1 ,3-PROPYLENE ETHER DERIVED COMPOUNDS FOR PERSONAL CARE

This application is related, and claims the benefit of priority of, U.S. Provisional Application No. 62/579,991, titled COMPOUNDS SUITABLE FOR PERSONAL CARE AND COSMETIC USES, fifed on 1 November 2017, the contents of which is incorporated herein by reference in its entirety for aii purposes.

Field of the Invention

The present invention relates to novel compounds, ether and ester derivatives of polytrtmethylene ether glycol, persona! care products containing them, methods of producing them, and their use as ingredients for persona! care and/or cosmetic formulations, in particular as agents to provide sensory and pigment wetting

properties.

Background of the Invention

Known polyalkyiene ether glycois include polyethylene glycol., poly- 1,2- propylene ether glycol, i,3-propylene ether glycol, poiytetramethy!ene ether glycol, poiyhexamethylene ether glycol and copolymers thereof. Examples of commerciaiiy important polyether glycols include polyethylene glycol, poly(l,2-propylene glycol), ethylene oxide/propy!ene oxide copolyols, and po!ytetramethyfene ether glycol.

The most widely used poiyether glycol is poiy{l,2-p opylene glycol) (PPG) because of its low cost. This polymer is non-crystalline, liquid at room temperature and easy to handle. However, PPG is derived from a non-renewable reactive epoxide and has secondary hydroxy! end groups.

Polytnmethylene ether glycol or poiy( l,3~propySene glycol) (PPDn) can be produced from non-epoxlde l,3~propanedioi, which can be advantageously derived from a renewable source. Polytnmethylene ether glycols have primary hydroxyl groups, have low me!ting points and are high!y flexible.

Polytnmethylene ether glycols have been known for a number of years, as well as fatty acid mono or di-ester derivatives. They are used in different technical fields, especially as functional fluids.

In the persona! care and cosmetic fields, po!ypropanediol-5 stearate is used as a surfactant or emulsifying formulation agent.

The aim of the present invention is to propose new compound derivatives of poiytrimethyiene ether giyco!, in particular for the field of personal care products.

Traditional cosmetic pigments are made in different ways from thermal decomposition, extraction and other filtration processes from solutions to produce a dry powder. However, these dry pigmentary powders come in muitipie forms of particle aggregates/aggiomerates that introduce difficulties in color properties when evaluated. Hence, they are oftentimes difficult for cosmetics chemists to formu!ate/stabiiize on various product forms like emulsions, anhydrous sticks or powder formulations. These dry powders need to be fully dispersed and their particle size reduced as much as possible to see the full development of coior. Pigment dispersion has been used by cosmetic scientists as a beneficial way to introduce/incorporate dry powders into their respective formuiations.

Dispersion is the process of wetting, separating and distributing pigment particles in a medium. It requires intense energy input through high sheering in liquids or pulverization in powders, it can also require specialized equipment like high sheer mixers, 3 roil mills, etc.

Some of the benefits of using dispersions are: the full development of color, enhanced color intensity, the prevention of agglomeration or reagg!omeration, the prevention of pigment striations on product formuiations, cost effscacy and the ease of incorporation in various product forms.

Summary of the Invention

The objective of the present invention is to address these and other

disadvantages associated with the prior art. A specific objective of the invention is to propose a compound or composition having interesting properties on dispersing inorganic pigments/dyes.

Accordingly, a first aspect of the present invention provide for a compound of formula i:

X-(OCH2CH2CH2)n"OR ( 1)

wherein:

n is an integer from 2 to 15,

R is a Cg to C3 hydrocarby! group,

X is R or R _; C(0), and

R| is a Cj to C35 hydrocarby! group.

According to a second aspect of the present invention, there is provided a composition comprising a mixture of two or more compounds according to the first aspect.

According to a third aspect of the present invention, there is provided a method of producing the compound of the first aspect of the invention or the composition of the second aspect of the invention.

A fourth aspect of the present inventio provides for a personal care product comprising the compound of the first aspect of the invention or the composition of the second aspect of the invention. A fifth aspect of the present invention provides for the use of a compound according to the first aspect of the invention, or a composition according to the second aspect of the invention, in a persona! care product.

Aii of the features described herein may be combined with any of the above aspects, in any combination.

The present invention is based in part on the recognition by the inventors that a compound or composition of the first or second aspect of the invention, respectively, has advantageous properties due to its particular combination of components.

It has surprisingly been discovered that capping polytri methylene ether glycol with a fatty alcohol group at least on one end side, the other end side being capped with an ester group, provides new ether derivative compounds, which can be named "ester-PPDn-ether" or "ether-PPDn-ether", possessing desirable rheoiogical properties for formulation purposes, in particular pigment wetting properties, and/or sensory properties. Such properties are presented through the examples given below.

Detailed description of the invention

It will be understood that any upper or lower quantity or range limit used herein may be independently combined.

It will be understood that, when describing the number of carbon atoms in a substituent group {e.g. "Ci to }, the number refers to the total numbe of carbon atoms present in the substituent group, including any present in any branched groups. Additionally,, when describing the number of carbon atoms in, for example fatty acids, this refers to the total number of carbon atoms including the one at the carboxyiic acid, and any present in any branch groups.

Many of the chemicals which may be used to produce the composition of the present invention are obtained from natural sources. Such chemicals typically include a mixture of chemical species due to their natural origin. Due to the presence of such mixtures, various parameters defined herein can be an average value and may be non- integral.

By the use of the term "hydrocarbyi" in the present specification, it is meant any moiety having the general structure -Cm t, or a structure based thereon (for example -CmHan wherein m is an integer between 2 and 36. Unless otherwise stated, the hydrocarbyi moiety may be linear or branched, saturated or unsaturated, unsubsfcituted or substituted for example with heterogroups such as organic functional groups comprising nitrogen, oxygen or sulphur atoms, and/or interrupted by one or more oxygen, sulphur, silicon atoms, or by silano or dialkyisilcon groups, or mixtures thereof. By the use of the term ""alky!" in the present specification, it is meant those hydrocarbyi groups as described above which are unsubstituted and saturated.

By the use of the term ^residue" in the present specification, it is meant the part of a reactant molecule which remains in the reaction product compound after a reaction has occurred.

Compound

In the compound of formuia (1), the va!ue of n is preferably in the range from 2 to 10, more preferably 3 to 7, particuiariy 3, 4 or 5, and especially 5.

The R group is preferably a Cg to C24, more preferabiy a Cjo to C20

particuiariy a C 2 to ¾§, and especiaiiy a C12 to C 4 hydrocarbyl, preferabiy a!kyi, group. R may be linear or branched, but is preferably a branched chain. When the chain is branched, it preferably has not more than two, and more preferably not more than one branch.

The Ri group is preferably a Cg to C24, more preferably a CJQ to€22 _?

particularly a C 4 to C20 and especiaiiy a€ ¾ to CJS hydrocarbyl, preferably aiky!, group. i may be linear or branched, but is preferably a linear chain.

In one embodiment, Ri is branched. When R¾. is branched, it preferabiy has not more than two branches, and more preferably not more than one branch. When Rj. is branched, the branches are preferably aikyi branches, more preferabiy methyl, ethyl or propyl branches, more preferabiy methyl branches. RJ may comprise a mixture of branch groups. In this case, the predominant branch group is preferably methyl.

R and/or Ri may be derived from mixtures of materials, in which case the aforementioned carbon chain lengths and/or number of branches refer to the average vaiues by moles or number.

Preferabiy the compound of the invention Is an ester-PFDn-ether compound

(otherwise termed an ester-(OCH2CHaCH2)n-ether compound) wherein in formuia (I), X is RiCiO).

R and R_ in formuia (1) may be the same as each other of different. Preferably, R and Ri in formula ( 1) are different to each other. In this embodiment, R may contain more carbon atoms than Ri or fewer carbon atoms than Rj, Preferably, R contains fewer carbon atoms than R< in formuia (1).

More preferabiy the compound of the invention is capryfate/caprate- (OCHjCHaCHz fsostearyi, wherein in formula (i) X is R C(0), with being C - 0, n

= 5, and R being an isostearyi group. In this embodiment, R is the residue of isostearyi aicohoi and Ri is the residue of caprylic/capric acid. The compound may comprise molecules having different values of n, in which case the aforementioned values of n refer to the average values by mo!es or number, and n may be a non-integer.

The compound of the first aspect of the invention is preferabiy the reaction product of a poiytrimethyiene ether giycoi, a monohydric alcohoi and a monocarboxyiic acid.

Preferabiy, the -{OCH2CH2CH2V in formula (1) is the residue of

poiytrimethyiene ether glycol. Preferably, the poiytrimethyiene ether giycoi has between 2 and 15 repeating residua! monomer 1,3-propane diol repeating units.

Preferabiy, the 1,3-propane dioi monomer residue repeating units are bonded together by ether linkages. The ether linkages are suitably formed by dehydration reaction between neighboring 1,3-propane dioi monomers.

Preferably, R in formula ( 1) is the residue of a monohydric aicohoi. The monohydric aicohoi is preferabiy a long-chain primary aicohoi, preferably with a chain length of 16 to 26 carbon atoms, which may be derived from natura! sources such as fats and oils. Preferably, the aicohoi is derived from vegetable sources, although it is aiso possible to derive the alcohols from animal sources or petrochemical sources. The alcohols used in the present invention will normally be obtained from naturally occurring esters by hydrogenation,

The monohydric aicohoi used in the present invention may be a mixture of alcohols of different chain lengths. In this case, the mixture may be a commercially available mixture, or may be made from a combination of different chain length aicohois.

The alcohol used in the present invention preferably contains from 6 to 36 carbon atoms, preferabiy from 8 to 24 carbon atoms, more preferabiy from 10 to 20 carbon atoms. The aicohoi may be selected from the group comprising capryl aicohoi, capric aicohoi, iauryi aicohoi, myristyl alcohol, cetyl aicohoi, cetostearyi aicohoi, paimitoleyi alcohol, stearyi aicohoi, isostearyi aicohoi, oleyi aicohoi, arachidyi aicohoi, beheny! aicohoi, isobehenyl aicohoi, erucyl alcohol, lignceryS alcohol, cerotinyl aicohoi, montanyi alcohol and melissyi aicohoi. Preferabiy, the alcohol used in the present invention is selected from iauryi alcohol, mysrity! aicohoi, cetyi alcohol, cetostearyi alcohol, stearyi aicohoi, isostearyi alcohol, arachidyi aicohoi, behenyf alcohol, isobehenyl aicohoi, lignceryl alcohol and cerotinyl alcohol.

Preferabiy, Ri in formula ( 1) is the residue of a monocarboxyiic acid. Preferably, the monocarboxyiic acid is a long-chain monocarboxyiic acid, preferabiy with a chain length of 8 to 18 carbon atoms, which may be derived from natural sources such as fats and oils. Preferably, the acid is derived from vegetable sources, although it is also possible to derive the acids from animal sources or petrochemical sources. The acids used in the present invention wiii normaiiy be obtained from naturally occurring trigiycerides.

The monocarboxyiic acid used in the present invention may be a mixture of monocarboxyiic acids of different chain lengths. In this case, the mixture may be a cornrnerciaiiy avaiiabie mixture, or may be made from a combination of different chain length acids.

The monocarboxyiic acid used in the present invention preferably contains from 2 to 36 carbon atoms, preferably from 4 to 24 carbon atoms, more preferably from 6 to 22 carbon atoms and desirably from S to 16 carbon atoms. The acid may be selected from the group comprising caproic acid, capryiic acid, capric acid, capric/capry!ic acid, iauric acid, myristic acid, paimitic acid, stearic acid, isostearic acid, oleic acid, arachidsc acid, behenic acid, isobehenic acid, erucic acid, iignceric acid, cerotinic acid, montanic acid, meiissic acid and dimer acid. Preferably, the acid used in the present invention is selected from the group comprising capryiic acid, capric acid, capric/caprylic acid, Iauric acid, myristic acid, palmitic acid, stearic acid, and isostearic acid.

Composition

The invention also provides for a composition comprising a mixture of compounds of the invention as recited above, which can be for example jointly

produced.

Preferably the composition comprises a mixture of at feast:

(i) the compound(s) ; iCiOMOCHaCHaCHaJn-OR Ua)„ i.e. ester- PPDn-ether compound(s) of the invention, and

(ii) the compound(s) : R-iOCHaCHzCH n-OR, (lb),

i.e. ether-PPDn-ether compound(s) of the invention, wherein

n, R and Ri are as recited above.

The composition according to the present invention suitably comprises:

(t) greater than 50% by weight, preferably greater than 60% by weight, more preferably in the range from 65 to 98%, particularly 70 to 95%, and especially 80 to 90% by weight of compound(s) of formula (la) (ester-PPDn- ether compound),

(ii) less than 30% by weight, preferably less than 20% by weight, more preferably in the range from 1 to 20%, particularly 3 to 15%, and especially 5 to 10% by weight of compound of formula (lb) (ether-PPDn-ether compound), all % given by weight based on the totai weight of the composition . Where R is the residue of a branched alcohol, for example isostearyl alcohol, it will be readily apparent to the skilled person that the compound of formula (lb) will be an alkyi ether-PPDn -alkyi ether compound,

The ratio by weight of compound(s) of formula (la) to compound(s) of formula (ib) in the composition is suitably greater than 2: 1, preferably in the range from 5 to 50: 1, more preferabiy 7 to 25: 1, particularly 8 to 15: 1, and especially 9 to 11 : 1,

The composition may also further comprise a di-ester compound of formula

( lc):

R2C{0)-{OCH2CH2CH ₃ :) _m -OC(0)R2 (lc),

wherein:

m is an integer from 2 to 15 and

R ² is a C2 to C?.6 hydrocarbyi group.

The value of m is preferably in the range from 2 to 10, more preferably 3 to 7, particularly 3 to 5, and especially 5. Preferabiy m is the same as n.

The 2 group is preferabiy a C¾ to C24, more preferably a C I Q to C22* particularly a C 4 to C Q, and especially a C1 to Cig hydrocarbyi, preferabiy a!ky!, group. 2 may be linear or branched, but is preferably a linear chain. When the chain is branched, it preferably has not more than two, and more preferabiy not more than one branch.

Preferabiy 2 is the same as Ri. Preferably Ra is Ri, which is the residue of a monocarboxyiic acid.

The composition according to the present invention suitably comprises less than

30%, preferabiy less than 20%, more preferably in the range from 0.1 to 15%, particufariy 0.5 to 10%, and especially 1 to 7% by weight of compound(s) of formula (lc) (ester-PPDn-este compound) based on the total weight of the mixture

composition.

, Ri and/or Ri may be derived from mixtures of materials, In which case the aforementioned carbon chain lengths and/or number of branches refer to the average values by moles or number.

The composition may further comprise unreacted polytrrmethylene ethe glycol

(PPDn) but suitably the mixture comprises less than 30%, preferably less than 20%, more preferably in the range from 0, 1 to 15%, particularly 0.5 to 10%, and especiaiiy 1 to 7% by weight of polytrimethyiene ether glycol (PPDn) based on the total weight of the mixture composition.

The composition may comprise compounds having molecules with different values of n and/or m, in which case the aforementioned vaiues of n and/or m refer to the average vaiues by moles or number, and n and/or m may be non-Integer. Preferabiy, the composition comprises compounds having the same value of n and/or m, in the range from 2 to 10, more preferabiy 3 to 7, particularly 3 to 5, and especially 5.

Preferabiy, the composition is anhydrous. By the use of the term anhydrous herein, it is meant that the composition preferably comprises a maximum of 10% by weight water. More preferably, the composition comprises a maximum of 7% by weight water, most preferably, 5% and desirably 2% by weight Preferabiy, the composition comprises 0.01% to 10% by weight water, preferabiy 0.05% to 5%, most preferabiy 0.1% to 2% by weight,

The present invention therefore further provides for a composition consisting essentia! iy of

(!) the compound(s) : (la);

00 the compound(s) : R-(OCHaCH ₂ CH2) _n -OR, (lb);

(Hi) the compounds) R ₂ C(0)-(OCH2CH2CH2>m-OC(0}Ra (lc); and

(iv) poly tri methylene ether giycoi;

wherein

n, R _t Ri and are as recited above.

Preferably, the composition comprises a mixture of compounds which are the reaction products of a po!ytrimethyiene ether glycol, a monohydric aicohol and a monocarboxylic acid.

The invention also provides for a production method of a compound of the invention or a composition of the invention, the method comprising :

~ a first step of preparing an etherified-poiytrimethyiene ether giycoi mixture by reacting polytrimethyiene ether giycoi and an alcoho! having the formula

R-OH in the presence of a strong acid catalyst; and

- a second step of esterifying the reaction product obtained in the first step with a fatty carboxyiic acid of formula Rj-COOH, in the presence of a strong acid catalyst,

wherein R and R< are as recited above.

According to the invention, the strong acid catalyst that ma be used may be selected from sulfu ic acid, hydrochloric acid, trifiuoromethanesuifo ic acid,

fiuorosuifuric acid-antimony pentafiuoride 1 : 1, preferably trifiuoromethanesuifonic acid.

More precisely, the first step can be performed at a temperature in the range of 150°C to 220*0 for 6 to 24 hours.

More precisely, the second step can be performed at a temperature in the range of 120°C to 180°C for 2 to l2hours. Persona! Care Product

The invention aiso provides for a persona! care product comprising a compound of the invention or a composition of the invention, as recited above.

The compounds and compositions of the invention may be suitable for use in persona! care products including, but not limited to, shampoos, conditioners, conditioning shampoos, body washes, cleansers, hair coloring products and hair dyes, hair re!axers, cosmetics, skin care products, organic sunscreens, inorganic sunscreens, deodorants, antiperspirants, depilatories, skin bronzers, cosmetics removers or the like, lipsticks, foundations, hair mousses, styling gels, anti-aging creams and lotions and anti-acne products. The compounds and compositions of the invention are in particular suitable for use in colour cosmetics, sunscreens, anti-perspirants, anti-aging and moisturizing products.

The present invention provides for the use of a compound of the invention or a composition according to the invention as a rheoiogy modifier in a persona! care product. Preferably, the compound or composition of the present invention may increase the viscosity of a persona! care product. This may provide a creamier- textured or solidified/semi -solidified persona! care product depending on th

concentration of the compound or composition of the present invention included.

The present invention provides for the use of a compound of the invention or a composition according to the invention as a sensory agent In a persona! care product. Preferably, the compound or composition of the present invention may improve or alter the skin fee! of a personal care product. This may for example provide a less greasy or silkier feeling product depending on the nature of the personal care product.

The present invention provides for the use of a compound of the invention or a composition according to the invention as a pigment dispersing agent and/or a pigment wetter in a personal care product- Preferably, the compound or composition of the present invention may increase the stability of a personal care product, and/or make its production easier, by improving the wetting of pigments and dispersing the solid pigment particles homogeneously in the product to prevent flocculation,

The compound or composition of the present invention is preferably used in a personal care product at a concentration in the range from 0.1 to 50%, preferably 0,5 to 40%, more preferably 1 to 30%, particularly 2 to 20%, and especially 3 to 3.0%, by weight of the total composition. The most suitable concentration for a particular persona! care product will depend on the specific product and the other ingredients contained therein.

The personal care product may comprise additional components, for example, additional emollients, carriers, surfactants and the like. Any additional emollients in the personal care product of the present invention wii! preferably mainiy be an emoiiient oii of the type used in persona! care or cosmetic products. The emoiiient can and usually will be an oily material which is liquid at ambient temperature. Alternatively it can be solid at ambient temperature, in which case in bulk it will usually be a waxy solid, provided it is liquid at an elevated temperature at which it can be included in and emulsified in the product. The manufacture of the product preferably uses temperatures up to 100°C, more preferably about 80 °C, and therefore such solid emoilients wii! preferabty have melting

temperatures of less than i00°C _f and more preferably less than ?0°€.

Suitable normally liquid emoiiient oils include non-polar oils, for example mineral or parafftn, especially isoparaffin, oils, such as that sold by Croda as Ar!amol (trade mark) HD; or medium polarity oils, for example vegetable ester oils such as jojoba oil, vegetable giyceride oils, animal giyceride oils, such as that sold by Croda as Crodamoi (trade mark) GTCC (capryiic/capric triglyceride), synthetic oils, for example synthetic ester oils, such as isopropyl paSmitate and those sold by Croda as Crodamoi IPM and Crodamoi DQA, ether oiis, particularly of two fatty e.g. CS to CIS aikyl residues, such as that sold by Cognis as Cetioi OE (dicapryl ether), guerbet alcohols such as that soid by Cognis as Eutanoi G (oetyi dodecanol), or silicone oils, such as dimethicione oil such as those sold by Dow Corning as DC200, cyclomethicone oil, or silicones having polyoxyalkyiene side chains to improve their hydrophiii ity; or highly polar oils including alkoxyiate emollients for example fatty alcohol propoxyiates such as that sold by Croda as AriamoS PS 15 (propoxy!ated steary! alcohol). Suitable emoiiient materials that can be solid at ambient temperature but liquid at temperatures typically used to make the compositions of this invention include jojoba wax, tallow and coconut wax/oil.

Mixtures of emoilients can be used, and in some cases solid emollients may dissolve wholly or partly in liquid emollients or in combination the freezing point of the mixture may be suitably low. Where the emollient composition is a solid (such as fatty alcohols) at ambient temperature, the resulting dispersion may technically not be an emulsion (although in most cases the precise phase of the oily disperse phase cannot readily be determined) but such dispersions behave as if they were true emulsions and the term emulsion is used herein to include such compositions.

In personal care products comprising water, the amount of water present is suitably greater than 5%, preferably in the range from 30 to 90%, more preferably 50 to 90%, particularly 70 to 85%, and especially 75 to 80% by weight of the total composition. The water phase may include a poSyol, e.g. glycerin. In this case, the total water phase including the ροίγοΐ present in the persona! care formulation is suitably greater than 5%, preferably in the range from 30 to 90%, more preferably 50 to 90%, particularly 70 to 85%, and especially 75 to 80% by weight of the total composition.

The persona! care products may further comprise choiesteroi as an additional moistu isation component. When present, the choiesteroi is present at an amount of 0.1 to 5% by weight of the total personal care product.

The persona! care product according to the present invention may also contain other additional surfactant materials which form part of the emuisifier system. Othe suitable surfactants include relatively hydrophiiic surfactants, e.g. having a HLB value of greater than 10, preferably greater than 12, and relatively hydrophobic surfactants e.g. having a HLB value of less than 10, preferably less than 8. Relatively hydrophiiic surfactants include alkoxyiate surfactants with an average in the range from about 10 to about 100 aikyiene oxide, particularly ethylene oxide residues; and relatively hydrophobic surfactants include alkoxyiate surfactants preferably with an average in the range from about 3 to about 10 aikyiene oxide, particularly ethylene oxide residues.

Personal care or cosmetic products can be divided by viscosity into milks and lotions, which preferably have a low shear viscosity (measured at shear rates of about 0.1 to 10 s ^'5 - as is typically used in Brookfieid viscometers) of up to 10,000 mPa.s, and creams which preferably have a low shear viscosity of more than 10,000 mPa.s.

Milks and lotions preferably have a low shear viscosity in the range from 100 to 10,000, more preferably 200 to 5,000, and particularly 300 to 1,000 mPa.s. The amount of the compound or composition according to the present invention present in a milk or lotion is preferably in the range from 2 to 3% by weight of the total composition.

Creams preferably have a low shear viscosity of at least 20,000, more preferably in the range from 30,000 to 80,000, and particularly 40,000 to 70,000 mPa.s, although even higher viscosities e.g. up to about iO ⁶ mPa.s, may also b used. The amount of compound or composition according to the present invention present in a cream is preferably in the range from 4 to 5.5% by weight of the total composition.

The personal care products of the invention may be made by conventional emulsification and mixing methods. For example, the compound or composition according to the present invention may be added to (i) the oil phase, which is then added to the aqueous phase, or (it) both the combined oil and water phases, or (iti) the water phase, which is then added to the oil phase. Method (iii) is preferred. In all of these methods, the resulting mixture can then be emulsified using standard techniques. It is preferred to either heat the aqueous and oil phases usua!!y above about 60°C, e.g. to about SO to 85°C, or to subject the aqueous phase to high intensity mixing at lower, e.g. about ambient, temperature. Vigorous mixing and the use of moderately elevated temperatures can be combined if desired. The heating and/or high intensity mixing can be carried out before, during or after addition of the oi phase but once emulsified, care should be taken not to destroy the liquid crystal system by excessive mixing or stirring.

The personal care products can also be made by inverse emulsification methods, whereby the compound or composition according to the present invention is added to either the oil phase or the aqueous phase, and the aqueous phase is mixed into the oil phase to initially form a water in oil emulsion. Aqueous phase addition is continued until the system inverts to form an oil in water emulsion. Plainly a substantial amount of aqueous phase will generally be needed to effect inversion and so this method is not likely to be used for high oil phase content emulsions. Vigorous mixing and the us of moderately elevated temperatures can be combined if desired. Heating can be carried out during or after addition of the aqueous phase and before, during or after inversion. High intensity mixing can be carried out during or after addition of th aqueous phase, and before or during inversion

The personal care products may for example be microemuisions or

nanoemulsions, having a mean droplet size over a wide range, preferably in the range from 10 to 10,000 nm. In one embodiment, the emulsion droplet size may be reduced, for example by high pressure homogenisation, preferably to a value in the range from 100 to 1,000 nm, more preferably 300 to 600 nm.

The personal care products according to the present invention are preferably stable for greater than one month, more preferably greater than two months, particularly greater than three months, and especially greater than four months at ambient temperature (23°C), and also preferably at 40°C. The stability at even higher temperatures can be particularly important, and therefore the personal care

formulation is preferably stable for greater than one week, preferably greater than two weeks, more preferably greater than 3 weeks, particularly greater than one month, and especially greater than two months at 50°C,

Many other components may be included in the personal care product. These components can be oil soluble, water soluble or non-soluble. Examples of such materials include:

(i) preservatives such as those based on parabens (alkyl esters of 4- hydroxybenzoic acid), phenoxyethanoi, substituted ureas and hydantoin derivatives e.g. those sold commercially under the trade names Germaben II Nipaguard BPX and Nipaguard DMDMH, when used preferably at a concentration in the range from 0.5 to 2% by weight of the totai composition;

(ii) perfumes, when used preferabiy at a concentration in the range from O.i to 10% more preferabiy up to about 5%, and particularly up to about 2% by weight of the totai composition;

(iii) humectants or solvents such as a!cohois, poSyois such as glycerol and polyethylene glycols, when used preferably at a concentration in the range from I to 10% by weight of the totai composition;

(iv) sunfiiter or sunscreen materiais including organic sunscreens and/or inorganic sunscreens including those based on titanium dioxide or zinc oxide; when used preferabiy at a concentration in the range from 0.1% to 20%, more preferabiy 1 to 15%, and particularly 2 to 10% by weight of the total composition;

(v) alpha hydroxy acids such as glycoiic, citric., lactic, malic, tartaric acids and their esters; self-tanning agents such as dihydroxyacetone, and beta hydroxy! acids such as salicylic acid and their esters;

(vi) anti-aging, celS-turnover-improving, and antimicrobial, particularly antiacne, components such as salicylic acid;

(vii) vitamins and their precursors including: (a) Vitamin A, e.g. as retiny! paimitate and other tretinoin precursor moiecuies, (b) Vitamin B, e.g. as panthenol and its derivatives, (c) Vitamin C, e.g. as ascorbic acid and its derivatives, (d) Vitamin E, e.g. as tocopheryi acetate, (e) Vitamin F, e.g. as polyunsaturated fatty acid esters such as gamma-iirsoiersic acid esters;

(viii) skin care agents such as ceramides either as natural materials or functional mimic of natural ceramides;

(ix) phospholipids, such as synthetic phospholipids or natural phospholipids, e.g. lecithin;

(x) vesicie-containing formulations;

(xi) botanical extracts with beneficial skin care properties;

(xii) skin whiteners such as ODA White, Mediatone (trade marks) sold by

Sederma, a member of Croda International Pic kojic acid, arbutsn and similar materials;

(xiii) skin repair compounds actives such as Aiiantoin and similar series;

(xiv) caffeine and similar compounds;

(xv) cooling additives such as menthol or camphor;

(xvi) insect repellents such as N,N~diethyl~3-methylbenzarnid (DEET) and citrus or eucalyptus oils;

(xvii) essential oils;

(xviii) ethano!; and (xix) pigments, including microfine pigments, particularly oxides and silicates, e.g. iron oxide, particularly coated iron oxides, and/or titanium dioxide, and ceramic materials such as boron nitride, or other solid components, such as are used in makeu and cosmetics, to give suspoemulsions, preferably used in an amount in the range from 1 to 15%, more preferabiy at least 5% and particularly approximately 10%.

The compound, composition and personal care product according to the present invention are suitable for use in a wide range of compositions and end-use applications, such as moisturizers, sunscreens, after sun products, body butters, gel creams, high perfume containing products, perfume creams, baby care products, hair conditioners, skin toning and skin whitening products, water-free products, anti-perspirants and deodorant products, tanning products, cleansers, 2-in-i foaming emulsions, multiple emulsions, preservative free products, emulsifier free products, mild formulations, scrub formulations e.g. containing solid beads, silicone in water formulations, pigment containing products, sprayable emulsions, coiour cosmetics, conditioners, shower products, foaming emulsions, make-υρ remover, eye make-up remover, and wipes.

Personal care products containing a compound or a composition according to the present invention may have a pH value over a wide range, preferably in the range from 3 to 13, more preferabiy 4 to 9, and especially 5 to 6,

Any of the above features may be taken in any combination and with any aspect of the invention.

Examples

The Invention is illustrated by the following non-limiting examples. AS! parts and percentages are given by weight unless otherwise stated.

It will be understood that ail tests and physical properties listed have been determined at atmospheric pressure and ambient temperature (i.e. about 23°C), unless otherwise stated herein, or unless otherwise stated in the referenced test methods and procedures.

Test Methods

In this specification the following test methods have been used;

(i) Emulsion stability was assessed by observing the emulsions after storage for 3 months at ambient temperature (23°C), cold at 5°C or under elevated

temperature storage at 40°C, 45°C and 50°C, Measuring storage stability at 50°C is a severe test. The emulsions were also assessed for their freeze-thaw stability using a cycling oven (-10°C to 4G°C in 24 hours). The composition was stable if no visibl separation of the emulsion occurred. The stability of the emulsions was also assessed by monitoring the size of the dispersed phase water particles over a three month period. The particle size was measured using a Malvern Mastersizer 2000 that measures the size of the dispersed phase particles using laser diffraction.

(ii) Emulsion viscosity was measured at 23°C with a Brookfieid LVT viscometer using an appropriate spindle (IVl, LV2, LV3 _> or LV4) depending on the viscosity of the emulsion. The emuision was tested at 10 rpm (0.1 Hz), i day after making the emuision and results are quoted in mPa.s.

(iif) The hydroxy! value is defined as the number of mg of potassium hydroxide equivalent to the hydroxy! content of i g of sample, and was measured by acetyiation followed by hydrolysation of excess acetic anhydride. The acetic acid formed was subsequently titrated with an ethanofic potassium hydroxide solution.

(iv) The acid value is defined as the number of mg of potassium hydroxide required to neutraiize the free acids in i g of sampie, and was measured by direct titration with a standard potassium hydroxide solution,

(v) The particle size was determined according to ASTM method D1210 - 05(2014) Standard Test Method for Fineness of Dispersion of Pigment-Vehicle Systems by Hegman-Type Guage.

Where mentioned herein, concentrations are given by weight based on the total weight of the compound / composition / formulation.

Preparation Examples

Exampl ,!; General method of preparation of a mixture composition of the invention comprising the RiC(0)-(OCH2CH2CH2) -OR compound of the invention.

First step of preparation of a precursor mixture composition comprising the -{OCH2CH2CH ₂ ) ~OH compound.

3-10 moies of vegetable derived 1,3-propanedioi, ί mole of fatty alcoho! of formula R-OH and concentrated sulfuric acid cataiyst were added to a reaction flask with nitrogen inlet, mechanical stirrer and a distillation head. The mixture was heated to i50-i?0°C with a nitrogen sparge and held for 2.5 hours. The temperature was then increased to i?5-250°C and held for up to 24 hours. At this point, the temperature was lowered to 75°C and a 45% OH solution and de-ionized water were added. The resuiting aqueous mixture was held at 75°C and stirred for 2-4 hours under nitrogen to hydroiyze the acid ester formed during the add catalyzed polycondensation and to neutraiize the residual acid. The reaction mixture was then allowed to stand for phase- separation with the bottom layer being the aqueous phase and the top Sayer being the organic phase. After the aqueous phase was removed, the organic phase was dried under vacuum and filtered. This step resulted in the preparation of a mixture composition comprising mostly the monocapped ether compound (in weight with regard to the totai weight of the composition).

The composition obtained also comprises in minor amount the dicapped compound R~ (OCH ₂ CHaCH2)n-OR.

Second step of estertftcation of the precursor mixture composition

1 mole of the product mixture prepared in the first step, 1 moie of fatty acid of formula R ⁵ COOH and 0,1 w/w% of tin II oxalate catalyst were added to a clean, dry flask with nitrogen iniet, mechantcai stirrer and a distillation head. The reaction mixture was heated to and held at between IS0~22G°C hiie being tracked by acid value drop. Once an acid value of <2 was achieved, the batch was cooled to 90°C, dried and filtered.

This step resulted in the preparation of a composition mostly comprising the monocapped compound of the invention and in minor amounts the dicapped compound of the invention R-{OCH2CH2CH2)n~OR formed in the first st -OCCC R ¹ .

propanediol, 657 g of isostearyi alcohol and 4,7 g concentrated sulfuric acid were added to a 3L four-neck round bottom fiask. After the reaction, 4.4 g of a 45% OH solution and 320 g of de-ionized water were added and the resulting aqueous mixture was held at 75°C and stirred for 4 hours under nitrogen.

Second step: 439 g of the product PPD- 5 isostearyi aicohoi prepared in the first step, 237 g of isostearic acid and 0.8 g tin II oxalate catalyst were added to a dean, dry 1 L four-neck round bottom fiask with nitrogen iniet, mechanical stirrer and a distillation head. The reaction mixture was heated to and held at between 18Q~220°C while being tracked by acid value drop.

Ex3fflpte 2: Distribution

The following table 1 outlines results of NMR data used to determine distribution for different products prepared according to the above mentioned first step of the method with different length PPD chains and fatty alcohol used for capping selected from Cetearyi alcohol (sold under the tradename Crodacol 1618 supplied by Croda Inc., comprising a distribution of cetyi (C16) and stearyi (C18) alcohols) and myristyi alcohol (sold under the tradename Crodacol M95 supplied by Croda Inc., consisting of C14 alcohol). Table is

The method of example 1 was appiied to prepare a mixture composition comprising the cetearyi-PPDS-caprylate/caprate compound of the invention (from a mixture of capryiic (CS) and caprtc (C10) acids reacted with the PPDS-cetearyi aicohol mixture mentioned above) - the distribution of the different compounds of the mixture was determined by NMR analysis (Standard iH and 13C NMR experiments) and is shown in the foiiowing table 2.

Table 2:

Ap.p Heats on £xa m pies

In the foiiowing examples, the mixture composition of the invention is used which comprises the ester-PPDn-ether compound as the major component, However, for simplification, the name "ester-PPDn-ether" is used in the text to designate the mixture,

E^ Pl®„,¾s Evaluation of caprate/ca ryfate-PPDS-isostearyi in color cosmetic products of the dispersing properties of inorganic solid

pigments / dy es.

The objective was to evaluate the pigment wetting capacity of the

caprate/caprylate-PPDS-ssosteary! of the invention compared to most commoniy used dispersion emollient media in colour cosmetics namely:

- Cromoiiient™ DP3A, a di-ester of propoxyiated myristy! aicohol and adiptc acid, marketed by Croda (INCI name: DI-PPG-3 Myristy! Ether Adipate);

- Crodamoi™ GTCC, a caprate/capryiate triglyceride (INCI name:

Capryiic/Capric Triglyceride); and - Castor oil (ISS!CI name: Rieinus Communis (Castor) Seed Oi!).

A red pigment (Red 7 Calcium Lake - 1NCI name: CI 15850) at a ratio media/pigment of 55:45 was tested. Each emollient/media was mixed with this pigment and the dispersion formed was mixed with an overhead stirrer for l/2hour, followed by three passes through a three roil mill.

Viscosity test:

Measurements of viscosity after stabilization (after 24hours) of the dispersions were taken with a Brookfield viscometer and are reported in the following table 3.

Table 3: Viscosity in cps of the dispersions

Emollient I Viscosity (cps)

Caprate/caprylate-PPDS-isostearyi 30,000

of the invention

Cromoiiient™ DP3A 1 25,000

Crodamol™ GTCC 5,000

Castor oil ! 250,000

Particle size test;

The standardized test of Hegman Gauge and Fineness of Grind was used to approximate the particle size. It consists of placing a small volume of product on the deep end and drawing it with a straight scraper toward the shallow end. The position on the scale where oversize particle and their tracks appear is rated for determination of dispersion. The results are reported in the following table 4,

Table 4; Parttcie size approximation in pm in the dispersions

Lower viscosity Is not directly proportional to better pigment dispersion. This is shown by the results above for the Crodamol GTCC exhibiting the lowest viscosity

(5,000cps) but the highest particle si2e (li.OOpm) in the dispersion.

In fact, dispersion mixture needs to be optimal and requires that pigmentary parttcie size is significantly reduced to prevent any agglomeration or re-agg!omeratton. A typical pigment dispersion particle size Is 5 um. Below 5pm depicts superiority in the dispersion. A synergy between iow particle size dispersion and a satisfactory viscosity is more favorable than a iow viscosity evaluation alone.

The caprate/capryfate-PPDS-isostearyl of the invention exhibits a particle size below 5 pm together with a satisfactory viscosity level comparable to conventional used emollient like the Cromoiiient^DPSA. Color intensity via ColoHmetry

The color intensity was performed by evaluating the L* and a* values of each dispersion.

Defined by the "Commission Internationale de I'Eclairage" (CIE), the L*a*b* color space was modeied after a coior-opponent theory stating that two colors cannot be red and green at the same time or yellow and blue at the same time,

L* indicates lightness/darkness of the sample,

a* is the red/green coordinate.

b* is the yellow/blue coordinate.

The following tabie 6 shows the results.

Table 6:

Emollient L* a* I c* I h*

Caprate/capryiate-PPDS-isostearyi 32.35 33,60 15.68 37, 10 25.10 of the invention

Cromol!ient™ DP3A 32.45 32.13 15.58 35.71 25,87

Crodamoi™ GTCC 32,45 35.33 16.96 39.19 25.64

Castor oil 31.30 36.78 12.78 1 38.97 1 19.31

Cromoliient DP3A and Crodamoi GTCC exhibit the lightest sample tested and the highest red coordinate belongs to castor oil. Overall, the lightness result of the compound of the invention (32.35) is only 0, 10% different than its counterparts Cromoiiient DP3A and Crodamoi GTCC (32.45), and the redness/red co!or intensity for the caprate/capry!ate-PPD5-isostearyi of the invention (33,60) is 8,00% different than the emollient that exhibits the highest color vibrancy. I can be concluded, therefore, that the color intensity of pigment dispersions with the compound of the invention is comparable to conventional used emollients,

Example 4: Personal care or cosmetic products according to the invention

The compounds of the invention have very good compatibility with many different types of skin care systems ranging from sticks, waxes, pigments, lotions, sunscreens, with excellent stability as for example shown by the following test.

Stability test:

A wax system was made for a simple lip balm chassis. The system consisted of waxes and super sterol ester. Two systems were made, one with the Cromoliient™ DP3A, and another with the caprate/capryiate-PPDS-isostearyl of the invention using 12% of each. Both were placed in S0°C oven for 24hours. The lip bairn with the Cromoi!iant ^'m OP3A experienced significant sweating while the system with the compound of the invention was completely intact and unchanged.

Examples of other personal care and cosmetic products according to the invention are given beiow. As shown in Tables 7-15 below, weights are collective for ail Parts. For example, as shown in Tabie 7, the sum of the weights in Parts A-C is 100%.

The esfcer-PPDn-ether compound of the invention mentioned in these

formulations is present either a!one or as part of a mixture composition according to the invention comprising the named compound as the major component (w/w) compared to the corresponding ether-PPDn-ether and ester-PPDn-ester components.

Jh, Sprayabie Sunscreen Lotion

Propylene Glycol, Dtazo!idinyl Urea, Methyl Paraben, Propyi Para ben 1.00

The sprayabie sunscreen disclosed in Table 7 was formed by heating deionized water to a temperature between about 75°C to about 80°C _f then adding the xanthan gum, and allowing the xanthan gum to compieteiy hydrate. The remaining ingredients of Part A in Table 7 were added one at a time, each ingredient being allowed to fully dissolve before adding the next ingredient, Separately, Part B was prepared fay combining the ingredients of Part B in Tabie 7 and heating to about 75°C. Once Part A and Part B were prepared, Parts A and B were combined and maintained at a temperature between about 75°C to about BO^C for about 15 minutes. The mixture of Parts A and B was then cooied to about 45°C, Once coo!ed. Part C was added to the mixture of Parts A and B. The combined mixture was then be cooied and packaged.

Table 8: Acid cream

Ingredients 1 Weight % |

CRODAFOS CS-20 ACID (Cetearyi Aicohoi, Ceteth-20 Phosphate, I 8.0 j Dicetyi Phosphate)

CRODACOL C-70 (Cetyi Aicohoi) 2.0 !

Mineral Oil 1 14,50 I

CRODAMOL STS (PPG-3 Benzyl Myristate) 3.00 !

SUPER STEROL ESTER (C10-C30 Cholesterol/Lanosteroi Esters) 1 5.00 !

The acid cream disclosed in Table S was formed by combining and heating the components of Part A to about 80°C, Part B added to Part A, and the acid crystals were allowed to dissolve. Separately, the components of Part C were combined and heated to about 80°C. Then, Part C was added to the existing mixture of Parts A and B while mixing. The combined mixture of Parts A, B and C were maintained at about 80 ^e C for about 20 minutes, and then cooled to room temperature without using a water bath.

Tafofe 9: Microemuision Styling Gel

The styling gel disclosed in Table 9 was formed by combining the ingredients of

Part A while mixing and heating at a temperature between about 90°C to about 95°C. Separately, the ingredients of Part 8 were combined while mixing and heating at a temperature between about 90°C to about 95°C. Then, Part B was added to Part A while rapidly mixing and maintaining the temperature for about 15 minutes. Then, the mixture of Parts A and B was cooled to about 60°C and poured into molds before the mixture reached a set point of about 50 to about 55 °C, pH: 6,00 ±0.50. Table 10: Cationic Skin Moisturizing Lotion

The moisturizing lotion disclosed in Table 10 was formed by combining the ingredients of Part A whiie mixing and heating at a temperature between about 75°C to about 80°C. The heating temperature of Part A was maintained for about 15 minutes., and then the mixture of Part A was cooled to about 50°C. The ingredients of Part B were then added Individually to Part A whiie mixing. The iotion was then be cooled and packaged.

Table 11; Conditioning Shampoo with UV Protection

The conditioning shampoo disclosed in Table 11 was formed by combining the initial three ingredients of Part A and mixing until the solid had dissolved. Then, the remaining ingredient, PEG 7M was added and mixed until hydrated. Then, the ingredients of Part B were added to the mixture of Part A at temperatures up to about 75°C and mixed until solids had dissolved. The Part A/Part B mixture was cooied to about 40°C, and then the ingredients of Part C were added. Once the ingredients of Part C had been dissolved in the Part A/ Part B mixture., the pH of the combined Part A/Part B/Part C mixture was be determined, if the pH was outside a range of about 5.5 to about 7.0, the pH was adjusted to be within that range. Then, the ingredients of Part D were added while siow!y mixing between about 100 to about 300 rotations per minute (rpm).

Table 12: Hair Conditioning Rinse with UV Protection

HYDROTRITICUM WAA (Wheat Amino Acids) 3.00

The hair conditioning rinse disclosed in Table 12 was formed by combining the ingredients of Part A while mixing and heating at a temperature between about 80°C to about 8S°C, Separately, the ingredients of Part B were heated at a temperature between about 80°C to about S5 ^Q C. Then, Part B was added to Part A while mixing and maintaining the temperature for about 15 minutes. Then, the mixture of Parts A and 8 was cooied to about 50°C. After cooling, the ingredients of Part C were added while mixing, followed by the ingredients of Part D,

T^bjejy|: Anti-Perspirartt

The antt-perspirartt disclosed n Table 13 was formed by combining the ingredients of Part A while mixing and heating at a temperature are then added to the mixture. Once the first two ingredients of Part A were dissolved, then the remaining ingredients of Part B were added. Each remaining ingredient of Part B was added individually. The mixture of Parts A and B was mixed until it was homogeneous. Then, the mixture is cooied to a temperature between about 60°C to about 65°C, While maintaining that temperature, the ingredients of Part C were added while mixing and the mixture was mixed until it was homogeneous. Then, the mixture is cooled to a temperature of about 50°C, and poured into molds to form a solid anti-perspirant

Table 14: Hair Color Creme

The hair color creme disclosed in Table 14 was formed by combining the ingredients of Part A while mixing and heating to a temperature of up to about 70°C, and until the ingredients were dissolved. Separately, the ingredients of Part B were heated up to about 70°C. Then, Part 8 was added to Part A whife mixing and maintaining the temperature for about 15 minutes. Then, the mixture of Parts A and B were cooied to at temperature of about 45°C. After cooiing, the ingredients of Part C were added whi!e mixing. After further cooiing or at a temperature of about 35°C,, the ingredients of Part 0 were added to Parts A/B/C and the mixture mixed for about 1 hour. The mixture may then be mixed with a hydrogen peroxide developer at a weight ratio of about 1 : 1, at the time of application to hair.

Table 15: Up Stick

_.. Ac byj _.. PaJmitate 0.05

The ftp stick disclosed in Table 15 was formed by combining the ingredients of

Part A while mixing and heating between a temperature of about 85°C to about 90°C, and until the mixture was dear, Separately, ingredients of Part S were mixed until particle size was iess than about 25 microns. In some embodiments, a three-roll mill was utilized to achieve the desired particie size. Then,, Part B was added to Part A while continuing to mix unti! the mixture of Parts A and 8 was homogeneous. Then, the mixture of Parts A and B was cooled to about 75°C. After cooling, the ingredients of Part C were added whiie mixing and then the mixture was poured into molds at a temperature of about 70°C, Table 16: Make-Up Remover

an ropy para en

The Make-up remover disclosed in Tabie 16 was formed by combining the ingredients of Part A while mixing and heating to a temperature of about 80°C.

Separately, ingredients of Part B were mixed and heated to a temperature of about 80°C, Part B was then added to Part A while continuing to mix and maintain heat at about 80C for 10 minutes. The mixture of Parts A and 8 was cooled to about 40 ^e C, and then Part C was added and the resulting formulation cooied to room temperature.

Although the invention herein has been described with reference to particuiar embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be

understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims.