodiment of the invention, the polymer, which comes from, is selected from C14-C22The monomer of the crystallizable chain of alkyl (methyl) acrylate of saturation.
As the particular instance for the structuring semi-crystalline polymer that can be used for the present composition, it is mentioned that: such as in " IntelimerIntelimer from supplier Landec described in polymers ", Landec IP22 (Rev.4-97) handbookProduct.
These polymer are that (25 DEG C) are solid forms at ambient temperature.They are loaded with crystallizable side chain.
The semi-crystalline polymer can be 0.1% to 30% weight of total weight relative to the composition there are content.
Composition of the invention may also comprise at least one lipophilic gelling agents.
Lipophilic gelling agents
The gelling agent that can be used in composition of the invention can be polymerization or molecule, organic or mineral, lipophilic gelling agents.
As the lipophilic gelling agents of mineral, it can be mentioned that the clay being optionally modified, for example, by C10To C22The hectorite of fatty acid ammonium chloride, for example, the hectorite being modified by distearyl acyl group alkyl dimethyl ammonium chloride, for example, by supplier Elementis with title Bentone 38VThe product of sale.
It can also be mentioned that the fumed silica possibly crossed by hydrophobic surface treatments, particle size is less than 1 μm.Possibly through making to cause the chemical reaction of the silanol quantity reduction existing for silica surface to carry out chemical modification to the surface of silica.Particularly, hydrophobic group substituted silane alcohol groups can be used, hydrophobic silica is then obtained.The hydrophobic group may is that
● trimethylsiloxy group group (trimethylsiloxyl), such as by the way that in the presence of hexamethyldisilazane, processing fumed silica is made.According to INCI (1995, sixth version), the silica handled in this way is referred to as " silica silylate ".For example, by supplier Degussa with title Aerosil R812The product of sale, and by supplier Cabot with title Cab-O-Sil TS-530The product of sale;With
● dimethylsilyl bis (dimethylsilyloxyl) or dimethyl silicone polymer base are such as particularly made by handling fumed silica in the presence of dimethyl silicone polymer or dimethyldichlorosilane.According to INCI (1995, sixth version), the silica handled in this way is referred to as " silylated dimethyl silica ".For example, by supplier Degussa with title Aerosil R972With Aerosil R974The product and supplier Cabot of sale are with title Cab-O-Sil TS-610With Cab-O-Sil TS-720The product of sale.
The particle size that the hydrophobicity fumed silica has can be nanoscale to micron-sized, for example, 5 nanometers (nm) to 200nm.
It can also use non-poly- with liquid oil phase (its liquid oil phase that can be composition of the invention) combination
Fit molecule organic gelling agent (also referred to as organic gelling agent), the organic gelling agent is the compound for the interaction that its molecule can be established physically between each other, causes molecule that self aggregation occurs and forms the Magnetic Properties of Three-Dimensional Supramolecular Complex reticular structure for causing liquid oil phase to form gelling.
Supermolecule network can be caused as the formation of the reticular structure (as caused by the accumulation or aggregation of organogel molecule) of small fiber, and the reticular structure of the small fiber can prevent liquid oil phase molecule mobile.
It forms the reticular structure of this small fiber and depends on the property (or chemical classes) of organic gel agent, the property of the property of substituent group and liquid oil phase that are had by the molecule for giving chemical classes to form the ability of gel.
The interaction physically has a variety of properties, but not including that cocrystallization.These interactions physically following classes in particular: self-complementary hydrogen coactive pattern (self-complementary hydrogen interaction) interaction;π interaction between unsaturated ring;Dipolar interaction;The coordinate bond of Organometallic derivatives;And their combination.In general, each molecule of organic gelling agent can establish a plurality of types of Physical interactions between surrounding molecular.Therefore, advantageously, organic gelling agent molecule according to the present invention contains group (more preferably at least two), at least one aromatic rings (more preferably at least two aromatic rings), at least one or more vinylation unsaturated bond and/or at least one or more asymmetric carbon atom that at least one can establish hydrogen bond.Preferably, the group for being capable of forming hydrogen bond is selected from hydroxyl, carbonyl, amine, carboxylic acid, amide, urea and benzyl, and combinations thereof.
The organic gelling agent dissolves in liquid oil phase after the heating, can obtain transparent uniform liquid phase.Under environment temperature (25 DEG C) and atmospheric pressure, it can be solid or liquid.
The molecule organic gelling agent that can be used in composition of the invention is in particular described at document " Specialist Surfactants ", D.Robb is edited, 1997, the 209-263 pages, 8th chapter, those of in P.Terech, European patent application EP-A-1068854 and EP-A-1086945 or even application WO-A-02/47031.
In these organic gelling agents, it can particularly refer to: the amide compound of carboxylic acid, the especially amide compound of tricarboxylic acids, such as, hexamethylene trimethamide (referring to application EP-A-1068854), have comprising 1 to 22 carbon atom (such as, 6-18 carbon atom) hydrocarbon chain diamides, the chain is non-substituted or selected replaces from least one of following substituent group substituent group: ester, urea and fluorine-based (referring to application
EP-A-1086945), the diamides especially obtained by the reaction of diaminocyclohexane (especially trans- diaminocyclohexane) and acid chloride, for example, N, N '-two-(dodecane acyl group) -1,2- diaminocyclohexane;N- acyl amino-acid amide, for example, the diamides reacted by N- acylamino acid with the amine with 1 to 22 carbon atom, for example, those of described in document WO-93/23008, and especially wherein acyl group represents C8-C22The N- acyl glutamic acid amides of alkyl chain, e.g., the N- lauroyl-Pidolidone dibutylamide and its mixture for being manufactured or being sold with title GP-1 by supplier Ajinomoto.
Organic lipophilic gelling agents of the polymerization are, such as:
● the elastic organic polyorganosiloxane with three-dimensional structure being partly or entirely crosslinked, for example, by Shin-Etsu company, supplier with title KSG6KSG16And KSG18Those of sale;The TrefilE-505C of supplier DowCorningOr Trefil E-506CThe Gransil SR-CYC of supplier Grant IndustriesSR DMF 10SR-DC556SR 5CYC gelSR DMF 10gelWith SRDC 556gelWith the SF 1204 of supplier General ElectricWith JK 113
● by the condensation polymer for the polyamide that polycondensation obtains between following substance: α) it is at least one sour, selected from the dicarboxylic acids at least 32 carbon atoms, for example, fatty acid dimer;And β) Alkylenediamine, especially ethylenediamine, wherein polyamide polymer includes at least one at least one monohydric alcohol of the carbon atom at least one with 12 to 30 straight chains and saturation or monoamine is esterified or amidated carboxylic end group, especially ethylenediamine and stearoyl dimerized linoleic acid ester copolymer, for example, the product sold by supplier Arizona Chemical with title Uniclear 100VG;
● the silicone polyamide of polysiloxane type, such as those of described in document US-A-5874069, US-A-5919441, US-A-6051216 and US-A-5981680, for example, by supplier Dow Corning with title Dow Corning 2-8179GellantThe product of sale;
● the alkyl chain being optionally saturated each of replaces sugar to have the galactomannans of one to six (especially two to four) hydroxyl, for example, by C1To C6(especially C1-C3) the alkylated guar gum of alkyl chain and its mixture;
● optionally hydrogenated " diblock ", " three block " or " emission type " sequential copolymer especially has styrene block and C3-C4Alkylene/alkylidene block.As diblock copolymer, preferably hydrogenate,
It can be mentioned that: styrene-ethylene and propylene copolymer, styrene-ethylene and butadiene copolymer.Diblock copolymer is in particular by supplier Kraton Polymers with title KratonThe product of G1701E sale.
The triblock copolymer preferably hydrogenated, it can be mentioned that following copolymer: styrene-ethylene and propylene-styrene copolymer;Styrene-ethylene and butadiene-styrene copolymer;Styrene-isoprene-styrene copolymer and styrene-butadiene-styrene.Triblock polymer is in particular by supplier Kraton Polymers with title KratonG1650、KratonG1652、KratonD1101、KratonD1102 and KratonD1160 sale.
The mixture of the styrene-butylene and ethylene-styrene copolymer and the star ethylene-propylene, Styrene copolymer of hydrogenation that three block can also be used to hydrogenate, what such mixture was in particular found in Permethyl 99A.For example, such mixture is by supplier Penreco with trade name VersagelM5960 and VersagelThe trade name sale of M5670.
Polystyrene and polyisoprene or polystyrene and polybutadiene copolymer can also be referred to, for example, by supplier BASF with title Luvitol HSBThose of sale.
In the lipophilic gelling agents being suitable for the invention in composition, it can be mentioned that the ester of dextrin and fatty acid, for example, dextrin palmitate, especially by supplier Chiba Flour with title Rheopearl TLOr Rheopearl KLThose of sale.
The lipophilic gelling agents can be 0.1% to 30% weight of total weight relative to the composition there are content.
Composition of the invention also may include at least one pulpous state compound.
Pulpous state compound
In the meaning of the present invention, term " pulpous state " should be understood as the lipophilicity aliphatic compound by reversible solid-liquid phase transformation, 23 DEG C at a temperature of, simultaneously include liquid part and solid portion.In other words, the initial fusion temperature of pulpous state compound is lower than 23 DEG C.When all quality of pulpous state compound are solid-state, pulpous state compound is considered as " solid-state ", and when all quality of pulpous state compound are liquid, pulpous state compound is considered as " liquid ".
The content of the liquid part of the pulpous state compound measured at 23 DEG C accounts for the 23% to 97% of the compound
Weight, preferably 25% to 85% weight of compound.
At 23 DEG C, the liquid part weight of pulpous state compound is equal to the ratio of the melting enthalpy of consumed melting enthalpy and pulpous state compound at 23 DEG C.
The melting enthalpy of pulpous state compound is by the compound as the solid state transformed amount for energy consumed by liquid.It is expressed as joule/gram (J/g).
Using iso standard 11357-3:1999, the melting enthalpy amount of the pulpous state compound is equal to the area under a curve in the thermogram measured using differential scanning calorimetry (DSC) (DSC) with 5 DEG C/min or 10 DEG C/min heatings, for example, the thermal analyzer sold using supplier TA Instrument with title MDSC 2920.
Consumed melting enthalpy is the amount being absorbed by the sample with by it from the solid state transformed energy for the phase being made of liquid part and solid portion having at 23 DEG C at 23 DEG C.
The liquid part of the pulpous state compound measured at 32 DEG C preferably comprises from 40% to 100% weight of the compound, 50% to 100% weight of the more preferably described compound.When the liquid part of the pulpous state compound measured at 32 DEG C is equal to 100%, the outlet temperature of the pulpous state compound melts is less than or equal to 32 DEG C.
The percentage of the liquid part of the pulpous state compound measured at 32 DEG C be equal at 32 DEG C consumed melting enthalpy divided by the melting enthalpy of the pulpous state compound ratio.Mode same with the melting enthalpy consumed at 23 DEG C with calculating, calculates the melting enthalpy consumed at 32 DEG C.
The pulpous state compound is preferably chosen from the compound of synthesis compound and plant origin.Pulpous state compound can be synthesized by the initial substance of plant origin and is made.
The pulpous state compound is advantageously selected from:
● lanolin and its derivative;
● the silicone compounds of optional aggregation;
● the fluoride of optional aggregation;
● polyvinyl, especially:
● olefin homo;
● olefin copolymer;With
● the homopolymer and copolymer of hydrogenated diene;
● preferably there is C8-C30The oligomer of the linear chain or branched chain of the homopolymer or copolymer of alkyl (methyl) acrylate of alkyl;;
● there is C8-C30The homopolymer and copolymer oligomer of the vinyl esters of alkyl;
● there is C8-C30The homopolymer and copolymer oligomer of the vinethene of alkyl;
● by one or more C2-C100Glycol (preferably C2-C50Glycol) between the obtained fat-soluble polyethers of poly- etherification,
● ester and polyester;With
● its mixture.
The pulpous state compound is preferably polymer, especially hydrocarbon.
Preferred siloxanes and fluorination pulpous state compound are the poly- methyl trifluoro that is manufactured by Shin-Etsu with title X22-1088 for hydroxypropyl methyl alkyl dimethicone.
When the pulpous state compound is siloxanes and/or fluorinated polymer, the composition advantageously comprises compatibilizing agent, for example, short-chain ester, such as isodecyl base ester.
In fat-soluble polyethers, particularly preferably there is long-chain C6-C30The weight ratio of alkylene oxide in the ethylene oxide of alkylene oxide and/or the copolymer of propylene oxide, more preferably ethylene oxide and/or propylene oxide and copolymer is the copolymer of (5/95) to (70/30).In this family, it can particularly refer to that the copolymer for the long chain alkylene oxide being for example distributed in block, the average molecular weight having are 1000 to 10000, such as, the block copolymer of polyoxyethylene and poly- dodecylene glycol, for example, by Akzo Nobel with trade mark Elfacos ST9The copolymer of the ether of the dodecanediol (22mol) and polyethylene glycol (45OE) of sale.
In these esters, following is particularly preferred:
● oligomeric glyceride, especially double glyceride, the condensation product of adipic acid and glycerol that especially wherein the part of hydroxyl of glycerol is reacted with fatty acid mixt, for example, especially by supplier Sasol with trade mark Softisan 649Those of sale, the fatty acid such as stearic acid, capric acid, isostearic acid and 12- hydroxy stearic acid;
● phytosterin ester;
● pentaerythritol ester;
● the ester formed by following substance:
● at least one alcohol, at least one alcohol are Guerbet (Guerbet) alcohol;With
● the diacid dimer formed by least one unsaturated fatty acid, for example, the ester of the tall oil fatty acid dimer with 36 carbon atoms and following mixture: i) with the Guerbet alcohol and ii of 32 carbon atoms) docosanol;The ester of linoleic acid dimer and the mixture of two kinds of Guerbet alcohols (2- myristyl-octadecanol (32 carbon atoms) and 2- cetyl eicosanol (36 carbon atoms));
● by C4-C50The carboxyl polyacid or dicarboxylic acids and C of linear chain or branched chain2-C50The noncrosslinking polyester that polyalcohol or glycol polycondensation obtain;
● the polyester being esterified by the polycarboxylic acid of hydroxyaliphatic carboxylic acids' ester, for example, the Risocast DA-L sold by Japanese supplier Kokyu Alcohol KogyoAnd RisocastDA-HIt is the ester obtained by the esterification of rilanit special and dilinoleic acid or isostearic acid,
● by the aliphatic ester (Salacos HCIS (the V)-L sold by supplier Nisshin Oil) for the ester that aliphatic carboxylic acid is esterified hydroxyaliphatic carboxylic acids' ester.
The aliphatic carboxylic acid has 4 to 30, is preferably 8 to 30 carbon atoms.It is preferably chosen from: caproic acid, enanthic acid, octanoic acid, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, Heptadecanoic acide, octadecanoid acid, isostearic acid, nonadecylic acid, arachic acid, different arachidic acid (isoarachidic acid), octyldodecanoic acid, heneicosanoic acid and behenic acid and its mixture.
The aliphatic carboxylic acid is preferably branch.
The hydroxyaliphatic carboxylic acids are advantageously derived from 2 to 40 carbon atoms (preferably 10 to 34, more preferably 12 to 28 carbon atoms) and 1 to 20 hydroxyl (preferably 1 to 10, more preferably 1 to 6 hydroxyl) hydroxylated fatty race carboxylic acid.Hydroxyaliphatic carboxylic acids' ester is selected from:
A) partial esterification for the straight chain monohydric aliphatic monocarboxylic acid being saturated or the ester being all esterified;
B) partial esterification of unsaturated monohydric aliphatic monocarboxylic acid or the ester being all esterified;
C) partial esterification for the monohydric aliphatic carboxyl polyacid being saturated or the ester being all esterified;
D) partial esterification for the polyhydroxy fatty race carboxyl polyacid being saturated or the ester being all esterified;
E) C reacted with monohydroxy or polyhydroxy fatty race monoacid or polyacid2-C16The partial esterification of aliphatic polyol or the ester being all esterified;With
F) its mixture.
The aliphatic ester of the ester is advantageously selected from:
● the ester or rilanit special list isostearate that rilanit special and isostearic acid are obtained in the ratio esterification of 1 to 1 (1/1);
● the ester or rilanit special diisopstearate that rilanit special and isostearic acid are obtained in the ratio esterification of 1 to 2 (1/2);
● three isostearate of ester or rilanit special that rilanit special and isostearic acid are obtained in the ratio esterification of 1 to 3 (1/3);With
● its mixture.
Preferably, the pulpous state compound is selected from the compound of plant origin.
Among these compounds, it can particularly refer to: the jojoba oil of isomerization, for example, by supplier DesertWhale with trade name Iso-Jojoba-50The part hydrogenated jojoba oil of the trans isomerism of manufacture or sale;Orange wax, for example, by supplier Koster Keunen with title Orange Peel WaxThe product of sale;Sher butter;Partially hydrogenated olive oil, for example, by supplier Soliance with title BeurroliveThe compound of sale;Cocoa fatty oil, mango oil, for example, the Lipex from supplier Aarhuskarlsnamn302。
The pulpous state compound can account for 0.5% to 20% based on composition total weight, preferably 1% to 15% weight.
Liquid oil phase
Composition of the invention may include liquid oil phase.
In the meaning of the present invention, term " liquid oil phase " should refer to the oily phase under environment temperature (25 DEG C) and atmospheric pressure (760 millimetress of mercury (mmHg)) for liquid, be made of at ambient temperature for the non-aqueous lipid matter of liquid one or more.These lipid matters are referred to as oil.
The oil can be selected from ethereal oil, nonvolatile oil and its mixture.
In the meaning of the present invention, term " ethereal oil " refers under environment temperature and atmospheric pressure the oil of interior evaporation when small less than one when touching skin or keratin fiber.Ethereal oil of the invention be at ambient temperature be volatile organic solvent and/or volatilization that liquid and vapour pressure at room temperature and atmospheric pressure are not zero
Property cosmetics oil, the vapour pressure especially 0.13pascals (Pa) to 40000Pa (i.e. 10-3- 300mmHg), in particular 1.3Pa to 13000Pa (i.e. 0.01mmHg to 100mmHg), more particularly 1.3Pa to 1300Pa (i.e. 0.01mmHg to 10mmHg).
On the contrary, " nonvolatile oil " refers to the oil being retained in the time at least over one hour on skin or keratin fiber under environment temperature and atmospheric pressure, the vapour pressure particularly having is less than 10-3MmHg is less than 0.13Pa.
These oil can be with hydrocarbon ils, silicone oil, fluorinated oil and its mixture.
Term " hydrocarbon ils " refers to that main includes the oil of hydrogen and carbon atom, it is also possible to include oxygen, nitrogen, sulphur and/or phosphorus atoms.
As the example for being suitable for the invention oil, it can be mentioned that:
● the hydrocarbon ils of animal origin, such as perhydro squalene;
● plant alkyl oil, such as the triglycerides of the fatty acid of 4 to 24 carbon atoms of liquid, such as, the triglycerides of enanthic acid or octanoic acid, or even sunflower oil, corn oil, soybean oil, bone marrow oil, grape seed oil, sesame seed oil, hazelnut oil, apricot kernel oil, macadimia nut oil, castor oil, Avocado Oil, caprylic/capric triglyceride, for example, by the supplier Stearineries Dubois product sold or product, the jojoba oil, galam butter sold by supplier Dynamit Nobel with title Miglyol 810,812 and 818;
● mineral or synthesis source linear chain or branched chain hydrocarbon, for example, paraffin oil and its derivative, vaseline, poly decene, polybutene, hydrogenated polybutene (for example, Parleam), the hydrocarbon ils with 8 to 16 carbon atoms, especially C8-C16Branched paraffin, for example, the C of petroleum resources8-C16Isoalkane (also referred to as isoparaffin), such as Permethyl 99A (also referred to as 2,2,4,4,6- five methylheptanes), isodecane and isohexadecane, and for example, with trade name IsoparsOr PermetylThe oil of sale, or even petroleum distillate, such as by supplier Shell with title Shell SoltThose of sale;
● the synthetic ester and ether of synthetic ester and ether, especially fatty acid, for example, chemical formula is R1COOR2Oil, wherein R1Indicate the higher fatty acid residue containing 1 to 40 carbon atom, R2Indicate the hydrocarbyl chain with 1 to 40 carbon atom, and R1+R2>=10, for example, purcellin oil, isononyl isononanoate, isopropyl myristate, palmitinic acid 2- ethylhexyl, stearic acid 2- octyldodecyl ester, erucic acid 2- octyldodecyl ester, isostearyl isostearate ester, trimellitic acid tridecane ester;Hydroxylating ester, for example, the different tristearin of lactic acid
Alcohol ester, octyl hydroxy stearic acid ester, octyldodecyl hydroxy stearic acid ester, two isooctadecanol ester of malic acid, three isohexadecane ester of citric acid, heptanoate, caprylate or the decylate of fatty alcohol;Polyol ester, for example, two sad propylene glycol esters, two enanthic acid neopentyl glycol ester or two isononanoic acid diethylene glycol (DEG) esters;And pentaerythritol ester, for example, pentaerythrite base pentaerythritol tetraisostearate;
● the fatty alcohol with 12 to 26 carbon atoms, for example, octyldodecanol, 2- butyl octanol, 2- hexyl decyl alcohol, 2- undecylpentadecanol, oleyl alcohol;
● fluorinated oil can be part hydrocarbon ils and/or silicone oil;
● silicone oil, for example, optionally volatile straight chain or cricoid dimethyl silicone polymer (PDMS);The dimethyl silicone polymer of the alkyl of side chain or end containing silicone chains, alkoxy or phenyl, these groups have 2 to 24 carbon atoms;Phenyl silicones, for example, phenyl front three polysiloxanes, phenyl dimethicone, phenyl trimethicone siloxy diphenyl siloxane, diphenyl dimethicone, diphenyl methyl diphenyl trisiloxanes or 2- phenylethyl trimethylsiloxysilicates, and
● its mixture.
Preferably, the molecular weight of the oil is greater than or equal to 250 grams/mol (g/mol), in particular 250g/mol to 10000g/mol, preferably larger or equal than 300g/mol, in particular 300g/mol to 8000g/mol, more preferably it is greater than or equal to 400g/mol, in particular 400g/mol to 5000g/mol.
The oil can be selected from:
● polybutene, such as, Indopol H-100 (molecular weight (MM) 965g/mol), Indopol H-300 (MM=1340g/mol) and the Indopol H-1500 (MM=2160g/mol) for being sold or being manufactured by supplier Amoco;
● Parleam, for example, the Panalane H-300E (MM=1340g/mol) for being sold or being manufactured by supplier Amoco, the Viseal 20000 (MM=6000g/mol) for being sold or being manufactured by supplier Synteal and by the small Rewopal PIB 1000 (MM=1000g/mol) for selling or manufacturing of supplier Witco;
● poly decene and Nexbase 2004, such as: the Puresyn 10 (MM=723g/mol) and Puresyn 150 (MM=9200g/mol) for being sold by supplier Mobil Chemicals or being manufactured,
● ester, such as:
● the straight-chain fatty acid ester that entire carbon atom is 30 to 70, for example, four pelargonate (MM of pentaerythrite
=697.05g/mol);
● hydroxylating ester, such as two isooctadecanol ester (MM=639g/mol) of malic acid;
● aromatic ester, such as trimellitic acid tridecane ester (MM=757.19g/mol);With
●C24-C28The fatty alcohol of branch or the ester of fatty acid, such as, applying for those described in EP-A-0955039, especially three isohexadecane ester (MM=865g/mol) of citric acid, four isononoate of pentaerythrite (MM=697.05g/mol), three glyceryl isostearates (MM=891.51g/mol), three (2- decyl) four glycerol decanoates (MM=1143.98g/mol), four isostearic acid pentaerythritol esters (MM=1202.02g/mol), -2 pentaerythritol tetraisostearate of polyglyceryl (MM=1232.04g/mol) or even pentaerythrite four (2- decyl) four decylates (MM=1538.66g/mol),
● the oil of plant origin, such as sesame oil (MM=820.6g/mol);With
● its mixture.
The liquid oil phase can account for 0.1% to 30% weight or 0.1% to 20% weight, particularly 2% to 10% weight based on composition total weight.
In specific exemplary embodiment, the composition does not contain any liquid oil phase.In the context of the present invention, " do not contain liquid oil phase " refers to containing less than 5%, the composition of preferably less than 1% liquid oil phase.
Composition of the invention can also include at least one film forming polymer, in particular selected from free radical film forming polymer, film forming condensation polymer and natural film forming polymer and its mixture.
Film forming polymer
In the present invention, term " film forming polymer " refers to by its own or is capable of forming in the presence of coalescing agent the suitable polymer for the continuous film of macroscopic view being attached on eyelashes, preferably sticking film, more preferably its cohesive force and the mechanical performance film that allows the film to be separated and can be used under discrete state, it is described can be under discrete state using for for example when preparing the film on inviscid surface (for example, teflon coating surface or silicone coating surface) by being poured over.
The film forming polymer suitable for the present composition, it is mentioned that free radical type synthetic polymer or condensation polymer type synthetic polymer, natural polymer and its mixture.
The dry matter content of the film forming polymer in the present compositions can be 0.1% to 30% weight of dry matter total weight relative to the composition, preferably 0.5% to 20% weight, more preferable 1% to 15% weight.
Composition of the invention also may include at least one free radical film forming polymer.
Free radical film forming polymer
Term " free radical film forming polymer ", which is used to refer to, polymerize obtained polymer by unsaturated monomer (especially ethylenically unsaturated monomer), and each monomer is suitable for homopolymerization (being different from polycondensation).
The free radical type film forming polymer can in particular polyvinyl or copolymer, especially acrylate copolymer.
Ethylene film forming polymer can be obtained by polymerizeing the polymerization ethylenically unsaturated monomer at least one acidic group and/or the ester of the acid monomers and/or the amide of the acid monomers.
As the monomer for being loaded with acidic group, α, β-ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid can be used.(methyl) acrylic acid and crotonic acid is preferably used, more preferred with (methyl) acrylic acid.
The ester of acid monomers is advantageously selected from the ester (also referred to as (methyl) acrylate) of (methyl) acrylic acid, especially alkyl (methyl) acrylate, especially C1-C30Alkyl (methyl) acrylate, it is therefore preferable to C1-C20Alkyl (methyl) acrylate, (methyl) acrylate of aryl, especially C6-C10Aryl (methyl) acrylate, hydroxyalkyl (methyl) acrylate, especially C2-C6Hydroxyalkyl (methyl) acrylate.
In alkyl (methyl) acrylate, it can be mentioned that methyl methacrylate, ethyl methacrylate, butyl methacrylate, Isobutyl methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate and cyclohexyl methacrylate.
In hydroxyalkyl (methyl) acrylate, it can be mentioned that hydroxy ethyl methacrylate, 2- hydroxypropyl acrylate, hydroxyethyl meth acrylate and 2- hydroxypropyl methacrylate.
In aryl (methyl) acrylate, it can be mentioned that benzyl acrylate and phenyl acrylate.
The ester of particularly preferred (methyl) acrylic acid is alkyl (methyl) acrylate.
In the present invention, the alkyl of ester can be fluorinated or fluoridized, that is, some or all of alcohol radical
Hydrogen atom is replaced by fluorine atoms.
In the amide of acid monomers, it can be mentioned that such as (methyl) acrylamide, especially N- alkyl (methyl) acrylamide, especially C2-C12Alkyl (methyl) acrylamide.In N- alkyl (methyl) acrylamide, it can be mentioned that N- ethyl acrylamide, N tert butyl acrylamide, N- t-octyl acrylamide and N- undecyl acrylamide.
The ethylene film forming polymer can also by selected from vinyl acetate monomer and styrene monomer homopolymerization or copolymerization obtain.Particularly, these monomers can polymerize with acid monomers and/or its ester and/or its amide, than those of as alluded to above.
As the example of vinyl acetate, it can be mentioned that vinyl acetate, vinyl neodecanoate, new vinyl acetate acid, vinyl benzoate and tert-butylbenzoate.
As styrene monomer, it can be mentioned that styrene and α-methylstyrene.
Composition of the invention also may include at least one film forming condensation polymer.
Form a film condensation polymer
In film forming condensation polymer, it can be mentioned that polyurethane, polyester, polyesteramide, polyamide, epoxy ester resin and polyureas.
Polyurethane can be selected from anion, cation, nonionic or amphotenic polkyurethanes, acroleic acid polyurethane, polyvinylpyrrolidone-polyurethane, polyester-polyurethane, polyether-polyurethane, polyureas, polyurea-polyuretahne and its mixture.
In accordance with known methods, polyester can be obtained by polycondensation dicarboxylic acids and polyalcohol (especially glycol).
The dicarboxylic acids can be aliphatic, alicyclic or aromatic.Example as such acid, it can be mentioned that: oxalic acid, malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2- dimethylated pentanedioic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3- cyclohexane diacid, 1,4- cyclohexane diacid, M-phthalic acid, terephthalic acid (TPA), 2, camphane dicarboxylic acids, diglycolic acid, thio-2 acid, 2 drop in 5-, 5- naphthylene dicarboxylic acid, 2,6- naphthylene dicarboxylic acid.These dicarboxylic acid monomers can be used alone or at least two dicarboxylic acid monomers are applied in combination.In these monomers, preferably phthalic acid, M-phthalic acid or terephthalic acid (TPA).
The dihydric alcohol can be selected from aliphatic, alicyclic and aromatic.Preferably, the glycol used is selected from: ethylene glycol, diethylene glycol (DEG), triethylene glycol, 1,3-PD, cyclohexanedimethanol, 4- butanediol.As other polyalcohols, glycerol, pentaerythrite, sorbierite, trimethylolpropane can be used.
It can be by mode identical with polyester, by the way that diacid and diamines or amino alcohol polycondensation are obtained polyesteramide.As diamines, ethylenediamine, hexamethylene diamine, neighbour or p-phenylenediamine can be used.As amino alcohol, monoethanolamine can be used.
The polyester can also include that at least one is loaded at least one-SO3M base (M indicates hydrogen atom), ammonium ion NH4 +Or metal ion (such as one of following ions: Na+、Li+、K+、Mg2+、Ca2+、Cu2+、Fe2+Or Fe3+Ion) monomer.Particularly, it can be used including this-SO3The difunctional aromatic monomer of M base.
Also it is loaded with-SO as described above3The aromatic rings of the difunctional aromatic monomer of M base can be selected from following ring: benzene, naphthalene, anthracene, biphenyl, oxo xenyl (oxydiphenyl), sulfonyl xenyl (sulfonylbiphenyl), methylenediphenyl base (methylenebiphenyl).As being also loaded with-SO3The example of the difunctional aromatic monomer of M base, it can be mentioned that: sulfoisophthalic acid, sulfoterephthalic, sulfosalicylic phthalate, 4- sulfo group naphthalene -2,7- dicarboxylic acids.
It is preferable to use copolymer be the copolymer obtained more particularly by polycondensation diethylene glycol (DEG), cyclohexane dimethanol, M-phthalic acid, sulfoisophthalic acid based on isophthalic acid ester and sulfoisophthalic acid ester.
In addition, composition of the invention may include at least one natural film forming polymer.
Natural film forming polymer
Natural optionally modified film forming polymer can be selected from: lac resin, sandarac, gum dammar, elemi glue, jade-like stone bar resin, cellulosic polymer and its mixture.
In an exemplary implementation scheme of composition of the invention, the film forming polymer can be water-soluble polymer, can reside in the water phase of composition;Then, the polymer is dissolved in the water phase of the composition.
In other modified example embodiments of the present composition, the film forming polymer can be dissolved in comprising organic solvent or oil liquid oil phase in polymer, such as those described above (at this point, this at
Membrane polymer is referred to as lipophilic polymer).Preferably, the liquid oil phase preferably includes ethereal oil, it may be possible to mix with nonvolatile oil, these oil can be selected from above-mentioned oil.
Example as lipophilic polymer, it is mentioned that vinyl acetate (the oxygen atom of vinyl Direct Bonding ester group, saturation with 1 to 19 carbon atom, straight chain or branch alkyl vinyl acetate bonding ester group carbonyl) and at least one other monomer copolymer, other monomers can be vinyl acetate (being different from existing vinyl acetate), alpha-olefin (has 8 to 28 carbon atoms), alkyl vinyl ester (wherein alkyl has 2 to 18 carbon atoms), allyl ester or methacrylic ester (methallylic the ester) (carbonyl of bonding ester group, saturation with 1 to 19 carbon atom, straight chain or branch alkyl).
These copolymers can be crosslinked under the auxiliary of reagent, the reagent can be any of ethylene type or allyl type or methallyl fundamental mode, for example, tetraallyloxyethane (tetraallyoxyethane), divinylbenzene, suberic acid diethyl enester, dodecanedioic acid diethyl enester and octadecane diacid diethyl enester.
As the example of these copolymers, it can be mentioned that following copolymers: vinyl acetate and stearic acid allyl ester;Vinyl acetate and vinyl laurate;Vinyl acetate and stearic acid vinyl ester;Vinyl acetate and octadecylene;Vinyl acetate and octadecyl vinyl ester;Vinyl propionate and lauric acid allyl ester;Vinyl propionate and vinyl laurate;Stearic acid vinyl ester and octadecene -1;Vinyl acetate and laurylene -1;Stearic acid vinyl ester and ethyl vinyl ether;Vinyl propionate and hexadecyl vinyl ether;Stearic acid vinyl ester and allyl acetate;2,2- dimethyl-octa acid esters and vinyl laurate;2,2- dimethyl valeric acid allyl esters and vinyl laurate;Dimethyl propylene vinyl acetate and stearic acid vinyl ester;Dimethyl propylene allyl propionate and stearic acid vinyl ester;With the vinyl propionate and stearic acid vinyl ester of 0.2% divinyl benzene crosslinked;With the dimethyl propylene vinyl acetate and vinyl laurate of 0.2% divinyl benzene crosslinked;With the vinyl acetate and octadecyl vinyl ether of the crosslinking of 0.2% tetraallyloxyethane;With the vinyl acetate and stearic allyl propionate of 0.2% divinyl benzene crosslinked;With the vinylacetate and 1- octadecene of 0.2% divinyl benzene crosslinked and with the propionic acid allyl ester of 0.2% divinyl benzene crosslinked and stearic allyl acid esters.
As film-forming liposoluble polymer, can also refer to fat-soluble copolymer, especially by with 9 to 22 carbon atoms vinyl acetate or acrylate or alkylmethacrylate those of be copolymerized to obtain, the alkyl has 10 to 20 carbon atoms.
Such fat-soluble copolymer can be selected from polyvinyl stearate, utilize divinylbenzene, two allyls
Base ether or polyvinyl stearate, poly- (methyl) stearyl acrylate alcohol ester, polyvinyl laurate and poly- (methyl) the lauryl alcohol ester of diallyl phthalate crosslinking, these poly- (methyl) acrylate can be to be crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol.
Fat-soluble copolymer defined above is known, and is particularly described in application FR-A-2232303;Its weight average molecular weight can be 2000 to 500000, it is therefore preferable to 4000 to 200000.
As being suitable for the invention film-forming liposoluble polymer, it can be mentioned that: polyolefin, especially C2-C20The copolymer of alkene, for example, polybutene, the C with the linear chain or branched chain being optionally saturated1To C8The alkylcellulose of alkyl, for example, ethyl cellulose and propyl cellulose, the copolymer of vinylpyrrolidone (VP), especially vinylpyrrolidone and C2To C40Alkene (preferably C3To C20) copolymer and vinyl pyrrolidone copolymer.As the example for being suitable for the invention VP copolymer, it can be mentioned that following copolymers: VP and vinyl acetate co-polymer;VP and ethyl methacrylate copolymers;Butylation polyvinylpyrrolidone (PVP);VP and ethyl methacrylate and methacrylic acid copolymer;VP and icosa alkene copolymer;VP and hexadecene copolymer;VP and 30 alkene copolymers;VP and styrol copolymer;VP and acrylic acid and lauryl methacrylate copolymer.
It can be mentioned that silicone resin, be the organo-siloxanes polymer of crosslinking, wherein resin is generally soluble in silicone oil or can be swollen by silicone oil.The nomenclature of silicone resin is known as " MDTQ ", and resin is described as the function for the different silicones monomeric unit that it contains, and each of " MDTQ " letter indicates a cell type.
As the example of commercially available obtainable poly methyl silsesquioxane resin, it can be mentioned that it is following those:
● it is sold by supplier Wacker with title Resin MK, such as Belsil PMS MK;With
● it is sold by supplier Shin-Etsu with title KR-220L.
As siloxysilicate material (siloxysilicate) resin, it can be mentioned that trimethylsiloxysilicate (TMS) resin, for example, being sold by supplier General Electric with title SR 1000 or sold with title TMS 803 by supplier Wacker.It can also refer to the trimethylsiloxysilicate resin sold in a solvent, such as, cyclomethicone, it is being sold by supplier Shin-Etsu with title " KF-7312J " and by supplier Dow Corning with title " DC 749 ", " DC 593 " sell.
The siloxane resin copolymer that can also be referred to, than those of as alluded to above and dimethyl silicone polymer
Copolymer, for example, by supplier Dow Corning with title Bio-PSAThe pressure-sensitive adhesive copolymer of sale, and description is in US 5162410, or the silicone copolymers even reacted as silicone resin (as escribed above those) and diorganosiloxane (such as document WO 2004/073626 described in).
In an exemplary implementation scheme of the invention, the film forming polymer is film forming linear sequence ethylenic polymer, at least one First ray and at least one second sequence with different glass conversion temperature (Tg) are preferably included, first and second sequence is by including that at least one intermediate sequence for constituting monomer and the monomer of at least one the second sequence of composition of First ray links together.
Advantageously, the first and second sequences of the sequential polymerization object are immiscible.
Such polymer for example describes in EP 1411069 or WO 04/028488.
The film forming polymer can also be present in the composition in the form of the particle being dispersed in water phase or nonaqueous solvents phase, it is commonly referred to as latex or pseudo-gums cream.It is well known to those skilled in the art for preparing the technology of this dispersion.
As the aqueous dispersion of film forming polymer, can be used by supplier Avecia-Neoresins with title Neocryl XK-90Neocryl A-1070Neocryl A-1090Neocryl BT-62NeocrylA-1079With Neocryl A-523The acrylic acid dispersion of sale;By supplier Dow Chemical with title Dow Latex 432The acrylic acid dispersion of sale;By supplier Daito Kasey Kogyo with 5000 AD of title DaitosolOr 5000 SJ of DaitosolThe acrylic acid dispersion of sale;By supplier Interpolymer with title Syntran 5760The acrylic acid dispersion of sale;The acrylic acid dispersion sold by supplier Rohm & Haas with title Allianz OPT;By supplier Johnson Polymer with trade name JoncrylThe acrylic acid of sale or the aqueous dispersion of styrene/acrylic polymer;Or even by supplier Avecia-Neoresins with title Neorez R-981With Neorez R-974The polyurethane aqueous dispersion body of sale;By supplier Goodrich with title Avalure UR-405Avalure UR-410AvalureUR-425Avalure UR-450Sancure 875Sancure 861Sancure 878With Sancure 2060The polyurethane aqueous dispersion body of sale;By supplier Bayer with title Impranil 85The polyurethane aqueous dispersion body of sale;Aquamere H-1511 from supplier HydromerBy supplier Eastman Chemical Products with trade name Eastman AQThe sulfopolyester of sale;Disperse with ethylene
Body, for example, the Mexomer PAM from supplier ChimexAnd its mixture.
The example of nonaqueous dispersion as film forming polymer, it can be mentioned that the acrylic acid dispersion in Permethyl 99A, such as the Mexomer PAP from supplier ChimexThe microparticle dispersion of the ethylenic polymer of grafting in liquid oil phase, preferably acrylate copolymer, the ethylenic polymer advantageously disperse in the case where additional stabilizer is not present in microparticle surfaces, are such as particularly described in file WO 04/055081.
Composition of the invention can also include at least one plasticizer that film forming polymer can be promoted to form film.Such plasticizer can be selected from all compounds known to those skilled in the art for being adapted for carrying out required function.
The composition can also be the composition forms comprising oil-continuous phase.The oil mutually may include at least one compound for being selected from wax as described above, semi-crystalline polymer, lipophilic gelling agents, pulpous state compound, oil and lipophilicity film forming polymer.
When the composition includes oil-continuous phase, existing content is preferably to be greater than 40%, preferably more than 45% weight based on composition total weight, more preferably greater than 50% weight.
In this case, the amount of wax as described above, semi-crystalline polymer, lipophilic gelling agents, pulpous state compound and lipophilicity film forming polymer preferably meets each independently as above sets;The amount of oil is preferably to be greater than 40%, preferably more than 45% weight based on composition total weight;Finally, it is preferable that the amount of water and/or water-soluble solvent, surfactant and hydrophilic gelling agent is each independently less than or equal to 10% weight, preferably less or equal to 5% weight.
Composition of the invention may also comprise at least one colorant.
Colorant
Composition of the invention may include at least one at least one colorant selected from flour, lipid-soluble dye and water-soluble dye.
Powdery colorant can be selected from pigment and nacre (mother-of-pearl).
The pigment can be white or colored, inorganic and/or organic, cated or uncoated.In inorganic pigment, it can be mentioned that oxide, manganese violet, ultramarine blue, hydrated chromium and the barba hispanica of titanium dioxide (after can be surface treatment), zirconium oxide, zinc oxide or cerium oxide and iron or chromium.In organic pigment,
It can be mentioned that carbon black, D & C type pigment, the color lake based on alkermes, barium, strontium, calcium or aluminium.
The mother-of-pearl can selected from white pearlescent pigment (such as, the mica coated by titanium or bismuth oxychloride), colored pearlescent pigment (such as, the odenite of odenite containing ferriferous oxide, particularly the odenite containing barba hispanica or chromium oxide, the organic pigment containing the above-mentioned type), and the pearlescent pigment based on bismuth oxychloride.
For example, the lipid-soluble dye is that tonyred, D&C be red 17, D&C is green 6, beta carotene, soybean oil, sudan brown, D&C Huang 11, D&C purple 2, D&C orange 5, quinoline yellow and annatto.
The colorant in the present compositions can be 0.01% to 30% weight relative to the composition total weight there are content.
Composition of the invention may also comprise at least one filler.
Filler
The filler can be selected from known to those skilled in the art and those of usually used in cosmetic composition.The filler can be organic or inorganic, stratiform or spherical.It can be mentioned that: talcum, mica, silica, kaolin, polyamide powder are (for example, by supplier Arkema France with title OrgasolThe Nylon of sale), poly- Beta-alanine and polyethylene, powder (such as the Teflon of tetrafluoro ethylene polymer), lauroyl lysine, starch, boron nitride, expansion hollow polymer microsphere (for example, by cenosphere of polyvinylidene chloride/acrylonitrile preparation), for example, by supplier Nobel Industrie with title ExpancelThose of sale, acrylic powder, for example, by supplier Dow Corning with title PolytrapThose of sale, poly methyl methacrylate particle and the thin pearl of silicone resin, for example, by supplier Toshiba with title TospearlsThose of sale, winnofil, magnesium carbonate and basic magnesium carbonate, hydroxyapatite, hollow silicon microballoon, for example, by supplier Maprecos with title Silica BeadsThose of sale, glass or ceramic microcapsules, the metallic soap derived from the organic carboxyl acid with 8 to 22 carbon atoms (especially 12 to 18), for example, zinc stearate, magnesium stearate or lithium stearate, zinc laurate and magnesium myristate.
The compound suitable for expanded by heating can also be used, especially hot expandable particle, such as, the Unexpanded Microspheres of the copolymer of vinylidene chloride and acrylonitrile and methyl methacrylate, or the Unexpanded Microspheres of acrylonitrile homopolymer copolymer, for example, being by supplier Akzo Nobel respectively with title Expancel820DU40 and ExpancelThose of 007WU sale.
The filler can account for 0.1% to 25% weight relative to composition total weight, especially 1% to 20% weight.
The colorant and/or the filler can also exist in the form of " particulate slurry (particulate paste) ".
When composition of the invention is comprising being at ambient temperature solid particle, it is prepared being added to them in composition in the form of colloidal dispersion (also referred to as " particulate slurry "), as described in the patent application WO 02/39961, the content of the patent is incorporated by reference into the application.
In the meaning of the present invention, term " aqueous colloidal dispersion " and " particulate slurry " refer to the colloidal dispersion of concentration of the particle of optionally coating in continuous media, are stabilized using dispersing agent or optionally without dispersing agent.These particles can be selected from pigment, mother-of-pearl, solid-filling agent and its mixture.The particle can be any shape, especially spherical or extending as fiber.They are insoluble in the medium.
The dispersing agent, which serves, protects discrete particles that aggregation or flocculated does not occur.It is the 0.3 milli gram/m (mg/m relative to granule surface area commonly used in stablizing the dispersant concentration of colloidal dispersion2) to 5mg/m2, preferably 0.5mg/m2To 4mg/m2.The dispersing agent can be loaded with one or more and particle to be dispersed surface have strong affinity functional group surfactant, oligomer, polymer or their mixture.Particularly, they can with physics or chemical attachment in surface of pigments.The functional group that also there is this dispersing agent at least one mutually perhaps to mix with the continuous media.Particularly, using 12- hydroxy stearic acid ester, especially C8To C20The 12- hydroxy stearic acid ester of the 12- hydroxy stearic acid ester and polyalcohol (such as glycerol or diglycerol) of fatty acid, such as, molecular weight is poly- (12- hydroxy stearic acid) stearate of 750g/mol, for example, by supplier Avecia with title SolsperseThose of 21000 sale, by supplier Henkel with title Dehymyls- 2 dimerization hydroxy stearic acid ester of polyglyceryl (INCI title) of PGPH sale, or even poly- hydroxy stearic acid, for example, by supplier Uniqema with title ArlacelThose of P100 sale and its mixture.
As the other dispersing agents for being suitable for the invention composition, it can be mentioned that the quaternary ammonium derivative of polycondensation fatty acid, for example, the Solsperse sold by supplier Avecia17000, the mixture of dimethyl silicone polymer and propylene oxide, for example, by supplier Dow Corning with those of title DC2-5185, DC2-5225C sale.
Para-dihydroxystearic acid and 12- hydroxy stearic acid ester are preferably used in alkyl or fluoro-containing medium, and aoxidize
The mixture of ethylene dimethyl silicone polymer and propylene oxide is preferably used in silicone medium.
The colloidal dispersion is suspension of the particle (usually micron order size, 10 μm of <) in continuous media.The volume fraction of particle is 20% to 40%, preferably greater than 30% in the dispersion of concentration, and according to the density of particle, corresponding weight content can achieve 70%.
The particle of dispersion in the medium can be formed by or mixtures thereof inorganic or organic particle, such as those of as described below.
The continuous media of the slurry can be any medium, can contain any solvent or liquid oleaginous base and its mixture.Advantageously, the liquid medium of the particulate slurry is expectation for the liquid oleaginous base or oil in composition, to become a part of the liquid oil phase.
Advantageously, described " particulate slurry " or aqueous colloidal dispersion are " graining paste " of the aqueous colloidal dispersion of the colored particles containing optional coating.These colored particles are the mixture of pigment, mother-of-pearl or pigment and/or mother-of-pearl.
Advantageously, the colloidal dispersion accounts for the 0.5% to 30% of the composition weight, it is therefore preferable to 2% to 20%, more preferably 2% to 15%.
Composition of the invention may also comprise at least one fiber.
Fiber
Term " fiber " refers to that length is L and diameter is D and L is far longer than the object of D, and wherein D is the diameter of a circle of inscribe fiber part.Particularly, ratio L/D (or form factor) is 3.5 to 2500, in particular 5 to 500, more particularly 5 to 150.
The fiber for being suitable for the invention composition can be synthesis or natural inorfil or organic fiber.They can be short or long, single or coherent, for example, weave into pigtail, and they can be it is hollow or solid.They can be any shape, and according to specific application purpose, section is round or polygon (square, hexagon or octagon) in particular.Particularly, end is blunt and/or polishing to avoid injury.
Particularly, the length of the fiber is 1 μm to 10mm, in particular 0.1mm to 5mm, more particularly 0.3mm to 3.5mm.Their section can be in particular 100nm to 100 μm, more particularly 1 μm to 50 μm in the circle that diameter is 2nm to 500 μm.The weight of the fiber is big
It is small usually to be indicated with danier or dtex, indicate the weight of the fiber in grams of every 9 km (km) length.The size that fiber of the invention can particularly have is 0.15 danier to 30 daniers, in particular 0.18 danier to 18 daniers.
Can be used for fiber in composition of the invention can be selected from rigidity or nonrigid fiber, source it is synthesis or natural, it is conventional or organic.
Further, fiber can be optionally is surface-treated, optionally coating, coloring or uncoloured.
As the fiber being suitable for the invention in composition, it can be mentioned that non-rigid fiber, such as Fypro (Nylon) or rigid fiber such as polyamides-nylon, for example, by supplier Rhodia with title KermelKermel TechThose of sale, or by supplier DuPont de Nemours with title KevlarPoly- (p-phenylene-p-phenylenediamine (p-phenyleneterephthalamide)) (or aromatic polyamides) fiber of sale.
The content that the fiber has in the present compositions can be 0.01% to 10% weight relative to composition total weight, in particular 0.1% to 5% weight, more particularly 0.3% to 3% weight.
Composition of the invention can be further containing any additive commonly used in cosmetics, for example, antioxidant, preservative, aromatic, neutralizer, thickener, vitamin, humidizer, smoke agent for shielding (especially opacifier), coalescent, plasticizer and its mixture.
Certainly, those skilled in the art can carefully select the amount of any other additive and/or additive, so that the advantageous feature of composition of the invention not will receive or not will receive substantially the expected adverse effect added.
Device
Fig. 1 shows an example of packaging and Unit for applying a product 1 of the invention.
Described device 1 includes handle component 2, is connected to the rod handle 3 of handle component 2, and is connected to the applicator component 4 of rod handle 3.
Composition P of the invention may include the above-mentioned ingredient referred to, and the shear stiffness that particularly can have is 375g/m to 5000g/m.
In the example of Fig. 1 and 2, composition P is 7 form of monolithic block completely around core 5.
Such as, protrude element 6 be mane or with tooth made of the injection moulded thermoplastic's material together of core 5, they have the proximal part 6a (when using first time) in embedment block 7, and the radial outside positioned at block 7 their distal end 6b.
In the example of figure 2, block 7 contact core 5, block 7 with a thickness of for example substantially with 360 degree of longitudinal axis Xs uniformly around core.
For example, protrude element 6 is arranged with tandem, every row has 5 to 40 protrude elements.
Certainly, any other arrangement for being suitable for the protrude element of cosmetic applications can be without departing from the scope of the present invention.Particularly, protrude element can have the arrangement of non-radioactive shape.
A possibility that applicator component that Fig. 3 display is constituted using the core brush of torsion.Such brush has the protrude element that is made of mane, falls between two metal branch of core, and wherein branch's wound upon themselves are together.
The block 7 of composition is at least in the part coating core 5 for being loaded with protrude element 6 of core.These elements have the distal portions stretched out from block 7.
The brush of delivery composition P can be any of type, and particularly it can be the earlier application in the applicant, such as any type occurred in patent application EP 1977661 and EP 1977662, is incorporated herein its content by quoting.
The enveloping surface limited by the free end of protrude element 6 can define the circular cross section (at least partly round) of profile, it such as around at least 180 ° of core is circular profile, or at least one point even full-circle spray pattern of the length along core, it is full-circle spray pattern particularly along its maximum length or along more than at least part length of core, such as in the whole length for the core segment for being loaded with protrude element is full-circle spray pattern.
The protrude element is also possible to the mane or tooth that core is loaded with, and the distal end of applicator element can be limited by core or at least one tooth.
Protrude element can be stretched out at least three different directions around core, they can limit enveloping surface, rise to maximum, then be reduced on cross section towards the free end of applicator component, for example, described apply
It is usually spherical for applying device component.
The scarf of enveloping surface at least one longitudinal section of maximum cross section two sides is angled to may be greater than 120 °, preferably more than 130 °, more preferably larger than 135 °.
The inclined-plane for defining angle can be and the close straight line being fitted of the enveloping surface of the two sides of maximum cross section.They can be a part of tangent with the enveloping surface close to maximum cross section, for example, the part extends along the length (it is equal to 1mm) of the longitudinal axis measurement of core.The inclined-plane is also possible to straight line, passes through maximum cross section, and with apart from the crosscutting enveloping surface of maximum cross section certain distance, the distance (it is equal to 1mm) is such as the longitudinal axis measurement along core.
It can be twice of the maximum gauge less than or equal to enveloping surface cross section along the total length of the enveloping surface longitudinal axis, it is therefore preferable to 1.75 times of the maximum gauge, more preferably 1.5 times or 1.25 times.
Term " maximum gauge " should be understood as the lateral dimension of enveloping surface, even if circular contour is not present in its cross section.
Term " total length " is it should be understood that be the total length of the enveloping surface of the longitudinal axis measurement along core limited by protrude element.
Cross section maximum gauge corresponding to enveloping surface may be greater than 2.5, preferably larger or equal than 3 divided by the ratio of core diameter, and the diameter of core corresponds to the diameter of a circle with the cross section inscribe of core.
As described above, the applicator component can have generally spherical enveloping surface, its surface can be related to the protrude element with variable-length or the diameter correlation with the core of variable support protrude element, wherein variation is arrived along the axial spotting of applicator component.
Figure 16 shows the applicator with enveloping surface, indicates that the cross section of profile is substantially circular.
As shown, the 20% of the enveloping surface can be spherical, and it is spherical at least extending to the part of the distal end 21 of applicator from the maximum plane of lateral dimension defined by the enveloping surface E.
Applicator may include the protrude element protruded towards the proximal end of applicator.Applicator may include protrude element 6 extend around core axially beyond four direction, preferably to extend around eight directions of the axis of core.
In the embodiment of display, the core is solid, however, can be hollow in the modification not shown at one.
As shown, core and enveloping surface E can pass through maximum cross section along the longitudinal axis of core with conventional axial position.
In the modification that Figure 17 is shown, protrude element 6 has variable height, therefore its free end limits the desired feature of enveloping surface E.For example, core is elongated shape, such as columned, as shown.
In figure 16 and 17, for clarity, the applicator of display does not have any composition.
No matter whether the core is made of material identical with protrude element 6, the block 7 of composition P can be various shapes, such as, it can have flat cross section, so that block 7 has opposite surface 7a, two surface 7a extend relatively large area, so that it is more easily applied the composition on eyelashes.
When first time using applicator component, all protrude elements are all exposed from block 7, or in a variant, some protrude elements, such as shortest mane, can be fully inserted into the block.These manes can gradually be exposed with the consumption of block 7.
It is non-uniform that the thickness of block 7 can be the longitudinal axis X around core, as shown in figure 5, for example because block 7 is relative to core bias.
The property of the deviation heart or the noncircular symmetry shape of block of block 7 can be improved it is cosmetic, for example, making it during application, it is possible to assign eyelashes some movements.
Fig. 6 shows the feasibility of the applicator component of the composition block including coating form, and the coating fully covers core 5, far more than the half of the height of protrude element 6 when using first time.
Fig. 7 show be not the block 7 of the composition only supported by core 5 but by protrude element 6 feasibility, such as it has by the annular gap 11 that is formed between the radially inner surface and core of block 7.Protrude element can with 7 close contact of block of composition, especially in heat when by the composition founding in protrude element 6.
In a variant, block 7 may include the channel formed before block is placed in core and protrude element, once block is placed, protrude element extends in the channel.
For example, it is contemplated that having a kind of includes one or more surfactant compositions, it is " care product " and a kind of composition comprising object of making up, or even a kind of composition of " can wash " composition and another " waterproof ".User can determine the one or another kind using the composition, or one of described composition be applied on another kind, such as water-proofing composition is applied on washable composition, to make its waterproof.
It is also contemplated that being selected with a kind of composition for extending eyelashes and another composition for keeping it upward, user according to dressing effect to be applied.
When it is fluid state, block 7 can be with casting or injection molding, to touch core 5 and protrude element 6, so that there is a possibility that using core and/or protrude element as the reinforcing element for mechanically enhancing composition block.
In this view it may be seen that the block 7 with branch 7b, the branch 7b are connected with core and protrude element 6.
Branch 7b longitudinally extends, and is connected to each other by annular section at both ends.
The composition can be carried optionally with reinforcing element 65, and the reinforcing element 65 is at least partly covered by composition, such as the reinforcing element made of thermoplastic material, as indicated at 11.Reinforcing element can have branch, and each branch is loaded with correspondent composition block 7, and the end of these branches links together.When carrier 65 is placed on core and protrude element, protrude element can be protruded via the gap extended between block 7.
After having consumed the composition, carrier can be replaced by new carrier or user can retain carrier, and the one or more composition blocks being in contact with it are molded by using suitable mold.
As shown in figure 12, the block is also possible to the form of spring, is carried by the spiral carrier being wrapped by composition.Such spring can be fixed on the brush of injection molding or the core of torsion paints, with such as lower section
Formula, protrude element protrusion is around between (turns), so as to applied cosmetics.Composition P can have the property that can be applied at ambient temperature, and particularly hardness is sufficiently low be attached to user at ambient temperature on eyelashes enough compositions.
When appropriate, it can use heater system 20 and at least heat the composition on the surface thereof, an example is shown in Figure 14.
In the figure, without being arranged in the protective cover to cover the block 7 of applicator component and composition in use, heater system 20 is merged into.
For example, the setting of handle component 2 is fixed in heater system 20.When handle component 2 is fixed in this way, user can set heater system and operate, such as utilize switch 22, the block of any suitable heater system heating combination P on the surface of the block of composition P can be passed through, the resistive element that the heater system for example extends around block 7, while applicator component being placed in heater system.
Other tools can be used to improve the temperature of composition for application purpose, such as the heater system being merged into core 5.In such a case, it is possible to select the temperature of heating combination block, to make it keep solid, while hardness is reduced.
Figure 18 shows the feasibility that range extends at an angle around the longitudinal axis X of applicator component of composition block 7, the angular range corresponds to less than one entire turn, such as the angular range of angle [alpha] is greater than 30 °, more preferably 45 ° or even 60 °, 90 °, 120 °, 180 ° or bigger.
When applicator component has in the protrude element 6 that applicator component longitudinal axis extends, this make it possible to applicator component from a part embedment composition P of the length of protrude element 6 and other protrude elements be not embedded in wherein it is benefited.
The applicator component can be any type, for example, the metal core with torsion brush or the brush that is prepared by injection molded thermoplastic's material.In modified example embodiment, the block 7 of composition P extends less than an entire week in applicator component longitudinal axis, and the thickness of composition is not constant.
At least partially in the applicator element 6 extended in composition P, with the applicator element not extended in composition P, it can have identical property, or it can have different property, such as different length, and/or different end-o f-pipe -controls is carried out, and/or with different surface state, and/or with different diameters
And/or it is made from a variety of materials.
The composition block is placed on core and protrude element
The composition block can be prepared apart with applicator component and protrude element, and the composition block can be placed to the position suitable with it, as set forth above, it is possible to be fixed on carrier.
The composition can also be injection molded into and be contacted with core and/or protrude element, after cooling and drying, the composition forms an one integral piece solid mass, wherein block remains fixed on core and protrude element when using applicator component.
For example, applicator component can be immersed in the mold comprising fluid composition, or the composition of liquid is cast in mold for casting the composition, then be inserted applicator component.
One acted in this way is the disadvantage is that all protrude elements all completely cover composition when being removed from the molds.In this case, block can be partially stripped or be worn away, so as to reveal the top of at least applicator element from block, to assign the ability that device is combed when using first time.
Also heat treatment can be used, to make superfluous composition re-melting, later, superfluous substance is removed by suction or foam absorbing.
As shown in figure 15, it can be used and be provided to receive protrude element 6 while avoiding the mold that the protrude element is completely covered by composition when composition is injection molded into mold.
Such as, mold may include the exterior section 43 for having the interior section 40 for the slot 41 by rows of protrude element 6 and can take up two positions, it does not cover a position of slot 41 wherein, so that applicator component be made to be inserted into mold, and is taken out by axial movement;A position being closed with its bracket groove 41, then closed rake 45 engages between protrude element 6, so as to seal between them it is existing outlet and when casting component, prevent composition from the outlet leak.
It can be used during manufacturing device, or mold as shown in figure 15 is optionally used by user, so as to after having consumed, remold composition block, this is there is a possibility that solid composition is introduced into mold by such as user, then so that it is become fluid by heating, or be introduced directly into the composition of liquid, while applicator component is present in mold.After cooling, user can be mobile relative to interior section 20
Exterior section 43, to separate rows of protrude element.
The composition can also reside in the handle 3 of device, which can include heater system in applicator component, as described in the FR 2914161.Core 5 may include hole, and when by heater system melt composition, which makes composition flow to the outside of core via hole.It is set in the mold by melting the composition, while by applicator component, the block 7 of composition can be formed in around core while cooling, and cover protrude element, at least cover its base portion.
In general, the applicator component being removably mounted on handle can be prepared, to convert applicator component after the consumption of composition block.A large amount of applicator components that different components can be loaded with are supplied to user, share handle for being optionally secured to according to pending processing.
Composition embodiment
Preparation
Meng Shi title | INCI title | % weight |
Tristerin | Tristerin | 2.79 |
PEG-30 tristerin | PEG-30 tristerin | 7.19 |
Beeswax | Cera alba | 9.29 |
Hydrogenated jojoba oil | Hydrogenated jojoba oil | 9.29 |
Butyl hydroxybenzoate | Butyl hydroxybenzoate | 0.16 |
Ethylparaben | Ethylparaben | 0.13 |
Polybutene | Polybutene | 1.30 |
2- oleoyl amido -1,3- octacosanol | 2- oleoyl amido -1,3- octacosanol | 0.13 |
Iron oxide | CI 77499* | 9.08 |
Polyquarternium-10 | Polyquarternium-10 | 5.02 |
Water | Water | 55.00 |
Glycerol | Glycerol | 0.13 |
Methyl hydroxybenzoate | Methylparaben | 0.31 |
EDETATE SODIUM | EDETATE SODIUM | 0.13 |
Sodium hydroxide | Sodium hydroxide | 0.006 |
100.00 |
*It is sold by supplier Evonik Goldschmidt with title Tagat S.
The method for manufacturing the composition of embodiment
The preparation of 150g is prepared using following proposal:
● in beaker, water phase (water, polyquartemium-10, methylparaben, EDTA and sodium hydroxide) is heated to 90 DEG C,
● in melting pot, at 90 DEG C, with the rotor-stator stirrer of Moritz type, by oily phase (tristerin, PEG-30 tristerin, beeswax, hydrogenated jojoba oil, butyl hydroxybenzoate, nipagin A, polybutene and pigment) homogenization;
● at strong mixing (4500 revs/min (rpm)), water phase is added in oily phase, lotion is obtained by inversion of phases;With
● it persistently stirs 10 minutes, then, which is cast to comprising brush and is arranged in 28 DEG C of mold 45 minutes.Block demoulds together with applicator component.
The present invention is not limited to the embodiments.
Statement " including (including) " should be understood as having the same meaning with " including (including) at least one (kind) ".
Claims (15)
1. a kind of at least one Solic cosmetic composition to be applied to the packaging and Unit for applying a product of eyelashes, eyebrow or hair, described device includes:
● handle component (2);
● it is connected to the rod handle (3) of the handle component;With
● it is connected to the applicator component (4) of the rod handle, which includes:
● it is fixed to the core (5) of the rod handle;With
● the axis (X) relative to the rod handle laterally extends to the applicator element (6) of the end opposite with the base portion from the base portion for being fixed to the core, the base portion of at least partly described applicator element is arranged on the inside of the solid mass (7) of the composition, the block have around the axis (X) it is whole around some or all of the upper outer envelope face extended, and before first time is using the device, the outer envelope face of the block is located between the base portion and the opposite end of the applicator element with the distance apart from the base portion and the opposite end non-zero of the applicator element;
When dry with the help of having heating or with the help of no heating, the composition is dispersible.
2. device according to claim 1, wherein the shear stiffness that the composition has is 200g/m to 5000g/m, it is therefore preferable to 375g/m to 5000g/m.
3. a kind of at least one Solic cosmetic composition to be applied to the packaging and Unit for applying a product of eyelashes, eyebrow or hair, described device includes:
● handle component (2);
● it is connected to the rod handle (3) of the handle component;With
● it is connected to the applicator component (4) of the rod handle, which includes:
● it is fixed to the core (5) of the rod handle;With
● the axis (X) relative to the rod handle laterally extends to the applicator element (6) of the end opposite with the base portion from the base portion for being fixed to the core, the base portion of at least partly described applicator element is arranged on the inside of the solid mass (7) of the composition, the block have around the axis (X) it is whole around some or all of the upper outer envelope face extended, and use the device in first time
The outer envelope face of foregoing description block is located between the base portion and the opposite end of the applicator element with the distance of the opposite end non-zero apart from the base portion and apart from the applicator element;
The shear stiffness that the composition has is 200g/m to 5000g/m, it is therefore preferable to 375g/m to 5000g/m.
4. according to the device of any one preceding claims, wherein the block (7) at least partly covers all protrude elements (6).
5. according to the device of any one preceding claims, wherein it is more than at least the 30% of its height in composition that protrude element (6), which is embedded to,.
6. according to the device of any one preceding claims, wherein, the composition can become fluid by heating, described device (1) includes heater system (20), especially includes that can separate with the applicator component to allow the heater system using the applicator component.
7. device according to claim 6, wherein the heater system (20) be it is separable with the applicator component (4), to contact the applicator component with the eyelashes, eyebrow or hair.
8. according to claim 1 to any one of 7 device, wherein the protrude element (6) is moulded together with core.
9. according to claim 1 to any one of 7 device, wherein the protrude element (6) is the mane carried by the core of torsion.
10. according to claim 1 to any one of 9 device, wherein the block (7) have non-circular cross section.
11. a kind of method of fiber of the coating selected from eyelashes, eyebrow or hair, the method includes the following steps:
● make at least part surface of the block of the composition of device of the fiber contacts as described in any one of claims 1 to 10;With
● so that the surface of the block and the fiber is moved relative to each other, to cause the block to disperse and to form on the fiber deposition of at least one layer of cosmetic composition.
12. method according to claim 11, wherein do not need to heat and applying said compositions in advance.
13. method according to claim 11, wherein the composition is applied after preparatory heating.
14. method according to claim 13, wherein the block of the composition is maintained in solid core during application.
15. any one of 0 to 14 method according to claim 1, wherein during manufacturing described device, when the composition and applicator component (4) contact, the composition is fluid state.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0951668A FR2943225B1 (en) | 2009-03-17 | 2009-03-17 | DEVICE FOR CONDITIONING AND APPLYING AT LEAST ONE SOLID COSMETIC COMPOSITION |
FR0951668 | 2009-03-17 | ||
US20268509P | 2009-03-26 | 2009-03-26 | |
US61/202,685 | 2009-03-26 | ||
PCT/IB2010/051136 WO2010106498A1 (en) | 2009-03-17 | 2010-03-16 | A packaging and applicator device for at least one solid cosmetic composition |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102355833A true CN102355833A (en) | 2012-02-15 |
Family
ID=41112509
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010800127712A Pending CN102355833A (en) | 2009-03-17 | 2010-03-16 | A packaging and applicator device for at least one solid cosmetic composition |
Country Status (6)
Country | Link |
---|---|
US (1) | US20120093560A1 (en) |
EP (1) | EP2408333A1 (en) |
CN (1) | CN102355833A (en) |
BR (1) | BRPI1009410A2 (en) |
FR (1) | FR2943225B1 (en) |
WO (1) | WO2010106498A1 (en) |
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US20230105622A1 (en) * | 2021-10-04 | 2023-04-06 | Lashify, Inc. | Electric applicator and method for re-affixing artificial lash extensions and curling natural lashes and artificial lash extensions attached to natural lashes |
USD984050S1 (en) | 2022-07-20 | 2023-04-18 | Lashify, Inc. | Combined curler and applicator for natural lashes and artificial lash extensions |
US20240245200A1 (en) * | 2021-10-04 | 2024-07-25 | Lashify, Inc. | Electric applicator and method for re-affixing artificial lash extensions and curling natural lashes and artificial lash extensions attached to natural lashes |
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IT1404139B1 (en) * | 2010-11-26 | 2013-11-15 | Color Cosmetics S R L | PROCESS FOR PACKAGING SOLID COSMETIC PRODUCTS WITHIN A CONTAINER |
JP2013090725A (en) * | 2011-10-25 | 2013-05-16 | Panasonic Corp | Hair shaping device |
US9408785B2 (en) | 2012-10-15 | 2016-08-09 | L'oreal | Hair styling compositions containing aqueous wax dispersions |
US10626294B2 (en) | 2012-10-15 | 2020-04-21 | L'oreal | Aqueous wax dispersions containing volatile solvents |
US10413496B2 (en) | 2012-10-15 | 2019-09-17 | L'oreal | Aqueous wax dispersions |
US8932573B2 (en) | 2013-03-22 | 2015-01-13 | L'oreal | Mascara compositions comprising a semicrystalline polymer, a silicone elastomer, and a hydrophilic gelling agent |
US10561596B2 (en) | 2014-04-11 | 2020-02-18 | L'oreal | Compositions and dispersions containing particles comprising a polymer |
FR3026944B1 (en) * | 2014-10-10 | 2018-02-23 | L'oreal | COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS |
FR3026943B1 (en) * | 2014-10-10 | 2018-02-23 | L'oreal | COSMETIC COMPOSITION FOR COATING KERATINIC FIBERS |
EP3092917A1 (en) * | 2015-05-12 | 2016-11-16 | Enrica Monica Ancorotti | Method for making a mascara packaging |
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Also Published As
Publication number | Publication date |
---|---|
US20120093560A1 (en) | 2012-04-19 |
BRPI1009410A2 (en) | 2016-10-18 |
WO2010106498A1 (en) | 2010-09-23 |
EP2408333A1 (en) | 2012-01-25 |
FR2943225A1 (en) | 2010-09-24 |
FR2943225B1 (en) | 2011-06-03 |
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