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WO2017178284A1 - Thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized tps and at least one peba - Google Patents

Thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized tps and at least one peba Download PDF

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Publication number
WO2017178284A1
WO2017178284A1 PCT/EP2017/057967 EP2017057967W WO2017178284A1 WO 2017178284 A1 WO2017178284 A1 WO 2017178284A1 EP 2017057967 W EP2017057967 W EP 2017057967W WO 2017178284 A1 WO2017178284 A1 WO 2017178284A1
Authority
WO
WIPO (PCT)
Prior art keywords
blend
tps
peba
equal
weight
Prior art date
Application number
PCT/EP2017/057967
Other languages
French (fr)
Inventor
Jean -Marie HERVET
François Rival
Jean-Marie Julien
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'oreal filed Critical L'oreal
Publication of WO2017178284A1 publication Critical patent/WO2017178284A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • A45D34/00—Containers or accessories specially adapted for handling liquid toiletry or cosmetic substances, e.g. perfumes
    • 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
    • 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
    • A45D40/0068—Jars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
    • B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
    • B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
    • B05B11/1042—Components or details
    • B05B11/1052—Actuation means
    • B05B11/1056—Actuation means comprising rotatable or articulated levers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/14—Containers for dispensing liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant
    • B65D83/16—Actuating means
    • B65D83/20—Actuator caps
    • B65D83/206—Actuator caps comprising cantilevered actuating elements, e.g. levers pivoting about living hinges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • Thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized TPS and at least one PEBA
  • the present invention relates to a thermoplastic elastomer blend with antistatic properties and also to a device for packaging and/or dispensing product, in particular cosmetic product, comprising at least one free outer surface made from such a thermoplastic blend.
  • cosmetic products is understood to mean any product as defined in Regulation (EC) No 1223/2009 of the European Parliament and Council of 30 November 2009, relating to cosmetic products.
  • the cosmetic product is intended to be applied to a body surface of a human being. It is for example present in the form of a solid such as a powder, in the form of a liquid, a gel or a cream or else in the form of a pasty product.
  • packaging devices such as vials, bottles or tubes, having an outer surface at least partially made from a thermoplastic elastomer.
  • a surface may be produced for example by overmoulding, in particular by a bi-injection moulding process as described in document WO 2006/101631 or US 2008/251492.
  • thermoplastic elastomer Such a surface produced from a thermoplastic elastomer provides great ease of use and makes it possible in particular to produce soft-touch and non-slip gripping surfaces.
  • cosmetic products are used outside or in dusty environments that comprise macroscopic particles, such as grains of sand.
  • sun protection products intended to protect a body surface of a user against exposure to solar radiation, in particular to ultraviolet radiation, which are used for example at the beach.
  • Such products may in particular be packaged in a pressurized container and dispensed in spray form (aerosol type device) or in pump-type devices, comprising a selective dispensing member, in this case a valve, capable of being actuated by the user by means in particular of an actuating and/or dispensing cap.
  • a selective dispensing member in this case a valve, capable of being actuated by the user by means in particular of an actuating and/or dispensing cap.
  • one solution is to render the device at least partially impermeable to these particles.
  • the actuating cap comprises at least one deformable zone that enables the user to control the dispensing valve.
  • the device comprises a body, a dispensing head arranged on this body and having a dispensing orifice, and a cap, connected to the main body and covering the dispensing head.
  • the cap comprises an overmoulded flexible skin capable of deforming during the actuation of the device while ensuring the impermeability of the cap.
  • this flexible skin is made from a thermoplastic elastomer.
  • the flexible skin is overmoulded to a rigid base (in particular made from a thermoplastic material, for example from polypropylene PP) that makes it possible to ensure the holding and fastening of the cap on/to the device.
  • a rigid base in particular made from a thermoplastic material, for example from polypropylene PP
  • Thermoplastic elastomers is generally intended to mean polymers or a blend of polymers that have, at the service temperature, properties similar to those of vulcanized rubber. These properties disappear at the processing temperature, making subsequent processing possible, but reappear when the material returns to the service temperature (cf. standard ISO 18064:2014).
  • thermoplastic elastomers For general information on thermoplastic elastomers, reference may in particular be made to the guide from Techniques de I'lngenieur [Techniques of the Engineer], Traite Plastiques et Composites [Treatise on Plastics and Composites] , AM 3 400 by Michel Biron published on 10 July 2000.
  • Choice materials for producing such surfaces are thermoplastic styrene elastomers (TPS or TPE-S) comprising in particular SEBS (styrene-ethylene-butadiene- styrene) and SBS (styrene-butadiene-styrene).
  • TPS thermoplastic styrene elastomers
  • SEBS styrene-ethylene-butadiene- styrene
  • SBS styrene-butadiene-styrene
  • SBSs and SEBSs comprise hard polystyrene segments and soft polybutadiene or poly(ethylene/butylene) segments.
  • these materials have a good aging resistance and in particular good UV resistance. They also have a relatively low cost.
  • thermoplastic elastomer In order to solve this problem, it is known to add an antistatic agent to the thermoplastic elastomer.
  • conductive materials include, for example, oxides, metals, etc.
  • thermoplastic material It is also possible to add conductive polymers to the thermoplastic material.
  • these polymers are generally speciality polymers and have a high cost.
  • Surfactants may also be used as antistatic agents and the prior art has in particular described antistatic agents such as ionic surfactants of ethoxylated amine or sulfonate type that are added to polymers.
  • the antistatic properties of the polymers then depend on the ambient humidity and they are not permanent since these agents migrate to the surface of the polymers and disappear.
  • thermoplastics are moulded, in particular by injection moulding, and in order to avoid the subsequent application of a coating, the present application relates to internal antistatic agents.
  • thermoplastic elastomers considering the deformable and flexible nature of thermoplastic elastomers, the adhesion of an external agent to such a material is particularly difficult.
  • copolymers containing polyamide blocks and hydrophilic polyether blocks have been proposed as antistatic agents, these agents have the advantage of not migrating and therefore of giving permanent antistatic properties that are more independent of the ambient humidity.
  • the PEBA used as antistatic agent is poorly compatible with styrene resins, in particular with the unfunctionalized styrene resins to which SEBS and SBS belong.
  • the prior art reveals either blends (i) of styrene resin and of polyether ester amide without compatibilizer, or blends (ii) of polyether ester amide and of functionalized styrene resin or else blends (iii) of polyether ester amide, of unfunctionalized styrene resin and of functionalized styrene resin, or blends (iv) of styrene resin and of polyether ester amide with compatibilizer.
  • the blends (i) are antistatic if the polyether ester amide is well chosen but have poor mechanical properties, in particular the elongation at break is much lower than that of the styrene resin alone.
  • thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized TPS and at least one PEBA, characterized in that:
  • the PEBA: TPS weight ratio, excluding optional inert mineral and organic fillers thereof, is greater than or equal to 8%,
  • the sum of the weight of TPS and the weight of PEBA is greater than or equal to 80% of the total weight of the blend, it comprises less than 1% of the total weight of the blend of various organic compounds such as dyes and additives,
  • apolar polymers i.e. that are essentially devoid of oxygen-containing functional groups such as alcohol, ester, ketone, amide, acid or anhydride groups
  • polar polymers i.e. that comprise oxygen-containing functional groups
  • (PEBA-type) polyamides are polar polymers and are not generally compatible with (nonpolar) polyolefms.
  • Styrene polymers are special cases since they are essentially devoid of oxygen groups but contain aromatic rings that give them a certain polarity.
  • styrene resins The polarity of styrene resins is generally insufficient to make them compatible with PEBA-type polyamides but is sufficient for these resins not to be very compatible with polyolefms.
  • TPSs did not require the addition of such a compatibilizer.
  • the PEBA:TPS weight ratio is greater than or equal to 10%.
  • the PEBA: TPS weight ratio is less than or equal to 30%>, preferably less than or equal to 20%.
  • the cost of the blend remains moderate.
  • the TPS comprises, preferably predominantly or even completely, SEBS.
  • the sum, by weight, of the TPS and of the PEBA is greater than or equal to 90%> of the total weight of the blend, preferably greater than or equal to 95%, or even greater than or equal to 99.9%, or even 100%.
  • said blend comprises less than 0.1 %, preferably less than 0.08% of various organic compounds.
  • the various organic compounds are in particular dyes and other additives, not specifically compatibilizing and not specifically antistatic. They are of course optional.
  • the various organic compounds are nonionic compounds.
  • the various organic compounds do not comprise a functional group from among carboxylic acid, carboxylic acid anhydride, alcohol, amide, ester and ether groups, in particular do not comprise an oxygen-containing functional group.
  • the inert mineral fillers are chosen from talc, CaC0 3 , preferably, preferably chosen from talc and CaC0 3 . These inert mineral fillers preferably do not specifically have an antistatic effect nor do they specifically have a compatibilizing effect.
  • the mineral fillers may also comprise reinforcing fibres such as glass fibres, polyester fibres, mineral fibres, carbon fibres.
  • the present application also relates to a device for packaging and/or dispensing product, in particular cosmetic product, such as a sun protection product, characterized in that it comprises at least one free surface produced from a blend according to the invention.
  • cosmetic product such as a sun protection product
  • it could be a surface intended to come into contact with a part of the human body, in particular a gripping part, or a manual bearing surface that makes it possible to control a selective dispensing system.
  • the surface may be an internal surface not intended to come into contact with a part of the human body.
  • said internal surface may be intended to be in contact with the cosmetic product contained in the device.
  • the internal surface may be at some point an outer surface likely to be exposed to dust and the like. Without antistatic properties said surface may build up dust and impurities, for example during temporary storage, that might pollute the cosmetic product after filing of the device.
  • the concerned inner surface of the device may be an outer surface of a distinct element that is assembled to the device before final packaging.
  • An example of such distinct element may be a wiper intended to remove excess product onto an applicator inserted through it.
  • a wiper is a separate element that is assembled at an orifice of a reservoir of the packaging device.
  • the present application also relates to a protective cap for a dispensing device, said cap comprising at least one flexible deformable surface made from a blend according to the invention. More specifically, the dispensing device is an aerosol device or a pump.
  • the flexible deformable surface produced from the blend according to the present application enables the actuation of a selective dispensing system such as a valve, in particular an aerosol valve or pump valve.
  • the blend has a Shore A hardness of less than 50.
  • the flexible deformable surface is overmoulded to a rigid assembly portion on the packaging and dispensing device.
  • the dispensing device is in particular a device for dispensing a product, especially a cosmetic product, such as a sun protection product.
  • the dispensing assembly comprises a cap according to the present application mounted on the dispensing device.
  • Figure 1 is a partial schematic representation of an assembly for packaging and dispensing a product equipped with a cap having a flexible deformable surface made from a blend in accordance with the present application
  • Figure 2 is a partial schematic representation of a bottle packaging and dispensing assembly having a gripping surface overmoulded using a blend in accordance with the present application.
  • Figure 1 shows a device 10 for packaging and dispensing a product.
  • the product is a cosmetic product, in particular a sun protection product.
  • the device 10 is a pump device comprising a container 12 containing the cosmetic product which is pressurized and equipped with a product dispensing member 14 (pump valve).
  • the device may also comprise a pressurized container of aerosol type, on which an aerosol valve is mounted.
  • the dispensing member 14 is mounted on an open end of the container 12. According to the embodiment represented, the dispensing member 14 is mounted inside a neck 12a of the container.
  • the dispensing member 14 is surmounted by a cap 16 covering a portion of the container 12 and the dispensing member 14.
  • the dispensing member 14 comprises an actuating mobile element 24 that can be moved along a longitudinal axis between a rest position, in which it does not enable the cosmetic product to leave the container 12, and a dispensing position in which it causes or enables the product to be dispensed.
  • the dispensing member 14 is in fluid communication with a dispensing duct
  • the diffusing nozzle 25 opens on the outside of the cap 16.
  • the diffusing nozzle 25 opens sideways but other positions can of course be envisaged.
  • the cap 16 is mainly made from a rigid thermoplastic, such as polypropylene. This rigid material enables the fastening thereof, in particular by clip fastening, to the container 12.
  • the cap 16 has a flexible and deformable upper part 17 made from a thermoplastic elastomer.
  • the thermoplastic elastomer is overmoulded to the rigid material forming a base structure of the cap 16.
  • the plastic elastomer is in particular based on SEBS.
  • the flexible upper part 17 is overmoulded to a rigid base part of the cap 16. This makes it possible to ensure a certain impermeability of the inside of the cap 16 and in particular to protect the valve 14.
  • the flexible deformable part comprises a textured bearing zone 17a used as finger pad.
  • the deformable upper part 17 extends over a rear part of the cap 16, located on the opposite side to the diffusing nozzle 25. It is capable of being deformed so that a user can bear against an actuating plate 15 of the valve 14.
  • the antistatic property of a material is mainly characterized by its surface resistivity which is expressed in ohm/m 2 and is evaluated according to the ASTM D257 standard.
  • the antistatic property of a material is evaluated by measuring, with the aid of a charge measurer, the time needed to bring the electrostatic potential of the material from a voltage of 1000 V to 100 V.
  • a discharge time of less than 30 seconds enables a good dissipation of the electrostatic charges and the material attracts little or no dust.
  • the measurements are carried out after stoving (20°C and at a moisture content set at 80% relative humidity) for 2 days in order to condition the material.
  • the blend according to the present application is prepared by customary thermoplastic blending techniques such as for example by extrusion or with the aid of twin-screw mixers, by compounding, using SEBS particles and PEBS particles.
  • the particles may also be ground in order to obtain a more intimate blend.
  • the blend is then melted and injected into a mould of the deformable upper part of the cap 16.
  • Figure 2 is a depiction of another embodiment using a blend according to the present application.
  • Figure 2 shows a bottle-type container 100 having a main body 101 delimiting an internal volume 102 intended to contain a product and surmounted by a neck 103 having a dispensing opening 104.
  • the neck 103 is equipped with an external thread 105 enabling the closure of the opening 104 and of the bottle 100 by a corresponding stopper.
  • the main body 101 has an outer gripping portion 106 (presence of indentations for receiving the fingers of one hand) produced by overmoulding using an antistatic blend according to the present application.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Packages (AREA)

Abstract

The present invention relates to a thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized TPS and at least one PEBA, characterized in that: - the PEBA:TPS weight ratio is greater than or equal to 8%, - the sum of the weight of TPS and of PEBA is greater than or equal to 80% of the total weight of the blend, - it comprises less than 1% of the total weight of the blend of various organic compounds such as dyes and additives, the remainder consisting of inert mineral fillers and/or unfunctionalized polyolefin fillers, and also to a device for packaging product comprising at least one free surface made from such a blend.

Description

Thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized TPS and at least one PEBA
The present invention relates to a thermoplastic elastomer blend with antistatic properties and also to a device for packaging and/or dispensing product, in particular cosmetic product, comprising at least one free outer surface made from such a thermoplastic blend.
More generally, the expression "cosmetic products" is understood to mean any product as defined in Regulation (EC) No 1223/2009 of the European Parliament and Council of 30 November 2009, relating to cosmetic products.
The cosmetic product is intended to be applied to a body surface of a human being. It is for example present in the form of a solid such as a powder, in the form of a liquid, a gel or a cream or else in the form of a pasty product.
Many cosmetic products are packaged in devices made completely or partly of plastic.
The formation and the retention of static electricity charges at the surface of most plastics are known. The presence of static electricity on thermoplastic films for example makes these films stick to one another, rendering the separation thereof difficult. The presence of static electricity on packaging films may give rise to the accumulation of dust on the objects to be packaged and thus hamper their use. Styrene resins such as for example polystyrene or ABS are used to make computer cases, telephones, televisions, photocopiers and numerous objects. Static electricity gives rise to the accumulation of dust but above all may also damage the microprocessors or the constituents of the electronic circuits contained in these objects.
Moreover, when the products are wrapped in a plastic film for the transport or packaging thereof before being put on display, the removal of this film also leads to the formation of electrostatic charges.
In the field of wrapping and packaging, in particular of cosmetic products, it is known to produce packaging devices, such as vials, bottles or tubes, having an outer surface at least partially made from a thermoplastic elastomer. Such a surface may be produced for example by overmoulding, in particular by a bi-injection moulding process as described in document WO 2006/101631 or US 2008/251492.
Such a surface produced from a thermoplastic elastomer provides great ease of use and makes it possible in particular to produce soft-touch and non-slip gripping surfaces.
Furthermore, certain cosmetic products are used outside or in dusty environments that comprise macroscopic particles, such as grains of sand.
This is in particular the case for sun protection products intended to protect a body surface of a user against exposure to solar radiation, in particular to ultraviolet radiation, which are used for example at the beach.
Such products may in particular be packaged in a pressurized container and dispensed in spray form (aerosol type device) or in pump-type devices, comprising a selective dispensing member, in this case a valve, capable of being actuated by the user by means in particular of an actuating and/or dispensing cap.
In order to protect the dispensing member, one solution is to render the device at least partially impermeable to these particles.
However, the user must remain able to actuate the dispensing member. In order to do this, the actuating cap comprises at least one deformable zone that enables the user to control the dispensing valve.
Such a device is described in particular in documents WO 2016/008930 and FR15/50057.
More specifically, the device comprises a body, a dispensing head arranged on this body and having a dispensing orifice, and a cap, connected to the main body and covering the dispensing head. The cap comprises an overmoulded flexible skin capable of deforming during the actuation of the device while ensuring the impermeability of the cap.
Like the soft-touch surfaces mentioned previously, this flexible skin is made from a thermoplastic elastomer. Advantageously, the flexible skin is overmoulded to a rigid base (in particular made from a thermoplastic material, for example from polypropylene PP) that makes it possible to ensure the holding and fastening of the cap on/to the device. "Thermoplastic elastomers" is generally intended to mean polymers or a blend of polymers that have, at the service temperature, properties similar to those of vulcanized rubber. These properties disappear at the processing temperature, making subsequent processing possible, but reappear when the material returns to the service temperature (cf. standard ISO 18064:2014).
For general information on thermoplastic elastomers, reference may in particular be made to the guide from Techniques de I'lngenieur [Techniques of the Engineer], Traite Plastiques et Composites [Treatise on Plastics and Composites] , AM 3 400 by Michel Biron published on 10 July 2000.
Choice materials for producing such surfaces are thermoplastic styrene elastomers (TPS or TPE-S) comprising in particular SEBS (styrene-ethylene-butadiene- styrene) and SBS (styrene-butadiene-styrene).
More specifically, SBSs and SEBSs comprise hard polystyrene segments and soft polybutadiene or poly(ethylene/butylene) segments.
Besides a soft touch, these materials have a good aging resistance and in particular good UV resistance. They also have a relatively low cost.
Furthermore, they withstand soiling well and can be cleaned easily.
It has been observed that these materials are particularly sensitive to the accumulation of electrostatic charges. Furthermore, when the elastomer surface is also an upper surface of the device, it attracts dust and particles even more.
In order to solve this problem, it is known to add an antistatic agent to the thermoplastic elastomer.
A distinction is generally made between two types of antistatic agents, namely conductors and surfactants.
Included among the conductive materials are, for example, oxides, metals, etc.
However, for quality and aesthetic reasons or for mechanical reasons (embrittlement, flexibility, feel), it is sometimes not desirable to add a large amount of mineral fillers.
Indeed, although the addition of such fillers reduces the cost of the TPS material, they may greatly impair its mechanical properties and its external appearance. It has for example been observed that highly filled TPSs, in particular SEBSs, were more prone to soiling, which posed problems during the transportation and handling thereof.
It is also possible to add conductive polymers to the thermoplastic material. However, these polymers are generally speciality polymers and have a high cost.
Surfactants may also be used as antistatic agents and the prior art has in particular described antistatic agents such as ionic surfactants of ethoxylated amine or sulfonate type that are added to polymers.
However, the antistatic properties of the polymers then depend on the ambient humidity and they are not permanent since these agents migrate to the surface of the polymers and disappear.
Finally, a distinction is also made between internal antistatic agents, designed to be directly incorporated into the material, and external agents, applied to the surface of the material.
Considering that many thermoplastics are moulded, in particular by injection moulding, and in order to avoid the subsequent application of a coating, the present application relates to internal antistatic agents.
Furthermore, considering the deformable and flexible nature of thermoplastic elastomers, the adhesion of an external agent to such a material is particularly difficult.
In order to overcome the problems mentioned above, copolymers containing polyamide blocks and hydrophilic polyether blocks have been proposed as antistatic agents, these agents have the advantage of not migrating and therefore of giving permanent antistatic properties that are more independent of the ambient humidity.
In particular it is known to use a copolymer containing polyamide blocks and hydrophilic polyether blocks (PEBA) as antistatic agent. Reference may in particular be made to application WO 01/10951 and to document US 5886097 describing such blends.
As emerges from these documents, the PEBA used as antistatic agent is poorly compatible with styrene resins, in particular with the unfunctionalized styrene resins to which SEBS and SBS belong.
In order to improve the blending thereof, it is common to add a compatibilizer.
Document WO 01/10951 describes addition of a compatibilizer bearing a carboxylic acid, carboxylic acid anhydride or epoxide functionality. In document US 5886097, the compatibilizer is a vinyl polymer bearing carboxyl groups.
Document EP 0 476 895 also mentions the need to blend PEBA with a compatible polymer in particular bearing amide or acid functionalities.
Document EP 0 781 308 makes provision for the use of maleic anhydride as compatibilizer.
Reference may also be made to the brochure from BASF regarding its product Irgastat® P that strongly recommends the addition of a compatibilizer.
Document WO 08/139111 itself uses a compatibilizer of aminosilicate type, the latter also having intrinsic antistatic properties.
Additionally, mention may also be made of document WO 14/167202 which discloses a blend of polymethyl methacrylate (PMMA) and PEBA as antistatic agent.
Thus, the prior art reveals either blends (i) of styrene resin and of polyether ester amide without compatibilizer, or blends (ii) of polyether ester amide and of functionalized styrene resin or else blends (iii) of polyether ester amide, of unfunctionalized styrene resin and of functionalized styrene resin, or blends (iv) of styrene resin and of polyether ester amide with compatibilizer.
As indicated in document WO 01/10951, the blends (i) are antistatic if the polyether ester amide is well chosen but have poor mechanical properties, in particular the elongation at break is much lower than that of the styrene resin alone.
As regards the blends (ii) and (iii), it is necessary to provide a functionalized styrene resin which is complicated and expensive.
The same is true for the blends (iv) which must take into account the addition of the compatibilizer.
The present invention aims to respond to the problems mentioned above and proposes, in order to do this, a thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized TPS and at least one PEBA, characterized in that:
the PEBA: TPS weight ratio, excluding optional inert mineral and organic fillers thereof, is greater than or equal to 8%,
- the sum of the weight of TPS and the weight of PEBA is greater than or equal to 80% of the total weight of the blend, it comprises less than 1% of the total weight of the blend of various organic compounds such as dyes and additives,
the remainder consisting of inert mineral fillers and/or unfunctionalized polyolefm fillers.
Thus, by adding at least 8% of PEBA to SEBS, it has been surprisingly observed that, contrary to what the prior art described above assumed, no compatibilizer was needed between a TPS and a PEBA in order to obtain an effective antistatic blend.
Indeed, it is known that apolar polymers, i.e. that are essentially devoid of oxygen-containing functional groups such as alcohol, ester, ketone, amide, acid or anhydride groups, are generally incompatible with polar polymers, i.e. that comprise oxygen-containing functional groups.
In particular, (PEBA-type) polyamides are polar polymers and are not generally compatible with (nonpolar) polyolefms.
Styrene polymers are special cases since they are essentially devoid of oxygen groups but contain aromatic rings that give them a certain polarity.
The polarity of styrene resins is generally insufficient to make them compatible with PEBA-type polyamides but is sufficient for these resins not to be very compatible with polyolefms.
This is why, as explained previously, these styrene compounds generally require the addition of a compatibilizer.
It has been observed that TPSs, and in particular SEBS, did not require the addition of such a compatibilizer.
Preferentially, the PEBA:TPS weight ratio is greater than or equal to 10%. Advantageously, the PEBA: TPS weight ratio is less than or equal to 30%>, preferably less than or equal to 20%. Thus, the cost of the blend remains moderate.
Preferentially, the TPS comprises, preferably predominantly or even completely, SEBS.
Preferentially, the sum, by weight, of the TPS and of the PEBA is greater than or equal to 90%> of the total weight of the blend, preferably greater than or equal to 95%, or even greater than or equal to 99.9%, or even 100%.
Preferentially, said blend comprises less than 0.1 %, preferably less than 0.08% of various organic compounds. The various organic compounds are in particular dyes and other additives, not specifically compatibilizing and not specifically antistatic. They are of course optional.
In particular, the various organic compounds are nonionic compounds.
Preferably, the various organic compounds do not comprise a functional group from among carboxylic acid, carboxylic acid anhydride, alcohol, amide, ester and ether groups, in particular do not comprise an oxygen-containing functional group.
Where appropriate, the inert mineral fillers are chosen from talc, CaC03, preferably, preferably chosen from talc and CaC03. These inert mineral fillers preferably do not specifically have an antistatic effect nor do they specifically have a compatibilizing effect.
Where appropriate, the mineral fillers may also comprise reinforcing fibres such as glass fibres, polyester fibres, mineral fibres, carbon fibres.
The present application also relates to a device for packaging and/or dispensing product, in particular cosmetic product, such as a sun protection product, characterized in that it comprises at least one free surface produced from a blend according to the invention. In particular, it could be a surface intended to come into contact with a part of the human body, in particular a gripping part, or a manual bearing surface that makes it possible to control a selective dispensing system.
Alternately, the surface may be an internal surface not intended to come into contact with a part of the human body. In particular said internal surface may be intended to be in contact with the cosmetic product contained in the device.
Indeed, although internal after filing and assembly of the device, the internal surface may be at some point an outer surface likely to be exposed to dust and the like. Without antistatic properties said surface may build up dust and impurities, for example during temporary storage, that might pollute the cosmetic product after filing of the device.
The concerned inner surface of the device may be an outer surface of a distinct element that is assembled to the device before final packaging.
An example of such distinct element may be a wiper intended to remove excess product onto an applicator inserted through it. Such a wiper is a separate element that is assembled at an orifice of a reservoir of the packaging device. The present application also relates to a protective cap for a dispensing device, said cap comprising at least one flexible deformable surface made from a blend according to the invention. More specifically, the dispensing device is an aerosol device or a pump. The flexible deformable surface produced from the blend according to the present application enables the actuation of a selective dispensing system such as a valve, in particular an aerosol valve or pump valve.
Advantageously, the blend has a Shore A hardness of less than 50. Preferentially, the flexible deformable surface is overmoulded to a rigid assembly portion on the packaging and dispensing device.
The dispensing device is in particular a device for dispensing a product, especially a cosmetic product, such as a sun protection product. The dispensing assembly comprises a cap according to the present application mounted on the dispensing device.
The present invention will be better understood in light of the following detailed description with reference to the appended drawing in which:
- Figure 1 is a partial schematic representation of an assembly for packaging and dispensing a product equipped with a cap having a flexible deformable surface made from a blend in accordance with the present application, Figure 2 is a partial schematic representation of a bottle packaging and dispensing assembly having a gripping surface overmoulded using a blend in accordance with the present application.
Figure 1 shows a device 10 for packaging and dispensing a product. The product is a cosmetic product, in particular a sun protection product.
In this case, the device 10 is a pump device comprising a container 12 containing the cosmetic product which is pressurized and equipped with a product dispensing member 14 (pump valve).
Of course, the device may also comprise a pressurized container of aerosol type, on which an aerosol valve is mounted.
The dispensing member 14 is mounted on an open end of the container 12. According to the embodiment represented, the dispensing member 14 is mounted inside a neck 12a of the container.
The dispensing member 14 is surmounted by a cap 16 covering a portion of the container 12 and the dispensing member 14. The dispensing member 14 comprises an actuating mobile element 24 that can be moved along a longitudinal axis between a rest position, in which it does not enable the cosmetic product to leave the container 12, and a dispensing position in which it causes or enables the product to be dispensed.
The dispensing member 14 is in fluid communication with a dispensing duct
18 terminated by a diffusing nozzle 25 that opens on the outside of the cap 16. According to the embodiment represented, the diffusing nozzle 25 opens sideways but other positions can of course be envisaged.
The cap 16 is mainly made from a rigid thermoplastic, such as polypropylene. This rigid material enables the fastening thereof, in particular by clip fastening, to the container 12.
In order to enable the actuation of the dispensing member 14, the dispensing head, the cap 16 has a flexible and deformable upper part 17 made from a thermoplastic elastomer. Preferentially, the thermoplastic elastomer is overmoulded to the rigid material forming a base structure of the cap 16. The plastic elastomer is in particular based on SEBS.
In particular, the flexible upper part 17 is overmoulded to a rigid base part of the cap 16. This makes it possible to ensure a certain impermeability of the inside of the cap 16 and in particular to protect the valve 14.
The flexible deformable part comprises a textured bearing zone 17a used as finger pad.
More specifically, the deformable upper part 17 extends over a rear part of the cap 16, located on the opposite side to the diffusing nozzle 25. It is capable of being deformed so that a user can bear against an actuating plate 15 of the valve 14.
The antistatic properties of the deformable upper part of the cap 16 made from various materials have been tested.
The antistatic property of a material is mainly characterized by its surface resistivity which is expressed in ohm/m2 and is evaluated according to the ASTM D257 standard.
More specifically, the antistatic property of a material is evaluated by measuring, with the aid of a charge measurer, the time needed to bring the electrostatic potential of the material from a voltage of 1000 V to 100 V. In the present packaging field, it will be considered that a discharge time of less than 30 seconds enables a good dissipation of the electrostatic charges and the material attracts little or no dust.
On the contrary, if the discharge time is greater than 60 seconds, then the material dissipates the electrostatic charges poorly and has a high tendency towards dust accumulation.
The measurements are carried out after stoving (20°C and at a moisture content set at 80% relative humidity) for 2 days in order to condition the material.
An unfunctionalized and unfilled SEBS was blended with various amounts of a PEB A, also unfilled.
The blend according to the present application is prepared by customary thermoplastic blending techniques such as for example by extrusion or with the aid of twin-screw mixers, by compounding, using SEBS particles and PEBS particles. The particles may also be ground in order to obtain a more intimate blend.
The blend is then melted and injected into a mould of the deformable upper part of the cap 16.
The results of the discharge times are presented in the table below:
Figure imgf000011_0001
Figure 2 is a depiction of another embodiment using a blend according to the present application. In this case, Figure 2 shows a bottle-type container 100 having a main body 101 delimiting an internal volume 102 intended to contain a product and surmounted by a neck 103 having a dispensing opening 104. The neck 103 is equipped with an external thread 105 enabling the closure of the opening 104 and of the bottle 100 by a corresponding stopper.
As can be seen in Figure 2, the main body 101 has an outer gripping portion 106 (presence of indentations for receiving the fingers of one hand) produced by overmoulding using an antistatic blend according to the present application.

Claims

1. Thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized TPS and at least one PEBA, characterized in that:
- the PEBA: TPS weight ratio, excluding optional inert mineral and organic fillers thereof, is greater than or equal to 8%,
the sum of the weight of TPS and the weight of PEBA is greater than or equal to 80% of the total weight of the blend,
it comprises less than 1% of the total weight of the blend of various organic compounds such as dyes and additives,
the remainder consisting of inert mineral fillers and/or unfunctionalized polyolefm fillers.
2. Blend according to Claim 1, characterized in that the PEBA:TPS weight ratio is greater than or equal to 10%.
3. Blend according to Claim 1, characterized in that the PEBA:TPS weight ratio is less than or equal to 30%>, preferably less than or equal to 20%>.
4. Blend according to any one of Claims 1 to 3, characterized in that the TPS comprises, preferably predominantly or even completely, an SEBS.
5. Blend according to any one of Claims 1 to 4, characterized in that the sum, by weight, of the TPS and of the PEBA is greater than or equal to 90% of the total weight of the blend, preferably greater than or equal to 95%, or even greater than or equal to 99.9%.
6. Blend according to any one of Claims 1 to 5, characterized in that said blend comprises less than 0.1 %, preferably less than 0.08 % of various organic compounds.
7. Blend according to any one of Claims 1 to 6, characterized in that the various organic compounds are nonionic compounds.
8. Blend according to any one of Claims 1 to 7, characterized in that the various organic compounds do not comprise a functional group from among carboxylic acid, carboxylic acid anhydride, alcohol, amide, ester and ether groups, in particular do not comprise an oxygen-containing functional group.
9. Device for packaging (100) and/or dispensing (10) product, in particular cosmetic product, such as a sun protection product, characterized in that it comprises at least one free surface (106, 17) , in particular an outer surface, produced from a blend according to any one of Claims 1 to 8.
10. Protective cap (16) for a dispensing device (10) according to Claim 9, said cap comprising at least one flexible deformable surface (17) made from a blend according to any one of Claims 1 to 8.
11. Protective cap (16) according to Claim 10, characterized in that the flexible deformable surface (17) is overmoulded to a rigid assembly portion on the packaging and dispensing device (10).
12. Device according to claim 9, characterized in that the free surface is an internal surface, in particular intended to be in contact with the cosmetic product to be contain in the device.
13. Device according to claim 12, characterized in that the free internal surface belongs to a assembled element of the packaging and/or dispensing device, for example to a wiper.
PCT/EP2017/057967 2016-04-15 2017-04-04 Thermoplastic elastomer blend with antistatic properties comprising at least one unfunctionalized tps and at least one peba WO2017178284A1 (en)

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FR1653324 2016-04-15
FR1653324A FR3050209B1 (en) 2016-04-15 2016-04-15 ELASTOMERIC THERMOPLASTIC MIXTURE WITH ANTISTATIC PROPERTIES COMPRISING AT LEAST ONE NON-FUNCTIONALIZED GST AND AT LEAST ONE PEBA

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242158A2 (en) * 1986-04-14 1987-10-21 Toray Industries, Inc. Intrinsically antistatic thermoplastic resin compositions
EP0705883A1 (en) * 1994-09-23 1996-04-10 Elf Atochem S.A. Anti-static card
EP0842969A1 (en) * 1996-11-19 1998-05-20 Elf Atochem S.A. Material containing a polyamide, a polyamide-polyether block polymer and a functionalised polyolefin, films and objects therefrom
WO2001010951A1 (en) * 1999-08-04 2001-02-15 Atofina Antistatic styrene polymer compositions
EP2914648A1 (en) * 2012-10-31 2015-09-09 Dow Global Technologies LLC Nanocomposites of copolymers and dielectric materials
WO2016008930A1 (en) * 2014-07-15 2016-01-21 L'oreal Actuating and product dispensing head, related device and method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242158A2 (en) * 1986-04-14 1987-10-21 Toray Industries, Inc. Intrinsically antistatic thermoplastic resin compositions
EP0705883A1 (en) * 1994-09-23 1996-04-10 Elf Atochem S.A. Anti-static card
EP0842969A1 (en) * 1996-11-19 1998-05-20 Elf Atochem S.A. Material containing a polyamide, a polyamide-polyether block polymer and a functionalised polyolefin, films and objects therefrom
WO2001010951A1 (en) * 1999-08-04 2001-02-15 Atofina Antistatic styrene polymer compositions
EP2914648A1 (en) * 2012-10-31 2015-09-09 Dow Global Technologies LLC Nanocomposites of copolymers and dielectric materials
WO2016008930A1 (en) * 2014-07-15 2016-01-21 L'oreal Actuating and product dispensing head, related device and method

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